Chem. Rev.

2007, 107, 2891−2959 2891

Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and

Applications
Xiaobo Chen* and Samuel S. Mao†
Lawrence Berkeley National Laboratory, and University of California, Berkeley, California 94720

Received March 27, 2006

Contents 5.2. Photovoltaic Applications 2932

5.2.1. The TiO2 Nanocrystalline Electrode in 2932
1. Introduction 2891 DSSCs
2. Synthetic Methods for TiO2 Nanostructures 2892 5.2.2. Metal/Semiconductor Junction Schottky 2938
2.1. Sol−Gel Method 2892 Diode Solar Cell
2.2. Micelle and Inverse Micelle Methods 2895 5.2.3. Doped TiO2 Nanomaterials-Based Solar 2938
2.3. Sol Method 2896 Cell
2.4. Hydrothermal Method 2898 5.3. Photocatalytic Water Splitting 2939
2.5. Solvothermal Method 2901 5.3.1. Fundamentals of Photocatalytic Water 2939
2.6. Direct Oxidation Method 2902 Splitting
2.7. Chemical Vapor Deposition 2903 5.3.2. Use of Reversible Redox Mediators 2939
2.8. Physical Vapor Deposition 2904 5.3.3. Use of TiO2 Nanotubes 2940
2.9. Electrodeposition 2904 5.3.4. Water Splitting under Visible Light 2941
2.10. Sonochemical Method 2904 5.3.5. Coupled/Composite Water-Splitting 2942
2.11. Microwave Method 2904 System
2.12. TiO2 Mesoporous/Nanoporous Materials 2905 5.4. Electrochromic Devices 2942
2.13. TiO2 Aerogels 2906 5.4.1. Fundamentals of Electrochromic Devices 2943
2.14. TiO2 Opal and Photonic Materials 2907 5.4.2. Electrochromophore for an Electrochromic 2943
Device
2.15. Preparation of TiO2 Nanosheets 2908
5.4.3. Counterelectrode for an Electrochromic 2944
3. Properties of TiO2 Nanomaterials 2909 Device
3.1. Structural Properties of TiO2 Nanomaterials 2909 5.4.4. Photoelectrochromic Devices 2945
3.2. Thermodynamic Properties of TiO2 2911 5.5. Hydrogen Storage 2945
Nanomaterials
5.6. Sensing Applications 2947
3.3. X-ray Diffraction Properties of TiO2 2912
Nanomaterials 6. Summary 2948
3.4. Raman Vibration Properties of TiO2 2912 7. Acknowledgment 2949
Nanomaterials 8. References 2949
3.5. Electronic Properties of TiO2 Nanomaterials 2913
3.6. Optical Properties of TiO2 Nanomaterials 2915 1. Introduction
3.7. Photon-Induced Electron and Hole Properties 2918
of TiO2 Nanomaterials Since its commercial production in the early twentieth
4. Modifications of TiO2 Nanomaterials 2920 century, titanium dioxide (TiO2) has been widely used as a
pigment1 and in sunscreens,2,3 paints,4 ointments, toothpaste,5
4.1. Bulk Chemical Modification: Doping 2921
etc. In 1972, Fujishima and Honda discovered the phenom-
4.1.1. Synthesis of Doped TiO2 Nanomaterials 2921 enon of photocatalytic splitting of water on a TiO2 electrode
4.1.2. Properties of Doped TiO2 Nanomaterials 2921 under ultraviolet (UV) light.6-8 Since then, enormous efforts
4.2. Surface Chemical Modifications 2926 have been devoted to the research of TiO2 material, which
4.2.1. Inorganic Sensitization 2926 has led to many promising applications in areas ranging from
5. Applications of TiO2 Nanomaterials 2929 photovoltaics and photocatalysis to photo-/electrochromics
5.1. Photocatalytic Applications 2929 and sensors.9-12 These applications can be roughly divided
5.1.1. Pure TiO2 Nanomaterials: First 2930 into “energy” and “environmental” categories, many of which
Generation depend not only on the properties of the TiO2 material itself
5.1.2. Metal-Doped TiO2 Nanomaterials: 2930 but also on the modifications of the TiO2 material host (e.g.,
Second Generation with inorganic and organic dyes) and on the interactions of
5.1.3. Nonmetal-Doped TiO2 Nanomaterials: 2931 TiO2 materials with the environment.
Third Generation An exponential growth of research activities has been seen
in nanoscience and nanotechnology in the past decades.13-17
* Corresponding author. E-mail: XChen3@lbl.gov. New physical and chemical properties emerge when the size
† E-mail: SSMao@lbl.gov. of the material becomes smaller and smaller, and down to
10.1021/cr0500535 CCC: $65.00 © 2007 American Chemical Society
Published on Web 06/23/2007
2892 Chemical Reviews, 2007, Vol. 107, No. 7
Dr. Xiaobo Chen is a research engineer at The University of California at
Berkeley and a Lawrence Berkeley National Laboratory scientist. He
obtained his Ph.D. Degree in Chemistry from Case Western Reserve
University. His research interests include photocatalysis, photovoltaics,
hydrogen storage, fuel cells, environmental pollution control, and the related
materials and devices development.
Dr. Samuel S. Mao is a career staff scientist at Lawrence Berkeley National
Laboratory and an adjunct faculty at The University of California at
Berkeley. He obtained his Ph.D. degree in Engineering from The University
of California at Berkeley in 2000. His current research involves the
development of nanostructured materials and devices, as well as ultrafast
laser technologies. Dr. Mao is the team leader of a high throughput
materials processing program supported by the U.S. Department of Ener-
gy.
the nanometer scale. Properties also vary as the shapes of
the shrinking nanomaterials change. Many excellent reviews
and reports on the preparation and properties of nanomaterials
have been published recently.6-44 Among the unique proper-
ties of nanomaterials, the movement of electrons and holes
in semiconductor nanomaterials is primarily governed by the
well-known quantum confinement, and the transport proper-
ties related to phonons and photons are largely affected by
the size and geometry of the materials.13-16 The specific
surface area and surface-to-volume ratio increase dramati-
cally as the size of a material decreases.13,21 The high surface
area brought about by small particle size is beneficial to many
TiO2-based devices, as it facilitates reaction/interaction
between the devices and the interacting media, which mainly
occurs on the surface or at the interface and strongly depends
on the surface area of the material. Thus, the performance
of TiO2-based devices is largely influenced by the sizes of
the TiO2 building units, apparently at the nanometer scale.
As the most promising photocatalyst,7,11,12,33 TiO2 mate-
rials are expected to play an important role in helping solve
Chen and Mao
many serious environmental and pollution challenges. TiO2
also bears tremendous hope in helping ease the energy crisis
through effective utilization of solar energy based on
photovoltaic and water-splitting devices.9,31,32 As continued
breakthroughs have been made in the preparation, modifica-
tion, and applications of TiO2 nanomaterials in recent years,
especially after a series of great reviews of the subject in
the 1990s.7,8,10-12,33,45 we believe that a new and compre-
hensive review of TiO2 nanomaterials would further promote
TiO2-based research and development efforts to tackle the
environmental and energy challenges we are currently facing.
Here, we focus on recent progress in the synthesis, properties,
modifications, and applications of TiO2 nanomaterials. The
syntheses of TiO2 nanomaterials, including nanoparticles,
nanorods, nanowires, and nanotubes are primarily categorized
with the preparation method. The preparations of mesopo-
rous/nanoporous TiO2, TiO2 aerogels, opals, and photonic
materials are summarized separately. In reviewing nanoma-
terial synthesis, we present a typical procedure and repre-
sentative transmission or scanning electron microscopy
images to give a direct impression of how these nanomate-
rials are obtained and how they normally appear. For detailed
instructions on each synthesis, the readers are referred to
the corresponding literature.
The structural, thermal, electronic, and optical properties
of TiO2 nanomaterials are reviewed in the second section.
As the size, shape, and crystal structure of TiO2 nanomate-
rials vary, not only does surface stability change but also
the transitions between different phases of TiO2 under
pressure or heat become size dependent. The dependence of
X-ray diffraction patterns and Raman vibrational spectra on
the size of TiO2 nanomaterials is also summarized, as they
could help to determine the size to some extent, although
correlation of the spectra with the size of TiO2 nanomaterials
is not straightforward. The review of modifications of TiO2
nanomaterials is mainly limited to the research related to
the modifications of the optical properties of TiO2 nanoma-
terials, since many applications of TiO2 nanomaterials are
closely related to their optical properties. TiO2 nanomaterials
normally are transparent in the visible light region. By doping
or sensitization, it is possible to improve the optical sensitiv-
ity and activity of TiO2 nanomaterials in the visible light
region. Environmental (photocatalysis and sensing) and
energy (photovoltaics, water splitting, photo-/electrochromics,
and hydrogen storage) applications are reviewed with an
emphasis on clean and sustainable energy, since the increas-
ing energy demand and environmental pollution create a
pressing need for clean and sustainable energy solutions. The
fundamentals and working principles of the TiO2 nanoma-
terials-based devices are discussed to facilitate the under-
standing and further improvement of current and practical
TiO2 nanotechnology.
2. Synthetic Methods for TiO2 Nanostructures
2.1. Sol−Gel Method
The sol-gel method is a versatile process used in making
various ceramic materials.46-50 In a typical sol-gel process,
a colloidal suspension, or a sol, is formed from the hydrolysis
and polymerization reactions of the precursors, which are
usually inorganic metal salts or metal organic compounds
such as metal alkoxides. Complete polymerization and loss
of solvent leads to the transition from the liquid sol into a
solid gel phase. Thin films can be produced on a piece of
Titanium Dioxide Nanomaterials
substrate by spin-coating or dip-coating. A wet gel will form
when the sol is cast into a mold, and the wet gel is converted
into a dense ceramic with further drying and heat treatment.
A highly porous and extremely low-density material called
an aerogel is obtained if the solvent in a wet gel is removed
under a supercritical condition. Ceramic fibers can be drawn
from the sol when the viscosity of a sol is adjusted into a
proper viscosity range. Ultrafine and uniform ceramic
powders are formed by precipitation, spray pyrolysis, or
emulsion techniques. Under proper conditions, nanomaterials
can be obtained.
TiO2 nanomaterials have been synthesized with the sol-
gel method from hydrolysis of a titanium precusor.51-78 This
process normally proceeds via an acid-catalyzed hydrolysis
step of titanium(IV) alkoxide followed by condensa-
tion.51,63,66,79-91 The development of Ti-O-Ti chains is
favored with low content of water, low hydrolysis rates, and
excess titanium alkoxide in the reaction mixture. Three-
dimensional polymeric skeletons with close packing result
from the development of Ti-O-Ti chains. The formation
of Ti(OH)4 is favored with high hydrolysis rates for a
medium amount of water. The presence of a large quantity
of Ti-OH and insufficient development of three-dimensional
polymeric skeletons lead to loosely packed first-order
particles. Polymeric Ti-O-Ti chains are developed in the
presence of a large excess of water. Closely packed first-
order particles are yielded via a three-dimensionally devel-
oped gel skeleton.51,63,66,79-91 From the study on the growth
kinetics of TiO2 nanoparticles in aqueous solution using
titanium tetraisopropoxide (TTIP) as precursor, it is found
that the rate constant for coarsening increases with temper-
ature due to the temperature dependence of the viscosity of
the solution and the equilibrium solubility of TiO2.63 Second-
ary particles are formed by epitaxial self-assembly of primary
particles at longer times and higher temperatures, and the
number of primary particles per secondary particle increases
with time. The average TiO2 nanoparticle radius increases
linearly with time, in agreement with the Lifshitz-Slyozov-
Wagner model for coarsening.63
Highly crystalline anatase TiO2 nanoparticles with different
sizes and shapes could be obtained with the polycondensation
of titanium alkoxide in the presence of tetramethylammonium
hydroxide.52,62 In a typical procedure, titanium alkoxide is
added to the base at 2 °C in alcoholic solvents in a three-
neck flask and is heated at 50-60 °C for 13 days or at 90-
100 °C for 6 h. A secondary treatment involving autoclave
heating at 175 and 200 °C is performed to improve the
crystallinity of the TiO2 nanoparticles. Representative TEM
images are shown in Figure 1 from the study of Chemseddine
et al.52
A series of thorough studies have been conducted by
Sugimoto et al. using the sol-gel method on the formation
of TiO2 nanoparticles of different sizes and shapes by tuning
the reaction parameters.67-71 Typically, a stock solution of
a 0.50 M Ti source is prepared by mixing TTIP with
triethanolamine (TEOA) ([TTIP]/[TEOA] ) 1:2), followed
by addition of water. The stock solution is diluted with a
shape controller solution and then aged at 100 °C for 1 day
and at 140 °C for 3 days. The pH of the solution can be
tuned by adding HClO4 or NaOH solution. Amines are used
as the shape controllers of the TiO2 nanomaterials and act
as surfactants. These amines include TEOA, diethylenetri-
amine, ethylenediamine, trimethylenediamine, and triethyl-
enetetramine. The morphology of the TiO2 nanoparticles
Chemical Reviews, 2007, Vol. 107, No. 7 2893
changes from cuboidal to ellipsoidal at pH above 11 with
TEOA. The TiO2 nanoparticle shape evolves into ellipsoidal
above pH 9.5 with diethylenetriamine with a higher aspect
ratio than that with TEOA. Figure 2 shows representative
TEM images of the TiO2 nanoparticles under different initial
pH conditions with the shape control of TEOA at [TEOA]/
[TIPO] ) 2.0. Secondary amines, such as diethylamine, and
tertiary amines, such as trimethylamine and triethylamine,
act as complexing agents of Ti(IV) ions to promote the
growth of ellipsoidal particles with lower aspect ratios. The
shape of the TiO2 nanoparticle can also be tuned from round-
cornered cubes to sharp-edged cubes with sodium oleate and
sodium stearate.70 The shape control is attributed to the tuning
of the growth rate of the different crystal planes of TiO2
nanoparticles by the specific adsorption of shape controllers
to these planes under different pH conditions.70
A prolonged heating time below 100 °C for the as-prepared
gel can be used to avoid the agglomeration of the TiO2 nano-
particles during the crystallization process.58,72 By heating
amorphous TiO2 in air, large quantities of single-phase ana-
tase TiO2 nanoparticles with average particle sizes between
7 and 50 nm can be obtained, as reported by Zhang and
Banfield.73-77 Much effort has been exerted to achieve highly
crystallized and narrowly dispersed TiO2 nanoparticles using
the sol-gel method with other modifications, such as a
semicontinuous reaction method by Znaidi et al.78 and a two-
stage mixed method and a continuous reaction method by
Kim et al.53,54
By a combination of the sol-gel method and an anodic
alumina membrane (AAM) template, TiO2 nanorods have
been successfully synthesized by dipping porous AAMs
into a boiled TiO2 sol followed by drying and heating
processes.92,93 In a typical experiment, a TiO2 sol solution is
prepared by mixing TTIP dissolved in ethanol with a solution
containing water, acetyl acetone, and ethanol. An AAM is
immersed into the sol solution for 10 min after being boiled
in ethanol; then it is dried in air and calcined at 400 °C for
10 h. The AAM template is removed in a 10 wt % H3PO4
aqueous solution. The calcination temperature can be used
to control the crystal phase of the TiO2 nanorods. At low
temperature, anatase nanorods can be obtained, while at
high temperature rutile nanorods can be obtained. The pore
size of the AAM template can be used to control the size of
these TiO2 nanorods, which typically range from 100 to 300
nm in diameter and several micrometers in length. Appar-
ently, the size distribution of the final TiO2 nanorods is
largely controlled by the size distribution of the pores of
the AAM template. In order to obtain smaller and mono-
sized TiO2 nanorods, it is necessary to fabricate high-quality
AAM templates. Figure 3 shows a typical TEM for TiO2
nanorods fabricated with this method. Normally, the TiO2
nanorods are composed of small TiO2 nanoparticles or
nanograins.
By electrophoretic deposition of TiO2 colloidal suspensions
into the pores of an AAM, ordered TiO2 nanowire arrays
can be obtained.94 In a typical procedure, TTIP is dissolved
in ethanol at room temperature, and glacial acetic acid mixed
with deionized water and ethanol is added under pH ) 2-3
with nitric acid. Platinum is used as the anode, and an AAM
with an Au substrate attached to Cu foil is used as the
cathode. A TiO2 sol is deposited into the pores of the AMM
under a voltage of 2-5 V and annealed at 500 °C for 24 h.
After dissolving the AAM template in a 5 wt % NaOH
solution, isolated TiO2 nanowires are obtained. In order to
2894 Chemical Reviews, 2007, Vol. 107, No. 7 Chen and Mao

Figure 1. TEM images of TiO2 nanoparticles prepared by hydrolysis of Ti(OR)4 in the presence of tetramethylammonium hydroxide.
Reprinted with permission from Chemseddine, A.; Moritz, T. Eur. J. Inorg. Chem. 1999, 235. Copyright 1999 Wiley-VCH.

Figure 2. TEM images of uniform anatase TiO2 nanoparticles. Reprinted from Sugimoto, T.; Zhou, X.; Muramatsu, A. J. Colloid Interface
Sci. 2003, 259, 53, Copyright 2003, with permission from Elsevier.

fabricate TiO2 nanowires instead of nanorods, an AAM with
long pores is a must.
TiO2 nanotubes can also be obtained using the sol-gel
method by templating with an AAM95-98 and other organic
compounds.99,100 For example, when an AAM is used as the
template, a thin layer of TiO2 sol on the wall of the pores of
the AAM is first prepared by sucking TiO2 sol into the pores
of the AAM and removing it under vacuum; TiO2 nanowires
are obtained after the sol is fully developed and the AAM is
removed. In the procedure by Lee and co-workers,96 a TTIP
solution was prepared by mixing TTIP with 2-propanol and
2,4-pentanedione. After the AAM was dipped into this
Titanium Dioxide Nanomaterials
Figure 3. TEM image of anatase nanorods and a single nanorod
composed of small TiO2 nanoparticles or nanograins (inset).
Reprinted from Miao, L.; Tanemura, S.; Toh, S.; Kaneko, K.;
Tanemura, M. J. Cryst. Growth 2004, 264, 246, Copyright 2004,
with permission from Elsevier.
Figure 4. SEM image of TiO2 nanotubes prepared from the AAO
template. Reprinted with permission from Liu, S. M.; Gan, L. M.;
Liu, L. H.; Zhang, W. D.; Zeng, H. C. Chem. Mater. 2002, 14,
1391. Copyright 2002 American Chemical Society.
solution, it was removed from the solution and placed under
vacuum until the entire volume of the solution was pulled
through the AAM. The AAM was hydrolyzed by water vapor
over a HCl solution for 24 h, air-dried at room temperature,
and then calcined in a furnace at 673 K for 2 h and cooled
to room temperature with a temperature ramp of 2 °C/h. Pure
TiO2 nanotubes were obtained after the AAM was dissolved
in a 6 M NaOH solution for several minutes.96 Alternatively,
TiO2 nanotubes could be obtained by coating the AAM
membranes at 60 °C for a certain period of time (12-48 h)
with dilute TiF4 under pH ) 2.1 and removing the AAM
after TiO2 nanotubes were fully developed.97 Figure 4 shows
a typical SEM image of the TiO2 nanotube array from the
AAM template.97
In another scheme, a ZnO nanorod array on a glass
substrate can be used as a template to fabricate TiO2
nanotubes with the sol-gel method.101 Briefly, TiO2 sol is
Chemical Reviews, 2007, Vol. 107, No. 7 2895
Figure 5. SEM of a TiO2 nanotube array; the inset shows the ZnO
nanorod array template. Reprinted with permission from Qiu, J. J.;
Yu, W. D.; Gao, X. D.; Li, X. M. Nanotechnology 2006, 17, 4695.
Copyright 2006 IOP Publishing Ltd.
deposited on a ZnO nanorod template by dip-coating with a
slow withdrawing speed, then dried at 100 °C for 10 min,
and heated at 550 °C for 1 h in air to obtain ZnO/TiO2
nanorod arrays. The ZnO nanorod template is etched-up by
immersing the ZnO/TiO2 nanorod arrays in a dilute hydro-
chloric acid aqueous solution to obtain TiO2 nanotube arrays.
Figure 5 shows a typical SEM image of the TiO2 nanotube
array with the ZnO nanorod array template. The TiO2
nanotubes inherit the uniform hexagonal cross-sectional
shape and the length of 1.5 µm and inner diameter of 100-
120 nm of the ZnO nanorod template. As the concentration
of the TiO2 sol is constant, well-aligned TiO2 nanotube arrays
can only be obtained from an optimal dip-coating cycle
number in the range of 2-3 cycles. A dense porous TiO2
thick film with holes is obtained instead if the dip-coating
number further increases. The heating rate is critical to the
formation of TiO2 nanotube arrays. When the heating rate
is extra rapid, e.g., above 6 °C min-1, the TiO2 coat will
easily crack and flake off from the ZnO nanorods due to
great tensile stress between the TiO2 coat and the ZnO
template, and a TiO2 film with loose, porous nanostructure
is obtained.
2.2. Micelle and Inverse Micelle Methods
Aggregates of surfactant molecules dispersed in a liquid
colloid are called micelles when the surfactant concentration
exceeds the critical micelle concentration (CMC). The CMC
is the concentration of surfactants in free solution in
equilibrium with surfactants in aggregated form. In micelles,
the hydrophobic hydrocarbon chains of the surfactants are
oriented toward the interior of the micelle, and the hydro-
philic groups of the surfactants are oriented toward the
surrounding aqueous medium. The concentration of the lipid
present in solution determines the self-organization of the
molecules of surfactants and lipids. The lipids form a single
layer on the liquid surface and are dispersed in solution below
the CMC. The lipids organize in spherical micelles at the
first CMC (CMC-I), into elongated pipes at the second CMC
(CMC-II), and into stacked lamellae of pipes at the lamellar
point (LM or CMC-III). The CMC depends on the chemical
composition, mainly on the ratio of the head area and the
tail length. Reverse micelles are formed in nonaqueous
media, and the hydrophilic headgroups are directed toward
the core of the micelles while the hydrophobic groups are
2896 Chemical Reviews, 2007, Vol. 107, No. 7 Chen and Mao

directed outward toward the nonaqueous media. There is no

obvious CMC for reverse micelles, because the number of
aggregates is usually small and they are not sensitive to the
surfactant concentration. Micelles are often globular and
roughly spherical in shape, but ellipsoids, cylinders, and
bilayers are also possible. The shape of a micelle is a function
of the molecular geometry of its surfactant molecules and
solution conditions such as surfactant concentration, tem-
perature, pH, and ionic strength.
Micelles and inverse micelles are commonly employed to
synthesize TiO2 nanomaterials.102-110 A statistical experi-
mental design method was conducted by Kim et al. to
optimize experimental conditions for the preparation of TiO2
nanoparticles.103 The values of H2O/surfactant, H2O/titanium
precursor, ammonia concentration, feed rate, and reaction
temperature were significant parameters in controlling TiO2
nanoparticle size and size distribution. Amorphous TiO2 Figure 6. TEM images of the shuttle-like and round-shaped (inset)
TiO2 nanoparticles. From: Zhang, D., Qi, L., Ma, J., Cheng, H. J.
nanoparticles with diameters of 10-20 nm were synthesized Mater. Chem. 2002, 12, 3677 (http://dx.doi.org/10.1039/b206996b).
and converted to the anatase phase at 600 °C and to the more s Reproduced by permission of The Royal Society of Chemistry.
thermodynamically stable rutile phase at 900 °C. Li et al.
developed TiO2 nanoparticles with the chemical reactions
between TiCl4 solution and ammonia in a reversed micro-
emulsion system consisting of cyclohexane, poly(oxyethyl-
ene)5 nonyle phenol ether, and poly(oxyethylene)9 nonyle
phenol ether.104 The produced amorphous TiO2 nanoparticles
transformed into anatase when heated at temperatures from
200 to 750 °C and into rutile at temperatures higher than
750 °C. Agglomeration and growth also occurred at elevated
temperatures.
Shuttle-like crystalline TiO2 nanoparticles were synthesized
by Zhang et al. with hydrolysis of titanium tetrabutoxide in
the presence of acids (hydrochloric acid, nitric acid, sulfuric
acid, and phosphoric acid) in NP-5 (Igepal CO-520)-
cyclohexane reverse micelles at room temperature.110 The
crystal structure, morphology, and particle size of the TiO2
nanoparticles were largely controlled by the reaction condi-
tions, and the key factors affecting the formation of rutile at
room temperature included the acidity, the type of acid used,
and the microenvironment of the reverse micelles. Ag-
glomeration of the particles occurred with prolonged reaction
times and increasing the [H2O]/[NP-5] and [H2O]/[Ti-
(OC4H9)4] ratios. When suitable acid was applied, round TiO2
nanoparticles could also be obtained. Representative TEM
images of the shuttle-like and round-shaped TiO2 nanopar-
ticles are shown in Figure 6. In the study carried out by Lim Figure 7. HRTEM images of a TiO2 nanoparticle after annealing.
et al., TiO2 nanoparticles were prepared by the controlled Reprinted with permission from Lin, J.; Lin, Y.; Liu, P.; Meziani,
hydrolysis of TTIP in reverse micelles formed in CO2 with M. J.; Allard, L. F.; Sun, Y. P. J. Am. Chem. Soc. 2002, 124, 11514.
the surfactants ammonium carboxylate perfluoropolyether Copyright 2002 American Chemical Society.
(PFPECOO-NH4+) (MW 587) and poly(dimethyl amino
ethyl methacrylate-block-1H,1H,2H,2H-perfluorooctyl meth- treatment in the solid state.108 This procedure could produce
acrylate) (PDMAEMA-b-PFOMA).106 It was found that the crystalline TiO2 nanoparticles with unchanged physical
crystallite size prepared in the presence of reverse micelles dimensions and minimal agglomeration and allows the
increased as either the molar ratio of water to surfactant or preparation of highly crystalline TiO2 nanoparticles, as shown
the precursor to surfactant ratio increased. in Figure 7, from the study of Lin et al.108
The TiO2 nanomaterials prepared with the above micelle
and reverse micelle methods normally have amorphous
2.3. Sol Method
structure, and calcination is usually necessary in order to The sol method here refers to the nonhydrolytic sol-gel
induce high crystallinity. However, this process usually leads processes and usually involves the reaction of titanium
to the growth and agglomeration of TiO2 nanoparticles. The chloride with a variety of different oxygen donor molecules,
crystallinity of TiO2 nanoparticles initially (synthesized by e.g., a metal alkoxide or an organic ether.111-119
controlled hydrolysis of titanium alkoxide in reverse micelles
in a hydrocarbon solvent) could be improved by annealing TiX4 + Ti(OR)4 f 2TiO2 + 4RX (1)
in the presence of the micelles at temperatures considerably
lower than those required for the traditional calcination TiX4 + 2ROR f TiO2 + 4RX (2)
Titanium Dioxide Nanomaterials
Figure 8. TEM image of TiO2 nanoparticles derived from reaction
of TiCl4 and TTIP in TOPO/heptadecane at 300 °C. The inset shows
a HRTEM image of a single particle. Reprinted with permission
from Trentler, T. J.; Denler, T. E.; Bertone, J. F.; Agrawal, A.;
Colvin, V. L. J. Am. Chem. Soc. 1999, 121, 1613. Copyright 1999
American Chemical Society.
The condensation between Ti-Cl and Ti-OR leads to the
formation of Ti-O-Ti bridges. The alkoxide groups can
be provided by titanium alkoxides or can be formed in situ
by reaction of the titanium chloride with alcohols or ethers.
In the method by Trentler and Colvin,119 a metal alkoxide
was rapidly injected into the hot solution of titanium halide
mixed with trioctylphosphine oxide (TOPO) in heptadecane
at 300 °C under dry inert gas protection, and reactions were
completed within 5 min. For a series of alkyl substituents
including methyl, ethyl, isopropyl, and tert-butyl, the reaction
rate dramatically increased with greater branching of R, while
average particle sizes were relatively unaffected. Variation
of X yielded a clear trend in average particle size, but without
a discernible trend in reaction rate. Increased nucleophilicity
(or size) of the halide resulted in smaller anatase nanocrystals.
Average sizes ranged from 9.2 nm for TiF4 to 3.8 nm for
TiI4. The amount of passivating agent (TOPO) influenced
the chemistry. Reaction in pure TOPO was slower and
resulted in smaller particles, while reactions without TOPO
were much quicker and yielded mixtures of brookite, rutile,
and anatase with average particle sizes greater than 10 nm.
Figure 8 shows typical TEM images of TiO2 nanocrystals
developed by Trentler et al.119
In the method used by Niederberger and Stucky,111 TiCl4
was slowly added to anhydrous benzyl alcohol under
vigorous stirring at room temperature and was kept at 40-
150 °C for 1-21 days in the reaction vessel. The precipitate
was calcinated at 450 °C for 5 h after thoroughly washing.
The reaction between TiCl4 and benzyl alcohol was found
suitable for the synthesis of highly crystalline anatase phase
TiO2 nanoparticles with nearly uniform size and shape at
very low temperatures, such as 40 °C. The particle size could
be selectively adjusted in the range of 4-8 nm with the
appropriate thermal conditions and a proper choice of the
relative amounts of benzyl alcohol and titanium tetrachloride.
The particle growth depended strongly on temperature, and
lowering the titanium tetrachloride concentration led to a
considerable decrease of particle size.111
Surfactants have been widely used in the preparation of a
variety of nanoparticles with good size distribution and
dispersity.15,16 Adding different surfactants as capping agents,
such as acetic acid and acetylacetone, into the reaction matrix
Chemical Reviews, 2007, Vol. 107, No. 7 2897
Figure 9. TEM of TiO2 nanorods. The inset shows a HRTEM of
a TiO2 nanorod. Reprinted with permission from Cozzoli, P. D.;
Kornowski, A.; Weller, H. J. Am. Chem. Soc. 2003, 125, 14539.
Copyright 2003 American Chemical Society.
can help synthesize monodispersed TiO2 nanoparticles.120,121
For example, Scolan and Sanchez found that monodisperse
nonaggregated TiO2 nanoparticles in the 1-5 nm range were
obtained through hydrolysis of titanium butoxide in the
presence of acetylacetone and p-toluenesulfonic acid at 60
°C.120 The resulting nanoparticle xerosols could be dispersed
in water-alcohol or alcohol solutions at concentrations
higher than 1 M without aggregation, which is attributed to
the complexation of the surface by acetylacetonato ligands
and through an adsorbed hybrid organic-inorganic layer
made with acetylacetone, p-toluenesulfonic acid, and wa-
ter.120
With the aid of surfactants, different sized and shaped TiO2
nanorods can be synthesized.122-130 For example, the growth
of high-aspect-ratio anatase TiO2 nanorods has been reported
by Cozzoli and co-workers by controlling the hydrolysis
process of TTIP in oleic acid (OA).122-126,130 Typically, TTIP
was added into dried OA at 80-100 °C under inert gas
protection (nitrogen flow) and stirred for 5 min. A 0.1-2 M
aqueous base solution was then rapidly injected and kept at
80-100 °C for 6-12 h with stirring. The bases employed
included organic amines, such as trimethylamino-N-oxide,
trimethylamine, tetramethylammonium hydroxide, tetrabut-
ylammonium hydroxyde, triethylamine, and tributylamine.
In this reaction, by chemical modification of the titanium
precursor with the carboxylic acid, the hydrolysis rate of
titanium alkoxide was controlled. Fast (in 4-6 h) crystal-
lization in mild conditions was promoted with the use of
suitable catalysts (tertiary amines or quaternary ammonium
hydroxides). A kinetically overdriven growth mechanism led
to the growth of TiO2 nanorods instead of nanoparticles.123
Typical TEM images of the TiO2 nanorods are shown in
Figure 9.123
Recently, Joo et al.127 and Zhang et al.129 reported similar
procedures in obtaining TiO2 nanorods without the use of
catalyst. Briefly, a mixture of TTIP and OA was used to
generate OA complexes of titanium at 80 °C in 1-octadecene.
2898 Chemical Reviews, 2007, Vol. 107, No. 7
Figure 10. TEM images of TiO2 nanorods with lengths of (A) 12 nm, (B) 30 nm, and (C) 16 nm. (D) 2.3 nm TiO2 nanoparticles. Inset
in parts C and D: HR-TEM image of a single TiO2 nanorod and nanoparticle. Reprinted with permission from Zhang, Z.; Zhong, X.; Liu,
S.; Li, D.; Han, M. Angew. Chem., Int. Ed. 2005, 44, 3466. Copyright 2005 Wiley-VCH.
The injection of a predetermined amount of oleylamine at
260 °C led to various sized TiO2 nanorods.129 Figure 10
shows TEM images of TiO2 nanorods with various lengths,
and 2.3 nm TiO2 nanoparticles prepared with this method.129
In the surfactant-mediated shape evolution of TiO2 nano-
crystals in nonaqueous media conducted by Jun et al.,128 it
was found that the shape of TiO2 nanocrystals could be
modified by changing the surfactant concentration. The
synthesis was accomplished by an alkyl halide elimination
reaction between titanium chloride and titanium isopro-
poxide. Briefly, a dioctyl ether solution containing TOPO
and lauric acid was heated to 300 °C followed by addition
of titanium chloride under vigorous stirring. The reaction
was initiated by the rapid injection of TTIP and quenched
with cold toluene. At low lauric acid concentrations, bullet-
and diamond-shaped nanocrystals were obtained; at higher
concentrations, rod-shaped nanocrystals or a mixture of
nanorods and branched nanorods was observed. The bullet-
and diamond-shaped nanocrystals and nanorods were elon-
gated along the [001] directions. The TiO2 nanorods were
found to simultaneously convert to small nanoparticles as a
function of the growth time, as shown in Figure 11, due to
the minimization of the overall surface energy via dissolution
and regrowth of monomers during an Ostwald ripening.
2.4. Hydrothermal Method
Hydrothermal synthesis is normally conducted in steel
pressure vessels called autoclaves with or without Teflon
Chen and Mao
liners under controlled temperature and/or pressure with the
reaction in aqueous solutions. The temperature can be
elevated above the boiling point of water, reaching the
pressure of vapor saturation. The temperature and the amount
of solution added to the autoclave largely determine the
internal pressure produced. It is a method that is widely used
for the production of small particles in the ceramics industry.
Many groups have used the hydrothermal method to prepare
TiO2 nanoparticles.131-140 For example, TiO2 nanoparticles
can be obtained by hydrothermal treatment of peptized
precipitates of a titanium precursor with water.134 The
precipitates were prepared by adding a 0.5 M isopropanol
solution of titanium butoxide into deionized water ([H2O]/
[Ti] ) 150), and then they were peptized at 70 °C for 1 h in
the presence of tetraalkylammonium hydroxides (peptizer).
After filtration and treatment at 240 °C for 2 h, the
as-obtained powders were washed with deionized water and
absolute ethanol and then dried at 60 °C. Under the same
concentration of peptizer, the particle size decreased with
increasing alkyl chain length. The peptizers and their
concentrations influenced the morphology of the particles.
Typical TEM images of TiO2 nanoparticles made with the
hydrothermal method are shown in Figure 12.134
In another example, TiO2 nanoparticles were prepared by
hydrothermal reaction of titanium alkoxide in an acidic
ethanol-water solution.132 Briefly, TTIP was added dropwise
to a mixed ethanol and water solution at pH 0.7 with nitric
acid, and reacted at 240 °C for 4 h. The TiO2 nanoparticles
Titanium Dioxide Nanomaterials
Figure 11. Time dependent shape evolution of TiO2 nanorods:
(a) 0.25 h; (b) 24 h; (c) 48 h. Scale bar ) 50 nm. Reprinted with
permission from Jun, Y. W.; Casula, M. F.; Sim, J. H.; Kim, S.
Y.; Cheon, J.; Alivisatos, A. P. J. Am. Chem. Soc. 2003, 125, 15981.
Copyright 2003 American Chemical Society.
synthesized under this acidic ethanol-water environment
were mainly primary structure in the anatase phase without
secondary structure. The sizes of the particles were controlled
to the range of 7-25 nm by adjusting the concentration of
Ti precursor and the composition of the solvent system.
Chemical Reviews, 2007, Vol. 107, No. 7 2899
Figure 12. TEM images of TiO2 nanoparticles prepared by the
hydrothermal method. Reprinted from Yang, J.; Mei, S.; Ferreira,
J. M. F. Mater. Sci. Eng. C 2001, 15, 183, Copyright 2001, with
permission from Elsevier.
Figure 13. TEM image of TiO2 nanorods prepared with the
hydrothermal method. Reprinted with permission from Zhang, Q.;
Gao, L. Langmuir 2003, 19, 967. Copyright 2003 American
Chemical Society.
Besides TiO2 nanoparticles, TiO2 nanorods have also been
synthesized with the hydrothermal method.141-146 Zhang et
al. obtained TiO2 nanorods by treating a dilute TiCl4 solution
at 333-423 K for 12 h in the presence of acid or inorganic
salts.141,143-146 Figure 13 shows a typical TEM image of the
TiO2 nanorods prepared with the hydrothermal method.141
The morphology of the resulting nanorods can be tuned with
different surfactants146 or by changing the solvent composi-
tions.145 A film of assembled TiO2 nanorods deposited on a
glass wafer was reported by Feng et al.142 These TiO2
nanorods were prepared at 160 °C for 2 h by hydrothermal
treatment of a titanium trichloride aqueous solution super-
saturated with NaCl.
TiO2 nanowires have also been successfully obtained with
the hydrothermal method by various groups.147-151 Typically,
TiO2 nanowires are obtained by treating TiO2 white powders
in a 10-15 M NaOH aqueous solution at 150-200 °C for
24-72 h without stirring within an autoclave. Figure 14
shows the SEM images of TiO2 nanowires and a TEM image
of a single nanowire prepared by Zhang and co-workers.150
TiO2 nanowires can also be prepared from layered titanate
particles using the hydrothermal method as reported by Wei
2900 Chemical Reviews, 2007, Vol. 107, No. 7 Chen and Mao

Figure 15. TEM images of TiO2 nanowires made from the layered
Na2Ti3O7 particles, with the HRTEM image shown in the inset.
Reprinted from Wei, M.; Konishi, Y.; Zhou, H.; Sugihara, H.;
Figure 14. SEM images of TiO2 nanowires with the inset showing Arakawa, H. Chem. Phys. Lett. 2004, 400, 231, Copyright 2004,
a TEM image of a single TiO2 nanowire with a [010] selected area with permission from Elsevier.
electron diffraction (SAED) recorded perpendicular to the long axis
of the wire. Reprinted from Zhang, Y. X.; Li, G. H.; Jin, Y. X.;
Zhang, Y.; Zhang, J.; Zhang, L. D. Chem. Phys. Lett. 2002, 365,
300, Copyright 2002, with permission from Elsevier.

et al.152 In their experiment, layer-structured Na2Ti3O7 was

dispersed into a 0.05-0.1 M HCl solution and kept at 140-
170 °C for 3-7 days in an autoclave. TiO2 nanowires were
obtained after the product was washed with H2O and finally
dried. In the formation of a TiO2 nanowire from layered
H2Ti3O7, there are three steps: (i) the exfoliation of layered
Na2Ti3O7; (ii) the nanosheets formation; and (iii) the nanow-
ires formation.152 In Na2Ti3O7, [TiO6] octahedral layers are
held by the strong static interaction between the Na+ cations
between the [TiO6] octahedral layers and the [TiO6] unit.
When the larger H3+O cations replace the Na+ cations in
the interlayer space of [TiO6] sheets, this static interaction
is weakened because the interlayer distance is enlarged. As
a result, the layered compounds Na2Ti3O7 are gradually
exfoliated. When Na+ is exchanged by H+ in the dilute HCl
solution, numerous H2Ti3O7 sheet-shaped products are
formed. Since the nanosheet does not have inversion sym-
metry, an intrinsic tension exists. The nanosheets split to form
nanowires in order to release the strong stress and lower the
total energy.152 A representative TEM image of TiO2
nanowires from Na2Ti3O7 is shown in Figure 15.152
The hydrothermal method has been widely used to prepare Figure 16. TEM image of TiO2 nanotubes. Reprinted with
TiO2 nanotubes since it was introduced by Kasuga et al. in permission from Kasuga, T.; Hiramatsu, M.; Hoson, A.; Sekino,
1998.153-175 Briefly, TiO2 powders are put into a 2.5-20 M T.; Niihara, K. Langmuir 1998, 14, 3160. Copyright 1998 American
NaOH aqueous solution and held at 20-110 °C for 20 h in Chemical Society.
an autoclave. TiO2 nanotubes are obtained after the products connection between the ends of the sheets, resulting in the
are washed with a dilute HCl aqueous solution and distilled formation of a tube structure. In this mechanism, the TiO2
water. They proposed the following formation process of nanotubes were formed in the stage of the acid treatment
TiO2 nanotubes.154 When the raw TiO2 material was treated following the alkali treatment. Figure 16 shows typical TEM
with NaOH aqueous solution, some of the Ti-O-Ti bonds images of TiO2 nanotubes made by Kasuga et al.153 However,
were broken and Ti-O-Na and Ti-OH bonds were formed. Du and co-workers found that the nanotubes were formed
New Ti-O-Ti bonds were formed after the Ti-O-Na and during the treatment of TiO2 in NaOH aqueous solution.161
Ti-OH bonds reacted with acid and water when the material A 3D f 2D f 1D formation mechanism of the TiO2
was treated with an aqueous HCl solution and distilled water. nanotubes was proposed by Wang and co-workers.171 It stated
The Ti-OH bond could form a sheet. Through the dehydra- that the raw TiO2 was first transformed into lamellar
tion of Ti-OH bonds by HCl aqueous solution, Ti-O-Ti structures and then bent and rolled to form the nanotubes.
bonds or Ti-O-H-O-Ti hydrogen bonds were generated. For the formation of the TiO2 nanotubes, the two-dimensional
The bond distance from one Ti to the next Ti on the surface lamellar TiO2 was essential. Yao and co-workers further
decreased. This resulted in the folding of the sheets and the suggested, based on their HRTEM study as shown in Figure
Titanium Dioxide Nanomaterials
Figure 17. (a) HRTEM images of TiO2 nanotubes. (b) Cross-
sectional view of TiO2 nanotubes. Reused with permission from
B. D. Yao, Y. F. Chan, X. Y. Zhang, W. F. Zhang, Z. Y. Yang, N.
Wang, Applied Physics Letters 82, 281 (2003). Copyright 2003,
American Institute of Physics.
17, that TiO2 nanotubes were formed by rolling up the single-
layer TiO2 sheets with a rolling-up vector of [001] and
attracting other sheets to surround the tubes.172 Bavykin and
co-workers suggested that the mechanism of nanotube
formation involved the wrapping of multilayered nanosheets
rather than scrolling or wrapping of single layer nanosheets
followed by crystallization of successive layers.156 In the
mechanism proposed by Wang et al., the formation of TiO2
nanotubes involved several steps.176 During the reaction with
NaOH, the Ti-O-Ti bonding between the basic building
blocks of the anatase phase, the octahedra, was broken and
a zigzag structure was formed when the free octahedras
shared edges between the Ti ions with the formation of
hydroxy bridges, leading to the growth along the [100]
direction of the anatase phase. Two-dimensional crystalline
sheets formed from the lateral growth of the formation of
oxo bridges between the Ti centers (Ti-O-Ti bonds) in the
[001] direction and rolled up in order to saturate these
dangling bonds from the surface and lower the total energy,
resulting in the formation of TiO2 nanotubes.176
2.5. Solvothermal Method
The solvothermal method is almost identical to the
hydrothermal method except that the solvent used here is
nonaqueous. However, the temperature can be elevated much
higher than that in hydrothermal method, since a variety of
organic solvents with high boiling points can be chosen. The
solvothermal method normally has better control than hy-
drothermal methods of the size and shape distributions and
the crystallinity of the TiO2 nanoparticles. The solvothermal
method has been found to be a versatile method for the
Chemical Reviews, 2007, Vol. 107, No. 7 2901
Figure 18. TEM micrographs of TiO2 nanoparticles prepared with
the solvothermal method. Reprinted with permission from Li, X.
L.; Peng, Q.; Yi, J. X.; Wang, X.; Li, Y. D. Chem.sEur. J. 2006,
12, 2383. Copyright 2006 Wiley-VCH.
synthesis of a variety of nanoparticles with narrow size
distribution and dispersity.177-179 The solvothermal method
has been employed to synthesize TiO2 nanoparticles and
nanorods with/without the aid of surfactants.177-185 For
example, in a typical procedure by Kim and co-workers,184
TTIP was mixed with toluene at the weight ratio of 1-3:10
and kept at 250 °C for 3 h. The average particle size of TiO2
powders tended to increase as the composition of TTIP in
the solution increased in the range of weight ratio of 1-3:
10, while the pale crystalline phase of TiO2 was not produced
at 1:20 and 2:5 weight ratios.184 By controlling the hydro-
lyzation reaction of Ti(OC4H9)4 and linoleic acid, redispers-
ible TiO2 nanoparticles and nanorods could be synthesized,
as found by Li et al. recently.177 The decomposition of NH4-
HCO3 could provide H2O for the hydrolyzation reaction, and
linoleic acid could act as the solvent/reagent and coordination
surfactant in the synthesis of nanoparticles. Triethylamine
could act as a catalyst for the polycondensation of the Ti-
O-Ti inorganic network to achieve a crystalline product and
had little influence on the products’ morphology. The chain
lengths of the carboxylic acids had a great influence on the
formation of TiO2, and long-chain organic acids were
important and necessary in the formation of TiO2.177 Figure
18 shows a representative TEM image of TiO2 nanoparticles
from their study.177
TiO2 nanorods with narrow size distributions can also be
developed with the solvothermal method.177,183 For example,
in a typical synthesis from Kim et al., TTIP was dissolved
in anhydrous toluene with OA as a surfactant and kept at
250 °C for 20 h in an autoclave without stirring.183 Long
dumbbell-shaped nanorods were formed when a sufficient
amount of TTIP or surfactant was added to the solution, due
to the oriented growth of particles along the [001] axis. At
a fixed precursor to surfactant weight ratio of 1:3, the
concentration of rods in the nanoparticle assembly increased
as the concentration of the titanium precursor in the solution
increased. The average particle size was smaller and the size
distribution was narrower than is the case for particles
synthesized without surfactant. The crystalline phase, diam-
eter, and length of these nanorods are largely influenced by
the precursor/surfactant/solvent weight ratio. Anatase nano-
2902 Chemical Reviews, 2007, Vol. 107, No. 7 Chen and Mao

Figure 20. TEM images of TiO2 nanowires synthesized by the

solvothermal method. From: Wen, B.; Liu, C.; Liu, Y. New J.
Chem. 2005, 29, 969 (http://dx.doi.org/10.1039/b502604k) s
Reproduced by permission of The Royal Society of Chemistry
(RSC) on behalf of the Centre National de la Recherche Scientifique
(CNRS).

Figure 19. TEM micrographs and electron diffraction patterns of

products prepared from solutions at the weight ratio of precursor/
solvent/surfactant ) 1:5:3. Reprinted from Kim, C. S.; Moon, B.
K.; Park, J. H.; Choi, B. C.; Seo, H. J. J. Cryst. Growth 2003, 257,
309, Copyright 2003, with permission from Elsevier.

rods were obtained from the solution with a precursor/

surfactant weight ratio of more than 1:3 for a precursor/
solvent weight ratio of 1:10 or from the solution with a
precursor/solvent weight ratio of more than 1:5 for a
precursor/surfactant weight ratio of 1:3. The diameter and
length of these nanorods were in the ranges of 3-5 nm and
18-25 nm, respectively. Figure 19 shows a typical TEM
image of TiO2 nanorods prepared from the solutions with
the weight ratio of precursor/solvent/surfactant ) 1:5:3.183
Similar to the hydrothermal method, the solvothermal
method has also been used for the preparation of TiO2
nanowires.180-182 Typically, a TiO2 powder suspension in an
5 M NaOH water-ethanol solution is kept in an autoclave
at 170-200 °C for 24 h and then cooled to room temperature
naturally. TiO2 nanowires are obtained after the obtained
sample is washed with a dilute HCl aqueous solution and
dried at 60 °C for 12 h in air.181 The solvent plays an
important role in determining the crystal morphology.
Solvents with different physical and chemical properties can
influence the solubility, reactivity, and diffusion behavior
of the reactants; in particular, the polarity and coordinating
ability of the solvent can influence the morphology and the
crystallization behavior of the final products. The presence
of ethanol at a high concentration not only can cause the
polarity of the solvent to change but also strongly affects
the ζ potential values of the reactant particles and the
increases solution viscosity. For example, in the absence of
ethanol, short and wide flakelike structures of TiO2 were
obtained instead of nanowires. When chloroform is used,
TiO2 nanorods were obtained.181 Figure 20 shows representa-
tive TEM images of the TiO2 nanowires prepared from the
solvothermal method.181 Alternatively, bamboo-shaped Ag-
doped TiO2 nanowires were developed with titanium butox-
ide as precursor and AgNO3 as catalyst.180 Through the
electron diffraction (ED) pattern and HRTEM study, the Ag
Figure 21. SEM morphology of TiO2 nanorods by directly
oxidizing a Ti plate with a H2O2 solution. Reprinted from Wu, J.
M. J. Cryst. Growth 2004, 269, 347, Copyright 2004, with
permission from Elesevier.
phase only existed in heterojunctions between single-crystal
TiO2 nanowires.180
2.6. Direct Oxidation Method
TiO2 nanomaterials can be obtained by oxidation of
titanium metal using oxidants or under anodization. Crystal-
line TiO2 nanorods have been obtained by direct oxidation
of a titanium metal plate with hydrogen peroxide.186-191
Typically, TiO2 nanorods on a Ti plate are obtained when a
cleaned Ti plate is put in 50 mL of a 30 wt % H2O2 solution
at 353 K for 72 h. The formation of crystalline TiO2 occurs
through a dissolution precipitation mechanism. By the
addition of inorganic salts of NaX (X ) F-, Cl-, and SO42-),
the crystalline phase of TiO2 nanorods can be controlled.
The addition of F- and SO42- helps the formation of pure
anatase, while the addition of Cl- favors the formation of
rutile.189 Figure 21 shows a typical SEM image of TiO2
nanorods prepared with this method.186
At high temperature, acetone can be used as a good oxygen
source and for the preparation of TiO2 nanorods by oxidizing
Titanium Dioxide Nanomaterials Chemical Reviews, 2007, Vol. 107, No. 7 2903

Figure 23. SEM images of TiO2 nanotubes prepared with anodic

Figure 22. SEM images of large-scale nanorod arrays prepared
by oxidizing a titanium with acetone at 850 °C for 90 min. From:
Peng, X.; Chen, A. J. Mater. Chem. 2004, 14, 2542 (http://
dx.doi.org/10.1039/b404750h) s Reproduced by permission of The
Royal Society of Chemistry.
oxidation. Reprinted with permission from Varghese, O. K.; Gong,
D.; Paulose, M.; Ong, K. G.; Dickey, E. C.; Grimes, C. A. AdV.
Mater. 2003, 15, 624. Copyright 2003 Wiley-VCH.

a Ti plate with acetone as reported by Peng and Chen.192

The oxygen source was found to play an important role.
Highly dense and well-aligned TiO2 nanorod arrays were
formed when acetone was used as the oxygen source, and
only crystal grain films or grains with random nanofibers
growing from the edges were obtained with pure oxygen or
argon mixed with oxygen. The competition of the oxygen
and titanium diffusion involved in the titanium oxidation
process largely controlled the morphology of the TiO2. With
pure oxygen, the oxidation occurred at the Ti metal and the
TiO2 interface, since oxygen diffusion predominated because
of the high oxygen concentration. When acetone was used
as the oxygen source, Ti cations diffused to the oxide surface
and reacted with the adsorbed acetone species. Figure 22
shows aligned TiO2 nanorod arrays obtained by oxidizing a
titanium substrate with acetone at 850 °C for 90 min.192
As extensively studied, TiO2 nanotubes can be obtained Figure 24. SEM images of TiO2 nanorods grown at 560 °C.
Reprinted with permission from Wu, J. J.; Yu, C. C. J. Phys. Chem.
by anodic oxidation of titanium foil.193-228 In a typical B 2004, 108, 3377. Copyright 2004 American Chemical Society.
experiment, a clean Ti plate is anodized in a 0.5% HF
solution under 10-20 V for 10-30 min. Platinum is used otherwise, it is called chemical vapor deposition (CVD). In
as counterelectrode. Crystallized TiO2 nanotubes are obtained CVD processes, thermal energy heats the gases in the coating
after the anodized Ti plate is annealed at 500 °C for 6 h in chamber and drives the deposition reaction.
oxygen.210 The length and diameter of the TiO2 nanotubes
Thick crystalline TiO2 films with grain sizes below 30 nm
could be controlled over a wide range (diameter, 15-120
as well as TiO2 nanoparticles with sizes below 10 nm can
nm; length, 20 nm to 10 µm) with the applied potential
be prepared by pyrolysis of TTIP in a mixed helium/oxygen
between 1 and 25 V in optimized phosphate/HF electro-
atmosphere, using liquid precursor delivery.230 When depos-
lytes.229 Figure 23 shows SEM images of TiO2 nanotubes
ited on the cold areas of the reactor at temperatures below
created with this method.208
90 °C with plasma enhanced CVD, amorphous TiO2 nano-
particles can be obtained and crystallize with a relatively
2.7. Chemical Vapor Deposition high surface area after being annealed at high temperatures.231
Vapor deposition refers to any process in which materials TiO2 nanorod arrays with a diameter of about 50-100 nm
in a vapor state are condensed to form a solid-phase material. and a length of 0.5-2 µm can be synthesized by metal
These processes are normally used to form coatings to alter organic CVD (MOCVD) on a WC-Co substrate using TTIP
the mechanical, electrical, thermal, optical, corrosion resis- as the precursor.232
tance, and wear resistance properties of various substrates. Figure 24 shows the TiO2 nanorods grown on fused silica
They are also used to form free-standing bodies, films, and substrates with a template- and catalyst-free MOCVD
fibers and to infiltrate fabric to form composite materials. method.233 In a typical procedure, titanium acetylacetonate
Recently, they have been widely explored to fabricate various (Ti(C10H14O5)) vaporizing in the low-temperature zone of a
nanomaterials. Vapor deposition processes usually take place furnace at 200-230 °C is carried by a N2/O2 flow into the
within a vacuum chamber. If no chemical reaction occurs, high-temperature zone of 500-700 °C, and TiO2 nanostruc-
this process is called physical vapor deposition (PVD); tures are grown directly on the substrates. The phase and
2904 Chemical Reviews, 2007, Vol. 107, No. 7
Figure 25. SEM images of the TiO2 nanowire arrays prepared by
the PVD method. Reprinted from Wu, J. M.; Shih, H. C.; Wu, W.
T. Chem. Phys. Lett. 2005, 413, 490, Copyright 2005, with
permission from Elsevier.
morphology of the TiO2 nanostructures can be tuned with
the reaction conditions. For example, at 630 and 560 °C
under a pressure of 5 Torr, single-crystalline rutile and
anatase TiO2 nanorods were formed respectively, while, at
535 °C under 3.6 Torr, anatase TiO2 nanowalls composed
of well-aligned nanorods were formed.233
In addition to the above CVD approaches in preparing
TiO2 nanomaterials, other CVD approaches are also used,
such as electrostatic spray hydrolysis,234 diffusion flame
pyrolysis,235-239 thermal plasma pyrolysis,240-246 ultrasonic
spray pyrolysis,247 laser-induced pyrolysis,248,249 and ultronsic-
assisted hydrolysis,250,251 among others.
2.8. Physical Vapor Deposition
In PVD, materials are first evaporated and then condensed
to form a solid material. The primary PVD methods include
thermal deposition, ion plating, ion implantation, sputtering,
laser vaporization, and laser surface alloying. TiO2 nanowire
arrays have been fabricated by a simple PVD method or
thermal deposition.252-254 Typically, pure Ti metal powder
is on a quartz boat in a tube furnace about 0.5 mm away
from the substrate. Then the furnace chamber is pumped
down to ∼300 Torr and the temperature is increased to 850
°C under an argon gas flow with a rate of 100 sccm and
held for 3 h. After the reaction, a layer of TiO2 nanowires
can be obtained.254 A layer of Ti nanopowders can be
deposited on the substrate before the growth of TiO2
nanowires,252,253 and Au can be employed as catalyst.252 A
typical SEM image of TiO2 nanowires made with the PVD
method is shown in Figure 25.252
2.9. Electrodeposition
Electrodeposition is commonly employed to produce a
coating, usually metallic, on a surface by the action of
reduction at the cathode. The substrate to be coated is used
as cathode and immersed into a solution which contains a
salt of the metal to be deposited. The metallic ions are
attracted to the cathode and reduced to metallic form. With
the use of the template of an AAM, TiO2 nanowires can be
obtained by electrodeposition.255,256 In a typical process, the
electrodeposition is carried out in 0.2 M TiCl3 solution with
Chen and Mao
Figure 26. Cross-sectional SEM image of TiO2 nanowires elec-
trodeposited in AAM pores. Reprinted from Liu, S.; Huang, K.
Sol. Energy Mater. Sol. Cells 2004, 85, 125, Copyright 2004, with
permission from Elsevier.
pH ) 2 with a pulsed electrodeposition approach, and
titanium and/or its compound are deposited into the pores
of the AAM. By heating the above deposited template at
500 °C for 4 h and removing the template, pure anatase TiO2
nanowires can be obtained. Figure 26 shows a representative
SEM image of TiO2 nanowires.256
2.10. Sonochemical Method
Ultrasound has been very useful in the synthesis of a wide
range of nanostructured materials, including high-surface-
area transition metals, alloys, carbides, oxides, and colloids.
The chemical effects of ultrasound do not come from a direct
interaction with molecular species. Instead, sonochemistry
arises from acoustic cavitation: the formation, growth, and
implosive collapse of bubbles in a liquid. Cavitational
collapse produces intense local heating (∼5000 K), high pres-
sures (∼1000 atm), and enormous heating and cooling rates
(>109 K/s). The sonochemical method has been applied to
prepare various TiO2 nanomaterials by different groups.257-269
Yu et al. applied the sonochemical method in preparing
highly photoactive TiO2 nanoparticle photocatalysts with
anatase and brookite phases using the hydrolysis of titanium
tetraisoproproxide in pure water or in a 1:1 EtOH-H2O
solution under ultrasonic radiation.109 Huang et al. found that
anatase and rutile TiO2 nanoparticles as well as their mixtures
could be selectively synthesized with various precursors
using ultrasound irradiation, depending on the reaction
temperature and the precursor used.259 Zhu et al. developed
titania whiskers and nanotubes with the assistance of
sonication as shown in Figure 27.269 They found that arrays
of TiO2 nanowhiskers with a diameter of 5 nm and nanotubes
with a diameter of ∼5 nm and a length of 200-300 nm could
be obtained by sonicating TiO2 particles in NaOH aqueous
solution followed by washing with deionized water and a
dilute HNO3 aqueous solution.
2.11. Microwave Method
A dielectric material can be processed with energy in the
form of high-frequency electromagnetic waves. The principal
Titanium Dioxide Nanomaterials Chemical Reviews, 2007, Vol. 107, No. 7 2905

Figure 28. SEM image of the mesoporous TiO2 film synthesized

from the acetic acid-modified precursor and autoclaved at 230 °C.
Reprinted with permission from Barbe, C. J.; Arendse, F.; Comte,
P.; Jirousek, M.; Lenzmann, F.; Shklover, V.; Grätzel, M. J. Am.
Ceram. Soc. 1997, 80, 3157. Copyright 1997 Blackwell Publishing.
Figure 27. TEM images of TiO2 nanotubes (A) and nanowhiskers
(B) prepared with the sonochemical method. From: Zhu, Y.; Li,
H.; Koltypin, Y.; Hacohen, Y. R.; Gedanken, A. Chem. Commun. surfactant templates.28,80,264,265,277-312 Barbe et al. reported the
2001, 2616 (http://dx.doi.org/10.1039/b108968b) s Reproduced by preparation of a mesoporous TiO2 film by the hydrothermal
permission of The Royal Society of Chemistry. method as shown Figure 28.80 In a typical experiment, TTIP
was added dropwise to a 0.1 M nitric acid solution under
frequencies of microwave heating are between 900 and 2450
vigorous stirring and at room temperature. A white precipitate
MHz. At lower microwave frequencies, conductive currents
formed instantaneously. Immediately after the hydrolysis, the
flowing within the material due to the movement of ionic con-
solution was heated to 80 °C and stirred vigorously for 8 h
stituents can transfer energy from the microwave field to the
for peptization. The solution was then filtered on a glass frit
material. At higher frequencies, the energy absorption is pri-
to remove agglomerates. Water was added to the filtrate to
marily due to molecules with a permanent dipole which tend
adjust the final solids concentration to ∼5 wt %. The solution
to reorientate under the influence of a microwave electric
was put in a titanium autoclave for 12 h at 200-250 °C.
field. This reorientation loss mechanism originates from the
After sonication, the colloidal suspension was put in a rotary
inability of the polarization to follow extremely rapid rever-
evaporator and evaporated to a final TiO2 concentration of
sals of the electric field, so the polarization phasor lags the
11 wt %. The precipitation pH, hydrolysis rate, autoclaving
applied electric field. This ensures that the resulting current
pH, and precursor chemistry were found to influence the
density has a component in phase with the field, and therefore
morphology of the final TiO2 nanoparticles.
power is dissipated in the dielectric material. The major
Alternative procedures without the use of hydrothermal
advantages of using microwaves for industrial processing are
processes have been reported by Liu et al.292 and Zhang et
rapid heat transfer, and volumetric and selective heating.
al.311 In the report by Liu et al., 24.0 g of titanium(IV)
Microwave radiation is applied to prepare various TiO2
n-butoxide ethanol solution (weight ratio of 1:7) was
nanomaterials.270-276 Corradi et al. found that colloidal titania
prehydrolyzed in the presence of 0.32 mL of a 0.28 M HNO3
nanoparticle suspensions could be prepared within 5 min to
aqueous solution (TBT/HNO3 ∼ 100:1) at room temperature
1 h with microwave radiation, while 1 to 32 h was needed
for 3 h. 0.32 mL of deionized water was added to the
for the conventional synthesis method of forced hydrolysis
prehydrolyzed solution under vigorous stirring and stirred
at 195 °C.270 Ma et al. developed high-quality rutile TiO2 nano-
for an additional 2 h. The sol solution in a closed vessel
rods with a microwave hydrothermal method and found that
was kept at room temperature without stirring to gel and
they aggregated radially into spherical secondary nanopartic-
age. After aging for 14 days, the gel was dried at room
les.272 Wu et al. synthesized TiO2 nanotubes by microwave
temperature, ground into a fine powder, washed thoroughly
radiation via the reaction of TiO2 crystals of anatase, rutile,
with water and ethanol, and dried to produce porous TiO2.
or mixed phase and NaOH aqueous solution under a certain
Upon calcination at 450 °C for 4 h under air, crystallized
microwave power.275 Normally, the TiO2 nanotubes had the
mesoporous TiO2 material was obtained.292
central hollow, open-ended, and multiwall structure with
Yu et al. prepared three-dimensional and thermally stable
diameters of 8-12 nm and lengths up to 200-1000 nm.275
mesoporous TiO2 without the use of any surfactants.265
Briefly, monodispersed TiO2 nanoparticles were formed
2.12. TiO2 Mesoporous/Nanoporous Materials initially by ultrasound-assisted hydrolysis of acetic acid-
In the past decade, mesoporous/nanoporous TiO2 materials modified titanium isopropoxide. Mesoporous spherical or
have been well studied with or without the use of organic globular particles were then produced by controlled conden-
2906 Chemical Reviews, 2007, Vol. 107, No. 7 Chen and Mao

sation and agglomeration of these sol nanoparticles under

high-intensity ultrasound radiation. The mesoporous TiO2 had
a wormhole-like structure consisting of TiO2 nanoparticles
and a lack of long-range order.265
In the template method used by the Stucky
group278-280,287,295,302,306-307,313 and other groups,264,293,297,303,309
structure-directing agents were used for organizing network-
forming metal oxide species in nonaqueous solutions. These
structure-directing agents were also called organic templates.
The most commonly used organic templates were amphi-
philic poly(alkylene oxide) block copolymers, such as HO-
(CH2CH2O)20(CH2CH(CH3)O)70(CH2CH2O)20H (designated
EO20PO70EO20, called Pluronic P-123) and HO(CH2CH2O)106-
(CH2CH(CH3)O)70(CH2CH2O)106H (designated EO106PO70-
EO106, called Pluronic F-127). In a typical synthesis, poly-
(alkylene oxide) block copolymer was dissolved in ethanol.
Then TiCl4 precursor was added with vigorous stirring. The
resulting sol solution was gelled in an open Petri dish at 40
°C in air for 1-7 days. Mesoporous TiO2 was obtained after
removing the surfactant species by calcining the as-made
sample at 400 °C for 5 h in air.306 Figure 29 shows typical
TEM images of the mesoporous TiO2. Besides triblock co-
polymers as structure-directing agents, diblock polymers were
also used such as [CnH2n-1(OCH2CH2)yOH, Brij 56 (B56, n/y
) 16/10) or Brij 58 (B58, n/y ) 16/20)] by Sanchez et al.285
Other surfactants employed to direct the formation of
mesoporous TiO2 include tetradecyl phosphate (a 14-carbon
chain) by Antonelli and Ying277 and commercially available
dodecyl phosphate by Putnam and co-workers,298 cetyltri-
methylammonium bromide (CTAB) (a cationic surfac-
tant),281,283,296 the recent Gemini surfactant,294 and dodecyl-
amine (a neutral surfactant).304 Carbon nanotubes310 and
mesoporous SBA-15286 have also been used as the skeleton
for mesoporous TiO2.

2.13. TiO2 Aerogels

The study of TiO2 aerogels is worthy of special men-
tion.314-326 The combination of sol-gel processing with
supercritical drying offers the synthesis of TiO2 aerogels with
morphological and chemical properties that are not easily
achieved by other preparation methods, i.e., with high surface
area. Campbell et al. prepared TiO2 aerogels by sol-gel
synthesis from titanium n-butoxide in methanol with the
subsequent removal of solvent by supercritical CO2.315 For
a typical synthesis process, titanium n-butoxide was added
to 40 mL of methanol in a dry glovebox. This solution was
combined with another solution containing 10 mL of
methanol, nitric acid, and deionized water. The concentration
of the titanium n-butoxide was kept at 0.625 M, and the
molar ratio of water/HNO3/titanium n-butoxide was 4:0.1:
1. The gel was allowed to age for 2 h and then extracted in
a standard autoclave with supercritical CO2 at a flow rate of Figure 29. TEM micrographs of two-dimensional hexagonal
24.6 L/h, at 343 K under 2.07 × 107 Pa for 2-3 h, resulting mesoporous TiO2 recorded along the (a) [110] and (b) [001] zone
in complete removal of solvent. After extraction, the sample axes, respectively. The inset in part a is selected-area electron
diffraction patterns obtained on the image area. (c) TEM image of
was heated in a vacuum oven at 3.4 kPa and 383 K for 3 h cubic mesoporous TiO2 accompanied by the corresponding (inset)
to remove the residual solvent and at 3.4 kPa and 483 K for EDX spectrum. Reprinted with permission from Yang, P.; Zhao,
3 h to remove any residual organics. The pretreated sample D.; Margolese, D. I.; Chmelka, B. F.; Stucky, G. D. Chem. Mater.
had a brown color and turned white after calcination at 773 1999, 11, 2813. Copyright 1999 American Chemical Society.
K or above. The resulting TiO2 aerogel, after calcination at
773 K for 2 h, had a BET surface area of >200 m2/g, 600 m2/g, as compared to a surface area of 50 m2/g for TiO2
contained mesopores in the range 2-10 nm, and was of the P25.316,317 Figure 30 shows a typical SEM image of a TiO2
pure anatase form. Dagan et al. found the TiO2 aerogels aerogel with a surface area of 447 m2/g and an interpore
obtanied by using a Ti/ethanol/H2O/nitric acid ratio of 1:20: structure constructed by near uniform grains of elliptical
3:0.08 could have a porosity of 90% and surface areas of shapes with 30 nm × 50 nm axes.326
Titanium Dioxide Nanomaterials Chemical Reviews, 2007, Vol. 107, No. 7 2907

Figure 30. SEM image of a TiO2 aerogel. Reprinted with

permission from Zhu, Z.; Tsung, L. Y.; Tomkiewicz, M. J. Phys.
Chem. 1995, 99, 15945. Copyright 1995 American Chemical
Society.

2.14. TiO2 Opal and Photonic Materials

The syntheses of TiO2 opal and photonic materials have
been well studied by various groups.327-358 Holland et al.
reported the preparation of TiO2 inverse opal from the
corresponding metal alkoxides, using latex spheres as
templates.334,335 Millimeter-thick layers of latex spheres were
deposited on filter paper in a Buchner funnel under vacuum
and soaked with ethanol. Titanium ethoxide was added
dropwise to cover the latex spheres completely while suction
was applied. Typical mass ratios of alkoxide to latex were
between 1.4 and 3. After drying the composite in a vacuum
desiccator for 3 to 24 h, the latex spheres were removed by
calcination in flowing air at 575 °C for 7 to 12 h, leaving
hard and brittle powder particles with 320- to 360-nm voids.
The carbon content of the calcined samples varied from 0.4
to 1.0 wt %, indicating that most of the latex templates had
been removed from the 3D host. Figure 31 shows an
illustration of the simple synthesis of TiO2 inverse opal and
an SEM image of TiO2 inverse opals. Similar studies have
also been carried out by other researchers.327,356
Dong and Marlow prepared TiO2 inversed opals with a
skeleton-like structure of TiO2 rods by a template-directed
method using monodispersed polystyrene particles of size
270 nm.328-330,345 Infiltration of a titania precursor (Ti(i-OPr)4 Figure 31. (A) Schematic illustration of the synthesis of a TiO2
inversed opal. (B) SEM image of the TiO2 inversed opal. Reprinted
in EtOH) was followed by a drying and calcination proce- with permission from Holland, B. T.; Blanford, C.; Stein, A. Science
dure. The precursor concentration was varied from 30% to 1998, 281, 538 (http://www.sciencemag.org). Copyright 1998
100%, and the calcination temperature was tuned from 300 AAAS.
to 700 °C. A SEM picture of the TiO2 inversed opal is shown
in Figure 32.329 The skeleton structure consists of rhombo- a sapphire substrate, which was then covered with a layer
hedral windows and TiO2 cylinders forming a highly regular of gold. After removing the PS spheres with toluene, ZnO
network. The cylinders connect the centers of the former nanorods were grown using a vapor-liquid-solid process.
octahedral and tetrahedral voids of the opal. These voids form Finally, a TiO2 layer was deposited on the ZnO nanorods
a CaF2 lattice which is filled with cylindrical bonds con- by introducing TiCl4 and water vapors into the atomic layer
necting the Ca and F sites. deposition chamber at 100 °C. Figure 34 shows SEM images
Wang et al. reported their study on the large-scale of a ZnO nanorod array and the TiO2-coated ZnO nanorod
fabrication of ordered TiO2 nanobowl arrays.354 The process array.
starts with a self-assembled monolayer of polystyrene (PS) Li et al. reported the preparation of ordered arrays of TiO2
spheres, which is used as a template for atomic layer opals using opal gel templates under uniaxial compression
deposition of a TiO2 layer. After ion-milling, toluene-etching, at ambient temperature during the TiO2 sol/gel process.337
and annealing of the TiO2-coated spheres, ordered arrays of The aspect ratio was controllable by the compression degree,
nanostructured TiO2 nanobowls can be fabricated as shown R. Polystyrene inverse opal was template synthesized using
in Figure 33. silica opals as template. The silica was removed with 40 wt
Wang et al. fabricated a 2D photonic crystal by coating % aqueous hydrofluoric acid. Monomer solutions consisting
patterned and aligned ZnO nanorod arrays with TiO2.355 PS of dimethylacrylamide, acrylic acid, and methylenebisacryl-
spheres were self-assembled to make a monolayer mask on amide in 1:1:0.02 weight ratios were dissolved in a water/
2908 Chemical Reviews, 2007, Vol. 107, No. 7
Figure 32. SEM picture of a TiO2 skeleton with a cylinder radius
of about 0.06a. a is the lattice constant of the cubic unit cell.
Reprinted from Dong, W.; Marlow, F. Physica E 2003, 17, 431,
Copyright 2003, with permission from Elsevier.
Figure 33. (A) Experimental procedure for fabricating TiO2
nanobowl arrays. (B) Low- and high- (inset) magnification SEM
image of TiO2 nanobowl arrays. Reprinted with permission from
Wang, X. D.; Graugnard, E.; King, J. S.; Wang, Z. L.; Summers,
C. J. Nano Lett. 2004, 4, 2223. Copyright 2004 American Chemical
Society.
ethanol mixture (4:7 wt/wt) with total monomer content 30
wt %. Ethanol was used to facilitate diffusion of the
monomer solution into the inverse opal polystyrene. After
the inverse opal was infiltrated by the monomer solution
containing 1 wt % of the initiator AIBN and a subsequent
free radical polymerization at 60 °C for 3 h, a solid composite
resulted. The initial inverse opal polystyrene template was
then removed with chloroform in a Soxhlet extractor for 12
h, whereupon the opal gel was formed. By using different
compositions of the monomer solution, hole sizes, and
stacking structures of the starting inverse opal templates, opal
Chen and Mao
Figure 34. (A) SEM images of short and densely aligned ZnO
nanorod array on a sapphire substrate. Inset: An optical image of
the aligned ZnO nanorods over a large area. (B) SEM image of
the TiO2-coated ZnO nanorod array. Reprinted with permission from
Wang, X.; Neff, C.; Graugnard, E.; Ding, Y.; King, J. S.; Pranger,
L. A.; Tannenbaum, R.; Wang, Z. L.; Summers, C. J. AdV. Mater.
2005, 17, 2103. Copyright 2005 Wiley-VCH.
gels with correspondingly different properties can be pro-
duced. Water was completely removed from the opal
hydrogel by repeatedly rinsing it with a large amount of
ethanol. Afterward, the opal gel was put into a large amount
of tetrabutyl titanate (TBT) at ambient temperature for 24
h. The TBT-swollen opal gel was then immersed in a water/
ethanol (1:1 wt/wt) mixture for 5 h to let the TiO2 sol/gel
process proceed. Figure 35A shows the opal structure of the
gel/titania composite spheres formed. After calcination, TiO2
opal with distinctive spherical contours could be found. The
compression degree, R, was adjusted by the spacer height
when the substrates were compressed. When the substrates
were slightly compressed against each other to the extent of
producing a 20% reduction in the thickness of the composi-
tion opal, the deformation of the template-synthesized titania
spheres was not substantial (Figure 35B). When the com-
pression degree was increased to the point of reaching 35%
deformation in the opal gel, noticeably deformed titania opals
could be obtained (Figure 35C and D).
2.15. Preparation of TiO2 Nanosheets
The preparation of TiO2 nanosheets has also been explored
recently.359-368 Typically, TiO2 nanosheets were synthesized
by delaminating layered protonic titanate into colloidal single
layers. A stoichiometric mixture of Cs2CO3 and TiO2 was
calcined at 800 °C for 20 h to produce a precursor, cesium
titanate, Cs0.7Ti1.82500.175O4 (0: vacancy), about 70 g of
which was treated with 2 L of a 1 M HCl solution at room
temperature. This acid leaching was repeated three times by
renewing the acid solution every 24 h. The resulting acid-
exchanged product was filtered, washed with water, and air-
dried. The obtained protonic titanate, H0.7Ti1.82500.175O4‚H2O,
was shaken vigorously with a 0.017 M tetrabutylammonium
hydroxide solution at ambient temperature for 10 days. The
solution-to-solid ratio was adjusted to 250 cm3 g-1. This
procedure yielded a stable colloidal suspension with an
Titanium Dioxide Nanomaterials Chemical Reviews, 2007, Vol. 107, No. 7 2909

Figure 35. SEM of the TiO2 opals. (A) A gel/titania composite opal fabricated without compressing the opal gel template during the
sol/gel process. (Inset) Image of the sample after calcination at 450 °C for 3 h. (B-D) (Main panel) Oblate titania opal materials after
calcination at 450 °C for 3 h, subject to compression degree R of (B) 20%, (C) 35%, and (D) 50%. The images were taken for the fractured
surfaces containing the direction of applied compression. (Inset) Image of the same sample, but with the fracture surface perpendicular to
the direction of applied compression. From: Ji, L.; Rong, J.; Yang, Z. Chem. Commun. 2003, 1080 (http://dx.doi.org/10.1039/b300825h)
s Reproduced by permission of The Royal Society of Chemistry.

opalescent appearance. Figure 36 shows TEM and AFM
images of TiO2 nanosheets with thicknesses of 1.2-1.3 nm,
which is the height of the TiO2 nanosheet with a monolayer
of water molecules on both sides (0.70 + 0.25 × 2) thick.366
3. Properties of TiO2 Nanomaterials
3.1. Structural Properties of TiO2 Nanomaterials
Figure 37 shows the unit cell structures of the rutile and
anatase TiO2.11 These two structures can be described in
terms of chains of TiO6 octahedra, where each Ti4+ ion is
surrounded by an octahedron of six O2- ions. The two crystal
structures differ in the distortion of each octahedron and by
the assembly pattern of the octahedra chains. In rutile, the
octahedron shows a slight orthorhombic distortion; in anatase,
the octahedron is significantly distorted so that its symmetry
is lower than orthorhombic. The Ti-Ti distances in anatase
are larger, whereas the Ti-O distances are shorter than those
in rutile. In the rutile structure, each octahedron is in contact
with 10 neighbor octahedrons (two sharing edge oxygen pairs
and eight sharing corner oxygen atoms), while, in the anatase
structure, each octahedron is in contact with eight neighbors
(four sharing an edge and four sharing a corner). These
differences in lattice structures cause different mass densities
and electronic band structures between the two forms of
TiO2.
Hamad et al. performed a theoretical calculation on TinO2n
clusters (n ) 1-15) with a combination of simulated
2910 Chemical Reviews, 2007, Vol. 107, No. 7 Chen and Mao

Figure 36. (A) TEM of Ti1-δO24δ- nanosheets. (B and C) AFM image and height scan of the TiO2 nanosheets deposited on a Si wafer.
(D) Structural model for a hydrated TiO2 nanosheet. Closed, open, and shaded circles represent Ti atom, O atom, and H2O molecules,
respectively. All the water sites are assumed to be half occupied. Reprinted with permission from Sasaki, T.; Ebina, Y.; Kitami, Y.; Watanabe,
M.; Oikawa, T. J. Phys. Chem. B 2001, 105, 6116. Copyright 2001 American Chemical Society.

amorphous transition regime at the smallest crystallite sizes,

Figure 37. Lattice structure of rutile and anatase TiO2. Reprinted
with permission from Linsebigler, A. L.; Lu, G.; Yates, J. T., Jr.
Chem. ReV. 1995, 95, 735. Copyright 1995 American Chemical
Society.
annealing, Monte Carlo basin hopping simulation, and
genetic algorithms methods.369 They found that the calculated
global minima consisted of compact structures, with titanium
atoms reaching high coordination rapidly as n increased. For
n g 11, the particles had at least a central octahedron
surrounded by a shell of surface tetrahedra, trigonal bipyra-
mids, and square base pyramids.
Swamy et al. found the metastability of anatase as a
function of pressure was size dependent, with smaller
crystallites preserving the structure to higher pressures.370
Three size regimes were recognized for the pressure-induced
phase transition of anatase at room temperature: an anatase-
an anatase-baddeleyite transition regime at intermediate
crystallite sizes, and an anatase-R-PbO2 transition regime
comprising large nanocrystals to macroscopic single crystals.
Barnard et al. performed a series of theoretical studies on
the phase stability of TiO2 nanoparticles in different environ-
ments by a thermodynamic model.371-375 They found that
surface passivation had an important impact on nanocrystal
morphology and phase stability. The results showed that
surface hydrogenation induced significant changes in the
shape of rutile nanocrystals, but not in anatase, and that the
size at which the phase transition might be expected increased
dramatically when the undercoordinated surface titanium
atoms were H-terminated. For spherical particles, the cross-
over point was about 2.6 nm. For a clean and faceted surface,
at low temperatures (a phase transition pointed at an average
diameter of approximately 9.3-9.4 nm for anatase nano-
crystals), the transition size decreased slightly to 8.9 nm when
the surface bridging oxygens were H-terminated, and the size
increased significantly to 23.1 nm when both the bridging
oxygens and the undercoordinated titanium atoms of the
surface trilayer were H-terminated. Below the cross point,
the anatase phase was more stable than the rutile phase.371
In their study on TiO2 nanoparticles in vacuum or water
environments, they found that the phase transition size in
water (15.1 nm) was larger than that under vacuum (9.6
nm).373 In their predictions on the transition enthalpy of
nanocrystalline anatase and rutile, they found that thermo-
chemical results could differ for various faceted or spherical
Titanium Dioxide Nanomaterials
Figure 38. Morphology predicted for anatase (top), with (a)
hydrogenated surfaces, (b) hydrogen-rich surface adsorbates, (c)
hydrated surfaces, (d) hydrogen-poor adsorbates, and (e) oxygenated
surfaces, and for rutile (bottom), with (f) hydrogenated surfaces,
(g) hydrogen-rich surface adsorbates, (h) hydrated surfaces, (i)
hydrogen-poor adsorbates, and (j) oxygenated surfaces. Reprinted
with permission from Barnard, A. S.; Curtiss, L. A. Nano Lett.
2005, 5, 1261. Copyright 2005 American Chemical Society.
nanoparticles as a function of shape, size, and degree of
surface passivation.372 Their study on anatase and rutile
titanium dioxide polymorphs passivated with complete
monolayers of adsorbates by varying the hydrogen to oxygen
ratio with respect to a neutral, water-terminated surface
showed that termination with water consistently resulted in
the lowest values of surface free energy when hydrated or
with a higher fraction of H on the surface on both anatase
and rutile surfaces, but conversely, the surfaces generally
had a higher surface free energy when they had an equal
ratio of H and O in the adsorbates or were O-terminated.375
They demonstrated that, under different pH conditions from
acid to basic, the phase transition size of a TiO2 nanoparticle
varied from 6.9 to 22.7 nm, accompanied with shape changes
of the TiO2 nanoparticles as shown in Figure 38.374
Enyashin and Seifert conducted a theoretical study on the
structural stability of TiO2 layer modifications (anatase and
lepidocrocite) using the density-functional-based tight bind-
ing method (DFTB).376 They found that anatase nanotubes
were the most stable modifications in a comparison of single-
walled nanotubes, nanostrips, and nanorolls. Their stability
increased as their radii grew. The energies for all TiO2
nanostructures relative to the infinite monolayer followed a
1/R2 curve.
Chen et al. found that severe distortions existed in Ti site
environments in the structures of 1.9 nm TiO2 nanoparticles
compared to those octahedral Ti sites in bulk anatase Ti using
K-edge XANES.377 The distorted Ti sites were likely to adopt
a pentacoordinate square pyramidal geometry due to the
truncation of the lattice. The distortions in the TiO2 lattice
were mainly located on the surface of the nanoparticles and
were responsible for binding with other small molecules.
Qian et al. found that the density of the surface states on
TiO2 nanoparticles was likely dependent upon the details of
the preparation methods.378 The TiO2 nanoparticles prepared
from basic sol were found to have more surface states than
those prepared from acidic sol based on a surface photo-
voltage spectroscopy study.
3.2. Thermodynamic Properties of TiO2
Nanomaterials
Rutile is the stable phase at high temperatures, but anatase
and brookite are common in fine grained (nanoscale) natural
Chemical Reviews, 2007, Vol. 107, No. 7 2911
Figure 39. Enthalpy of nanocrystalline TiO2. Reprinted with
permission from Ranade, M. R.; Navrotsky, A.; Zhang, H. Z.; Ban-
field, J. F.; Elder, S. H.; Zaban, A.; Borse, P. H.; Kulkarni, S. K.;
Doran, G. S.; Whitfield, H. J. Proc. Natl. Acad. Sci. U.S.A. 2002,
99, 6476. Copyright 2002 National Academy of Sciences, U.S.A.
and synthetic samples. On heating concomitant with coarsen-
ing, the following transformations are all seen: anatase to
brookite to rutile, brookite to anatase to rutile, anatase to
rutile, and brookite to rutile. These transformation sequences
imply very closely balanced energetics as a function of
particle size. The surface enthalpies of the three polymorphs
are sufficiently different that crossover in thermodynamic
stability can occur under conditions that preclude coarsening,
with anatase and/or brookite stable at small particle size.73,74
However, abnormal behaviors and inconsistent results are
occasionally observed.
Hwu et al. found the crystal structure of TiO2 nanoparticles
depended largely on the preparation method.379 For small
TiO2 nanoparticles (<50 nm), anatase seemed more stable
and transformed to rutile at >973 K. Banfield et al. found
that the prepared TiO2 nanoparticles had anatase and/or
brookite structures, which transformed to rutile after reaching
a certain particle size.73,380 Once rutile was formed, it grew
much faster than anatase. They found that rutile became more
stable than anatase for particle size > 14 nm.
Ye et al. observed a slow brookite to anatase phase
transition below 1053 K along with grain growth, rapid
brookite to anatase and anatase to rutile transformations
between 1053 K and 1123 K, and rapid grain growth of rutile
above 1123 K as the dominant phase.381 They concluded that
brookite could not transform directly to rutile but had to
transform to anatase first. However, direct transformation
of brookite nanocrystals to rutile was observed above 973
K by Kominami et al.382
In a later study, Zhang and Banfield found that the
transformation sequence and thermodynamic phase stability
depended on the initial particle sizes of anatase and brookite
in their study on the phase transformation behavior of
nanocrystalline aggregates during their growth for isothermal
and isochronal reactions.74 They concluded that, for equally
sized nanoparticles, anatase was thermodynamically stable
for sizes < 11 nm, brookite was stable for sizes between 11
and 35 nm, and rutile was stable for sizes > 35 nm.
Ranade et al. investigated the energetics of the TiO2
polymorphs (rutile, anatase, and brookite) by high-temper-
ature oxide melt drop solution calorimetry, and they found
the energetic stability crossed over between the three phases
as shown in Figure 39.383 The dark solid line represents the
phases of lowest enthalpy as a function of surface area. Rutile
was energetically stable for surface area < 592 m2/mol (7
m2/g or >200 nm), brookite was energetically stable from
2912 Chemical Reviews, 2007, Vol. 107, No. 7 Chen and Mao

592 to 3174 m2/mol (7-40 m2/g or 200-40 nm), and anatase

was energetically stable for greater surface areas or smaller
sizes (<40 nm). The anatase and rutile energetics cross at
1452 m2/mol (18 m2/g or 66 nm). Assuming spherical
particles, the calculated average diameters of rutile and
brookite for a 7 m2/g surface area were 201 and 206 nm,
and those of brookite and anatase for a 40 m2/g surface area
are 36 and 39 nm. These differences in particle size at the
same surface area existed because of the differences in
density. If the phase transformation took place without further
coarsening, the particle size should be smaller after the
transformation. Phase stability in a thermodynamic sense is
governed by the Gibbs free energy (∆G ) ∆H - T∆S) rather
than the enthalpy. Rutile and anatase have the same entropy.
Thus, the T∆S will not significantly perturb the sequence of
stability seen from the enthalpies. For nanocrystalline TiO2,
if the initially formed brookite had surface area > 40 m2/g,
it was metastable with respect to both anatase and rutile,
and the sequence brookite to anatase to rutile during
coarsening was energetically downhill. If anatase formed
initially, it could coarsen and transform first to brookite (at
40 m2/g) and then to rutile. The energetic driving force for
the latter reaction (brookite to rutile) was very small,
explaining the natural persistence of coarse brookite. In
contrast, the absence of coarse-grained anatase was consistent
with the much larger driving force for its transformation to
rutile.383
Li et al. found that only anatase to rutile phase transforma- Figure 40. (A) Changes in particle sizes of anatase and rutile
tion occurred in the temperature range of 973-1073 K.384 phases as a function of the annealing temperatures. (B) Arrenhius
Both anatase and rutile particle sizes increased with the plot of ln(AR/A0) vs 1/T for activation energy calculations as a
increase of temperature, but the growth rate was different, function of the size of the TiO2 nanoparticles. AR and A0 are the
as shown in Figure 40. Rutile had a much higher growth integrated diffraction peak intensity from rutile (110), and the total
rate than anatase. The growth rate of anatase leveled off at integrated anatase (101) and rutile (110) peak intensity, respectively.
Reused with permission from W. Li, C. Ni, H. Lin, C. P. Huang,
800 °C. Rutile particles, after nucleation, grew rapidly, and S. Ismat Shah, Journal of Applied Physics, 96, 6663 (2004).
whereas anatase particle size remained practically unchanged. Copyright 2004, American Institute of Physics.
With the decrease of initial particle size, the onset transition
temperature was decreased. An increased lattice compression domains reinforces the diffraction of the X-ray beam,
of anatase with increasing temperature was observed. Larger resulting in a tall narrow peak. If the crystals are randomly
distortions existed in samples with smaller particle size. The arranged or have low degrees of periodicity, the result is a
values for the activation energies obtained were 299, 236, broader peak. This is normally the case for nanomaterial
and 180 kJ/mol for 23, 17, and 12 nm TiO2 nanoparticles, assemblies. Thus, it is apparent that the fwhm of the
respectively. The decreased thermal stability in finer nano- diffraction peak is related to the size of the nanomaterials.
particles was primarily due to the reduced activation energy Figure 41 shows the XRD patterns for TiO2 nanoparticles
as the size-related surface enthalpy and stress energy of different sizes111 and for TiO2 nanorods of different
increased. lengths.129 As the nanoparticle size increased, the diffraction
peaks became narrower. In the anatase nanoparticle and
3.3. X-ray Diffraction Properties of TiO2 nanorods developed by Zhang et al., the diameters of the
Nanomaterials TiO2 nanoparticles and nanorods were both around 2.3 nm.
XRD is essential in the determination of the crystal The nanorods were elongated along the [001] direction with
structure and the crystallinity, and in the estimate of the preferred anisotropic growth along the c-axis of the anatase
crystal grain size according to the Scherrer equation lattice, which was indicated by the strong peak intensity and
narrow width of the (004) reflection and relatively lower
Kλ intensity and broader width for the other reflections. With
D) (3) an increase in length of the nanorods, the (004) diffraction
β cos θ
peak became much stronger and sharper, whereas other peaks
remained similar in shape and intensity.129 Similar results
where K is a dimensionless constant, 2θ is the diffraction have been observed by other groups.123,127,177,183
angle, λ is the wavelength of the X-ray radiation, and β is
the full width at half-maximum (fwhm) of the diffraction
peak.385 Crystallite size is determined by measuring the
3.4. Raman Vibration Properties of TiO2
broadening of a particular peak in a diffraction pattern
Nanomaterials
associated with a particular planar reflection from within the As the size of TiO2 nanomaterials decreases, the featured
crystal unit cell. It is inversely related to the fwhm of an Raman scattering peaks become broader.255,318,370,386-395 The
individual peaksthe narrower the peak, the larger the size effect on the Raman scattering in nanocrystalline
crystallite size. The periodicity of the individual crystallite TiO2 is interpreted as originating from phonon confine-
Titanium Dioxide Nanomaterials
Figure 41. (A) Powder XRD patterns of TiO2 samples of different
diameters: (a) 5 nm; (b) 7 nm; (c) 13 nm. Reprinted with permission
from Niederberger, M.; Bartl, M. H.; Stucky, G. D. Chem. Mater.
2002, 14, 4364. Copyright 2002 American Chemical Society. (B)
Powder XRD patterns of TiO2 samples of diameter 2.3 nm: (a)
spherical particles; (b) 16-nm nanorods; (c) 30-nm nanorods.
Reprinted with permission from Zhang, Z.; Zhong, X.; Liu, S.; Li,
D.; Han, M. Angew. Chem., Int. Ed. 2005, 44, 3466. Copyright
2005 Wiley-VCH.
ment,255,318,370,386,387,395 nonstoichiometry,391,392 or internal
stress/surface tension effects.390 Among these theories, the
most convincing is the three-dimensional confinement of
phonons in nanocrystals.255,318,370,386,387,394,395 The phonon
confinement model is also referred to as the spatial correla-
tion model or q vector relaxation model. It links the q vector
Chemical Reviews, 2007, Vol. 107, No. 7 2913
selection rule for the excitation of Raman active optical
phonons with long-range order and crystallite size.318,370 In
a perfect “infinite” crystal, conservation of phonon momen-
tum requires that only optic phonons near the Brillouin zone
(BZ) center (q ≈ 0) are involved in first-order Raman
scattering. In an amorphous material lacking long-range
order, the q vector selection rule breaks down and the Raman
spectrum resembles the phonon density of states. For
nanocrystals, the strict “infinite” crystal selection rule is
replaced by a relaxed version. This results in a range of
accessible q vectors (as large as ∆q ≈ 1/L (L diameter))
due to the uncertainty principle.
The anatase TiO2 has six Raman-active fundamentals in
the vibrational spectrum: three Eg modes centered around
144, 197, and 639 cm-1 (designated here Eg(1), Eg(2), and Eg(3),
respectively), two B1g modes at 399 and 519 cm-1 (desig-
nated B1g(1) and B1g(2d)), and an A1g mode at 513 cm-1.370
As the particle size decreases, the Raman peaks show
increased broadening and systematic frequency shifts (Figure
42).370 The most intense Eg(1) mode shows the maximum blue
shift and significant broadening with decreasing crystallite
size. A small blue shift is seen for the Eg(2) mode, while the
B1g(1) mode and the B1g(2)+A1g modes show very small blue
shifts and red shifts (the latter peak represents a combined
effect of two individual modes), respectively. Whereas the
frequency shifts for the A1g and B1g modes are not pro-
nounced, increased broadening with decreasing crystallite
size is clearly seen for these modes. The Eg(3) mode shows
significant broadening and a red shift with decreasing
crystallite size.
Choi et al. found a volume contraction effect in anatase
TiO2 nanoparticles due to increasing radial pressure as
particle size decreases, and they suggested that the effects
of decreasing particle size on the force constants and
vibrational amplitudes of the nearest neighbor bonds con-
tributed to both broadening and shifts of the Raman bands
with decreasing particle diameter.388
3.5. Electronic Properties of TiO2 Nanomaterials
The DOS of TiO2 is composed of Ti eg, Ti t2g (dyz, dzx,
and dxy), O pσ (in the Ti3O cluster plane), and O pπ (out of
the Ti3O cluster plane), as shown in Figure 43A.396 The upper
valence bands can be decomposed into three main regions:
the σ bonding in the lower energy region mainly due to O
pσ bonding; the π bonding in the middle energy region; and
O pπ states in the higher energy region due to O pπ
nonbonding states at the top of the valence bands where the
hybridization with d states is almost negligible. The contri-
bution of the π bonding is much weaker than that of the σ
bonding. The conduction bands are decomposed into Ti eg
(>5 eV) and t2g bands (<5 eV). The dxy states are dominantly
located at the bottom of the conduction bands (the vertical
dashed line in Figure 43A). The rest of the t2g bands are
antibonding with p states. The main peak of the t2g bands is
identified to be mostly dyz and dzx states.
In the molecular-orbital bonding diagram in Figure 43B,
a noticeable feature can be found in the nonbonding states
near the band gap: the nonbonding O pp orbital at the top
of the valence bands and the nonbonding dxy states at the
bottom of the conduction bands. A similar feature can be
seen in rutile; however, it is less significant than in anatase.397
In rutile, each octahedron shares corners with eight neighbors
and shares edges with two other neighbors, forming a linear
chain. In anatase, each octahedron shares corners with four
2914 Chemical Reviews, 2007, Vol. 107, No. 7 Chen and Mao

Figure 42. (A) Ambient pressure Raman spectra of anatase with an average crystallite size of 4 ( 1 nm (A), 8 ( 2 nm (B), 20 ( 8 nm
(C), and 34 ( 5 nm (D). The spectrum marked “E” is from a bulk anatase. (B) The Raman line width (fwhm) of the Eg(1) mode versus
crystallite size. Reprinted with permission from Swamy, V.; Kuznetsov, A.; Dubrovinsky, L. S.; Caruso, R. A.; Shchukin, D. G.; Muddle,
B. C. Phys. ReV. B 2005, 71, 184302/1 (http://link.aps.org/abstract/PRB/v71/p184302). Copyright 2005 by the American Physical Society.
neighbors and shares edges with four other neighbors, surrounded by six oxygen atoms in an elongated octahedral
forming a zigzag chain with a screw axis. Thus, anatase is geometry (D2d). The further splitting of the 3d levels of Ti3+
less dense than rutile. Also, anatase has a large metal-metal due to the asymmetric crystals is shown for rutile and anatase
distance of 5.35 Å. As a consequence, the Ti dxy orbitals at structures. The fine electronic structure of TiO2 can be
the bottom of the conduction band are quite isolated, while directly probed by Ti K-edge X-ray-absorption near-edge
the t2g orbitals at the bottom of the conduction band in rutile structure (XANES), and the right panel of Figure 44B
provide the metal-metal interaction with a smaller distance contains O K-edge experimental electron-energy-loss near-
of 2.96 Å. edge structure (ELNES) spectra.398
The electronic structure of TiO2 has been studied with Hwu et al. found that the crystal field splitting of
various experimental techniques, i.e., with X-ray photoelec- nanocrystal TiO2 was approximately 2.1 eV, slightly smaller
tron and X-ray absorption and emission spectroscop- than that of bulk TiO2, as shown in Figure 45A.379 Luca et
ies.379,398-405 Figure 44 shows a schematic energy level al. found that 1s f np transitions broadened as particle size
diagram of the lowest unoccupied MOs of a [TiO6]8- cluster (increased or decreased) in the postedge region in the X-ray
with Oh, D2h (rutile), and D2d (anatase) symmetry and the Ti absorption spectroscopy for TiO2 nanoparticles.403 Also, a
K-edge XANES and O K-edge ELNES spectra for rutile and clear trend in the X-ray absorption spectroscopy for different
anatase.398 The anatase structure is a tetragonally distorted sized TiO2 nanoparticles was observed, as shown in Figure
octahedral structure in which every titanium cation is 45B from the study by Choi et al.401
Titanium Dioxide Nanomaterials
Figure 43. (A) Total and projected densities of states (DOSs) of
the anatase TiO2 structure. The DOS is decomposed into Ti eg, Ti
t2g (dyz, dzx, and dxy), O pσ (in the Ti3O cluster plane), and O pπ
(out of the Ti3O cluster plane) components. The top of the valence
band (the vertical solid line) is taken as the zero of energy. The
vertical dashed line indicates the conduction-band minimum as a
guide to the eye. (B) Molecular-orbital bonding structure for anatase
TiO2: (a) atomic levels; (b) crystal-field split levels; (c) final
interaction states. The thin-solid and dashed lines represent large
and small contributions, respectively. Reprinted with permission
from Asahi, R.; Taga, Y.; Mannstadt, W.; Freeman, A. J. Phys.
ReV. B 2000, 61, 7459 (http://link.aps.org/abstract/PRB/v61/p7459).
Copyright 2000 by the American Physical Society.
It is well-known that for nanoparticles the band gap energy
increases and the energy band becomes more discrete with
decreasing size.84,406,407 As the size of a semiconductor
Chemical Reviews, 2007, Vol. 107, No. 7 2915
nanoparticle falls below the Bohr radius of the first excitation
state or becomes comparable to the de Broglie wavelength
of the charge carriers, the charge carriers begin to behave
quantum mechanically and the charge confinement leads to
a series of discrete electronic states.408 However, there is a
discrepancy in this critical size below which quantization
effects are observed for TiO2 nanomaterials with indirect
band gaps. The estimated critical diameter depends critically
on the effective masses of the charge carriers.409 Kormann
et al. estimated the excitation radii for titania particles to be
between 7.5 and 19 Å.84 Quantum confinement size effects
were observed for TiO2 nanoparticles with a small apparent
band gap blue shift (<0.1-0.2 eV) caused by quantum size
effects for spherical particles sizes down to 2 nm.58,60 Such
small effects are mainly due to the relatively high effective
mass of carriers in TiO2 and an exciton radius in the
approximate range 0.75-1.90 nm.84 On the other hand,
Serpone et al. suggested that the blue shifts in the effective
band gap of TiO2 with particle sizes of 21, 133, and 267 Å
may in fact not be a quantum confinement effect.410 Mon-
ticone et al. did an excellent study on the quatum size effects
in anatase nanoparticles and found no quantum size effect
in anatase TiO2 nanoparticles for sizes 2R g 1.5 nm, but
they did find unusual variation of the oscillator strength of
the first allowed direct transition with particle size.411
3.6. Optical Properties of TiO2 Nanomaterials
The main mechanism of light absorption in pure semi-
conductors is direct interband electron transitions. This
absorption is especially small in indirect semiconductors, e.g.,
TiO2, where the direct electron transitions between the band
centers are prohibited by the crystal symmetry. Braginsky
and Shklover have shown the enhancement of light absorp-
tion in small TiO2 crystallites due to indirect electron
transitions with momentum nonconservation at the inter-
face.412 This effect increases at a rough interface when the
share of the interface atoms is larger. The indirect transitions
are allowed due to a large dipole matrix element and a large
density of states for the electron in the valence band.
Considerable enhancement of the absorption is expected in
small TiO2 nanocrystals, as well as in porous and micro-
crystalline semiconductors, when the share of the interface
atoms is sufficiently large. A rapid increase in the absorption
takes place at low (hν < Eg + Wc, where Wc is the width of
the conduction band) photon energies. Electron transitions
to any point in the conduction band become possible when
hν ) Eg + Wc. Further enhancement of the absorption occurs
due to an increase of the electron density of states in only
the valence band. The interface absorption becomes the main
mechanism of light absorption for the crystallites that are
smaller than 20 nm.412
Sato and Sakai et al. showed through calculation and
measurement that the band gap of TiO2 nanosheets was larger
than the band gap of bulk TiO2, due to lower dimensionality,
i.e., a 3D to 2D transition, as shown in Figure 46. 360,413 From
the measurement, it was found that the lower edge of the
conduction band for the TiO2 nanosheet was approximately
0.1 V higher, while the upper edge of the valence band was
0.5 V lower than that of anatase TiO2.360 The absorption of
the TiO2 nanosheet colloid blue shifted (>1.4 eV) relative
to that of bulk TiO2 crystals (3.0-3.2 eV), due to a size-
quantization effect, accompanied with a strong photolumi-
nescence of well-developed fine structures extending into
the visible light regime.362,363 The band gap energy shift, ∆Eg,
2916 Chemical Reviews, 2007, Vol. 107, No. 7 Chen and Mao

Figure 44. (A) Schematic energy level diagram of the lowest unoccupied MOs of a [TiO6]8- cluster with Oh, D2h (rutile), and D2d (anatase)
symmetry. (B) Ti K-edge XANES and O K-edge ELNES spectra for rutile (a) and anatase (b). Reprinted with permission from Wu, Z. Y.;
Ouvrared, G.; Gressier, P.; Natoli, C. R. Phys. ReV. B 1997, 55, 10382 (http://link.aps.org/abstract/PRB/v55/p10382). Copyright 1997 by
the American Physical Society.

by exciton confinement in anisotropic two-dimensional crystallite dimensions in the parallel and perpendicular
crystallites is formulated as follows: directions with respect to the sheet, respectively. Since the

( )
first term can be ignored, the blue shift is predominantly
h2 1 1 h2 governed by the sheet thickness. The onset of a 270 nm peak
∆Eg ) + + (4)
8µxz L 2 L 2 8µyLy2 in the photoluminescence of TiO2 nanosheets was assigned
x z
to resonant luminescence. The series of peaks extending into
where h is Plank’s constant, µxz and µy are the reduced a longer wavelength region were attributed to interband levels
effective masses of the excitons, and Lx, Ly, and Lz are the generated by the intrinsic Ti site vacancies. The contrasting
Titanium Dioxide Nanomaterials Chemical Reviews, 2007, Vol. 107, No. 7 2917

sharp peaks were also attributed to the subnanometer

thickness and its uniformity.362
Bavykin et al. studied the optical absorption and photolu-
minescence of colloidal TiO2 nanotubes with internal diam-
eter in the range of 2.5-5 nm, and they found that, in spite
of the different diameters, all the TiO2 nanotubes had similar
optical properties.158 They attributed this to the complete
smearing of all 1-dimensional effects due to the large
effective mass of charge carriers in TiO2, which resulted in
an apparent 2D behavior of TiO2 nanotubes. Figure 47 shows
the absorption, photoluminescence, and luminescence excita-
tion spectra of TiO2 nanotubes of different mean diameters.158
Within the effective mass model, the energy spectrum of
2D TiO2 nanosheets can be described by eq 10, where the
“plus” and “minus” signs correspond to the conduction and
valence bands, respectively, EG is the energy gap, p is
Planck’s constant, and me and mh are the effective masses
of the electrons and holes, respectively.
EG p2k2
E(
2D ) ( ( (5)
2 2me,h

The electronic band structure of a TiO2 nanotube can be

obtained from this relation by zone-folding and is given by
a series of quasi-1D sub-bands with different indices n
(Figure 48b):
EG p2 2n 2
(
En1D )(
2
(
2me,h [
k|2 +
d ( )] (6)

This transition from the 2D to the quasi-1D energy spectrum

has a dramatic effect on the energy density of states. In the
2D case, the density of states, G2D ) mc.h/πp2, has a constant
value for energies outside the energy gap (see Figure 48c).
In the quasi-1D case, however, the density of states of each
sub-band

{ }
me,h 1/2
Gn,1D(E) ) ( (7)
2π2p2[E - En(0)]
diverges at the band edge En(0), leading to van Hove
singularities. The resulting density of state is formed by a
series of sharp peaks with long overlapping tails (Figure 48c).
The energy gap between the valence and conductance bands
in the quasi-1D case is larger than that in the parental 2D
material, and the difference increases with decreasing
diameter of the nanotube. The change in the energy gaps
between a nanosheet and a nanotube is
Figure 45. (A) Ti L2.3 absorption of nanocrystal and bulk TiO2.
Reprinted from Hwu, Y.; Yao, Y. D.; Cheng, N. F.; Tung, C. Y.;
Lin, H. M. Nanostruct. Mater. 1997, 9, 355, Copyright 1997, with
permission from Elsevier. (B) Ti L2.3 absorption of TiO2 nano-
crystals with different sizes. Reprinted with permission from Choi,
H. C.; Ahn, H. J.; Jung, Y. M.; Lee, M. K.; Shin, H. J.; Kim, S.
B.; Sung, Y. E. Appl. Spectrosc. 2004, 58, 598. Copyright 2004
Society for Applied Spectroscopy.
corresponding bulk phase.376 The valence band of both bulk
TiO2 and their nanostructures was composed of 3d Ti-2p
O states, and the lower part of the conduction band was
formed by 3d Ti states. The differences between these
nanostructures were insignificant. All anatase systems were

( )
2p2 1 1 the lepidocrocite nanotubes were semiconductors with an
∆EG ) E1D
G - EG )
2D
+ (8)
d2 me mh
In TiO2, the effective masses of electrons me can vary
between 5m0 and 30m0, and the mass of holes mh is more
than 3m0. With me ) 9m0 and mh ) 3m0, the difference
between energy gaps of nanotubes with diameters 2.5 and 5
nm is 8 meV. The energy difference between the two first
peaks in the density of states G1D(E) (Figure 48) is less than
24 meV for d ) 2.5 nm and 6 meV for d ) 5 nm, which are
too small to be resolved in room-temperature experiments
due to the thermal fluctuations of kT ) 26 meV.158
In the theoretical study conducted by Enyashin and Seifert
recently, the band structures for anatase nanotubes, nano-
strips, and nanorolls were similar to the DOS of the
semiconductors with a wide direct band gap (∼4.2 eV), while
indirect band gap (∼4.5 eV). Independent from the specific
topology of the titania nanostructures, the band gap ap-
proached the band gap of the corresponding nanocrystals with
radii of about 25 Å.376
In addition to the above investigation on the bulk electronic
structures for various TiO2 nanomaterials, Mora-Seró and
Bisquert investigated the Fermi level of surface states in TiO2
nanoparticles by the nonequilibrium steady-state statistics of
electrons.414 They found that the electrons trapped in surface
states did not generally equilibrate to the free electrons’ Fermi
level, EFn, and a distinct Fermi level for surface states, EFs,
could be defined consistent with Fermi-Dirac statistics,
determining the surface states’ occupancy far from equilib-
rium. The difference between the free electrons’ Fermi level
2918 Chemical Reviews, 2007, Vol. 107, No. 7 Chen and Mao

Figure 46. (A) Total and partial densities of states for (a) stacked TiO2 sheets, (b) a single-layered TiO2, (c) rutile, and (d) anatase.
Reprinted with permission from Sato, H.; Ono, K.; Sasaki, T.; Yamagishi, A. J. Phys. Chem. B 2003, 107, 9824. Copyright 2003 American
Chemical Society. (B) Schematic illustration of electronic band structure: (a) TiO2 nanosheets; (b) anatase. Reprinted with permission
from Sakai, N.; Ebina, Y.; Takada, K.; Sasaki, T. J. Am. Chem. Soc. 2004, 126, 5851. Copyright 2004 American Chemical Society. (C)
UV-visible spectra of (a) TiO2 sheets and (b) a film of nanosheets on a SiO2 glass substrate. The data for the colloidal suspension is
denoted by a dashed trace. Reprinted with permission from Sasaki, T.; Watanabe, M. J. Phys. Chem. B 1997, 101, 10159. Copyright 1997
American Chemical Society.

and the surface Fermi level (∆EFn - EFs) was found to applications of TiO2 nanoparticles. These fundamental
depend on the rate constants for charge transfer and detrap- processes can be expressed as follows:415
ping and could reach several hundred millielectron-
volts.414
TiO2 + hυ 98e- + h+ (9)
3.7. Photon-Induced Electron and Hole Properties
of TiO2 Nanomaterials e- + Ti(IV)O-H f Ti(III)O-H-(X) (10)
After TiO2 nanoparticles absorb, impinging photons with
energies equal to or higher than its band gap (>3.0 eV),
electrons are excited from the valence band into the unoc- h+ + Ti(IV)O-H f Ti(IV)O•-H+(Y) (11)
cupied conduction band, leading to excited electrons in the
conduction band and positive holes in the valence band.
These charge carriers can recombine, nonradiatively or 1 1
radiatively (dissipating the input energy as heat), or get h+ + O2-lattice T O2(g) + vacancy (12)
2 4
trapped and react with electron donors or acceptors adsorbed
on the surface of the photocatalyst. The competition between
these processes determines the overall efficiency for various e-| + O2,s f O2,s- (13)
Titanium Dioxide Nanomaterials Chemical Reviews, 2007, Vol. 107, No. 7 2919

O2,s- + H+ T HO2,s (14)

h+ + Ti(III)O-H- f Ti(IV)O-H (15)

e- + Ti(IV)O•-H+ f Ti(IV)O-H (16)

O2,s + Ti(IV)O•-H+ f Ti(IV)O-H + O2,s (17)

Reaction 8 is the photon absorption process. Reactions 10-

14 are photocatalytic redox pathways, whereas reactions 15-
17 represent the recombination channels. Reactions 11 and
12 are the competition pathways for holes, leading to bound
OH radicals and O vacancies, respectively. The reverse of
reaction 12 generates O adatom intermediates upon exposing
defective surfaces to O2-(g).415 Electrons and holes generated
in TiO2 nanoparticles are localized at different defect sites
on the surface and in the bulk. Electron paramagnetic
resonance (EPR) results showed that electrons were trapped
as two Ti(III) centers, while the holes were trapped as
oxygen-centered radicals covalently linked to surface tita-
nium atoms.416-419 Howe and Grätzel found that irradiation
at 4.2 K in vacuo produced electrons trapped at Ti4+ sites
within the bulk and holes trapped at lattice oxide ions
immediately below the surface, which decayed rapidly in
the dark at 4.2 K. In the presence of O2, trapped electrons
were removed and the trapped holes were stable to 77 K.
Warming to room-temperature caused loss of trapped holes
and formation of O2- at the surface.416,417 Hurum et al. found
that, upon band gap illumination, holes appeared at the
surface and preferentially recombined with electrons in
surface trapping sites for mixed-phase TiO2, such as Degussa
P25, and recombination reactions were dominated by surface
reactions that followed charge migration.419
Colombo and Bowman studied the charge carrier dynamics
of TiO2 nanoparticles with femtosecond time-resolved diffuse
reflectance spectroscopy and found a dramatic increase in
the population of trapped charge carriers within the first few
picoseconds.420,421 Skinner et al. found that the trapping time
for photogenerated electrons on 2 nm TiO2 nanoparticles in
acetonitrile by ultrafast transient absorption was about 180
fs.422 Serpone et al. found that localization (trapping) of the
electron as a Ti3+ species occurred with a time scale of about
30 ps and about 90% or more of the photogenerated electron/ Figure 47. (A) (a) Absorption spectrum and (b) luminescence
hole pairs recombined within 10 ns.409 They suggested that excitation spectrum (wavelength of emission light is 400 nm) of
colloidal TiO2 nanotubes of different mean diameters: (1) 2.5 nm;
photoredox chemistry occurring at the particle surface (2) 3.1 nm; (3) 3.5 nm; (4) 5 nm. The curves are shifted vertically
emanated from trapped electrons and trapped holes rather for clarity. (B) Photoluminescence spectra of colloidal TiO2
than from free valence band holes and conduction band nanotubes of different mean diameters: (1) 2.5 nm; (2) 3.1 nm;
electrons. Bahnemann et al. found that, in 2.4 nm TiO2 (3) 3.5 nm; (4) 5 nm. Room temperature, excitation wavelength
nanoparticles, electrons were instantaneously trapped within 237 nm, slits width 5 nm. The range of wavelengths, 455-490
the duration of the laser flash (20 ns). Deeply trapped holes nm, in the spectra is omitted due to the high signal of the second
harmonic from scattered excitation light. The curves are shifted
were rather long-lived and unreactive, and shallowly trapped vertically for clarity. Vertical lines (5) show the positions of the
holes were in a thermally activated equilibrium with free peaks in the PL spectrum of the nanosheets. Reprinted with
holes which exhibited a very high oxidation potential.423 permission from Bavykin, D. V.; Gordeev, S. N.; Moskalenko, A.
Szczepankiewicz and Hoffmann et al. found that O2 was V.; Lapkin, A. A.; Walsh, F. C. J. Phys. Chem. B 2005, 109, 8565.
an efficient scavenger of conduction band electrons at the Copyright 2005 American Chemical Society.
gas/solid interface and the buildup of trapped carriers
eventually resulted in extended surface reconstruction in- types of TiO-H stretch, shallow electron-trapping states
volving Ti-OH functionalities.415 They found that photo- produced a homogeneous electric field and were suggested
generated free conduction band electrons were coupled with not to be associated with localized structures, but rather
acoustic phonons in the lattice and their lifetimes were delocalized across the TiO2 surface.424
lengthened when dehydrated.424 The photoexcited charge Berger et al. studied UV light-induced electron-hole pair
carriers in TiO2 nanoparticles produced Stark effect intensity excitations in anatase TiO2 nanoparticles by electron para-
and wavelength shifts for surface TiO-H stretching vibra- magnetic resonance (EPR) and IR spectroscopy.425 The
tions. Although deep electron-trapping states affected certain localized states such as holes trapped at oxygen anions (O-)
2920 Chemical Reviews, 2007, Vol. 107, No. 7
Figure 48. Schematic presentation of the transformation of the electron band structure of the nanosheet semiconductor accompanying the
formation of nanotubes: (a) band diagram of a 2-dimensional nanosheet; (b) band diagram of quasi-1-D nanotubes; (c) energy density of
states for nanosheets (G2D) and nanotubes (G1D). EG1D and EG2D are the band gaps of the 1D and 2D structures, respectively. kx and ky are
the wave vectors. Reprinted with permission from Bavykin, D. V.; Gordeev, S. N.; Moskalenko, A. V.; Lapkin, A. A.; Walsh, F. C. J. Phys.
Chem. B 2005, 109, 8565. Copyright 2005 American Chemical Society.
Figure 49. Scheme of UV-induced charge separation in TiO2.
Electrons from the valence band can either be trapped (a) by defect
states, which are located close to the conduction band (shallow
traps), or (b) in the conduction band, where they produce absorption
in the IR region. Electron paramagnetic resonance spectroscopy
detects both electrons in shallow traps, Ti3+, and hole centers, O-.
Reprinted with permission from Berger, T.; Sterrer, M.; Diwald,
O.; Knoezinger, E.; Panayotov, D.; Thompson, T. L.; Yates, J. T.,
Jr. J. Phys. Chem. B 2005, 109, 6061. Copyright 2005 American
Chemical Society.
and electrons trapped at coordinatively unsaturated cations
(Ti3+ formation) were accessible to EPR spectroscopy.
Delocalized and EPR silent electrons in the conduction band
may be traced by their IR absorption, which results from
their electronic excitation within the conduction band in the
infrared region (Figure 49). They found that, during continu-
ous UV irradiation, photogenerated electrons were either
Chen and Mao
trapped at localized sites, giving paramagnetic Ti3+ centers,
or remained in the conduction band as EPR silent species
which may be observed by their IR absorption and that the
EPR-detected holes produced by photoexcitation were O-
species, produced from lattice O2- ions. It was also found
that, under high-vacuum conditions, the majority of photo-
excited electrons remained in the conduction band. At 298
K, all stable hole and electron states were lost.
4. Modifications of TiO2 Nanomaterials
Many applications of TiO2 nanomaterials are closely
related to its optical properties. However, the highly efficient
use of TiO2 nanomaterials is sometimes prevented by its wide
band gap. The band gap of bulk TiO2 lies in the UV regime
(3.0 eV for the rutile phase and 3.2 eV for the anatase phase),
which is only a small fraction of the sun’s energy (<10%),
as shown in Figure 50.11
Thus, one of the goals for improvement of the performance
of TiO2 nanomaterials is to increase their optical activity by
shifting the onset of the response from the UV to the visible
region.21,426-428 There are several ways to achieve this goal.
First, doping TiO2 nanomaterials with other elements can
narrow the electronic properties and, thus, alter the optical
properties of TiO2 nanomaterials. Second, sensitizing TiO2
with other colorful inorganic or organic compounds can
improve its optical activity in the visible light region. Third,
coupling collective oscillations of the electrons in the
conduction band of metal nanoparticle surfaces to those in
the conduction band of TiO2 nanomaterials in metal-TiO2
nanocomposites can improve the performance. In addition,
the modification of the TiO2 nanomaterials surface with other
semiconductors can alter the charge-transfer properties
between TiO2 and the surrounding environment, thus im-
Titanium Dioxide Nanomaterials
Figure 50. Solar spectrum at sea level with the sun at its zenith.
Reprinted with permission from Linsebigler, A. L.; Lu, G.; Yates,
J. T., Jr. Chem. ReV. 1995, 95, 735. Copyright 1995 American
Chemical Society.
proving the performance of TiO2 nanomaterials-based de-
vices.
4.1. Bulk Chemical Modification: Doping
The optical response of any material is largely determined
by its underlying electronic structure. The electronic proper-
ties of a material are closely related to its chemical
composition (chemical nature of the bonds between the atoms
or ions), its atomic arrangement, and its physical dimension
(confinement of carriers) for nanometer-sized materials. The
chemical composition of TiO2 can be altered by doping.
Specifically, the metal (titanium) or the nonmetal (oxygen)
component can be replaced in order to alter the material’s
optical properties. It is desirable to maintain the integrity of
the crystal structure of the photocatalytic host material and
to produce favorable changes in electronic structure. It
appears easier to substitute the Ti4+ cation in TiO2 with other
transition metals, and it is more difficult to replace the O2-
anion with other anions due to differences in charge states
and ionic radii. The small size of the nanoparticle is beneficial
for the modification of the chemical composition of TiO2
due to the higher tolerance of the structural distortion than
that of bulk materials induced by the inherent lattice strain
in nanomaterials.426,429
4.1.1. Synthesis of Doped TiO2 Nanomaterials
4.1.1.1. Metal-Doped TiO2 Nanomaterials. Different
metals have been doped into TiO2 nanomaterials.313,430-465
The preparation methods of non-metal-doped TiO2 nanoma-
terials can be divided into three types: wet chemistry, high-
temperature treatment, and ion implantation on TiO2 nano-
materials. Wet chemistry methods usually involve hydrolysis
of a titanium precursor in a mixture of water and other
reagents, followed by heating. Choi et al. performed a
systematic study of TiO2 nanoparticles doped with 21 metal
ions by the sol-gel method and found the presence of metal
ion dopants significantly influenced the photoreactivity,
charge carrier recombination rates, and interfacial electron-
transfer rates.434 Li et al. developed La3+-doped TiO2 by the
sol-gel process and found that the lanthanum doping could
inhibit the phase transformation of TiO2, enhance the thermal
stability of the TiO2, reduce the crystallite size, and increase
the Ti3+ content on the surface.442 Nagaveni et al. prepared
W, V, Ce, Zr, Fe, and Cu ion-doped anatase TiO2 nanopar-
ticles by a solution combustion method and found that the
solid solution formation was limited to a narrow range of
concentrations of the dopant ions.448 Wang et al. prepared
Chemical Reviews, 2007, Vol. 107, No. 7 2921
Nd3+-doped and Fe(III)-doped TiO2 nanoparticles with a
hydrothermal method and found that anatase, brookite, and
a trace of hematite coexisted at lower pH (1.8 and 3.6) when
the Fe(III) content was as low as 0.5% and the distribution
of iron ions was nonuniform between particles, but at higher
pH (6.0), the uniform solid solution of iron-titanium oxide
formed.460,463
Anpo et al. prepared TiO2 nanoparticles doped with Cr
and V ions with an ion-implantation method.466-471 Bessekh-
ouad et al. investigated alkaline (Li, Na, K)-doped TiO2
nanoparticles prepared by sol-gel and impregnation technol-
ogy and found that the crystallinity level of the products was
largely dependent on both the nature and the concentration
of the alkaline, with the best crystallinity obtained for Li-
doped TiO2 and the lowest for K-doped TiO2.430 Cao et al.
prepared Sn4+-doped TiO2 nanoparticle films by the plasma-
enhanced CVD method and found that, after doping by Sn,
more surface defects were present on the surface.433 Gracia
et al. synthesized M (Cr, V, Fe, Co)-doped TiO2 by ion beam
induced CVD and found that TiO2 crystallized into the
anatase or rutile structures depending on the type and amount
of cations present with partial segregation of the cations in
the form of M2On after annealing.438 Wang et al. synthesized
Fe(III)-doped TiO2 nanoparticles using oxidative pyrolysis
of liquid-feed organometallic precursors in a radiation-
frequency (RF) thermal plasma and found that the formation
of rutile was strongly promoted with iron doping compared
to the anatase phase being prevalent in the undoped TiO2.246
4.1.1.2. Nonmetal-Doped TiO2 Nanomaterials. Various
nonmetal elements, such as B, C, N, F, S, Cl, and Br, have
been successfully doped into TiO2 nanomaterials. C-doped
TiO2 nanomateirals have been obtained by heating titanium
carbide472-474 or by annealing TiO2 under CO gas flow at
high temperatures (500-800 °C)475 or by direct burning of
a titanium metal sheet in a natural gas flame.476
N-doped TiO2 nanomaterials have been synthesized by
hydrolysis of TTIP in a water/amine mixture and the post-
treatment of the TiO2 sol with amines426,428,477-482 or directly
from a Ti-bipyridine complex483 or by ball milling of TiO2
in a NH3 water solution.484 N-doped TiO2 nanomaterials were
also obtained by heating TiO2 under NH3 flux at 500-600
°C485,486 or by calcination of the hydrolysis product of
Ti(SO4)2 with ammonia as precipitator487 or by decomposition
of gas-phase TiCl4 with an atmosphere microwave plasma
torch488 or by sputtering/ion-implanting techniques with
nitrogen489,490 or N2+ gas flux.491
S-doped TiO2 nanomaterials were synthesized by mixing
TTIP with ethanol containing thiourea492-494 or by heating
sulfide powder495,496 or by using sputtering or ion-implanting
techniques with S+ ion flux.497-499 Different doping methods
can induce the different valence states of the dopants. For
example, the incorporated S from thiourea had S4+ or S6+
state,492-494 while direct heating of TiS2 or sputtering with
S+ induced the S2- anion.496-499
F-doped TiO2 nanomaterials were synthesized by mixing
TTIP with ethanol containing H2O-NH4F,500-502 or by
heating TiO2 under hydrogen fluoride503,504 or by spray
pyrolysis from an aqueous solution of H2TiF6505,506 or using
ion-implanting techniques with F+ ion flux.507 Cl- and Br-
co-doped nanomaterials were synthesized by adding TiCl4
to ethanol containing HBr.508
4.1.2. Properties of Doped TiO2 Nanomaterials
4.1.2.1. Electronic Properties of Doped TiO2 Nanoma-
terials. 4.1.2.1.1. Metal-Doped TiO2 Nanomaterials. Ac-
2922 Chemical Reviews, 2007, Vol. 107, No. 7
Figure 51. (A) Bonding diagram of TiO2. (B) DOS of the metal-doped TiO2 (Ti1-xAxO2: A ) V, Cr, Mn, Fe, Co, or Ni). Gray solid lines:
total DOS. Black solid lines: dopant’s DOS. The states are labeled (a) to (j). Reprinted from Umebayashi, T.; Yamaki, T.; Itoh, H.; Asai,
K. J. Phys. Chem. Solids 2002, 63, 1909, Copyright 2002, with permission from Elsevier.
cording to Soratin and Schwarz’s study, the electronic states
of TiO2 can be decomposed into three parts: the σ bonding
of the O pσ and Ti eg states in the lower energy region; the
π bonding of the O pπ and Ti eg states in the middle energy
region; and the O pπ states in the higher energy region
(Figure 51A).397,509 The bottom of the lower conduction band
(CB) consisting of the Ti dxy orbital contributes to the metal-
metal interactions due to the σ bonding of the Ti t2g-Ti t2g
states. At the top of the lower CB, the rest of the Ti2g states
are antibonding with the O pπ states. The upper CB consists
of the σ antibonding orbitals between the O pσ and Ti eg
states.
The electronic structures, i.e., the densities of states
(DOSs), of V-, Cr-, Mn-, Fe-, Co-, and Ni-doped TiO2 were
analyzed by ab initio band calculations based on the density
functional theory with the full-potential linearized augmented
plane wave (FLAPW) method by Umebayashi et al. (Figure
51B).509 They found that when TiO2 was doped with V, Cr,
Mn, Fe, or Co, an electron occupied level formed and the
electrons were localized around each dopant. As the atomic
number of the dopant increased, the localized level shifted
to lower energy. The energy of the localized level due to
Co doping was low enough that it lay at the top of the valence
band while the other metals produced midgap states. The
electrons from the Ni dopant were somewhat delocalized,
thus significantly contributing to the formation of the valence
band with the O p and Ti 3d electrons. The states due to the
3d dopants shifted to a lower energy as the atomic number
of the dopant increased. For Ti1-xVxO2: two localized levels
occurred at 1.5 eV above the VB (a) and between the lower
and upper CBs (b). Level a was occupied by one electron
consisting of the V t2g and O pπ states and was localized
around V. Level b consisted of the V eg and O pσ states
forming the σ antibonding orbital. For Cr- and Mn-doped
TiO2, state c was localized at 1.0 eV (0.5 eV for Mn) above
the VB due to Cr (Mn) t2g and O pπ, the former of which
was occupied by 2 (3) electrons. The σ antibonding orbital
Chen and Mao
formed by the Cr (Mn) eg and O pσ states occurred within
the lower CB. For Fe- and Co-doped TiO2, the localized level
(e) was situated 0.2 eV above the VB (or at the top of the
VB for Co) due to the π antibonding of the Fe eg and O pπ
states. This level was occupied by four (or five for Co)
electrons. The Fe (Co) eg state was split into dz2 (f) and dx2-y2
(g) orbitals in the band gap. For Ni-doped TiO2, the π
antibonding of the Ni t2g and O pπ states was somewhat
delocalized and appeared within the VB (h) due to the Ni eg
states from the dz2 and dx2-y2 orbitials situated in the band
gap. The electron densities around the dopant were large in
the VB and small in the CB compared to the case of pure
TiO2. The metal-O interaction strengthened, and the metal-
metal interaction became weak as a result of the 3d metal
doping.
Li et al. found that 1.5 at % Nd3+-doped TiO2 nanoparticles
reduced the band gap by as much as 0.55 eV and that the
band gap narrowing was primarily attributed to the substi-
tutional Nd3+ ions, which introduced electron states into the
band gap of TiO2 to form the new lowest unoccupied
molecular orbital (LUMO).444 Wang and Doren found that
Nd 4f electrons changed the electronic structure of Nd-doped
TiO2 into the half-metallic or the insulating ground state510
and that V 3d states were located at the bottom of the
conduction band of the TiO2 host in V-doped TiO2, which
was shown to be a half-metal or an insulator from their
theoretical studies.511
4.1.2.1.2. Nonmetal-Doped TiO2 Nanomaterials. Recent
theoretical and experimental studies have shown that the
desired band gap narrowing of TiO2 can also be achieved
by using nonmetal dopants (refs 385, 428, 444, 489, 481,
482, 484, 503, 504, and 512-547). Asahi and co-workers
calculated the electronic band structures of anatase TiO2 with
different substitutional dopants, including C, N, F, P, or S,
using the FLAPW method in the framework of the local
density approximation (LDA) as shown in Figure 52.489 In
this study, C dopant introduced deep states in the gap.489
Titanium Dioxide Nanomaterials
Figure 52. (A) Total DOSs of doped TiO2 and (B) the projected
DOSs into the doped anion sites, calculated by FLAPW, for the
dopants F, N, C, S, and P located at a substitutional site for an O
atom in the anatase TiO2 crystal (eight TiO2 units per cell). Ni-
doped stands for N doping at an interstitial site, and Ni+s-doped
stands for doping at both substitutional and interstitial sites.
Reprinted with permission from Asahi, R.; Morikawa, T.; Ohwaki,
T.; Aoki, K.; Taga, Y. Science 2001, 293, 269 (http://www-
.sciencemag.org). Copyright 2001 AAAS.
Nakano et al. found three deep levels located at ap-
proximately 0.86, 1.30, and 2.34 eV below the conduction
band in C-doped TiO2, which were attributed to the intrinsic
nature of TiO2 for the first one and the two levels newly
introduced by the C doping.522 In particular, the pronounced
2.34 eV band contributed to band gap narrowing by mixing
with the O 2p valence band.522 Lee et al., in their first-
principles density-functional LDA pseudopotential calcula-
Chemical Reviews, 2007, Vol. 107, No. 7 2923
tions of electronic properties of C-doped TiO2, found that
the bands originating from C 2p states appeared in the band
gap of TiO2; however, the mixing of C with O 2p states
was too weak to produce a significant band gap narrowing.517
In Asahi’s study, the substitutional doping of N was the
most effective in the band gap narrowing because its p states
mixed with O 2p states, while the molecularly existing
species, e.g., NO and N2 dopants, gave rise to the bonding
states below the O 2p valence bands and antibonding states
deep in the band gap (Ni and Ni+s), and were well screened
and hardly interacted with the band states of TiO2.489 Di
Valentin et al. found that, for nitrogen doping in both anatase
and rutile polymorphs, N 2p localized states were just above
the top of the O 2p valence band.512,513 In anatase, these
dopant states caused a red shift of the absorption band edge
toward the visible region, while, in rutile, an overall blue
shift was found by the N-induced contraction of the O 2p
band.512 Experimental evidence supported the statement that
nitrogen-doped TiO2 formed nitrogen-induced midgap levels
slightly above the oxygen 2p valence band.486 Lee et al., in
their first-principles density-functional LDA pseudopotential
calculations of electronic properties of N-doped TiO2, found
that the bands originating from N 2p states appeared in the
band gap of TiO2; however, the mixing of N with O 2p states
was too weak to produce a significant band gap narrowing.517
Wang and Doren found that N doping introduced some states
at the valence band edge and thus made the original band
gap of TiO2 smaller, and that a vacancy could induce some
states in the band gap region, which acted as shallow
donors.510 Nakano et al. found that, in N-doped TiO2, deep
levels located at approximately 1.18 and 2.48 eV below the
conduction band were attributed to the O vacancy state as
an efficient generation-recombination center and to the N
doping which contributed to band gap narrowing by mixing
with the O 2p valence band, respectively.523 Okato et al.
found that, at high doping levels, N was difficult to substitute
for O to contribute to the band gap narrowing, instead giving
rise to the undesirable deep-level defects.524
S dopant induced a similar band gap narrowing as
nitrogen,489 and the mixing of the sulfur 3p states with the
valence band was found to contribute to the increased width
of the valence band, leading to the narrowing of the band
gap.495,497 When S existed as S4+, replacing Ti4+, sulfur 3s
states induced states just above the O 2p valence states, and
S 3p states contributed to the conduction band of TiO2 as
shown in Figure 53A.494
When F replaced the O in the TiO2 lattice, F 2p states
were localized below the O 2p valence states without any
mixing with the valence or conduction band as shown in
Figure 53B, and additional states appeared just below the
conduction edge, due to the electron occupied level composed
of the t2g state of the Ti 3d orbital.507 The electronic change
induced by F dopant was considered to be similar to the O
vacancy, thus reducing the effective band gap and improving
visible light photoresponse.507 Li et al. found that F doping
produced several beneficial effects including the creation of
surface oxygen vacancies, the enhancement of surface
acidity, and the increase of Ti3+ ions, and doped N atoms
formed a localized energy state above the valence band of
TiO2, whereas doped F atoms themselves had no influence
on the band structure in N-F-co-doped TiO2.519
4.1.2.2. Optical Properties of Doped TiO2 Nanomate-
rials. 4.1.2.2.1. Optical Properties of Metal-Doped TiO2
Nanomaterials. A red shift in the band gap transition or a
2924 Chemical Reviews, 2007, Vol. 107, No. 7
Figure 53. (A) Total DOS of S-doped TiO2. Reprinted with
permission from Ohno, T.; Akiyoshi, M.; Umebayashi, T.; Asai,
K.; Mitsui, T.; Matsumura, M. Appl. Catal. A 2004, 265, 115,
Copyright 2004, with permission from Elsevier. (B) Total DOSs
of F-doped TiO2 calculated by FLAPW. Eg indicates the (effective)
band gap energy. The impurity states are labeled (I) and (II).
Reprinted from Yamaki, T.; Umebayashi, T.; Sumita, T.; Yama-
moto, S.; Maekawa, M.; Kawasuso, A.; Itoh, H. Nucl. Instrum.
Methods Phys. Res., Sect. B 2003, 206, 254, Copyright 2003, with
permission from Elsevier.
visible light absorption was observed in metal-doped TiO2
(refs 433-435, 438, 444, 445, 448, 449, 460-463, 465, 466,
470, 509, 548, and 549). For V-, Mn-, or Fe-doped TiO2,
the absorption spectra shifted to a lower energy region with
an increase in the dopant concentration.434,445,460 This red shift
was attributed to the charge-transfer transition between the
d electrons of the dopant and the CB (or VB) of TiO2. Metal-
ion doped TiO2 prepared by ion implantation with various
transition-metal ions such as V, Cr, Mn, Fe, and Ni was
found to have a large shift in the absorption band toward
the visible light region, with the order of the effectiveness
in the red shift being V > Cr > Mn > Fe > Ni.466-471 Anpo
et al. found that the absorption band of Cr-ion-implanted
TiO2 shifted smoothly toward the visible light region, with
the extent of the red shift depending on the amount of metal
ions implanted as shown in Figure 54A.470 Impregnated or
chemically Cr-ion-doped TiO2 showed no shift in the
absorption edge of TiO2; however, a new absorption band
appeared at around 420 nm as a shoulder peak due to the
formation of an impurity energy level within the band gap,
with its intensity increasing with the number of Cr ions
(Figure 54B).470
In the study by Umebayashi et al., visible light absorption
of V-doped TiO2 was due to the transition between the VB
and the V t2g level.509 The holes in the VB produced an
anodic photocurrent. The photoexcitation processes under
visible light of V-, Cr-, and Mn-doped TiO2 are illustrated
in Figure 55. Photoexcitation for V-, Cr-, Mn-, and Fe-doped
TiO2 occurred via the t2g level of the dopant. The visible
light absorption for Mn- and Fe-doped TiO2 was due to the
optical transitions from the impurity band tail into the CB.
The Mn (Fe) t2g level was close to the VB and easily
Chen and Mao
Figure 54. (A) The UV-vis absorption spectra of TiO2 (a) and
Cr ion-implanted TiO2 photocatalysts (b-d). The amount of
implanted Cr ions (µmol/g) was (a) 0, (b) 0.22, (c) 0.66, or (d) 1.3.
(B) The UV-vis absorption spectra of TiO2 (a) and Cr ion-doped
TiO2 (b′-d′) photocatalysts prepared by an impregnation method.
The amount of doped Cr ions (wt%) was (a) 0, (b′) 0.01, (c′) 0.1,
(d′) 0.5, or (e′) 1. Reprinted from Anpo, M.; Takeuchi, M. J. Catal.
2003, 216, 505, Copyright 2003, with permission from Elsevier.
overlapped in highly impure media. The visible light
absorption for the Cr-doped TiO2 can be attributed to a donor
transition from the Cr t2g level into the CB and the acceptor
transition from the VB to the Cr t2g level.
Stucky et al. found that up to 8 mol % Eu3+ ions could be
doped into mesoporous anatase TiO2, and excitation of the
TiO2 electrons within their band gap led to nonradiative
energy transfer to the Eu3+ ions with a bright red lumines-
cence.287 The mesoporous TiO2 acted as a sensitizer.
4.1.2.2.2. Optical Properties of Nonmetal-Doped TiO2
Nanomaterials. Nonmetal doped TiO2 normally has a color
from white to yellow or even light gray, and the onset of
the absorption spectra red shifted to longer wavelengths (refs
385, 426, 478, 483, 489, 494, 495, 497, 498, 505, 506, 512,
516, 518, 519, 521, and 529). In N-doped TiO2 nanomate-
rials, the band gap absorption onset shifted 600 nm from
380 nm for the undoped TiO2, extending the absorption up
to 600 nm, as shown in Figure 56.426 The optical absorption
of N-doped TiO2 in the visible light region was primarily
located between 400 and 500 nm, while that of oxygen-
deficient TiO2 was mainly above 500 nm from their density-
functional theory study.520 N-F-co-doped TiO2 prepared by
spray pyrolysis absorbs light up to 550 nm in the visible
light spectrum.518 The S-doped TiO2 also displayed strong
absorption in the region from 400 to 600 nm.494 The red shifts
in the absorption spectra of doped TiO2 are generally
attributed to the narrowing of the band gap in the electronic
structure after doping.489 C-doped TiO2 showed long-tail
absorption spectra in the visible light region.472,543 Cl-, Br-,
and Cl-Br-doped TiO2 had increased optical response
compared to the case of pure TiO2 in the visible region.508
Livraghi et al. recently found that N-doped TiO2 contained
single atom nitrogen impurity centers localized in the band
gap of the oxide which were responsible for visible light
Titanium Dioxide Nanomaterials
Figure 55. Schematic diagram to illustrate the photoexcitation
process under visible light of metal-doped TiO2: (a) Ti1-xVxO2;
(b) Ti1-xFexO2; (c) Ti1-xCrxO2. Reprinted from Umebayashi, T.;
Yamaki, T.; Itoh, H.; Asai, K. J. Phys. Chem. Solids 2002, 63,
1909, Copyright 2002, with permission from Elsevier.
absorption with promotion of electrons from the band gap
localized states to the conduction band.547 Nick Serpone
“proposed that the commonality in all...doped titanias rests
with formation of oxygen vacancies and the advent of color
centers...that absorb the visible light radiation, and he argued
that the red shift of the absorption edge is in fact due to
formation of the color centers.546
Chemical Reviews, 2007, Vol. 107, No. 7 2925
Figure 56. Reflectance spectra of N-doped TiO2 nanoparticles and
pure TiO2 nanoparticles. Reprinted with permission from Burda,
C.; Lou, Y.; Chen, X.; Samia, A. C. S.; Stout, J.; Gole, J. L. Nano
Lett. 2003, 3, 1049. Copyright 2003 American Chemical Society.
Figure 57. IPCEλ and APCEλ curves for N-doped TiO2 and TiO2.
SE stands for the substrate/electrode (SE) interface. The action
spectra are recorded with light incident onto the SE interface.
Reprinted from Lindgren, T.; Lu, J.; Hoel, A.; Granqvist, C. G.;
Torres, G. R.; Lindquist, S. E. Sol. Energy Mater. Sol. Cells 2004,
84, 145, Copyright 2004, with permission from Elsevier.
4.1.2.3. Photoelectrical Properties of Doped TiO2 Nano-
materials. The photoelectrical properties of a material can
be measured with an “action spectrum” curve using a photo-
to-current conversion setup.385,486,497,521 In this setup, light
from a xenon lamp passing through a monochromator is
radiated onto the electrode, and the photocurrents from the
electrodes are measured as a function of wavelength.385,486,497,521
The incident photo-to-current efficiency as a function of
wavelength, IPCEλ, is called an “action spectrum”. IPCEλ
can be calculated by
hc Iph,λ
IPCEλ ) (18)
e Pλλ
where Iph,λ is the photocurrent, Pλ is the power intensity of
the light at wavelength λ, and h, c, and e are Planck’s
constant, the speed of light, and the elementary charge,
respectively.385 The IPCEλ curve normally has a similar shape
and trend as the absorption spectrum. When the IPCEλ is
divided by the absorption, the absorbed photon-to-current
efficiency (APCEλ; also called the quantum yield) is
obtained.521 Figure 57 shows IPCEλ and APCEλ curves for
N-doped TiO2 and TiO2.521 The photoelectrochemical onset
for TiO2-xNx is shifted to around 550 nm into the visible
region of the spectrum, and some ultraviolet (UV) efficiency
for TiO2-xNx is lost compared to that of TiO2, suggesting
2926 Chemical Reviews, 2007, Vol. 107, No. 7
the TiO2-xNx has a typical photoelectrochemical behavior
of a material with states in the band gap which act as
recombination centers for light-induced charge carriers.521
In another study, the action spectrum of N-doped TiO2 also
displayed a higher response in the visible region than that
of pure TiO2.486 The photocurrent spectra for the pure and
S-doped crystals showed that the photocurrent spectrum edge
shifted to the low-energy region below 2.9 eV for the
S-doped crystal, compared to 3.0 eV for pure TiO2, due to
the transition of electrons across the narrowed band gap
between the VB and the CB.497
4.2. Surface Chemical Modifications
When a photocurrent is generated with light energy less
than that of the semiconductor band gap, the process is
known as sensitization and the light-absorbing dyes are
referred to as sensitizers.9,10 TiO2 is a semiconductor with a
wide band gap, with optical absorption in the UV region
(<400 nm). Any materials with a narrower band gap or
absorption in the visible or infrared regime can be used as a
sensitizer for TiO2 materials. These materials include inor-
ganic semiconductors with narrow band gaps, metals, and
organic dyes. How efficiently the sensitized TiO2 can interact
with the light depends largely on how efficiently the
sensitizer interacts with the light. A common and key step
in the photosensitization of TiO2 is the efficient charge
transfer from the excited sensitizer to TiO2, and the resulting
charge separation. The match between the electronic struc-
tures of the sensitizer and TiO2 plays a large role in this
process, as does the structure of the interface, including the
grain boundaries and bonding between the sensitizer and
TiO2. Careful design is needed to avoid the charge trapping
and recombination which eventually harm the performance
of sensitized TiO2.9,10,550
4.2.1. Inorganic Sensitization
4.2.1.1. Sensitization by Narrow Band Gap Semicon-
ductors. Narrow band gap semiconductors have been used
as sensitizers to improve the optical absorption properties
of TiO2 nanomaterials in the visible light region by various
groups.551-559 The preparation method for these inorganic
semiconductor sensitized TiO2 nanomaterials systems is
usually the sol-gel method.551-558 Hoyer et al. reported the
sensitization of a nanocrystalline TiO2 matrix by small PbS
nanoparticles (<2.5 nm), and they found that the photogen-
erated excess electrons could be directly injected from the
PbS to the TiO2, resulting in strong photoconductance in the
visible region.553 Fitzmaurice et al. found that excitation of
the sensitizer AgI on TiO2 nanoparticles resulted in a
stabilization of electron-hole pairs with a lifetime well
beyond 100 µs and in electron migration from AgI to TiO2.551
Vogel et al. studied the sensitization of nanoporous TiO2 by
CdS, PbS, Ag2S, Sb2S3, and Bi2S3 and found that the relative
positions of the energetic levels at the interface between the
quantum size particles and TiO2 could be optimized for
efficient charge separation by using the size quantization
effect and that the photostability of the electrodes could be
significantly enhanced by surface modification of the TiO2
nanoparticles with CdS nanoparticles.558
Qian et al. found from surface photovoltage spectra (SPS)
measurements that the large surface state density present on
the TiO2 nanoparticles could be efficiently decreased by
sensitization using CdS nanoparticles and that the slow
photocurrent response disappeared and the steady-state
Chen and Mao
photocurrent increased drastically after the TiO2 nanopar-
ticulate thin film was sensitized using CdS nanoparti-
cles.378,555 Sant and Kamat found that quantum size effects
played an important role in interparticle electron transfer in
the CdS-TiO2 semiconductor systems in that electron
transfer from photoexcited CdS to TiO2 was found to depend
on the size of TiO2 nanoparticles.560 Charge transfer occurred
only when TiO2 nanoparticles were sufficiently large (>1.2
nm) that the conduction band of the nanoparticles was located
below that of CdS nanoparticles.560 Shen et al. studied
nanostructured TiO2 electrodes with different nanocrystals
sizes sensitized with CdSe nanoparticles and found that
photoelectrochemical currents in the visible region in the
CdSe-sensitized TiO2 nanostructured electrodes were largely
dependent on both the structure and electron diffusion
coefficient of the TiO2 electrodes.556 Zaban et al. studied
nanocrystalline TiO2 electrodes sensitized with InP quantum
dots, and found they exhibited strong photoconduction in
the visible region and had a photocurrent action spectrum
consistent with the absorption spectrum of the InP QDs,
indicating electron transfers from InP QDs into TiO2 nano-
particles under visible light illumination.559
Kamat et al. recently reported the sensitization of meso-
scopic TiO2 films using bifunctional surface modifiers (SH-
R-COOH) linked with CdSe nanoparticles. Upon visible light
excitation, CdSe nanoparticles injected electrons into TiO2
nanocrystallites.561 The TiO2-CdSe composite exhibited a
photon-to-charge carrier generation efficiency of 12% when
employed as a photoanode in a photoelectrochemical cell.
4.2.1.2. Sensitization by Metal Nanoparticles. Ohko et
al. found that when the TiO2 nanoparticle films were
sensitized with Ag nanoparticles, the color of the film could
be reversely switched back and forth between brownish-gray
under UV light and the color of illuminating visible light
due to the oxidation of Ag by O2 under visible light and
reduction of Ag+ under UV light.562 The color of the film
under visible light could be tuned from green to red and white
by changing the size of the Ag nanoparticles due to the
plasmon-based absorption of Ag and the dielectric confine-
ment of the TiO2 nanoparticle film matrix. Figure 58 shows
absorption spectra and photographs of Ag-TiO2 films.
Naoi et al. found that the chromogenic properties of the
Ag-TiO2 films could be improved by simultaneous irradia-
tion during Ag deposition with UV and blue lights to
suppress the formation of anisotropic Ag particles and that
nonvolatilization of a color image could be achieved by
removing Ag+ that was generated during the irradiation with
a colored light.563 The color of the film was further found to
be affected by the resonance wavelengths of the Ag particles,
the TiO2 film, and the nanopores in the TiO2 film. They
found that the photochromism and rewritability of Ag-TiO2
films could be deactivated by modification of Ag nanopar-
ticles with thiols to make it possible to retain color images
displayed on the films, and that the deactivated properties
could be fully reactivated by UV irradiation (Figure 59A).564
Kawahara et al. proposed the mechanism of charge
separation at the interface between Ag and TiO2 nanoparticles
shown in Figure 59B.565 They found that, in the multicolor
photochromism of TiO2 nanoporous films loaded with
photocatalytically deposited or electrodeposited and com-
mercially available Ag nanoparticles, visible light-induced
electron transfer from Ag to oxygen molecules played an
essential role. Some of the photoexcited electrons on Ag were
transferred to oxygen molecules via TiO2 and nonexcited
Titanium Dioxide Nanomaterials
Figure 58. (A) Absorption spectra of a Ag-TiO2 film by
ultraviolet light irradiation and after visible light irradiation.
Corresponding photographs are also shown. (B) Photograph of
multicolored spots on the Ag-TiO2 film on a glass substrate
irradiated successively with monochromatic lights. A xenon lamp
and an ultraviolet-cut filter (blocking light below 400 nm) was used
with a 450 nm (blue), 530 nm (green), 560 nm (yellowish-green),
600 nm (orange), or 650 nm (red) bandpass filter (fwhm, 10 nm),
or without any bandpass filter (white). Reprinted with permission
from Ohko, Y.; Tatsuma, T.; Fujii, T.; Naoi, K.; Niwa, C.; Kubota,
Y.; Fujishima, A. Nature Mater. 2003, 2, 29. Copyright 2003 Nature
Publishing Group.
Ag, and replacement of the nonexcited Ag with Pt accelerated
the electron transport from the photoexcited Ag to oxygen
molecules and the photochromic behavior.
Tian and Tatsuma found that nanoporous TiO2 films
loaded with Ag and Au nanoparticles exhibit negative
potential changes and anodic currents in response to visible
light irradiation, with potential applications for photovoltaic
cells, photocatalysts, and plasmon sensors.566 They found that
for the Au-TiO2 system photoaction spectra for open-circuit
potential and short-circuit current agreed with the absorption
spectrum of Au nanoparticles in the TiO2 film. After the Au
nanoparticles were photoexcited due to plasmon resonance,
charge separation occurred by the transfer of photoexcited
electrons from the Au particle to the TiO2 conduction band
with the simultaneous transfer of compensating electrons
from a donor in solution to the Au particles.567 Cozzoli et
al. found that, following UV illumination, TiO2 nanorods
sensitized with Ag or Au nanoparticles could sustain a higher
degree of conduction band electron accumulation than pure
TiO2.126
4.2.1.3. Organic Dye Sensitization. Organic dyes have
been widely employed as sensitizers for TiO2 nanomaterial
to improve its optical properties, i.e., in dye-sensitized
Chemical Reviews, 2007, Vol. 107, No. 7 2927
Figure 59. (A) Schematic illustrations for photochromism of the
Ag-TiO2 film (a, b) and deactivation (c) and reactivation (d) of
the photochromism. From: Naoi, K.; Ohko, Y.; Tatsuma, T. Chem.
Commun. 2005, 1288 (http://dx.doi.org/10.1039/b416139d) s
Reproduced by permission of The Royal Society of Chemistry. (B)
Proposed mechanism of the charge separation at the interface
between Ag and TiO2 nanoparticles. From: Kawahara, K.; Suzuki,
K.; Ohko, Y.; Tatsuma, T. Phys. Chem. Chem. Phys. 2005, 7, 3851
(http://dx.doi.org/10.1039/b511489f) s Reproduced by permission
of the PCCP Owner Societies.
nanocrystalline solar cells (DSSCs).18,246,312,568-673Organic
dyes are usually transition metal complexes with low lying
excited states, such as polypyridine complexes, phthalocya-
nine, and metalloporphyrins.568-673 The metal centers for the
dyes include Ru(II), Zn(II), Mg(II), Fe(II), and Al(III), while
the ligands include nitrogen heterocyclics with delocalized
π or aromatic ring systems.
These organic dyes are normally linked to TiO2 nanopar-
ticle surfaces via functional groups by various interactions
between the dyes and the TiO2 nanoparticle substrate: (a)
covalent attachment by directly linking groups of interest or
via linking agents, (b) electrostatic interactions via ion
exchange, ion-pairing, or donor-acceptor interactions, (c)
hydrogen bonding, (d) van der Waals forces, etc. Most of
the dyes of interest link in the first way. Groups such as
silanyl (-O-Si-), amide (-NH-(CdO)-), carboxyl (-O-
(CdO)-), and phosphonato (-O-(HPO2)-) have been
shown to from stable linkages with the surface hydroxyl
groups on TiO2 substrates.610 Carboxylic and phosphonic acid
derivatives react with the hydroxyl groups to form esters,
while amide linkages are obtained via the reaction of amine
derivatives and dicyclohexyl carbodiimide on TiO2. The most
common and successful functional groups are based on
carboxylic acids. Qu and Meyer found spectroscopic evi-
dence for ester linkages after carboxylic acids react with the
surface titanol groups dehydratively.674 Metal cyano com-
pounds in acidic solutions were found to link to TiO2 surfaces
by a single cyanide ligand with a C4V symmetry, i.e., TiIV-
NC-FeII(CN)5.668,669,675
The interfacial charge separation between the adsorbed
dyes and TiO2 nanomaterials involves one of three mecha-
2928 Chemical Reviews, 2007, Vol. 107, No. 7
nisms, which differ by the nature of the donor that transfers
the electron to the semiconductor: (1) excited state; (2)
reduced state; or (3) molecule-to-particle charge-transfer
complex.550 For complete knowledge of the charge transfer
between the dye sensitizers and the TiO2 nanomaterials,
please refer to other excellent reviews.10,18,19,550,676,677 Ultrafast
electron transfer from metal-to-ligand charge transfer (MLCT)
excited states to anatase TiO2 is the most common category
in dye-sensitized TiO2.572,595,606,618,619,677-683 The mechanism
of the dye sensitization of TiO2 nanoparticles normally
involves the excitation of the dye and the charge transfer
from the dye to TiO2 nanoparticles. The low-lying MLCT
and ligand-centered (π-π*) excited states of these complexes
are fairly long-lived, allowing them to participate in electron-
transfer processes. As an efficient photosensitizer, the dye
has to meet several requirements. First, the dye should have
high absorption efficiency and a wide spectral range of
coverage of light absorption in the visible, near-IR, and IR
regions. Second, the excited states of the dye should have a
long lifetime and a high quantum yield. Third, the dye should
have matched electronic structures for the ground and excited
states with TiO2 nanoparticles to ensure the efficient charge
transfer between them; that is, the energy level of the excited-
state should be well matched to the lower bound of the
conduction band of TiO2 to minimize energetic losses during
the electron-transfer reaction.550
The electron transfer from the dye to TiO2 usually is very
fast, in the range of tens of femtoseconds. Hannappel et al.
found that electron transfer from the excited electronic singlet
state of chemisorbed ruthenium(II) cis-di(isothiocyanato)-
bis(2,2′-bipyridyl-4,4′-dicarboxylate) into empty electronic
states in a colloidal anatase TiO2 film was on the time scale
of <25 fs.595 Rehm et al. found the charge injection from a
surface-bound coumarin 343 to the conduction band of TiO2
occurred on a time scale of ∼200 fs due to strong electronic
coupling between the dye and TiO2 energy levels.684 The
electron transport and recombination in dye-sensitized TiO2
solar cells with different electrolytes had been investigated,
including iodine-doped ionic liquids (diethylmethylsulfo-
nium, dibutylmethylsulfonium, or 3-hexyl-1-methylimida-
zolium iodide) and an organic solvent (3-methoxypropion-
itrile with LiI, I2, and 1-methylbenzimidazole).685 The most
viscous electrolytes showed a clear limitation in photocurrent
attributed to a low diffusion coefficient for the triiodide that
transports positive charge to the counterelectrode. The
electron transport of the solar cells appeared to be dominated
by the properties of the nanostructured TiO2 film, and the
electron lifetime depended on the type of cation used in the
ionic liquid. Bulky, less absorptive cations seem to give
longer lifetimes. Schwarzburg et al. found a time constant
of 13 fs for electron transfer from the excited singlet state
of the chromophore perylene bonded to the surface via a
carboxyl group into anatase TiO2.686 The electron-transfer
time of perylene became much longer (3.8 ps) at a distance
of about 1.3 nm. Wenger et al. found that carefully controlled
deposition of Ru(II) complex dye molecules onto nanocrys-
talline TiO2 consistently yielded monophasic injection dy-
namics with a time constant shorter than 20 fs.687 The
anchoring of ruthenium dye {(C4H9)4N}[Ru(Htc-terpy)-
(NCS)3] (tc-terpy ) 4,4′,4′′-tricarboxy-2,2′:6′,2′′-terpyridine),
the so-called black dye, onto nanocrystalline TiO2 films
occurs by a bidentate binuclear coordination mode.577 The
electron injection process from the dye excited state into the
TiO2 conduction band was biexponential with a fast com-
Chen and Mao
ponent (200 ( 50 fs) and a slow component (20 ps),
attributed to the electron injection from the initially formed
and the relaxed dye excited states, respectively.577
In the reduced sensitizer injection mechanism, the sensi-
tizer excited state(s) is first quenched by an external donor,
and subsequently the reduced state of the dye, S-, transfers
an electron across the semiconductor interface.550,688 A
potential advantage of this mechanism is that the reduced
sensitizer is a stronger reductant than the MLCT excited state,
typically by 0.3-0.5 eV. Thus, sensitizers that are weak
photoreductants may sensitize TiO2 efficiently after reductive
quenching. This mechanism may be exploited to produce
large open-circuit photovoltages or enhanced light harvesting
in the near-IR regions. The observation of ultrafast electron
injection coupled with the weak oxidizing power of the
excited sensitizers currently in use strongly suggests that an
excited-state injection mechanism is operative in regenerative
solar cells based on these materials. The reduced sensitizer
injection mechanism was reported by Thompson,688 Haque,598
and Wang.659
The metal-to-particle charge-transfer mechanism involves
interfacial chemistry between the compounds and the TiO2
surface which produces color changes, observed by Grätzel
and identified as molecule-to-particle charge-transfer transi-
tions.689 Metal cyanides, [M(CN)x]4- (M ) FeII, RuII, OsII,
ReIII, MoIV, or WIV, x ) 6, 7, or 8), such as ferrocyanide,
FeII(CN)64-, bind to TiO2 through ambidentate cyano ligands.
For example, FeII(CN)64- does not absorb light above 380
nm, but a deep orange color with an absorption maximum
centered at 420 nm was observed for FeII(CN)64-/TiO2, due
to a MPCT complex formed between FeII(CN)64- and surface
Ti4+ ions, Fe(II)fTi(IV).550 The metal-to-particle charge-
transfer mechanism was consistent with the subpicosecond
infrared spectroscopy study on the FeII(CN)64-/TiO2 nano-
particle by Weng et al., where a mid-infrared absorption was
assigned to TiO2 electrons in the semiconductor.690 The
injection rate constant could not be time-resolved with a 50-
fs instrument response function. The MPCT was also found
by Yang et al. in their study on Fe(bpy)(CN)42--sensitized
TiO2, where the absorption spectra were well modeled by a
sum of MLCT (Fe f bpy) and metal-to-particle (Fe(II) f
Ti(IV)) bands. The MLCT bands were solvatochromic, while
the MPCT bands were not.668,669 Benkoe et al. found that
the larger the TiO2 particle and the better its overall
crystallinity, the faster the process of electron injection from
the dye fluorescein 27 to the anatase TiO2 film.578 Haque et
al. found that a supramolecule dye with a remarkably long-
lived (4 s) charge-separation state could be obtained by
controlling the spatial separation between the cation center
of the dye and the electrode surface.597 The dyes were Ru-
(II) complexes containing carboxylated polypyridyl chro-
mophores and a bipyridyl ligand with aromatic amine-based
electron donor substituents.597
The kinetics and mechanisms of the injections, transport, re-
combination, and photovoltaic properties of electrons in nano-
structured TiO2 solar cells have been thoroughly discussed
in recent reviews676,691-694 and will only be briefly mentioned
below. Considerable effort has been devoted to the kinetics
and energetics of transport and recombination in dye-sensi-
tized solar cells with various techniques, such as intensity
modulated photocurrent spectroscopy (IMPS),640,695-702 inten-
sity modulated photovoltage spectroscopy (IMVS),639,700,703,704
electrical impedance spectroscopy (EIS),700,705-710 transient
photocurrent,695,706,711-718 and transient photovoltage.715,719 For
Titanium Dioxide Nanomaterials
example, Searson and Cao studied the photocurrent response
of dye-sensitized, porous nanocrystalline TiO2 cells with
photocurrent transient measurements and intensity-modulated
photocurrent spectroscopy and found that the electron
transport in the TiO2 film can be fitted with a diffusion model
where the diffusion coefficient for electrons in the particle
network was a function of the light intensity.695 Using
intensity modulated photocurrent spectroscopy, Vanmaekele-
bergh et al. found that the electronic transport was controlled
by trapping and detrapping of photogenerated electrons in
interfacial band gap states, distributed in energy, and that
the localization time of a trapped electron was controlled
by the steady-state light intensity and interfacial kinetics.696,697
Peter et al. recently found that the electron transport in dye-
sensitized nanocrystalline solar cells appeared to be a slow
diffusion-controlled process, attributed to multiple trapping
at energy levels distributed exponentially in the band gap of
the nanocrystalline TiO2.720
Frank et al. summarized that the electron motion is
essentially ambipolarly diffusional and the morphology and
defect structure of the TiO2 film had a strong influence on
electron transport.676 The recombination predominates at the
interface and depends on the spatial region of photoinjected
charge buildup in the cell, the redox electrolyte, and the
surface properties of both the TiO2 nanoparticle film and
the TCO substrate. For the recombination, two mechanisms
assume either a dismutation reaction or an interfacial
electron-transfer reaction as rate-limiting, while the third
mechanism states electron transport limits recombination.676
The spatial location of the traps limiting electron transport
in nanocrystalline TiO2 has been a long standing issue. These
traps have been speculated to locate either at the particle
surface,640,721,722 in the bulk of the particles,723 or at inter-
particle grain boundaries.568 Kopidakis et al. recently inves-
tigated the dependence of the electron diffusion coefficient
and the photoinduced electron density on the internal surface
area of TiO2 nanoparticle films in dye-sensitized solar cells
by photocurrent transient measurements.724 They found that
the density of electron traps in the films changed in direct
proportion with the internal surface area, which was varied
by altering the average particle size of the films, and the
scaling of the electron diffusion coefficient with the internal
surface area. They suggested that the traps were located
predominately at the surface of TiO2 particles instead of in
the bulk of the particles or at interparticle grain boundaries,
and that surface traps limited transport in TiO2 nanoparticle
films. Kopidakis et al. found that the traps were located
predominately at the surface of TiO2 particles instead of in
the bulk of the particles or at interparticle grain boundaries
and that surface traps limited transport in TiO2 nanoparticle
films in the dye-sensitized TiO2 solar cell.724
5. Applications of TiO2 Nanomaterials
The existing and promising applications of TiO2 nanoma-
terials include paint, toothpaste, UV protection, photoca-
talysis, photovoltaics, sensing, and electrochromics as well
as photochromics. TiO2 nanomaterials normally have elec-
tronic band gaps larger than 3.0 eV and high absorption in
the UV region. TiO2 nanomaterials are very stable, nontoxic,
and cheap. Their optical and biologically benign properties
allow them to be suitable for UV protection applications.725-730
A surface is defined as superhydrophilic or superhydro-
phobic if the water-surface contact angle is larger than 130°
or less than 5°, respectively.731 TiO2 nanomateirals can be
Chemical Reviews, 2007, Vol. 107, No. 7 2929
imparted with antifogging functions on various glass prod-
ucts, i.e., mirrors and eyeglasses, having superhydrophilic
or superhydrophobic surfaces.332,732-734 For example, Feng
et al. found that reversible superhydrophilicity and super-
hydrophobicity could be switched back and forth for TiO2
nanorod films.142 When the TiO2 nanorod films were
irradiated with UV light, the photogenerated hole reacted
with lattice oxygen to form surface oxygen vacancies. Water
molecules kinetically coordinated to these oxygen vacancies,
and the spherical water droplet filled the grooves along the
nanorods and spread out on the film with a contact angle of
about 0°, resulting in superhydrophilic TiO2 films. After the
hydroxy group adsorption, the surface transformed into an
energetically metastable state. When the films were placed
in the dark, the adsorbed hydroxy groups were gradually
replaced by atmospheric oxygen, and the surface evolved
back to its original state. The surface wettability converted
from superhydrophilic to superhydrophobic.142 Stain-proof-
ing, self-cleaning properties can also be bestowed on many
different types of surfaces due to the superhydrophilic or
superhydrophobic surfaces.735-744 TiO2 nanomaterials have
also been used as sensors for various gases and humidity
due to the electrical or optical properties which change upon
adsorption.745-751
One of the most important research areas for future clean
energy applications is to look for efficient materials for the
production of electricity and/or hydrogen. When sensitized
with organic dyes or inorganic narrow band gap semicon-
ductors, TiO2 can absorb light into the visible light region
and convert solar energy into electrical energy for solar cell
applications.28,30,752 For example, an overall solar to current
conversion efficiency of 10.6% has been reached by the
group led by Grätzel with DSSC technology.31 TiO2 nano-
materials have been widely studied for water splitting and
hydrogen production due to their suitable electronic band
structure given the redox potential of water.198,475,476,753-770
Another application of TiO2 nanomaterials when sensitized
with dyes or metal nanoparticles is to build photochromic
devices.562,565,771-777 Of course, one of the many applications
of TiO2 nanomaterials is the photocatalytic decomposition
of various pollutants.
5.1. Photocatalytic Applications
TiO2 is regarded as the most efficient and environmentally
benign photocatalyst, and it has been most widely used for
photodegradation of various pollutants.121,127,132,430,442,778-822
TiO2 photocatalysts can also be used to kill bacteria, as has
been carried out with E. coli suspensions.793,799 The strong
oxidizing power of illuminated TiO2 can be used to kill tumor
cells in cancer treatment.782,785,820,823-825
The photocatalytic reaction mechanisms are widely stud-
ied.7,12,20,33,406 The principle of the semiconductor photocata-
lytic reaction is straightforward. Upon absorption of photons
with energy larger than the band gap of TiO2, electrons are
excited from the valence band to the conduction band,
creating electron-hole pairs. These charge carriers migrate
to the surface and react with the chemicals adsorbed on the
surface to decompose these chemicals. This photodecom-
position process usually involves one or more radicals or
intermediate species such as •OH, O2-, H2O2, or O2, which
play important roles in the photocatalytic reaction mecha-
nisms. The photocatalytic activity of a semiconductor is
largely controlled by (i) the light absorption properties, e.g.,
light absorption spectrum and coefficient, (ii) reduction and
2930 Chemical Reviews, 2007, Vol. 107, No. 7
oxidation rates on the surface by the electron and hole, (iii)
and the electron-hole recombination rate. A large surface
area with a constant surface density of adsorbents leads to
faster surface photocatalytic reaction rates. In this sense, the
larger the specific surface area, the higher the photocatalytic
activity is. On the other hand, the surface is a defective site;
therefore, the larger the surface area, the faster the recom-
bination. The higher the crystallinity, the fewer the bulk
defects, and the higher the photocatalytic activity is. High-
temperature treatment usually improves the crystallinity of
TiO2 nanomaterials, which in turn can induce the aggregation
of small nanoparticles and decrease the surface area. Judging
from the above general conclusions, the relation between the
physical properties and the photocatalytic activities is
complicated. Optimal conditions are sought by taking these
considerations into account and may vary from case to case.20
5.1.1. Pure TiO2 Nanomaterials: First Generation
As the size of the TiO2 particles decreases, the fraction of
atoms located at the surface increases with higher surface
area to volume ratios, which can further enhance the catalytic
activity. The increase in the band gap energy with decreasing
nanoparticle size can potentially enhance the redox potential
of the valence band holes and the conduction band electrons,
allowing photoredox reactions, which might not otherwise
proceed in bulk materials, to occur readily. One disadvantage
of TiO2 nanoparticles is that they can only use a small
percentage of sunlight for photocatalysis. Practically, there
exists an optimal size for a specific photocatalytic reaction.
Anpo et al. investigated the photocatalytic activity of TiO2
nanoparticles on hydrogenation reactions of CH3CCH with
H2O, and they found the activity increased as the diameter
of the TiO2 particles decreased, especially below 10 nm.406
They suggested that the dependence of the yields on the
particle size arose from the differences in the chemical
reactivity and not from the physical properties of these
catalysts.
Wang et al. found that there was an optimal size for TiO2
nanoparticles for maximum photocatalytic efficiency in the
decomposition of chloroform.815 They observed an improve-
ment in activity when the particle size was decreased from
21 to 11 nm, but the activity decreased when the size was
reduced further to 6 nm. They concluded that for this
particular reaction the optimum particle size was about 10
nm. In large TiO2 nanoparticles, bulk recombination of the
charge carriers was the dominant process, which could be
reduced by a decrease in particle size; as the particle size
was lowered below a certain limit, surface recombination
processes became dominant, since most of the electrons and
holes were generated close to the surface and surface
recombination was faster than interfacial charge carrier
transfer processes.826
Chae et al. studied the photocatalytic activity of four sizes
of TiO2 nanoparticles on the decomposition of 2-propanol,
and they found that 7-nm particles showed 1.6 times better
photocatalytic activity than TiO2 P25 and that 15- and 30-
nm particles showed lower photocatalytic efficiencies.132
Mesoporous TiO2, TiO2 nanorods, and nanotubes have
been demonstrated to have high photocatalytic performance
under suitable conditions.127,187,265,281,296,818 Peng et al. pre-
pared mesoporous TiO2 with a high specific surface area,
which showed significant activity on the oxidation of
Rhodamine B due to the large surface area, small crystal
size, and well-crystallized anatase mesostructure.296 Figure
Chen and Mao
Figure 60. Photocatalytic properties of mesoporous TiO2 samples
as prepared and calcined at different temperature as well as TiO2
P25 nanoparticles (RB, c0 ) 1.0 × 10-5 M, pH ) 6.0) under UV-
light radiation. Reprinted with permission from Peng, T.; Zhao,
D.; Dai, K.; Shi, W.; Hirao, K. J. Phys. Chem. B 2005, 109, 4947.
Copyright 2005 American Chemical Society.
60 shows the photocatalytic properties of mesoporous TiO2
samples as prepared and calcined at different temperatures
compared to those of TiO2 P25 nanoparticles. All mesopo-
rous TiO2 showed better activity than Deguessa P25 TiO2.
The optimum reactivity was obtained with the sample
calcined at 400 °C, and the photoactivity gradually decreased
with further increases in calcination temperature.
Yang et al. found that TiO2 nanotubes treated with H2-
SO4 solutions showed photocatalytic activity on degradation
of acid orange II in the following order: TiO2 nanotubes
treated with 1.0 mol/L H2SO4 solution > TiO2 nanotubes
treated with 0.2 mol/L H2SO4 solution > untreated TiO2
nanotubes > TiO2 nanoparticles, since TiO2 nanotubes treated
with H2SO4 were composed of smaller particles and had
higher specific surface areas.818
TiO2 aerogels were also suggested as promising candidates
for photocatalysts.316,317,319 Degan et al. prepared TiO2
aerogels with a porosity of 90% and surface areas of 600
m2/g, and they found that the photodegradation of salicylic
acid on TiO2 aerogels, after 1 h of near-UV illumination,
was about 10 times faster than that on the Degussa TiO2.316,317
Figure 61 shows photodegradation profiles for the aerogel
before and after annealing, as compared to the commercial
Degussa P25 powder.
5.1.2. Metal-Doped TiO2 Nanomaterials: Second
Generation
Over the past decades, metal-doped TiO2 nanomaterials
have been widely studied for improved photocatalytic
performance on the degradation of various organic pollutants,
i.e., under visible light irradiation (refs 21, 430, 433-435,
444, 446, 450-452, 455-457, 490, 515, 548, 810, 827-
836). Choi et al. conducted a systematic study on the
photocatalytic activity of TiO2 nanoparticles doped with 21
transition metal elements on the oxidation of CHCl3 and the
reduction of CCl4 and found that the photocatalytic activity
was related to the electron configuration of the dopant ion
in that dopant ions with closed electron shells had little or
no effect on the activity.434,435 Doping with Fe3+, Mo5+, Ru3+,
Os3+, Re5+, V4+, and Rh3+ at 0.1-0.5 at % significantly
increased the photoreactivity, while Co3+ and Al3+ doping
decreased the photoreactivity. The presence of metal ion
dopants in the TiO2 matrix significantly influenced the charge
carrier recombination rates and interfacial electron-transfer
Titanium Dioxide Nanomaterials
Figure 61. Photodegradation profiles of salicylic acid on annealed
(Ela) and nonannealed (El) TiO2 aerogels as compared to a
commercial Degussa P25. Reprinted with permission from Dagan,
G.; Tomkiewicz, M. J. Phys. Chem. 1993, 97, 12651. Copyright
1993 American Chemical Society.
rates. The photoreactivity of doped TiO2 appeared to be a
complex function of the dopant concentration, the energy
level of dopants within the TiO2 lattice, their d electronic
configurations, the distribution of dopants, the electron donor
concentrations, and the light intensity.
Sn4+ ion-doped TiO2 nanoparticle films prepared by the
plasma-enhanced CVD method displayed a higher photo-
catalytic activity for photodegradation of phenol than pure
TiO2 under both UV and visible light, and the Sn4+ dopant
was found profitable to the separation of photogenerated
carriers under both UV and visible light excitation.433 Figure
62 shows the photocatalytic decomposition of phenol with
reaction time under UV and visible light using Sn4+-doped
TiO2 nanoparticles as photocatalyst.433
Fe-doped nanocrystalline TiO2 was shown to display
higher photocatalytic activity with lower Fe content (optimal
0.05% mass fraction) than TiO2 in the treatment of paper-
making wastewater,837 and it was shown to be more efficient
in the photoelectrocatalytic disinfection of E. coli than pure
TiO2.827 V-doped TiO2 photocatalyst photooxidized ethanol
under visible radiation and had comparable activity under
UV radiation to that of pure TiO2.548 Pt4+ ion-doped TiO2
nanoparticles exhibited higher visible light photocatalytic
activities on the degradations of dichloroacetate and 4-chlo-
rophenol,830 and Ag-TiO2 nanocatalysts displayed enhanced
photocatalytic activity in the degradation of 2,4,6-trichlo-
rophenol due to a better separation of photogenerated charge
carriers and improved oxygen reduction inducing a higher
extent of degradation of atoms.809
Wei et al. synthesized La- and N-co-doped TiO2 nano-
particles with superior catalytic activity under visible light,
where N doping was responsible for the band gap narrowing
of TiO2 and La3+ doping prevented the aggregation of
nanoparticles.833 Chang et al. reported Cr- and N-co-doped
TiO2 nanomaterials with visible light absorbance generally
led to a reduction in photocatalytic efficacy in the decolori-
zation of methylene blue, except at the low nitrogen doping
concentration.490 Bessekhouad et al. found that low concen-
tration alkaline (Li, Na, K)-doped TiO2 nanoparticles were
promising materials for organic pollutants degradation.430
Peng et al. found that in Be2+-doped TiO2 nanomaterials,
Chemical Reviews, 2007, Vol. 107, No. 7 2931
Figure 62. Variation of phenol concentration with reaction time
under (A) UV and (B) visible light: (a) pure TiO2 catalyst; (b)
Sn4+-doped TiO2. From: Cao, Y.; Yang, W.; Zhang, W.; Liu, G.;
Yue, P. New J. Chem. 2004, 28, 218 (http://dx.doi.org/10.1039/
b306845e) s Reproduced by permission of The Royal Society of
Chemistry (RSC) on behalf of the Centre National de la Recherche
Scientifique (CNRS).
when the doping ions were in the shallow surface, the doping
was beneficial, while, in the deep bulk, the doping was
detrimental.451
However, not all the metal-doped TiO2 nanomaterials
showed higher photocatalytic activities than pure TiO2
nanomaterials. Martin found V-doped TiO2 nanoparticles had
reduced photocatalytic activity on the photooxidation of
4-chlorophenol compared to pure TiO2 nanoparticles. Va-
nadium appeared to reduce the photoreactivity of TiO2 by
promoting charge-carrier recombination with electron trap-
ping at VO2+ centers or with hole trapping at V4+ impurity
centers, which shunted charge carriers away from the solid/
solution interface.446 Hermann et al. found that although Cr-
doped (0.85 atomic %) TiO2 absorbed in the visible region,
its activity for oxidation of oxalic acid, propene, and
2-propanol and for O isotope exchange was null under visible
illumination and was smaller under UV light than that of
pure TiO2, due to an increase in electron-hole recombination
at the Cr3+ ion sites.440 Luo et al. reported that the
photoactivity of TiO2 doped with 1.5 mol % Mo, 1 mol %
V, 0.1 mol % V plus 1 mol % Al, or 0.1 mol % V plus 1
mol % Pb decreased, since the d electrons of Mo(4d) and
V(3d), as majority carriers in TiO2, could effectively quench
the high-energy photogenerated holes at the impurity levels
introduced by doping within the band gap of TiO2.445
5.1.3. Nonmetal-Doped TiO2 Nanomaterials: Third
Generation
Nonmetal-doped TiO2 nanomaterials have been regarded
as the third generation photocatalyst. Various nonmetal-
2932 Chemical Reviews, 2007, Vol. 107, No. 7
Figure 63. Photocatalytic properties of TiO2-xNx and TiO2 based
on decomposition rates [measuring the change in absorption of the
reference light (∆abs)] of methylene blue as a function of the cutoff
wavelength of the optical high-path filters under fluorescent light.
The inset shows the decomposition rates of methylene blue in the
aqueous solution under visible light as a function of the ratio of
the decomposed area in the XPS spectra with the peak at 396 eV
to the total area of N 1s. The total N concentrations were 1.0 atom
% (a), 1.1 atom % (b), 1.4 atom % (c), 1.1 atom % (d), and 1.0
atom % (e). Reprinted with permission from Asahi, R.; Morikawa,
T.; Ohwaki, T.; Aoki, K.; Taga, Y. Science 2001, 293, 269 (http://
www.sciencemag.org). Copyright 2001 AAAS.
doped TiO2 nanomaterials have been widely studied for their
visible light photocatalytic activities (refs 21, 385, 426, 428,
452, 472-474, 481-487, 490, 492-494, 496, 505, 518, 520,
524, 525, 527, 532, 533, 802, 838-847). Nonmetal-doped
TiO2 nanomaterials have been demonstrated to have im-
proved photocatalytic activities compared to those for pure
TiO2 nanomaterials, especially in the visible light re-
gion.426,428,485,489,833,848
Figure 63 shows the decomposition of methylene blue
using N-doped TiO2 as measured by Asahi and co-wokers.489
It was found that N-doped TiO2 had much higher photo-
catalytic activity than pure TiO2 in the visible light region,
while displaying lower activity in the UV-light region. A
nitrogen concentration dependent performance of the pho-
tocatalytic activity of the nitrogen-doped TiO2 was found in
the visible region, and the active sites of N for photocatalysis
under visible light were identified with the atomic β-N states
peaking at 396 eV in the XPS spectra.489 In the study of Irie
and co-workers, the concentration dependent photocatalytic
activity of the N-doped TiO2 was attributed to the fact that
the band structure of the N-doped TiO2 with lower nitrogen
concentration (<2%) was different from that with higher
concentration.483 It was found that the significant increase
in photocatalytic activity in N-doped TiO2 nanoparticles was
due to the O-Ti-N bond formation as oxynitride during
the substitutional doping process.428,477 The photocatalytic
oxidation of organic compounds by N-doped TiO2 under
visible illumination was mainly via reactions with surface
intermediates of water oxidation or oxygen reduction, not
by direct reactions with holes trapped at the N-induced
midgap level.486 N-doped TiO2 nanotubes also exhibited high
photocatalytic oxidation activity for decomposition of gas-
eous isopropanol into acetone and carbon dioxide when
illuminated with visible light.528
The photocatalytic activity of sulfur-doped TiO2 has also
been studied.492-494,496 The S-doped TiO2 was found to
display a higher photocatalytic activity in the visible region
but a lower photocatalytic activity in the UV region.492-494
S-doped TiO2 prepared with different methods showed
Chen and Mao
different photocatalytic activity under visible light due the
different carrier behavior in these samples.849
A noticeable photocatalytic activity on decompositions of
methylene blue and isopropanal in the visible region was
demonstrated for C-doped TiO2 made from a TiC precur-
sor.472,473 C-doped TiO2 made by pyrolyzing Ti metal in a
natural gas flame displayed a much higher photoactivity in
water splitting than pure TiO2.476 C-doped TiO2 nanoparticles
also displayed high photoactivity in degradation of trichlo-
roacetic acid under visible light.474
Yu et al. found that F-doped TiO2 showed higher photo-
catalytic activity on the oxidation of acetone into CO2 than
did Degeussa P25 in the photodecomposition study of
acetone under proper preparation conditions.502 N/F-doped
TiO2 nanomaterials had high visible light photocatalytic
activities for decompositions of both acetaldehyde and
trichloroethylene due to the creation of surface oxygen
vacancies rather than the improvement of optical absorption
properties.505,506,518,519 Luo et al. found that chlorine- and
bromine-co-doped TiO2 displayed a much higher photocata-
lytic activity than chlorine- or bromine-doped TiO2.508
5.2. Photovoltaic Applications
5.2.1. The TiO2 Nanocrystalline Electrode in DSSCs
Photovoltaics based on TiO2 nanocrystalline electrodes
have been widely studied.9,28-32 A schematic presentation
of the structure and operating principles of the DSSC is given
in Figure 64. At the heart of the system is a nanocrystalline
mesoporous TiO2 film with a monolayer of the charge-
transfer dye attached to its surface. The film is placed in
contact with a redox electrolyte or an organic hole conductor.
Photoexcitation of the dye injects an electron into the
conduction band of TiO2. The electron can be conducted to
the outer circuit to drive the load and make electric power.
The original state of the dye is subsequently restored by
electron donation from the electrolyte, usually an organic
solvent containing a redox system, such as the iodide/
triiodide couple. The regeneration of the sensitizer by iodide
prevents the recapture of the conduction band electron by
the oxidized dye. The iodide is regenerated in turn by the
reduction of triiodide at the counterelectrode, with the circuit
being completed via electron migration through the external
load. The voltage generated under illumination corresponds
to the difference between the Fermi level of TiO2 and the
redox potential of the electrolyte. Overall, the device
generates electric power from light without suffering any
permanent chemical transformation.9,28-32
Cahen et al. explained the cause for the photocurrent and
photovoltage in nanocrystalline mesoporous dye-sensitized
solar cells in terms of the separation, recombination, and
transport of electronic charge as well as in terms of electron
energetics.721 The basic cause for the photovoltage is the
change in the electron concentration in the nanocrystalline
electron conductor that results from photoinduced charge
injection from the dye. Pichot and Gregg found that the
photovoltage was determined by photoinduced chemical
potential gradients, not by equilibrium electric fields.635 The
maximum photovoltage is given by the difference in electron
energies between the redox level and the bottom of the
conduction band of the electron conductor, rather than by
any difference in electrical potential in the cell, in the dark.
Charge separation occurs because of the enthalpic and
entropic driving forces that exist at the dye/electron conductor
Titanium Dioxide Nanomaterials
Figure 64. (A) Structure and (B) principle of operation and energy
level scheme of the dye-sensitized nanocrystalline solar cell.
Photoexcitation of the sensitizer (S) is followed by electron injection
into the conduction band of an oxide semiconductor film. The dye
molecule is regenerated by the redox system, which itself is
regenerated at the counterelectrode by electrons passed through the
load. Potentials are referred to the normal hydrogen electrode
(NHE). The open circuit voltage of the solar cell corresponds to
the difference between the redox potential of the mediator and the
Fermi level of the nanocrystalline film indicated with a dashed line.
The energy levels drawn for the sensitizer and the redox mediator
match the redox potentials of the doubly deprotonated N3 sensitizer
ground state and the iodide/triiodide couple. Reprinted from Grätzel,
M. J. Photochem. Photobiol. A: Chem. 2004, 164, 3, Copyright
2004, with permission from Elsevier.
interface, with charge transport aided by such driving forces
at the electron conductor/contact interface. The mesoporosity
and nanocrystallinity of the semiconductor are important not
only because of the large amount of dye that can be adsorbed
on the very large surface but also for two additional
reasons: (a) they allow the semiconductor small particles
to become almost totally depleted upon immersion in the
electrolyte (allowing for large photovoltages), and (b) the
proximity of the electrolyte to all particles makes screening
of injected electrons, and thus their transport, possible.721
Many ruthenium complexes containing anchoring groups
such as carboxylic acid, dihydroxy, and phosphonic acid on
pyridyl ligands have been used as dyes in the DSSCs. Grätzel
et al. have been leading the research in this field since their
breakthrough in the early 1990s. Tris(2,2′-bipyridyl-4,4′-
carboxylate) ruthenium(II) was used in DSSCs until the
announcement in 1991 of a sensitized electrochemical
photovoltaic device with a conversion efficiency of 7.1%
Chemical Reviews, 2007, Vol. 107, No. 7 2933
under solar illumination with polypyridyl ruthenium and
osmium sensitizers with the general structure ML2(X)2, where
L stands for 2,2′-bipyridyl-4,4′-dicarboxylic acid, M is Ru
or Os, and X presents a halide, cyanide, thiocyanate, acetyl
acetonate, thiacarbamate, or water substituent.88 The dye-
sensitized solar cells with cis-dithiocyanatobis(4,4′-dicar-
boxylic acid-2,2′-bipyridine)ruthenium(II) (N3) displayed
absorption maxima at 518 and 380 nm and emission at 750
nm with a lifetime of 60 ns.625,850 In 2001 the “black dye”
tri(cyanato)-2,2′,2′′-terpyridyl-4,4′,4′′-tricarboxylate) ruthe-
nium(II) was found to achieve 10.4% conversion efficiency
in full sunlight.631 Amphiphilic heteroleptic N3 equivalent
dyes were recently applied to solar cells.673 These amphiphilic
heteroleptic sensitizers had several advantages compared to
the N3 complex: (a) The ground-state pKa of the 4,4′-
dicarboxy-2,2′-bpy was higher to enhance the binding of the
complex onto the TiO2 surface. (b) The decreased charge
on the sensitizer attenuated the electrostatic repulsion and
increased the dye loading. (c) The presence of the hydro-
phobic moiety on the ligand increased the stability of solar
cells toward water-induced desorption. (d) The oxidation
potential of these complexes was cathodically shifted com-
pared to that of the N3 sensitizer, which increased the
reversibility of the ruthenium III/II couple, leading to
enhanced stability. Combining the N3 dye with guanidinium
thiocyanate brought a further increase in the open-circuit
voltage of the solar cell.30,31
Unlike the large amount of effort put forth to optimize
the organic dyes in DSSCs in the past decades, attention has
only recently been paid to the TiO2 nanocrystalline electrode,
and some important results have been obtained. In the
following, various research efforts on the use of the TiO2
nanocrystalline electrode for DSSCs are briefly summarized.
5.2.1.1. Mesoporous TiO2 Nanocrystalline Electrodes.
Zukalova et al. found that ordered mesoporous TiO2 nano-
crystalline films showed enhanced solar conversion efficiency
by about 50% compared to traditional films of the same
thickness made from randomly oriented anatase nanocrys-
tals.312 The TiO2 nanocrystalline film was prepared via layer-
by-layer deposition with Pluronic P123 as template. The
sensitizer used was cis-dithiocyanato(4,4′-dicarboxy-2,2′-
bipyridine)(4,4′-di-(2-(3,6-dimethoxyphenyl)ethenyl)-2,2′-bi-
pyridine) ruthenium(II), N945. Figure 65 shows the photo-
current-voltage characteristics for solar cells based on ordered
and nonordered TiO2 films. When sensitized by N945, the
0.95-µm-thick nonorganized anatase film gave a conversion
efficiency of only 2.21%, which increased to 2.74% with
surface treatment by TiCl4 prior to dye deposition. Under
standard global AM 1.5 solar conditions, the cell with an
ordered mesoporous TiO2 nanocrystallinne film gave a
photocurrent density of Ip ) 7 mA/cm2, an open circuit
potential of UOC ) 0.799 V, and a fill factor of ff ) 0.72,
yielding 4.04% conversion efficiency. This improvement
resulted from a remarkable enhancement of the short circuit
photocurrent, due to the huge surface area accessible to both
the dye and the electrolyte.312
5.2.1.2. TiO2 Nanotube Electrode. Adachi et al. found
that dye-sensitized solar cells with electrodes made of
disordered single-crystalline TiO2 nanotubes (10-nm diam-
eter, 30-300-nm length) displayed an efficiency of 4.88%,
showing more than double the short-circuit current density
compared to those made of TiO2 nanoparticles of Deguessa
P-25 in a similar thin-film thickness region.569 Macak et al.
found that, for Ru-dye (N3) sensitization of self-organized
2934 Chemical Reviews, 2007, Vol. 107, No. 7 Chen and Mao

Figure 66. Photocurrent-photovoltage characteristics of a TiO2

nanotube array DSSC under 100% AM-1.5 illumination. The inset
Figure 65. Photocurrent-voltage characteristics of a solar cell, shows an SEM image of TiO2 nanotubes. Reprinted with permission
based on TiO2 films sensitized by N945, cis-dithiocyanato(4,4′- from Mor, G. K.; Shankar, K.; Paulose, M.; Varghese, O. K.;
dicarboxy-2,2′-bipyridine)(4,4′-di-(2-(3,6-dimethoxyphenyl)ethenyl)- Grimes, C. A. Nano Lett. 2006, 6, 215. Copyright 2006 American
2,2′-bipyridine) ruthenium(II). (1) Pluronic-templated three-layer Chemical Society.
film, 1.0-µm-thick; (2) nonorganized anatase treated by TiCl4, 0.95-
µm-thick; (3) nonorganized anatase nontreated by TiCl4, 0.95-µm-
thick. The inset shows the SEM image of Pluronic-templated three-
layer TiO2 films. Reprinted with permission from Zukalova, M.;
Zukal, A.; Kavan, L.; Nazeeruddin, M. K.; Liska, P.; Grätzel, M.
Nano Lett. 2005, 5, 1789. Copyright 2005 American Chemical
Society.

TiO2 nanotubes grown by Ti anodization, IPCEmax values

(at 540 nm) of 3.3% and 1.6% (at 530 nm) were obtained
for 2.5-µm- and 500-nm-long nanotubes, respectively.219
Ohsaki et al. found that the higher efficiency of solar cells
with TiO2 nanotube-based electrodes resulted from an
increase in electron density in nanotube electrodes compared
to P25 electrodes.851
Grimes et al. fabricated highly ordered nanotube arrays
(46-nm pore diameter, 17-nm wall thickness, and 360-nm
length) grown perpendicular to an F-doped SnO2-coated glass
substrate by anodic oxidization.201 After crystallization by
oxygen annealing and treatment with TiCl4, the nanotube
arrays were integrated into a DSC structure using a com-
mercially available ruthenium-based dye N719. The cell
generated a photocurrent of 7.87 mA/cm2 with a photocurrent
efficiency of 2.9%, using a 360-nm-thick electrode under
AM 1.5 illumination. They found that the highly ordered
TiO2 nanotube arrays had superior electron lifetimes and
provided excellent pathways for electron percolation in
comparison to nanoparticulate systems. Figure 66 shows the
photocurrent-photovoltage characteristics of the TiO2 nano-
tube DSSC.201 They also found that backside illuminated
solar cells based on 6-µm-long highly ordered nanotube-
array films sensitized by bis(tetrabutylammonium)-cis- Figure 67. (A) Current-voltage (I-V) curves for an inversed opal
cell obtained in the dark and under white light illumination using
(dithiocyanato)-N,N-bis(4-carboxylato-4-carboxylic acid-2,2- an AM 1.5 simulator (Isc ) 1.8 × 10-7 A/cm2, Voc ) 0.78 V, FF
bipyridine)ruthenium(II) (commonly called “N719”) showed ) 0.33). The inset shows an SEM image of an inverse opal TiO2
a power conversion efficiency of 4.24% under AM 1.5 film. (B) Current-voltage (I-V) characteristic of a nanocrystalline
illumination.203 TiO2 cell in the dark and under white light illumination using an
5.2.1.3. Inversed TiO2 Opal. The relatively low efficiency AM 1.5 simulator (Isc ) 8.5 × 10-9 A/cm2, Voc ) 0.87 V, FF )
0.40). Reprinted from Somani, P. R.; Dionigi, C.; Murgia, M.;
obtained in solid-state DSSCs is attributed to the poor Palles, D.; Nozar, P.; Ruani, G. Sol. Energy Mater. Sol. Cells 2005,
penetration of the material into pores of the thick TiO2 films 87, 513, Copyright 2005, with permission from Elsevier.
and the consequent noncontact of the hole transport layer
with the titania electrode. A novel approach to increase the indicated that light conversion efficiency increased by at least
efficiency of solid-state Grätzel solar cells was presented by 1 order of magnitude by the usage of the inversed opal TiO2
Somani et al., using large-surface titania inverse opal films films rather than nanocrystalline TiO2 films (Figure 67). The
as electrodes in fabricating solid-state dye-sensitized organic- better performance of inversed opal cells was due to the wide
inorganic hybrid Grätzel solar cells.352 Direct comparison and well-connected pores in mesoporous TiO2 films that
Titanium Dioxide Nanomaterials
Figure 68. Photocurrent density versus voltage for the photoelec-
trochemical cells based on the pure anatase (TiO2 II) and anatase-
rutile (TiO2 I) nanocrystalline TiO2 electrodes sensitized by N3.
The effective area for illumination is 0.5 cm2. The thicknesses of
the sputter deposited layer and the nanocrystalline layer are 20 nm
and 6 µm, respectively. Conditions: electrolyte, 0.5 M LiI + 0.04
M I2 in propylene carbonate (PC); room temperature; light intensity,
98 mW/cm2; AM1.5 spectral radiation. Inset: Performance param-
eters of solar cells. Reprinted Figure 2 from Han, H.; Zan, L.;
Zhong, J.; Zhao, X. J. Mater. Sci. 2005, 40, 4921, Copyright 2005,
with kind permission of Springer Science and Business Media.
allowed easy penetration of the hole transporting material,
allowing good contact with the dye and hence the best
efficiency of the cell.
5.2.1.4. Hybrid TiO2 Nanocrystalline Electrode. 5.2.1.4.1.
Anatase-Rutile TiO2 Nanocrystalline Electrode. Han et al.
found that a hybrid TiO2 electrode composed of a mixture
of anatase and rutile phases showed a higher solar-to-electric
energy conversion efficiency than one made of pure ana-
tase.852,853 Figure 68 shows the performance of the photo-
electrochemical cells built with pure anatase (TiO2 II) and
anatase-rutile (TiO2 I) nanocrystalline TiO2 electrodes
sensitized by N3. These electrodes had the same crystalline
sizes and surface areas (26 nm, BET 57 m2/g).852 TiO2 I had
71% anatase phase with 29% rutile phase, while TiO2 II had
pure anatase phase. The anatase-rutile-based DSSC showed
higher performance (efficiency η ) 6.8%, short-circuit
photocurrents density Jsc ) 19.4 mA/cm2, open-circuit
photovoltage VOC ) 652 mV, fill factor ff ) 0.53) than the
pure TiO2 (η ) 5.3%, Jsc ) 18.4 mA/cm2, VOC ) 582 mV,
ff ) 0.51).
5.2.1.4.2. Nanocrystalline Electrode with a Buffer Layer.
In a standard nanoporous electrode during DSSC operation,
two main problems are associated with the porous geom-
etry: (a) the high-area cross section for recombination of
photoinjected electrons with holes that are transferred to the
electrochemical mediator and (b) the image field opposing
the separation process that is distributed inside the TiO2
nanoporous electrode. The conversion efficiency of a DSSC
decreases due to recombination losses of photoinjected
electrons with oxidized dye molecules or a redox couple at
the surface of nanocrystalline TiO2. Various methods have
been adopted to prevent this loss. Kang et al. added a buffer
layer of a TiO2-WO3 composite material between a TCO
substrate (Figure 69) and a TiO2 layer and found that the
buffer layer effectively isolated dye molecules and electro-
lytes from directly contacting the conducting substrate.854 In
the presence of the buffer layer having 15-75 mol % WO3,
Chemical Reviews, 2007, Vol. 107, No. 7 2935
Figure 69. Schematic band diagrams of working electrodes
consisting of a TiO2-WO3 buffer layer between TCO and a P25
layer. From: Kang, T. S.; Moon, S. H.; Kim, K. J. J. Electrochem.
Soc. 2002, 149, E155. Copyright 2002. Reproduced by permission
of The Electrochemical Society, Inc.
both open-circuit photovoltage and short-circuit photocurrent
were enhanced. In the case of the electrode having a buffer
layer of less than about 10 mol % WO3, due to the large
negative VFB, a potential barrier to the conduction band
electrons from TiO2 emerged at the TiO2-WO3/TiO2 junc-
tion. This resulted in a drop in photoinjection efficiency and
subsequently in the photocurrent. For electrodes having more
than about 75 mol % WO3, the conduction band edge of the
buffer layer lay close to or lower than that of TCO, and the
relative conduction band energy of the buffer layer was not
particularly beneficial for the electron injection from the
conduction band of TiO2.854
5.2.1.4.3. Core-Shell Structured Nanocrystalline Elec-
trode. Under the operating conditions of a DSSC, the
electrons need to diffuse several micrometers into the TiO2
layer surrounded by electron acceptors at a distance of only
several nanometers. The nanoporous structure of the TiO2
layer provides a large surface area, allowing absorption of
enough dye molecules to achieve significant optical den-
sity.10,855 However, the structure also enhances the recom-
bination processes and decreases the total conversion effi-
ciency of DSSC.856-858 The recombination processes are
completely prohibited due to the lack of a significant electric
field that could assist the separation of electrons from holes
in the TiO2 layer, since small TiO2 nanoparticles allow only
limited band bending at the electrode surface.721,856,857,859
Core-shell TiO2 electrodes consisting of a nanoporous TiO2
covered with a shell of another metal oxide have been shown
to slow the recombination processes by the formation of an
energy barrier at the TiO2 surface.560,648,649,860-865 The con-
duction band potential of the shell should be more negative
than that of TiO2 in order to generate an energy barrier for
the reaction of the electrons present in TiO2 with the oxidized
dye or the redox mediator in solution. Two approaches are
employed to fabricate the nanoporous core-shell electrodes.
The first approach involves synthesis of core-shell nano-
particles that are applied onto the conducting sub-
strate.560,648,649,863,866 An energy barrier forms not only at the
electrode/electrolyte interface but also between the individual
TiO2 nanoparticles. The second approach involves a nano-
porous TiO2 electrode coated with the thin shell lay-
er.670,860-862,864,865,867 The TiO2 nanoparticles are connected
directly to each other allowing electron transport through
TiO2.
The approach involving nanoporous electrodes in a well-
defined core-shell configuration is usually a TiO2 core
coated with Al2O3,596,865,868-870 MgO,871 SiO2,865 ZrO2,865 or
Nb2O5.860,670 For example, Zaban et al. found that TiO2/Nb2O5
2936 Chemical Reviews, 2007, Vol. 107, No. 7
Figure 70. (A) Schematic view of the new bilayer nanoporous
electrode which consists of a nanoporous TiO2 matrix covered with
a thin layer of Nb2O5. The Nb2O5 coating forms an inherent energy
barrier at the electrode/electrolyte interface, which reduces the
recombination rate of the photoinjected electrons. From: Zaban,
A.; Chen, S. G.; Chappel, S.; Gregg, B. A. Chem. Commun. 2000,
2231 (http://dx.doi.org/10.1039/b005921h) s Reproduced by per-
mission of The Royal Society of Chemistry. (B) I-V curves of
four DSSCs differing by the nanoporous electrodes used to fabricate
them: the TiO2 reference electrode (a), and three bilayer electrodes
(b-d). The Nb2O5 coating was made by a 30 s dipping of a 6 µm
TiO2 matrix in a 5 mM solution of NbCl5 in dry ethanol (b), Nb-
(isopropoxide)5 in 2-propanol (c), and Nb(ethoxide)5 in ethanol (d).
Reprinted with permission from Chen, S. G.; Chappel, S.; Diamant,
Y.; Zaban, A. Chem. Mater. 2001, 13, 4629. Copyright 2001
American Chemical Society.
nanoporous electrodes could improve the performance of
dye-sensitized solar cells by >35%.670,860 Figure 70 shows
a bilayer nanoporous electrode which consists of a nanopo-
rous TiO2 matrix covered with a thin layer of Nb2O5 and
the performance of three TiO2 electrodes coated with Nb2O5.
For the best coating condition, the photocurrent increased
from 10.2 to 11.4 mA/cm2, the photovoltage from 661 to
730 mV, and the fill factor from 51.0 to 56.5%. As a result,
the conversion efficiency of the solar cell increased by 35%
from 3.62 to 4.97%.860 They also found that sometimes the
shell material shifted the conduction band potential of the
core rather than forming an energy barrier. For example,
coating of TiO2 with a SrTiO3 shell resulted in a shift of the
TiO2 conduction band in the negative direction.861,862 Con-
sequently, introduction of a SrTiO3-coated TiO2 electrode
to a DSSC increased the open circuit photovoltage while
reducing the short circuit photocurrent compared to that of
the noncoated TiO2 electrode.861,862 Diamant et al. found that
the mechanism by which the shell affected the electrode
properties depended on the coating material. Coating materi-
als included Nb2O5, ZnO, SrTiO3, ZrO2, Al2O3, and SnO2.862
The coating Nb2O5 formed a surface energy barrier, which
slowed the recombination reactions, while the other shell
materials each formed a surface dipole layer that shifted the
conduction band potential of the core TiO2. The shift
direction and magnitude depended on the dipole parameters
Chen and Mao
Figure 71. Schematic view of the collector-shell electrode. This
core shell electrode consists of a conductive nanoporous matrix
that is coated with TiO2. Reprinted with permission from Chappel,
S.; Grinis, L.; Ofir, A.; Zaban, A. J. Phys. Chem. B 2005, 109,
1643. Copyright 2005 American Chemical Society.
which were induced by the properties of the two materials
at the core/shell interface.862
Palomares et al. found that the conformal growth of an
overlayer of Al2O3 on a nanocrystalline TiO2 film resulted
in a 4-fold retardation of interfacial charge recombination
and a 30% improvement in photovoltaic device efficiency.870
Fabregat-Santiago et al. found that the alumina barrier
reduced the recombination of photoinjected electrons to both
the dye cations and the oxidized redox couple, due to two
effects: (a) almost complete passivation of surface trap states
in TiO2 that were able to inject electrons to acceptor species
and (b) slowing down by a factor of 3-4 of the rate of
interfacial charge transfer from conduction band states.868
O’Regan found that the Al2O3 layer acted as a tunnel barrier,
thus increasing Voc and the fill factor.869 Palomares et al.
prepared SiO2, Al2O3, and ZrO2 overlayers by dipping
mesoporous nanocrystalline TiO2 films in organic solutions
of their respective alkoxides, followed by sintering at 435
°C.865 The metal oxide overlayers acted as barrier layers for
interfacial electron-transfer processes. The most basic over-
layer coating, Al2O3 (pzc ) 9.2), was optimal for retarding
interfacial recombination losses under negative applied bias,
with an increase in open-circuit voltage of up to 50 mV and
a 35% improvement in overall device efficiency. Diamant
et al. found that SrTiO3-coated nanoporous TiO2 electrodes
increased the open circuit photovoltage while reducing the
short circuit photocurrent and resulting in a 15% improve-
ment of the overall conversion efficiency of the solar cell.861
The SrTiO3 layer shifted the conduction band of the TiO2 in
the negative direction due to a surface dipole rather than
forming an energy barrier at the TiO2/electrolyte inter-
face.861,862 The shell having a more negative conduction band
potential acted as an energy barrier that slowed recombination
reactions. Photoexcitation of dye molecules anchored to
ultrathin (e1 nm) outer shells of insulators or semiconductors
on n-type semiconductor crystallites resulted in electron
transfer to the inner core material.
However, there is still considerable recombination that
increases with the distance between the electron injection
point and the current collector. In other words, the limited
lifetime of the injected electron and the slow diffusion rate
inside the porous structure limit the effective thickness of
the nanoporous electrode. Chappel et al. proposed a electrode
design, shown in Figure 71, with a core shell configuration
based on a conductive ITO or Sb-doped SnO2 matrix coated
with TiO2.872 In principle, the conducting core extended the
current collector into the nanoporous network and was
Titanium Dioxide Nanomaterials
Figure 72. (a) SEM of a cross section of the bilayer photonic crystal-nano-TiO2 photoelectrode. The conductive glass is at the top of the
image in part a. The photonic crystal layer and the nanocrystalline TiO2 layer are enlarged in parts b and c, respectively. Reprinted with
permission from Nishimura, S.; Abrams, N.; Lewis, B. A.; Halaoui, L. I.; Mallouk, T. E.; Benkstein, K. D.; van de Lagemaat, J.; Frank,
A. J. J. Am. Chem. Soc. 2003, 125, 6306. Copyright 2003 American Chemical Society.
denoted the nanoporous “collector shell electrode”. Conse-
quently, the distance between the injection spot and the
current collector should decrease to several nanometers
throughout the nanoporous electrode, in contrast to several
micrometers with the standard electrode. All electrons
injected into the electrode, including those generated several
micrometers away from the substrate, had to travel a very
short distance before reaching the current collector. As shown
by several studies, transport shorter than 1 µm provides 100%
collection efficiency. In addition, the new collector-shell
electrode contained inherent screening capability due to the
high doping level of the conducting matrix. Theoretically,
the new design should enable efficient charge separation and
collection for thick nanoporous layers and solid electro-
chemical mediators. They found that, unless the TiO2 coating
was thicker than 6 nm, the electrode performance was very
low due to fast recombination.872
5.2.1.4.4. Electrode Coupled with Photonic Crystals.
Development of photosensitizers with improved spectral
response at the low-energy end of the solar spectrum has
not proven so successful because dye molecules with high
red absorbance have lower excited-state excess free energy,
thus lowering the quantum yield for charge injection.
Increasing the thickness of the film beyond 10-12 µm in
order to increase the absorbance in the red results in an
increase in the electron transport length and the recombina-
tion rate, and a decrease in the photocurrent. An alternative
approach to improving efficiency was to increase the path
length of light by enhancing light scattering in the TiO2
films.873-878 While the small size of TiO2 nanoparticles (10-
30 nm) employed to ensure a high surface area makes
conventional nanocrystalline TiO2 films poor light scatterers,
mixing the nanoparticles with larger particles or applying a
scattering layer to the nanocrystalline film has been shown
to increase light harvesting by enhancing the scattering of
light.873-878
Chemical Reviews, 2007, Vol. 107, No. 7 2937
Nishimura347 and Halaoui333 reported an enhancement in
the light conversion efficiency of dye-sensitized TiO2 solar
cells by coupling a conventional nanocrystalline TiO2 film
to a TiO2 inverse opal, with a 26% increase in the IPCE
relative to that of a nanocrystalline film of the same overall
thickness in the 550-800 nm spectral range. They found
that the bilayer architecture, rather than enhanced light
harvesting within the inverse opal structures, was responsible
for the bulk of the gain in the IPCE.333 Figure 72 shows an
SEM image of a cross section of the bilayer photonic
crystal-nano-TiO2 photoelectrode.347
Figure 73 shows the sketch for the mechanism of the
photonic crystal in enhancing absorption in certain regimes.347
The fact that light waves were localized in different parts of
the structure, depending on their energy, implied that an
absorber in the high dielectric medium should interact more
strongly with light at wavelengths to the red of the stop band,
and less strongly to the blue. Effectively, the red part of the
spectrum of this absorber would “borrow” intensity from the
blue part.
Figure 74A shows the effect of the TiO2 photonic crystal
as compared to a film of nanocrystalline TiO2 on the
absorption spectra when dye is adsorbed to the surface.347
In a comparison of the spectrum of dye molecules adsorbed
to the TiO2 photonic crystal film with that of a conventional
nanocrystalline TiO2 film, there was a substantial enhance-
ment absorbance on the red side of the stop band, as well as
a slight attenuation of absorbance on the blue side of the
stop band. The enhanced absorbance was most pronounced
between 500 and 550 nm, but it persisted to a lesser degree
at longer wavelengths. Figure 74B shows the enhancement
of the performance of a bilayer electrode compared to a
conventional nanocrystalline TiO2 photoelectrode.347 Between
400 and 530 nm, there was little difference between the two
kinds of electrodes. The close similarity in the maximum
photocurrent from the two electrodes was consistent with
2938 Chemical Reviews, 2007, Vol. 107, No. 7
Figure 73. (A) Simplified optical band structure of a photonic
crystal. Near the Brillouin zone center, light travels with velocity
c0/n, where c0 is the speed of light in a vacuum and n is the average
refractive index. At photon energies approaching a full band gap
or a stop band from the red side, the group velocity of light
decreases and light can be increasingly described as a sinusoidal
standing wave that has its highest amplitude in the high-refractive-
index part of the structure. At energies above the band gap or stop
band, the standing wave is predominantly localized in the low index
part of the photonic crystal, i.e., in the air voids. (B) Illustration of
the effect of standing wave localization on dye absorbance. In an
isotropic medium, the dye absorbs strongly in the blue but weakly
in the red (heavy line). If the stop band is tuned to the position
shown by the arrow, the blue absorbance is diminished and the red
absorbance is increased when the dye is confined to the high-
refractive-index part of the photonic crystal (dotted line). Reprinted
with permission from Nishimura, S.; Abrams, N.; Lewis, B. A.;
Halaoui, L. I.; Mallouk, T. E.; Benkstein, K. D.; van de Lagemaat,
J.; Frank, A. J. J. Am. Chem. Soc. 2003, 125, 6306. Copyright 2003
American Chemical Society.
the fact that both contain the same amount of dye. Between
540 and 750 nm, the short circuit photocurrent was substan-
tially increased in the bilayer electrode. The overall gain,
integrated over the visible spectrum (400-750 nm), was
about 30%. Localization of heavy photons at the edges of
the photonic stop band347,879,880 from Bragg diffraction in the
periodic lattice and multiple scattering events at disordered
regions in the photonic crystal or at disordered films led
ultimately to enhanced backscattering.333 This largely ac-
counted for the enhanced light conversion efficiency in the
red spectral range (600-750 nm), where the sensitizer was
a poor absorber.333
5.2.2. Metal/Semiconductor Junction Schottky Diode Solar
Cell
McFarland and Tang reported a multilayer photovoltaic
device structure in which photon absorption occurred in
photoreceptors deposited on the surface of an ultrathin metal/
semiconductor junction Schottky diode.881 The device struc-
ture was a solid-state multilayer with a photoreceptor layer
deposited on a 10-50 nm Au film, which capped 200 nm
of TiO2 on an ohmic metal back contact (Figure 75). The
photon-to-electron conversion in this device occurred in four
Chen and Mao
Figure 74. (A) Absorption spectra of the TiO2 photonic crystal
(a), the N719 dye adsorbed on the photonic crystal (b), and the
dye adsorbed on a film of nanocrystalline TiO2 (c). The position
of the stop band at 486 nm is indicated by the arrow. (B)
Wavelength dependence of the short-circuit photocurrent in the
bilayer electrode (a) and the conventional nanocrystalline TiO2
photoelectrode (b). The position of the stop band maximum in the
bilayer electrode was 610 nm. Reprinted with permission from
Nishimura, S.; Abrams, N.; Lewis, B. A.; Halaoui, L. I.; Mallouk,
T. E.; Benkstein, K. D.; van de Lagemaat, J.; Frank, A. J. J. Am.
Chem. Soc. 2003, 125, 6306. Copyright 2003 American Chemical
Society.
steps. First, light absorption occurred in the surface-absorbed
photoreceptors, giving rise to energetic electrons. Second,
electrons from the photoreceptor excited state were injected
into the conduction levels of the adjacent conductor, where
they travelled ballistically through the metal at an energy,
1e, above the Fermi energy, Ef. Third, provided that 1e was
greater than the Schottky barrier height, f, and the carrier
mean-free path was long compared to the metal thickness,
the electrons traversed the metal and entered the conduction
levels of the semiconductor (internal electron emission). The
absorbed photon energy was preserved in the remaining
excess electron free energy when it was collected at the back
ohmic contact, giving rise to the photovoltage, V. The
photooxidized dye was reduced by transfer of thermalized
electrons from states near Ef in the adjacent metal. Devices
fabricated by using a fluorescein photoreceptor on an Au/
TiO2/Ti multilayer structure had typical open-circuit photo-
voltages of 600-800 mV and short-circuit photocurrents of
10-18 mA cm-2 under 100 mW cm-2 visible light illumina-
tion: the internal quantum efficiency (electrons measured
per photon absorbed) was 10%. This alternative approach
to photovoltaic energy conversion might provide the basis
for durable low-cost solar cells using a variety of materials.
5.2.3. Doped TiO2 Nanomaterials-Based Solar Cell
Lindgren et al. found that N-doped TiO2 nanocrystalline
porous thin films showed visible light absorption in the
wavelength range from 400 to 535 nm and generated an
incident photon-to-current efficiency response in good agree-
Titanium Dioxide Nanomaterials
Figure 75. Electron transfer in the operating photovoltaic device:
(process A) photon absorption and electron excitation from the
chromophore ground state, S, to the excited state, S*; (process B)
energetic electron transfer from S* into and (ballistically) through
the conducting surface layer and over the potential energy barrier
into the semiconductor; (process C) conduction of electrons as
majority carriers within the semiconductor to the ohmic back-contact
and through the load; (process D) reduction of the oxidized
chromophore, S, by a thermal electron from the conductor surface.
Shown schematically are the relative energies of the electron levels
within the device structures, the Schottky barrier, f, the Fermi
energy, Ef, and the semiconductor band gap, Eg. Reprinted with
permission from McFarland, E. W.; Tang, J. Nature 2003, 421,
616. Copyright Nature Publishing Group.
Figure 76. Reaction schemes for semiconductor photocatalysts.
Reprinted Figure 2 from Kudo, A. Catal. SurV. Asia 2003, 7, 31,
Copyright 2003, with kind permission of Springer Science and
Business Media.
ment with the optical spectra.385 For the best nitrogen-doped
TiO2 electrodes, the photoinduced current due to visible light
and at moderate bias increased around 200 times compared
to the behavior of pure TiO2 electrodes.
5.3. Photocatalytic Water Splitting
5.3.1. Fundamentals of Photocatalytic Water Splitting
An enormous research effort has been dedicated to the
study of the properties and applications of TiO2 under light
illumination since the discovery of photocatalytic splitting
of water on a TiO2 electrode in 1972 (Fujishima and
Honda).6-8 Photocatalytic splitting of water into H2 and O2
using TiO2 nanomaterials continues to be a dream for clean
and sustainable energy sources.882
Figure 76 shows the principle of water splitting using a
TiO2 photocatalyst.761 When TiO2 absorbs light with energy
larger than the band gap, electrons and holes are generated
in the conduction and valence bands, respectively. The
photogenerated electrons and holes cause redox reactions.
Water molecules are reduced by the electrons to form H2
Chemical Reviews, 2007, Vol. 107, No. 7 2939
and oxidized by the holes to form O2, leading to overall water
splitting.883-885 The width of the band gap and the potentials
of the conduction and valence bands are important. The
bottom level of the conduction band has to be more negative
than the reduction potential of H+/H2 (0 V vs NHE), while
the top level of the valence band has to be more positive
than the oxidation potential of O2/H2O (1.23 V). The potential
of the band structure of TiO2 is just the thermodynamical
requirement. Other factors such as charge separation, mobil-
ity, and lifetime of photogenerated electrons and holes also
affect the photocatalytic properties of TiO2. These factors
are strongly affected by the bulk properties of the material
such as crystallinity. Surface properties such as surface states,
surface chemical groups, surface area, and active reaction
sites are also important.768 The water-splitting process in
return affects the local pH environment and surface structures
of the TiO2 electrode.769
Salvador conducted a thermodynamic and kinetic consid-
eration of water-splitting and competitive reactions in the
photoelectrochemical cell, and they found that the overvolt-
age for evolution of O must be minimized, which was on
the order of 0.6 eV for n-TiO2 electrodes loaded with
RuO2.767 Cocatalysts such as Pt and NiO are often loaded
on the surface in order to introduce active sites for H2
evolution. Thus, suitable bulk and surface properties and
energy structure are demanded for photocatalysts.
Laser-induced photocatalytic oxidation/splitting of water
over TiO2 catalysts was studied.883,886,887 Sayama and Ara-
kawa found that addition of carbonate salts to Pt-loaded TiO2
suspensions led to highly efficient water splitting.888 The
carbonate ions affected both the Pt particles and the TiO2
surface. The Pt was covered with some titanium hydroxide
compounds and the rate of the back reaction on the Pt was
suppressed effectively in the presence of carbonate ions. The
carbonate species aided desorption of O2 from the TiO2
surface.888 Khan and Akikusa found that bare n-TiO2
nanocrystalline film electrodes were unstable during water-
splitting reactions under illumination of light and their
stability could be significant improved when covered with
Mn2O3.759
5.3.2. Use of Reversible Redox Mediators
It has been reported that pure TiO2 could not easily split
water into H2 and O2 in the simple aqueous suspension
system.413,754,889 The main problem is the fast, undesired
electron-hole recombination reaction.762 Therefore, it is
important to prevent the electron-hole recombination pro-
cess. The Pt-TiO2 system could be illustrated as a “short-
circuited” photoelectrochemical cell, where a TiO2 semi-
conductor electrode and a platinum-metal counterelectrode
are brought into contact. Well-dispersed metal particles act
as miniphotocathodes, trapping electrons, which reduces
water to hydrogen.
The role of sacrificial reagents is shown in Figure 77.761
When the photocatalytic reaction is carried out in aqueous
solutions including easily oxidizable reducing reagents,
photogenerated holes irreversibly oxidize the reducing
reagents instead of water. This makes the photocatalyst
electron-rich, and a H2 evolution reaction is enhanced as
shown in Figure 77a. On the other hand, in the presence of
electron acceptors such as Ag+ and Fe3+, the photogenerated
electrons in the conduction band are consumed by them and
an O2 evolution reaction is enhanced as shown in Figure
77b. These reactions using sacrificial reagents are regarded
2940 Chemical Reviews, 2007, Vol. 107, No. 7
Figure 77. Photocatalytic H2 (a) or O2 (b) evolution in the presence
of sacrificial reagents. Reprinted Figure 5 from Kudo, A. Catal.
SurV. Asia 2003, 7, 31, Copyright 2003, with kind permission of
Springer Science and Business Media.
Figure 78. Proposed reaction mechanism for overall photocatalytic
water splitting using a IO3-/I- redox mediator and a mixture of
Pt-TiO2-antase and TiO2-rutile photocatalysts. Reprinted with
permission from Abe, R.; Sayama, K.; Domen, K.; Arakawa, H.
Chem. Phys. Lett. 2001, 344, 339. Copyright 2001 Elsevier.
as half reactions and are often employed for test reactions
of photocatalytic H2 or O2 evolution. However, one should
realize that the results do not guarantee a photocatalyst to
be active for overall water splitting into H2 and O2 in the
absence of sacrificial reagents.
A sacrificial reagent helps to control the electron-hole
recombination process. The photoefficiency of the process
can be improved by the addition of sacrificial reagents.754,889,890
The sacrificial reagents help separation of the photoexcited
electrons and holes. Various compounds such as methanol,
ethanol, EDTA (an ethylenediaminetetraacetic derivative),
Na2S, and Na2SO4 or ions such as I-, IO3-, CN-, and Fe3+
have been used as sacrificial reagents.753-755,757,890,891
Abe et al. conducted a series of experiments on water
splitting under sunlight.753-755 They designed a new photo-
catalytic reaction that split water into H2 and O2 by a two-
step photoexcitation system composed of an IO3-/I- shuttle
redox mediator and two different TiO2 photocatalysts: Pt-
loaded TiO2-anatase for H2 evolution and TiO2-rutile for O2
evolution (Figure 78).753 Simultaneous gas evolution of H2
(180 mmol/h) and O2 (90 mmol/h) was observed from a basic
(pH ) 11) NaI aqueous suspension of two different TiO2
photocatalysts under UV radiation. The overall water splitting
proceeded by the redox cycle between IO3- and I- under
basic conditions as follows: (a) water reduction to H2 and
Chen and Mao
I- oxidation to IO3- over Pt-TiO2-anatase, and (b) IO3-
reduction to I- and water oxidation to O2 over TiO2-rutile.
IO3- reduction to I- over Pt-TiO2-anatase is an undesirable
reaction. If this reaction is suppressed, the total water-splitting
reaction will take place more efficiently. The advantage of
this system is that H2 gas is evolved over the Pt-TiO2-
anatase photocatalyst only and that O2 gas is evolved over
the TiO2-rutile photocatalyst only, even from a mixture of
IO3- and I- in a basic aqueous solution. Therefore, another
undesirable backward reaction, H2O formation from H2 and
O2 on Pt particles, was suppressed.753 They found that
addition of a small amount of iodide anion, I-, into the
aqueous suspension of Pt-TiO2-anatase photocatalyst sig-
nificantly improved the splitting into H2 and O2 with a
stoichiometric ratio. The iodide anion was adsorbed prefer-
entially onto the Pt cocatalyst as iodine atom. This iodine
layer effectively suppressed the backward reaction of water
formation from H2 and O2 to H2O over the Pt surface.754
Fujihara et al. studied the photochemical splitting of water
by combining the reduction of water to hydrogen using
bromide ions and the oxidation of water to oxygen using
FeIII ions.892 The bromide ions were oxidized to bromine on
Pt-loaded TiO2 nanoparticles, and the FeIII ions were reduced
to FeII ions on TiO2 nanoparticles. These two reactions were
carried out in separated compartments and combined via
platinum electrodes and cation-exchange membranes as
shown in Figure 79. At the electrodes, FeII ions were oxidized
by bromine, and protons were transported through the
membranes to maintain the electrical neutrality and pH of
the solutions in the two compartments. As a result, water
was continuously split into hydrogen and oxygen under
radiation. The reversible reactions on photocatalysts which
often suffered from the effects of back reactions were largely
prevented due to the low concentration of the products in
solution.
Lee et al. found that a considerable amount of photocata-
lytic H2 was produced from water over NiO/TiO2 in
proportion to the hole scavenger CN-.890 Galinska and
Walendziewski studied water splitting over a Pt-TiO2
catalyst with various sacrificial reagents, such as methanol,
Na2S, EDTA, and I- and IO3- ions, and they found that the
sacrificial reagents had a key role in hydrogen production
via the photocatalyzed water-splitting reaction.757 Photocata-
lytic water splitting was obtained when EDTA and Na2S were
used. They acted as effective hole scavengers, preventing
oxygen formation and the recombination reaction of oxygen
with hydrogen.
5.3.3. Use of TiO2 Nanotubes
Mor et al. found that highly ordered TiO2 nanotube arrays
efficiently decomposed water under UV radiation.198 The
authors found that the nanotube wall thickness was a key
parameter influencing the magnitude of the photoanodic
response and the overall efficiency of the water-splitting
reaction. For TiO2 nanotubes with 22-nm pore diameter and
34-nm wall thickness (Figure 80A), upon 320-400 nm
illumination at an intensity of 100 mW/cm2, hydrogen gas
was generated at the power-time normalized rate of 960
mmol/h W (24 mL/h W) at an overall conversion efficiency
of 6.8% as shown in Figure 80B.198,199 They also claimed
that, for illumination at 320-400 nm (98 mW/cm2), the TiO2
nanotube-array photoanodes could generate H2 by H2O
photoelectrolysis with a photoconversion efficiency of
12.25%.212 Park et al. further found that, when doped with
Titanium Dioxide Nanomaterials
Figure 79. (A) Schematic of the photocatalytic reaction cell for
splitting water. (B) Energy diagram of splitting of water by
combined photocatalytic reactions. From: Fujihara, K.; Ohno, T.;
Matsumura, M. Faraday Trans. 1998, 94, 3705 (http://dx.doi.org/
10.1039/a806398b) s Reproduced by permission of The Royal
Society of Chemistry.
carbon, TiO2-xCx nanotube arrays showed more efficient
water splitting under UV and visible light illumination (>420
nm) than pure TiO2 nanotube arrays.475
5.3.4. Water Splitting under Visible Light
5.3.4.1. Water Splitting over Doped TiO2 Nanomate-
rials. In general, the conduction bands of stable oxide
semiconductor photocatalysts consisting of metal cations with
a d0 and d10 configuration consist of empty orbitals (LUMO)
of the metal cations. On the other hand, the valence bands
consist of O2p orbitals. The potential of this valence band
(about +3 eV) is considerably more positive than the
oxidation potential of H2O to O2 (E0 ) 1.23 V). Therefore,
the band gaps of oxide semiconductor photocatalysts with
the potential for H2 evolution inevitably become wide.
Accordingly, a valence band or an electron donor level
consisting of orbitals of some element, except for O2p, has
to be formed to make the band gaps or the energy gaps
Chemical Reviews, 2007, Vol. 107, No. 7 2941
Figure 80. (A) SEM images, top view, of 20 V TiO2 nanotube
arrays anodized at 5 °C. (B) Photoconversion efficiency as a
function of measured potential [vs Ag/AgCl] for 10 V samples
anodized at four temperatures [i.e., 5, 25, 35, and 50 °C]. Reprinted
with permission from Mor, G. K.; Shankar, K.; Paulose, M.;
Varghese, O. K.; Grimes, C. A. Nano Lett. 2005, 5, 191. Copyright
2005 American Chemical Society.
Figure 81. Strategy of the development of photocatalysts with a
visible light response. Reprinted Figure 6 from Kudo, A. Catal.
SurV. Asia 2003, 7, 31, Copyright 2003, with kind permission of
Springer Science and Business Media.
narrow. New photocatalysts having the band structure shown
in Figure 81 are necessary in order to develop materials for
splitting water into H2 and O2 under visible light.761 The
created levels have to possess not only the thermodynamical
potential for oxidation of H2O but also the catalytic properties
for the four-electron oxidation reaction. The following
strategies can be considered for the development of visible
light-driven photocatalysts: (i) forming a donor level above
a valence band by doping some element into conventional
photocatalysts with wide band gaps such as TiO2; (ii) creating
2942 Chemical Reviews, 2007, Vol. 107, No. 7
a new valence band employing some element; and (iii)
controling the band structure by making a solid solution.761
Borgarello et al. found that water cleavage could be
induced with visible light in colloidal solutions of Cr-doped
TiO2 nanoparticles deposited with ultrafine Pt or RuO2.431
A pronounced synergistic effect in catalytic activity was
noted when both RuO2 and Pt were co-deposited onto the
particle. Jin and Lu found that Pt/B-doped TiO2 was a good
system for water splitting under a B4O72- environment
without sacrificial electron donor reagents.893 Luo et al. found
that Br-- and Cl--co-doped nanocrystalline TiO2 with the
absorption edge shifted to a lower energy region displayed
higher efficiency for water splitting than pure TiO2.508 Jing
et al. found that a Ni-doped mesoporous TiO2 photocatalyst
with 0.2 wt % Pt accomplished hydrogen evolution at nearly
125.6 lmol/h compared to 81.2 lmol/h for TiO2 P25.894 N-,
B-doped TiO2 nanomaterials have displayed higher activity
than pure TiO2 in water splitting, i.e., under visible light
illumination.529,889 Khan et al. found that a C-doped TiO2
nanocrystalline film with visible light response obtained by
controlled combustion of Ti metal in a natural gas flame
had a high water-splitting performance with a total conver-
sion efficiency of 11% and a maximum photoconversion
efficiency of 8.35% when illuminated at 40 mW/cm2,476
although there were questions about its solar-to-hydrogen
conversion efficiency by other researchers.895-897
Matsuoka et al. developed visible light responsive TiO2
nanocrystalline thin films by the radio frequency magnetron
sputtering method, which decomposed water when Pt-loaded
and in the presence of a sacrificial reagent such as methanol
or silver nitrate under visible light.763,764
5.3.4.2. Water Splitting over Dye-Sensitized TiO2.
Duonghong et al. found that TiO2 loaded simultaneously with
ultrafine Pt and RuO2 displayed extremely high activity as
an H2O decomposition catalyst under band gap excitation
of the TiO2 and that, when Ru(bipy)32+ or rhodamine B was
used as a sensitizer, H2O was decomposed under visible
light.898
Abe et al. investigated H2 production over merocyanine
or coumarin dye C343 or Ru complex dye N3 dye-sensitized
Pt/TiO2 photocatalysts under visible light in a water-
acetonitrile solution containing iodide as an electron donor.756
They found that the rates of H2 evolution decreased with
increasing proportion of water in the solutions because of a
decrease in the energy gap between the redox potential of
I3-/I- and the HOMO levels of the dyes, which decreases
the efficiency of electron transfer from I- to dye. The energy
diagram and the mechanism for the H2 production from water
over the dye-sensitized Pt/TiO2 photocatalyst system are
shown in Figure 82. The two key electron-transfer steps,
electron injection from an excited state of the dye to the TiO2
conduction band and oxidation of I- to I3- (steps 2 and 5),
occurred efficiently in acetonitrile solvent. The increased ratio
of water hindered electron transfer from I- to the HOMO
level of the oxidized dye (step 5).
In addition, Park and Bard designed two different kinds
of cells with bipolar dye-sensitized TiO2/Pt panels connected
so that their photovoltages added to provide vectorial electron
transfer for unassisted water splitting to yield the separated
products H2 and O2.765
5.3.5. Coupled/Composite Water-Splitting System
Akikusa et al. found that a self-driven system for water
splitting under illumination could be achieved with the
Chen and Mao
Figure 82. Energy diagram of H2 production from water over dye-
sensitized Pt/TiO2 photocatalysts in the presence of I- or EDTA
as an electron donor. Reprinted with permission from Abe, R.;
Sayama, K.; Sugihara, H. J. Sol. Energy Eng. 2005, 127, 413.
Copyright 2005 by ASME.
combination of single-crystal p-SiC and nanocrystalline
n-TiO2 photoelectrodes.899 Both photoelectrodes (p-SiC and
n-TiO2) were placed side by side facing the light source and
in contact with an electrolyte of 0.5 M H2SO4. The open
circuit potential was found to be 1.24 V between the n-TiO2
and p-SiC photoelectrodes, with a maximum photocurrent
density of 0.05 mA cm-2 under a closed circuit potential of
0.23 V, corresponding to an efficiency of 0.06%. The low
cell photocurrent density and the photoconversion efficiency
for the p-SiC/n-TiO2 self-driven system for the water-splitting
reaction were due to the high band gap energies of both
semiconductors and high recombination of photogenerated
carriers mainly in the covalently bonded p-SiC.
Takabayashi et al. proposed a solar water-splitting system
based on a composite polycrystalline-Si/doped TiO2 thin-
film electrode for high-efficiency and low-cost by combining
the advantages of Si and doped TiO2: (1) an n-Si electrode
with surface alkylation and a metal nanodot coating gave
an efficient and stable photovoltaic characteristic, and (2)
TiO2 doped with other elements, such as nitrogen and sulfur,
could cause water photooxidation (oxygen photoevolution)
under visible light illumination.770 The structure and working
mechanism of solar water splitting with this system is shown
in Figure 83. Although a high solar-to-chemical conversion
efficiency of more than 10% was calculated for this system,
several major problems needed to be solved before the real
device could show promising performance.770
5.4. Electrochromic Devices
TiO2 nanomaterials have been widely explored as elec-
trochromic devices, such as electrochromic windows and
displays.611,634,772,900-916 Electrochromism can be defined as
the ability of a material to undergo color change upon
oxidation or reduction. Electrochromic devices are able to
vary their throughput of visible light and solar radiation upon
electrical charging and discharging using a low voltage. A
small voltage applied to the windows will cause them to
darken; reversing the voltage causes them to lighten. Thus,
one can regulate the amount of energy entering through a
“smart window” so that the need for air conditioning in a
cooled building decreases. The energy efficiency inherent
in this technology can be large, provided that the control
strategy is adequate. Additionally, the transmittance regula-
tion can impart glare control as well as user control of the
indoor environment. The absorbance, rather than the reflec-
Titanium Dioxide Nanomaterials
Figure 83. (A) Schematic illustration and (B) the operation
principle of solar water splitting with a composite polycrystalline-
Si/doped TiO2 semiconductor electrode. Reprinted from Takaba-
yashi, S.; Nakamura, R.; Nakato, Y. J. Photochem. Photobiol., A:
Chem. 2004, 166, 107, Copyright 2004, with permission from
Elsevier.
tance, is modulated so that the electrochromic devices tend
to heat up in their low-transparent state.752
Two types of electrochromism of nanocrystalline thin film
TiO2 electrodes have been reported. The first type is the
electrochromism of nanocrystalline TiO2 electrodes in Li-
containing electrolytes related to the reversible insertion of
Li+ into the anatase lattice of the nanoparticles.912 Hagfeldt
et al. found that forward biasing of transparent nanocrystal-
line TiO2 films in lithium ion-containing organic electrolytes
led to rapid and reversible coloration due to electron
accumulation and Li+ intercalation in the anatase lattice.912
Absorption of >90% light throughout the visible and near
IR could be switched on and off within a few seconds. The
nanocrystalline morphology of the film played a role in
enhancing the electrochromic process. Ottaviani et al. found
that the rate of the electrochromic process was controlled
by the diffusion of the Li+ ions throughout the TiO2 lattice.914
It was convenient to drive the electrochromic process with
potentiostatic pulses, and under these conditions, many cycles
with initially good color contrast and efficiencies which
approached 100% were obtained with TiO2 thin film
electrodes.
Chemical Reviews, 2007, Vol. 107, No. 7 2943
The second type is the electrochromism of nanocrys-
talline TiO2 electrodes modified with viologens and/or
anthrachinons equipped with a surface anchoring
group.902-904,906-908,910,917-919 This category usually has fast
switching times and considerable optical dynamics, due to
the combination of good conductivity between the TiO2
nanoparticles and the fast electron exchange between TiO2
and the monolayer of the electrochromic compound covering
each particle.904 Bach et al. demonstrated high-quality paper-
like electrochromic displays based on nanostructured TiO2
films modified with electrochromophores with excellent ink-
on-paper optical qualities, fast response times, and low power
consumption.901 Moeller et al. demonstrated electrochromic
pictures with unprecedented resolution (360 dpi) in transpar-
ent and reflective electrochromic displays (ECD) based on
ink-jet printing technology and cascade-type crosslinking
reactions of viologens in the mesopores of a TiO2 electrode,
with a completely transparent counterelectrode based on
mesoporous antimony tin oxide coated with CeO2.913
5.4.1. Fundamentals of Electrochromic Devices
Figure 84A shows the principle of the electrochromism
of a molecular monolayer adsorbed on TiO2.902 A molecule,
which functions as the electrochromophore and exhibits
different colors in different oxidation states, must be chosen
such that its redox potential lies above the conduction band
edge of the TiO2 nanocrystalline electrode at the liquid/solid
interface. In this way, electrons can be transferred reversibly
from the conduction band to the molecule. The TiO2
electrode in fact behaves like a conductor for the adsorbed
electroactive species. If the redox potential is situated below
the conduction band edge, the reduction process is irrevers-
ible. Figure 84B shows the TiO2 nanocrystalline electro-
chromic devices based on viologen (solvent: glutarodinitrile)
with a counterelectrode made of Prussian blue.902 The device
could be switched back and forth between the colorless and
the colored states within 1 s.
The nanocrystalline structure of the TiO2 film makes
possible 100- to 1000-fold amplification compared to a flat
surface as shown in Figure 85.902 The combination of high
conductivity of the nanocrystalline TiO2 particles, fast
electron exchange with the molecular monolayer, optical
amplification by the porous structure, and fast charge
compensation by ions in the contacting liquid makes the
nanocrystalline electrodes highly attractive electrochromic
elements. The principle of efficiency relies on fast interfacial
electron transfer between the nanocrystalline TiO2 and the
adsorbed modifier as well as on the high surface area of the
TiO2 support that amplifies optical phenomena by 2 or 3
orders of magnitude.902 The investigated TiO2 nanocrystalline
electrodes include ordered905 and disordered902-904 mesopo-
rous films. Ordered mesoporous nanocrystalline TiO2 elec-
trodes were found to display enhanced color contrast yet have
similar conduction band edge energy levels and electron
percolation ability as electrodes made from nanocrystalline
TiO2, attributed to the uniform and ordered mesopore
architecture and the large accessible surface area for tethering
viologen molecules.905
5.4.2. Electrochromophore for an Electrochromic Device
The viologen group (N,N′-disubstituted-4,4′-bipyridinium)
has been commonly chosen as an electrochromophore, for
its remarkable stability in both the oxidized and the reduced
(radical cation) states (Figure 86).902,904,906,907 Oxidized vi-
2944 Chemical Reviews, 2007, Vol. 107, No. 7 Chen and Mao

Figure 84. (A) Principle of the electrochromism of a molecular monolayer adsorbed on a semiconductor surface. Electrons are injected
from the conducting substrate into the conduction band of the semiconductor and from there reduce the adsorbed electroactive molecule.
Provided the redox potential of that molecule lies above the conduction band edge, the process is reversible by application of a positive
potential to the conductive substrate. (B) Nanocrystalline electrochromic devices based on viologen (solvent: glutarodinitrile) with a
counterelectrode made of Prussian blue, in the colorless and in the colored state. Reprinted from Bonhote, P.; Gogniat, E.; Campus, F.;
Walder, L.; Grätzel, M. Displays 1999, 20, 137, Copyright 1999, with permission from Elsevier.

ologen is colorless, while the radical cation can be blue,
violet, purple, or green, depending on the substituents. The
associated first reduction potential is between 0.2 and -0.6
V (vs NHE). The typical absorption spectrum of reduced
N,N′-dialkylviologen in an organic solvent has a maximum
around 600 nm. With N,N′-diarylviologens, the absorption
band is shifted by about 50 nm to the red. In concentrated
solution or in the solid state, viologen radical cations form
dimers, with their blue-shifted absorption maximum in the
550 nm region. A second reduced state can be reached at
potentials which are more negative by 0.2-0.4 V. This state
is neutral and almost colorless (yellowish). This second
reduction is reversible in organic solvents like acetonitrile
but not in water. The anchoring groups with strong affinity
toward TiIV include carboxylates, salicylates, or phospho-
nates.902
Bonhote et al. examined phosphonated triarylamine as an
electrochromophore due to its oxidation by the stable
triarylamminum radical cation, which is accompanied by a
blue coloration with the absorption band at 730 nm.903
Vayssieres et al. studied bis(phthalocyaninato)lutetium(III)
complexes (Pc2Lu) as electrochromophores, and they found
that the typical neutral green state of Pc2Lu was reduced to
a brown state at potentials < -0.3 V vs Ag/AgCl at neutral
pH when Pc2Lu was adsorbed onto a nanostructured TiO2
electrode.916
Ag-TiO2 films, prepared by loading nanoporous films
with Ag nanoparticles by photocatalytic means, exhibited
multicolor photochromism, which was related to the oxida-
tion and reduction of Ag nanoparticles under UV and visible
radiation.773 Please also see section 4.2.1.2 on Sensitization
by Metal Nanoparticles.
5.4.3. Counterelectrode for an Electrochromic Device
Closed cells are built by combining a transparent nano-
crystalline electrode with a counterelectrode able to provide
Titanium Dioxide Nanomaterials
Figure 85. Principle of signal amplification by a TiO2 nanocrystalline film. Sintered 20-nm particles of TiO2 form a several millimeter
thick film characterized by a very high surface area. Once derivatized with a molecular adsorbate, the structure contains the equivalent of
hundreds of superposed monolayers. Reprinted from Bonhote, P.; Gogniat, E.; Campus, F.; Walder, L.; Grätzel, M. Displays 1999, 20, 137,
Copyright 1999, with permission from Elsevier.
Figure 86. Electrochromism mechanism of a viologen chro-
mophore. Reprinted from Bonhote, P.; Gogniat, E.; Campus, F.;
Walder, L.; Grätzel, M. Displays 1999, 20, 137, Copyright 1999,
with permission from Elsevier.
enough electrons to allow complete reduction of viologen.
The simplest counterelectrode is conducting glass.
Prussian blue (PB) is an inorganic polymeric material (iron
phexacyanoferrate) that is commonly used on a conducting
glass substrate as a counterelectrode. Being blue in the
oxidized state and colorless in the reduced state, it is a
suitable complementary electrochromic material to the
nanocrystalline viologen electrode. When the latter electrode
turns blue by reduction, the PB counterelectrode turns blue
by oxidation.902,904 Bonhote et al. studied nanocrystalline
WO3 films as counterelectrodes for electrochromic applica-
tions since they turn from colorless to blue by reduction and
lithium ion insertion.903
Fitzmaurice et al. constructed an electrochromic window
based on a modified transparent nanostructured TiO2 film
supported on conducting glass and modified with the
electrochromophore bis(2-phosphonoethyl)-4,4′-bipyridinium
dichloride, the electrolyte LiClO4, and ferrocene in γ-butyro-
lactone.906 They used a counterelectrode of conducting glass,
which had excellent electrochromic performance with a
coloration efficiency of 170 cm2 C-1 at 608 nm, a switching
time of 1 s, and stability over 10,000 steady test cycles. They
upgraded this system with a counterelectrode based on a
transparent nanostructured SnO2 film supported on conduct-
Chemical Reviews, 2007, Vol. 107, No. 7 2945
ing glass and modified by the electrochromophore [β-(10-
phenothiazyl)propoxy]phosphonic acid, which displayed
cycles-switching times of <250 ms, a coloration efficiency
of 270 cm2 C-1, and steady-state currents of <6 mA cm-2.908
Zinc can be used as a counterelectrode instead of PB for
displays applications.902 When the two electrodes are short-
circuited, the electrons flow from the zinc, which oxidizes
to Zn2+ ions, to the viologens of the nanocrystalline electrode.
The process can be reversed under a potential of 1-2 V.
5.4.4. Photoelectrochromic Devices
Pichot et al. demonstrated a photoelectrochromic smart
window with flexible substrates and solid-state electrolytes
based on a dye-sensitized TiO2 electrode spin-coated onto
In-Sn oxide-coated polyester substrates coupled with a WO3
electrochronic counterelectrode, separated by a cross-linked
polymer electrolyte containing LiI (Figure 87).634 The devices
typically transmitted 75% of visible light in the bleached
state. After a few minutes of exposure to white light, the
windows turned dark blue, transmitting only 30% of visible
light. They spontaneously bleached back to their initial
noncolored state upon removal of the light source. The
photoelectrochromic device ideally behaved like a capaci-
tor: There was initially no mobile oxidized species (i.e., I2)
present in the electrolyte. A schematic representation of the
components and the electron and ion transfers in the solid-
state photoelectrochromic device is shown in Figure 87. The
ultimate electron acceptor (WO3) is localized as an insoluble
material on the back electrode. Only the electron donor (I-),
which serves as a regenerator to the oxidized dye, is initially
present in the electrolyte introduced as LiI. Upon coloration
of the device at short-circuiting under illumination, I2 is
generated at the TiO2 electrode and Li+ intercalates in WO3.
5.5. Hydrogen Storage
Lim et al. found that TiO2 nanotubes could reproducibly
store up to approximately 2 wt % H2 at room temperature
2946 Chemical Reviews, 2007, Vol. 107, No. 7 Chen and Mao

Figure 87. Schematic representation of the components and the

electron and ion transfers in a solid-state photoelectrochromic
device. Upon illumination, electrons are injected into the TiO2
conduction band (CB), travel through the external circuit, and reduce
the WO3 counterelectrode. Upon lithium ion intercalation into the
reduced WO3 film, a “tungsten bronze” is formed that absorbs
visible and near-IR radiation, presumably via an intervalence
charge-transfer absorption. TCO stands for transparent conducting
oxide, which is typically ITO or fluorine-doped tin oxide. From:
Pichot, F.; Ferrere, S.; Pitts, R. J.; Gregg, B. A. J. Electrochem.
Soc. 1999, 146, 4324, Copyright 1999. Reproduced by permission
of The Electrochemical Society, Inc.

and 6 MPa.165 About 75% of this stored hydrogen could be Figure 88. (a) Pressure-concentration isotherms of TiO2 nanotubes
released when the hydrogen pressure was lowered to ambient and bulk TiO2 at room temperature. (b) Pressure-concentration
conditions due to physisorption. Approximately 13% was isotherms of TiO2 nanotubes at 24, 70, and 120 °C. Reprinted with
weakly chemisorbed and could be released at 70 °C as H2, permission from Lim, S. H.; Luo, J.; Zhong, Z.; Ji, W.; Lin, J.
Inorg. Chem. 2005, 44, 4124. Copyright 2005 American Chemical
and approximately 12% was strongly bonded to oxide ions Society.
and released only at temperatures above 120 °C as H2O. The
P-C isotherms of TiO2 nanotubes are shown in Figure 88.
At room temperature and a pressure of ∼900 psi (6 MPa),
the atomic ratio H/TiO2 was ∼1.6, corresponding to ∼2.0
wt % H2 for TiO2 nanotubes, compared to a much lower
hydrogen concentration of ∼0.8 wt % for bulk TiO2. When
the pressure was reduced, only ∼75% of the stored hydrogen
could be released, whereas 25% of adsorbed hydrogen
molecules were retained due to chemical adsorption.
Bavykin et al. studied the sorption of hydrogen between
the layers of the multilayered wall of nanotubular TiO2 in
the temperature range of -195 to 200 °C and at pressures
of 0 to 6 bar.157 Hydrogen could intercalate between layers
in the walls of TiO2 nanotubes forming host-guest com-
pounds TiO2‚xH2, where x e 1.5 and decreases at higher
temperature. The rate of hydrogen uptake increased with
temperature, and the characteristic time for hydrogen sorption Figure 89. Isotherm for (9) hydrogen sorption into and (O)
in TiO2 nanotubes was several hours at 100 °C. The hydrogen desorption out of the pores of TiO2 nanotubes at -196 °C. Reprinted
adsorption isotherm for TiO2 nanotubes at -195 °C is shown with permission from Bavykin, D. V.; Lapkin, A. A.; Plucinski, P.
in Figure 89. Almost 1.5 hydrogen molecules per one Ti K.; Friedrich, J. M.; Walsh, F. C. J. Phys. Chem. B 2005, 109,
19422. Copyright 2005 American Chemical Society.
atom could be adsorbed at a hydrogen partial pressure of 2
bar. During the desorption of hydrogen, a large hysteresis of the square of nanotube length from their proposed
was observed; even at 0 bar of pressure, the uptake of diffusion model.
hydrogen achieved a 1.25 molar ratio (point B). The Recently, Xu et al. studied the hydrogen storage properties
adsorption of hydrogen was a reversible process. Heating of a series of five pristine micro- and mesoporous Ti oxide
the sample in a vacuum to 200 °C led to a complete materials, synthesized from C6, C8, C10, C12, and C14
desorption of hydrogen, returning the weight of the sample amine templates possessing BET surface areas ranging from
to its initial value (point A). The author found that the 643 to 1063 m2/g, and they found that at 77 K the isotherms
diffusion of hydrogen molecules in the axial direction for all materials gently rose sharply at low pressure and
between the layers in multilayered walls of TiO2 nanotubes continued to rise in a linear fashion from 10 atm onward to
was the rate-limiting step of the process of intercalation and 65 atm and then return on desorption without significant
the rate of hydrogen intercalation depended on the inverse hysteresis. Extrapolation to 100 atm could yield total storage
Titanium Dioxide Nanomaterials Chemical Reviews, 2007, Vol. 107, No. 7 2947

Figure 90. Plot of real-time variation of resistance before, during, and after cleaning the contaminant, motor oil 10W-30, with UV exposure.
The plot, broken into four parts for clarity, shows (a) the original sensor behavior from time 10 to 1000 s, (b) the behavior of the sensor
over time 100-6000 s, during which the sensor is contaminated with oil, losing its hydrogen-sensing capabilities, and is initially exposed
to UV light, and (c) the behavior of the sensor from time 5000 s to 45,000 s. At time 7000 s, the UV is turned off, with the sensor regaining
its nominal starting resistance of approximately 100,000 Ω, at which point it is exposed to 1000 ppm hydrogen and its resistance changes
by a factor of approximately 50. The sensor is then again exposed to UV, from roughly time 15,000 s to 29,000 s. After this second UV
exposure, the sensor is again exposed to 1000 ppm hydrogen, showing an approximate factor of 500 change in electrical resistance. The
sensor is once again exposed to UV, from time 36,000 s. (d) Sensor behavior from time 45,000 to 70,000 s continues with UV exposure
of the sensor until time 52,000 s, after which the sensor is repeatedly cycled between air and 1000 ppm hydrogen, showing a relative
change in impedance of approximately 1000×. Compared to the hydrogen sensitivity of a noncontaminated sensor, the relative response of
the “recovered” sensor is within a factor of 2. Reprinted with permission from Mor, G. K.; Carvalho, M. A.; Varghese, O. K.; Pishko, M.
V.; Grimes, C. A. J. Mater. Res. 2004, 19, 628. Copyright 2004 Materials Research Society.

values as high as 5.36 wt % and 29.37 kg/m3, and surface
Ti reduction by the appropriate organometallic reagent
provided an increase in performance, possibly because of a
Kubas-type interaction.920
5.6. Sensing Applications
TiO2 nanocrystalline films have been widely studied as
sensors for various gases (refs 194, 196, 202, 206-209, 211,
322, 745-747, 750, 751, and 921-961). Grimes et al.
conducted a series of excellent studies on sensing using TiO2
nanotubes.194,196,206-209,211 They found that TiO2 nanotubes
were excellent room-temperature hydrogen sensors not only
with a high sensitivity of 104 but also with an ability to self-
clean photoactively after environmental contamination.196 At
24 °C, in response to 1000 ppm of hydrogen, the sensors
showed a fully reversible change in electrical resistance of
approximately 175,000%. The hydrogen-sensing capabilities
of the sensors were largely recovered by ultraviolet (UV)
light exposure after being completely extinguished by a rather
extreme means of sensor contamination: immersion of the
sensor in motor oil. Figure 90 shows a plot of real-time
variation of resistance before, during, and after cleaning the
contaminant, motor oil 10W-30, with UV exposure.
Many types of TiO2 nanomaterial-based room-temperature
hydrogen sensors are based on Schottky barrier modulation
of devices like Pd/TiO2 or Pt/TiO2.922,947,954 Elevated tem-
perature hydrogen sensors examine the electrical resistance
change with hydrogen concentration. Birkefeld et al. found
that the resistance of anatase TiO2 varied in the presence of
CO and H2 at temperatures above 500 °C, but on doping
with 10% alumina it became selective for hydrogen.922
Shimizu et al. reported that anodized nanoporous titania films
with a Pd Schottky barrier were sensitive to hydrogen at 250
°C.951,952 Kobayashi et al. investigated the mechanism of
hydrogen sensing by Pd/TiO2 Schottky diodes, and they
found that the formation of adsorbed water from adsorbed
oxygen at the Pd/TiO2 interface was the dominant reaction
for the Pd/TiO2(001) diodes throughout the hydrogen con-
centration range of 0-3000 ppm; for the Pd/TiO2(100)
diodes, this reaction was dominant only for hydrogen
concentrations below 100 ppm and the hydrogen adsorption
on bare Pd atoms became dominant for higher hydrogen
concentrations.939,940 Carney et al. found that sensors based
on SnO2-TiO2 with higher surface areas were more sensitive
to H2 in the presence of O2 by measuring the change in the
electrical resistance of the sensor upon exposure to different
hydrogen concentrations under a constant hydrogen gas flow
rate.923 Devi et al. found that ordered mesoporous TiO2
exhibited higher H2 and CO sensitivities than sensors made
from common TiO2 powders due to increased surface area,
and the sensitivity could be further improved by loading the
sensor with 0.5 mol % Nb2O5.929 Gao et al. found that
nanoscale TiO2 displayed higher performance in H2 sensing
than microscale TiO2 due to larger surface area.932
Oxygen sensors based on TiO2 nanomaterials include
TiO2-x,961 TiO2-Nb2O5,928 CeO2-TiO2,957 and Ta-,935
2948 Chemical Reviews, 2007, Vol. 107, No. 7
Figure 91. (A) Conductance response of TiO2 nanoparticle films
to methanol in concentrations going from zero (baseline) to 50
µmol/mol in 10 µmol/mol steps, sequentially, at a sensor temper-
ature of 450 °C. Between the steps, the analyte concentration was
returned to 0 µmol/mol. The thickness of the films was controlled
by the number of drops of the nanoparticle dispersion used to
deposit the film. (B) Comparison of the sensitivity of a TiO2 thin
film deposited by CVD (solid line) and that of a TiO2 thin film
composed of 15-nm-diameter anatase nanoparticles (dotted line).
Reprinted from Benkstein, K. D.; Semancik, S. Sens. Actuators, B
2006, 113, 445, Copyright 2006, with permission from Else-
vier.
Nb-,949 949 950
Cr-, and Pt-doped TiO2. Pt-doped TiO2 sensors
showed improved gas sensitivity, low operation temperature
(350-800 °C), and short response time (<0.1 s).941,950,958 The
oxygen-sensing mechanism was the combination of Pt/TiO2
interfaces in a Schottky-barrier mechanism and an oxygen-
vacancy bulk effect mechanism.959 At high temperatures,
TiO2 devices can be used as thermodynamically controlled
bulk defect sensors to detect oxygen over a large range of
partial pressures; at low temperatures, Pt/TiO2 Schottky
diodes make extremely sensitive oxygen detection possible.938
In Ta-doped TiO2 sensors, oxygen vacancies formed by
photoirradiation acted as oxygen-sensing sites.935 Sotter et
al. found Nb-doped TiO2 nanomaterials to be good sensor
materials for O2.953 Nb- and Cr-doped TiO2 nanocrystalline
films displayed higher O2 sensitivity than pure TiO2 films949
in that Nb5+-doped TiO2 showed 65 times enhancement in
the sensitivity compared to undoped material at a lower
operating temperature.474
TiO2 nanomaterials are promising candidates for CO
sensing927,945 and for methanol and ethanol sensing.933,946,955,956
Chen and Mao
Ruiz et al. found that La-doped TiO2 nanoparticles were good
sensing materials for ethanol based on electrical resistance,746
while Cu- or Co-doped TiO2 nanoparticles were good
candidates for CO sensing.747 Garzella et al. found W-doped
TiO2 displayed better performance for ethanol sensing than
pure TiO2.934 The addition of Ta and Nb to TiO2 was
beneficial for stabilization of the nanophase, resulting in
selectivity enhancement toward CO930,931 and NO2.930,960
Comini et al. found that the sensitivity enhancement toward
ethanol and methanol of TiO2 films could be improved when
doped with Pt and Nb.926
Benkstein and Semancik found that mesoporous TiO2
nanoparticle thin films prepared on MEMS micro-hot-plate
platforms could be used as high-sensitivity conductometric
gas sensor materials.921 The nanoparticle films were deposited
onto selected micro-hot-plates in a multielement array via
microcapillary pipet and were sintered using the micro-hot-
plate. Figure 91A shows the conductometric response of four
TiO2 nanoparticle films. The relative thickness of the films
was varied by using one, two, three, or four drops of 6%
mass fraction TiO2 to cast the film. Sensitivity was defined
as the ratio of the film conductance in the presence of an
analyte to the baseline conductance measured in dry air (S
) G/G0). The thicker films showed a higher baseline
conductance and a higher overall sensitivity to methanol (G/
G0(1 drop) ) 4.1, G/G0(4 drops) ) 7.5). Shown in Figure
91B are sensitivity responses to µmol/mol levels of methanol
of a mesoporous TiO2 nanoparticle film and a CVD TiO2
film. The nanoparticle films were found to demonstrate
higher sensitivity to target analytes, attributed to the high
internal surface area of the porous nanoparticle films.
Montesperelli et al. found K-doped TiO2 nanocrystalline
films showed high sensitivity of magnitude of 107 with great
stability over time.943 Yadav et al. fabricated TiO2 nano-
crystalline films as optical humidity sensors based on the
variations in the intensity of light with in humidity changes.750
The sensor element consisted of a thin U-shaped borosil glass
rod with a film of TiO2 deposited on it. Both the ends of the
glass rod were coupled to optical fibers. Light from a He-
Ne laser was launched into the sensing element through one
of them. Light received from the other fiber was fed into an
optical power meter.
6. Summary
Over the past decades, the tremendous effort put into TiO2
nanomaterials has resulted in a rich database for their
synthesis, properties, modifications, and applications. The
continuing breakthroughs in the synthesis and modifications
of TiO2 nanomaterials have brought new properties and new
applications with improved performance. Accompanied by
the progress in the synthesis of TiO2 nanoparticles are new
findings in the synthesis of TiO2 nanorods, nanotubes,
nanowires, as well as mesoporous and photonic structures.
Besides the well-know quantum-confinement effect, these
new nanomaterials demonstrate size-dependent as well as
shape- and structure-dependent optical, electronic, thermal,
and structural properties. TiO2 nanomaterials have continued
to be highly active in photocatalytic and photovoltaic
applications, and they also demonstrate new applications
including electrochromics, sensing, and hydrogen storage.
This steady progress has demonstrated that TiO2 nanoma-
terials are playing and will continue to play an important
role in the protections of the environment and in the search
for renewable and clean energy technologies.
Titanium Dioxide Nanomaterials
7. Acknowledgment
The authors acknowledge the financial support from
Lawrence Berkeley National Laboratory and the U.S.
Department of Energy. We thank M. C. Schriver and K. R.
Carrington for critical reading of the manuscript.
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