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Journal of Advanced Ceramics

2015, 4(3): 159182


DOI: 10.1007/s40145-015-0159-8

ISSN 2226-4108
CN 10-1154/TQ

Review

Low-dimensional nanostructured photocatalysts


Hao-Min XU, Huan-Chun WANG, Yang SHEN, Yuan-Hua LIN*, Ce-Wen NAN
State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering,
Tsinghua University, Beijing 100084, China
Received: June 03, 2015; Revised: June 21, 2015; Accepted: June 24, 2015
The Author(s) 2015. This article is published with open access at Springerlink.com

Abstract: Low-dimensional nanostructures are a promising class of ideal high-performance candidates


for energy storage and conversion owing to their unique structural, optical, and chemical properties.
Low-dimensional nanostructured photocatalysts have attracted ever-growing research attention. In this
review, we mainly emphasize on summarizing the 0-, 1-, and 2-dimensional nanostructured
photocatalysts systematically, including their photocatalytic performance, synthesis methods, and
theoretical analysis. From the viewpoint of dimension, we try to figure out the way to design more
high-efficiency photocatalysts towards numerous applications in the field of solar energy conversion,
hoping to promote efficient control and rational development of photocatalysts.
Keywords: low-dimension; photocatalysis; nanostructure

1 Introduction
The utilization of solar energy, including solar cell,
solar water splitting, and organic pollution degrading,
varies in peoples daily life. The energy crisis and
environmental problem have triggered photocatalysis
research widely. Pollution could be degraded and clean
energy could be generated from water by being
illuminated with the sun light. As 43% of the sun light
is in the visible range and 50% is near infrared, it is
considerably essential to extend the absorbable range
to improve the utilization efficiency of the sun light for
photocatalysts (PCs).
In general, the optical absorption performance of a
semiconductor is related to its electronic structure,
microstructure, defect, band gap, etc. [1]. The key
issues influencing photocatalytic (PC) capability of a
semiconductor include its energy band configuration as
well as the nature of its surface/interface, e.g., the

* Corresponding author.
E-mail: linyh@tsinghua.edu.cn

surface energy, chemisorption properties, and surface


area [2]. Therefore, the advanced low-dimensional PCs
have attracted researchers attention due to their unique
advantages of large surface area, high electronhole
pair (eh) separating efficiency, and other irregular
surface properties [3].
Low-dimensional structured materials refer to those
0-dimensional (0-D), 1-dimensional (1-D), and
2-dimensional (2-D) materials composed of ultra-fine
particles under 100 nm in size. In low-dimensional
structured materials, 0-D materials include quantum
dots, nanoparticles, and nanoclusters; 1-D materials
include nanotubes, nanorods, and nanowires; and 2-D
materials refer to the extension of the two spatial
coordinates like nanofilms and superlattices. Generally,
low-dimensional PCs have better PC performance than
bulk materials mostly due to the larger surface area and
size effect [46]. Take 0-D nanostructures for example.
Nanoparticles and quantum dots (QDs) have tunable
electronic and optical properties as a function of size,
called quantum-size effect. Materials in quantum dot
form display special properties such as variation in

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band gap. Cui et al. [7] prepared Bi2WO6 nanosheets


with Bi2WO6 quantum dots dispersed randomly by a
facile solvothermal route. Their products possess
excellent visible light absorption and PC efficiency
compared to Bi2WO6 nanoparticles or nanoplates. It
was believed that there are different gaps between the
quantum dots and the nanosheet substrates in the
Bi2WO6 nanostructure, which promote the migration of
photo generated electrons and holes from one side to
another, thus favoring the separation of carriers.
Although sometimes the band gap increases with
respect to the decrease of size of particles in specific
range induced by quantum-size effect which makes it
harder for PCs to utilize more light, the band gap
would decrease with the decrease of particle size in a
certain range which may further help improve the PC
efficiency. For example, in TiO2 nanocrystalline, the
band gap varies from 3.173 to 3.239 eV as the particle
size increases from 17 to 29 nm [8,9]. They believed
that the delocalization of molecular orbitals induced by
crystal defects in the conduction band (CB) edge
creates traps in electronic energy, and consequently
brings about the red shift of the absorption spectra.
The low-dimensional nanostructured PCs vary in
types, mechanisms, and applications, making them a
promising prospect. In this review, we briefly cover the
recent progress in the morphology control, mechanism
explanation, and advanced synthesis methods of
low-dimensional nanostructured PCs to make
contribution to the further exploration on novel PCs.

0-dimensional: quantum dots,


nano-/micro-particles

We first come to the 0-D structured PCs. Generally the


0-D structure refers to those particles of which
three-dimensional sizes are in nanoscale, like the dots
without specific shape. A quantum dot is a
semiconductor nanocrystal that is small enough to
exhibit quantum mechanical properties with its
excitons confined in all three spatial dimensions. As
mentioned above, QDs show extremely obvious size
effect and always act as the decoration when
composited with other materials. Thus we will discuss
QD PCs later in Section 5.
Since the nano-/micro-sized paritcles with various
morphologies occupy important position in modern
PCs, we classify them into 0-D as well. The particles
of powdered catalysts with nanoscale dimensions

could increase total surface area and the number of


available reaction sites. However, the small size of the
particles brings several disadvantages. When the
dimensions of the crystal are comparable to the width
of the depletion layer, the photo generated eh will be
spatially confined in close proximity, and the
interfacial space charge and band bending which tends
to separate electrons and holes will not be present [10].
Moreover, the back reaction of intermediate chemical
species would become more likely in close proximity.
All of these features lead to a loss of efficiency. Good
PCs balance in all aspects of factors including
crystallite size and morphology. It is found that the size,
morphology, and facet of nanoparticles have effect on
the PC ability.
The shapes of the nano-/micro-particle PCs include
cube, sphere, box, spindle, flower, cage, etc. (Fig. 1).
The catalysts in similar size but different morphology
could display different PC effect. The reason could be
the difference of the oriented facet surface energy or
the chemical potential gradient [1113]. Different
theories have been used to explain the effect of the
shape, facet, and morphology of particular PCs on their
PC properties. It is very inspiring that people could
select the facets exposed and control the PC reaction
process. Bi et al. [12] believed a higher surface energy
of Ag3PO4 {110} facets than that of {100} planes
contributes significantly to the enhanced PC activity of
the {110} facets. A study on the two types of WO3
crystals (Figs. 2(a)2(c)) showed that the difference in
electronic band edges caused by crystal facet electronic
structure effect would optimize the PC activity for
targeted reactions [14]. The normalized oxygen
evolution rate of the quasi-cubic-like WO3 crystals by
specific surface area is 8.4 times higher than that of the
rectangular sheet-like crystals (Fig. 2(e)), and the much
higher oxygen evolution rate of the quasi-cubic-like
crystals can be attributed to the stronger oxidative
power of photo excited holes generated from the lower
valence band maximum (VBM) (Fig. 2(d)). Harn et al.
[15] obtained a series of Ag2O with shapes evolving
from edge and corner-truncated cube (ECTC) to
rhombicuboctahedron (RO), and to hexapods (HP)
(Figs. 3(a)3(i)) by simply maintaining a certain ratio
of AgNO3 to NH4NO3 and adding NaOH of various
concentrations, and found that the {100} facets exhibit
the highest PC activity in methyl orange (MO) solution
under full-spectrum light irradiation, followed by the
{110} facets, then the {111} facets (Fig. 3(j)). They
believed that different amounts of catalytically active

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Fig. 1 SEM images of BFO particle photocatalysts in shapes of (a) microsphere, (b) microcube, (c) submicrocube,
(d) spindle-like, and (e) hollow sphere. Reproduced with permission from (ac) Ref. [17], 2006 WILEY-VCH Verlag GmbH
& Co. KGaA, Weinheim, and (d, e) Ref. [18], 2010 Royal Society of Chemistry.

Fig. 2 (a) and (b) SEM images of quasi-cubic-like WO3 crystals and rectangular sheet-like WO3 crystals, respectively.
(c) TEM image of rectangular sheet-like WO3 crystals. (d) Determined VB and CB edges versus NHE (pH = 7) of
(i) quasi-cubic-like WO3 crystals and (ii) rectangular sheet-like WO3 crystals. (e) Oxygen evolution rate from water splitting in
the presence of AgNO3 as an electron acceptor under visible light ( > 400 nm) and CH4 generation rate from photo reduction of
CO2 in the presence of H2O vapor under UVVis light. Reproduced with permission from Ref. [14], 2012 Royal Society of
Chemistry.

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C /C 0

162

Irradiation time (min)


Fig. 3 SEM images of the Ag2O crystals with morphologies: (a) and (d) ECTC, (b) and (e) RO, and (c) and (f) HP.
(g)(i) Corresponding schematic drawings of the Ag2O crystals. (j) Photo degradation rate of MO dye by various PCs under
full-spectrum light irradiation. Reproduced with permission from Ref. [15], 2015 WILEY-VCH Verlag GmbH & Co.
KGaA, Weinheim.

sites resulted by the atomic arrangements of facets


contribute to this phenomenon. And for the
ferroelectric PCs, the polarization state along crystal
orientation of the particle also affects the PC efficiency.
Giocondi and Rohrer [16] found that patterns of
reduced silver on microcrystals of BaTiO3 (Fig. 4) and
Sr2Nb2O7 are consistent with the orientations of the
ferroelectric domains within the samples, indicating
that the associated dipolar fields that separate photo
generated charge carriers cause the spatial localization
of reaction products on the surfaces of ferroelectric
microcrystals. The thought of fabricating crystal-facet-

controlled PCs in order to further enhance or optimize


the PC properties can also be applied in 1-D and 2-D
structured semiconductors, which we will discuss in
the following sections.
Numerous methods have been employed to fabricate
0-D PCs including coprecipitation or chemical
precipitation,
hydrothermal/solvothermal
process
[19,20], solgel, solid state reaction (SSR), spray
pyrolysis [2123], combustion [24,25], reversemicroemulsion [26,27], and modified approaches
based on them. The morphology and performance of
photocatalyst crystal intensely depend on the synthesis

Fig. 4 SEM images of faceted BaTiO3 crystals after reaction in aqueous AgNO3. The speckled white contrast corresponds
to silver containing deposits. Silver was deposited on only one of the exposed {100} facets, which happened to be the
orientation of polarization. Reproduced with permission from Ref. [16], 2008 Springer Science+Business Media, LLC.

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approach, even the parameters employed during the


synthesis process. Different approaches always result
in different crystal appearance, different surface
physicochemical property, different specific surface
area, and finally different PC activity. Yin et al. [27]
synthesized cage-like Bi2MoO6 hollow spheres
successfully by SSR with the assistant of colloidal
carbon spheres. In fabrication of hollow-structured
photocatalyst particles with SSR, a preprocessing of
absorption and precipitation is often necessary.
Moreover, the hollow structure is always composed
of smaller crystalline grain, which leads to the porosity
of the hollow sphere. Solgel is a low-cost
and convenient method for making pure phase or
element doping particles. Nano Bi2WO6 catalyst with
visible light response was prepared by solgel [28].
Hydrothermal/solvothermal treatments are widely
employed to synthesize photocatalyst particles,
especially ternary and quaternary complex oxides, with
the advantage of facile morphology and structure
control. Zhang et al. synthesized highly crystalline
particles
with
high
orthorhombic
Bi2MoO6
visible light PC activity via a facile hydrothermal
process without adding any surfactant. The
morphologies of Bi2MoO6 can be selectively obtained
by adjusting the pH value of the reactant. The similar
phenomenon was reported by many other groups [29].

Nut-like, potato-like, and broccoli-like monoclinic


BiVO4 were fabricated in different solvents. The
crystal phase could also be modulated by varying the
pH value of reaction system. Monoclinic BiVO4
nanoparticles with small crystal size and large band
gap exhibit remarkable PC performance [30]. Besides,
surfactants affect the products in hydrothermal method
[3133]. In the process of hydrothermal/solvothermal
treatment, the precursor ions undergo a period
of nucleation and growth (dissolution and
recrystallization). The main effect of pH value is to
modulate the kinetics of nucleation and growth of the
crystal by controlling the surface free energy. The
preferential adsorption of ions in solution onto
different crystal facets directs the growth of particles
into various shapes by controlling the growth rates
along different crystal axes. The crystal plane with a
higher surface energy is expected to have a faster
growth rate.

3 1-dimensional nanostructures
Since the discovery of carbon nanotubes, 1-D
nanostructures (including nanobelts, nanotubes (NTs),
nanorods (NRs), nanofibers, and other large aspect
ratio nanostructures (Fig. 5)) have attracted

Fig. 5 SEM images of (a) TiO2 nanotubes, (b) BFO nanofibers, (c) TiO2 nanobelts, and (d) ZnO nanorods. Reproduced with
permission from (a) Ref. [34], 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, (b) Ref. [35], 2013 Xuehui
Zhang et al., (c) Ref. [36], 2010 American Chemical Society, and (d) Ref. [37], 2013 Royal Society of Chemistry.

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ever-increasing attention in many fields for energy


harvesting and storage, and sensors and electronic
devices.
Besides the change of energy band structure brought
by the novel structure, recombination of photo induced
electronhole pairs decreases in this nanostructure,
resulting in the improved PC efficiency [38]. The
outstanding properties of 1-D nanostructure are
considered to be pertinent to the facts that: the
quantum mechanical effects emerge and count a lot
when the radial dimension of the 1-D nanostructure
comes to or below certain characteristic lengths,
leading to large surface-to-volume ratio and large
aspect ratio which are beneficial to chemical activity
and energy transfer, which are different from those
corresponding bulk counterparts. Moreover, facilitating
fast and long-distance electron transport, light
absorption, and scattering based on the high
length-to-diameter ratio is thought to be made-to-order
as PCs. More recently, many 1-D nanostructures are
fabricated and investigated as heterogeneous
photocatalysts. The greater charge mobility in the 1-D
along the longitudinal dimension of the crystals, plus
the enhanced charge separation and fewer localized
states due to the surface state of specific facet of
nanocrystalline, makes high-efficiency PCs.
In this part, we will emphasize on three kinds of 1-D
structured PCs: nanorods, nanowires (nanofibers,
nanobelts), and nanotubes.
3. 1

crystalline NRs could be fabricated (Fig. 6). They have


different optical properties and band gaps, which may
affect the PC performance [40].
3. 2

Nanowires, nanofibers, and nanobelts

These kinds of 1-D structure are longer in length than


NRs, always with the longitudinal dimension on the
micrometer scale and the lateral dimension on
nanoscale, and they also exhibit excellent PC ability.
Cha et al. [41] reported enhanced PC behavior of TiO2
rutile nanobelts. They prepared hierarchical TiO2
nano-architectures by one-pot hydrothermal synthesis
in concentrated HCl. Moreover, the dislocations in
nanostructured materials strongly influence not only
the construction of nanoscale architectures, but also the
band structure and the behavior of photo induced
electronhole pairs. High-crystallinity CdS nanowires
in ethylenediamine were observed to have better PC
activity over nanoparticles [42]. The mechanism of the
enhanced property arising from 1-D CdS nanostructure
could be in line with that in single phase 1-D TiO2
nanostructure [4348].
Single crystalline 1-D nanostructure with almost
ideal crystal structure and morphology usually requests
rigorous conditions and has low yields. From the
viewpoint
of
engineering
and
application,
polycrystalline materials are much easier to fabricate.

Nanorods

NR PCs have been proved to possess great PC ability,


which could be synthesized by various methods like in
situ hydrothermal growth reaction method and electro
deposition method. For a photocatalyst, NRs could act
better than their particle or 2-D forms. Bai et al. [39]
have compared the PC activity of g-C3N4 nanoplates
and NRs by transforming nanoplates into NRs in reflux
process. They observed about 1.5 times enhanced PC
activity and 2.0 times the intensity of the photocurrent
response of g-C3N4 NRs under visible light. They
proposed that the increase of active lattice face and
elimination of surface defects in high-crystallinity
g-C3N4 NRs may accelerate the transfer of photo
induced charges and inhibit the recombination of eh.
The facet effect mentioned in the 0-D structure is
also applicable in the 1-D. In single crystalline NRs,
due to the anisotropic growth of the crystallographic
planes, two different preferentially oriented single

Fig. 6 SEM and SAED pattens of single crystalline


rutile TiO2 NRs with two different preferentially oriented
facets. Reproduced with permission from Ref. [40],
2014 Royal Society of Chemistry.

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recombination rate than the nanospheres, which may


explain the better PC degradation ability of TiO2
nanobelts (Fig. 7(c)).
3. 3

Nanotubes

Since the effective surface area is vital for


photocatalysis, the construction of hollow 1-D
nanostructure, also called tube in nano or micro scale,
will much enhance the PC performance. What is more,
the tube structure appears favoring electron transfer
and has lower charge recombination than that in
particles or bulk, which occurs at the activity sites on
the photocatalyst surface. Nanotube-type graphitic
C3N4 shown in Fig. 8(a) exhibits excellent visible light
PC performance compared to the bulk graphitic C3N4
and P25 (Fig. 8(b)) [54].
Nanotube PCs can be fabricated by several methods,
either with the assistant of template or not [5557].
AAO and carbon with proper processing are the most
representative hard templates. The polymer fiber or
carbon fiber can also be used as templates. Bi2MoO6
microtube was fabricated by using electrospun
polyacrylonitrile microfibers as template following
with the ethylene glycol solvothermal method [58]. By
optimizing the synthesis parameters, hollow structure
with high crystallinity and moderate grain size could
be obtained.
Based on the nanotube shape, more evolved
nanotube-like structure can be fabricated and applied
in PCs. For example, Liu et al. [59] synthesized 1-D
hierarchical Bi2WO6 hollow tubes with porous walls
(Fig. 9(a)) by solvothermal treatment using Bi2O3 rods
as both template and reactant. The hierarchical Bi2WO6
hollow tubes show the best PC degradation efficiency
of RhB under the sun light compared to P25 and
sphere-shaped samples (Fig. 9(c)). The nanotube PCs
are usually made into oriented arrays, which are

50 nm

Methyl orange concentration change, C /C 0

Several mature methods can be employed to synthesize


polycrystalline
nanowires/nanofibers,
including
hydrothermal/solvothermal process, electro spinning
technology, wet chemical method with proper
templates, and even physical method based on the
growth mechanism of crystal nature. Gao et al. [49]
synthesized perovskite-type polycrystalline BiFeO3
(BFO) nanowires with anodic aluminum oxide (AAO)
as a template. BFO nanowires with 50 nm in diameter
and 5 m in length were obtained when removing the
template, revealing good photo induced oxidation
ability. Many polycrystalline nanofiber metal oxide
PCs were fabricated by electro spinning method, e.g.,
Bi2WO6 [50], BFO [51], TiO2 [52], and Bi4Ti3O12 [53].
In the process of electro spinning, metal salts are
dissolved in appropriate solvent stoichiometrically to
form precursor sol, and polymers (e.g., PVP, PAN,
PVB) are added to adjust the viscosity to a practicable
value. The fibers are obtained impelled by the field
between the sol and the collector after annealing in air.
By adjusting the proportion and concentration of the
precursor sol, the diameter of the fibers can be tuned.
Obviously, this kind of fibers composed of
nanoparticles connected end-to-end is different from
single crystalline 1-D nanostructure derived from wet
chemical method.
The nanobelt photocatalyst is similar to the
nanowire or nanofiber, but it is more likely to get
preferential oritantion facet in nanobelts which
involves in determining the PC result. Wu et al. [36]
designed and prepared single crystalline anatase TiO2
(101) nanobelts by hydrothermal treatment (Figs. 7(a)
and 7(b)). Their calculations showed that the exposed
(101) facet of the nanobelts yields an enhanced
reactivity and exhibits a lower electronhole

Nanospheres
Nanobelts

Irradiation time (min)

Fig. 7 (a) SEM image of the anatase TiO2 nanobelts. (b) Bright-field TEM image of a TiO2 nanobelt; the inset is an SAED
pattern taken along the [100] direction of the nanobelt. (c) Degradation of MO in an aqueous solution by the TiO2 nanobelts
and the nanospheres as a function of exposure time to UV irradiation. Reproduced with permission from Ref. [36], 2010
American Chemical Society.
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166

Without light
Photolysis
P25
Bulk g-C3N4
Tube-like g-C3N4

Time (min)

C/C0

Fig. 8 (a) SEM image of C3N4 tubes. (b) PC degradation of MB over samples under visible light irradiation. Reproduced
with permission from Ref. [54], 2013 Royal Society of Chemistry.

Fig. 9 (a) and (b) SEM images of Bi2WO6 hollow tubes. (c) Photo degradation efficiencies of RhB with different PCs under
the sun light. Reproduced with permission from Ref. [59], 2013 Royal Society of Chemistry.

suitable as electrodes. An oriented nanoarray possesses


an independent point contacting with current collector,
producing a large junction area with electrolyte, thus it
provides expedite charge transport pathways
throughout the electrode that could maximize the
charge separation ability [60].
In general, 1-D nanostructure is more and more
concerned for its outstanding performance in visible
light photocatalysis. Besides the advantage of specific
surface area and the energy band modulated by
morphology, the superior charge transfer properties
and multiple adjustability are also attractive. One
photocatalyst in shape of nanorod, nanowire, or
nanotube may display different PC activities.
Considering the similar dimension of the comparable
1-D nanostructures (nanobelts, nanoflowers, and
nanowires), the status of dislocations in nanobelts,
nanowires, and nanoflowers can be considered as a
primary reason for different PC activities.

4 2-dimensional structures
4. 1

Nanosheets and nanoplates

Nanosheet materials usually refer to sheet-like


crystallites of molecular thickness and extremely high
two-dimensional anisotropy [61,62]. A variety of
promising PCs belong to this category, such as
SnNb2O6 [63], ZnGa2O [64], Bi2WO6 [65], BiVO4 [13],
as well as various oxides and sulfide, like ZnO and
TiO2.
This kind of nanoscale materials can exhibit
intriguing charge-bearing properties due to large
area nonstoichiometry on the surface, and photo
induced carriers can survive longer on the nanosheets,
which contribute to the high PC activity. Meanwhile,
through controlling growth conditions, some
nanosheets provide almost 100% exposed active sites
[64].

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Hydrothermal method is one of the most used


methods to prepare nanosheet samples. For example,
Li et al. [66] obtained layered La2Ti2O7 nanosheets
through the one-step hydrothermal method at 200
for 24 h when the NaOH concentration equaled 1 M.
La2Ti2O7 nanosheets of 150 nm in width and 300 nm
in length display superior PC properties through
photo decolonization on MO and the high H2
evolution rate from waterethanol solution (Fig. 10).
Two-dimensional nanosheets can also be produced by
liquid exfoliation of layered materials, especially some
transition metal dichalcogenides like MoS2, which is
possibly extended to transition metal oxides [62].
Moreover,
nanosheets
can
form
various
constructions like nanoflowers, nanosheet-scaffolded
microspheres, and nanowalls. Liu et al. [64] obtained
hierarchical microspheres scaffolded from ultra-thin

ZnGa2O4 (Figs. 11(a) and 11(b)) through a


solvothermal route with ethylenediamine/H2O binary
solvents. They possessed greater PC performance than
those of the bulk ZnGa2O4 and mesoporous ZnGa2O4
due to the higher surface area, and that the ultra-thin
geometry allows charge carriers move quickly from the
interior to the surface to participate in the photo
reduction reaction. The nanowalls are aligned
nanosheets, namely, vertically aligned nanosheet array.
This kind of structure combines advantages of oriented
nanoarray and 2-D nanosheets.
For nanoplates, thickness can be a little larger
(Fig. 12(a)). The single nanoplate is always single
crystal, which can be determined by TEM results. As
we mentioned above, people have found that facets
with higher surface energy have higher PC activity
[12,67], thus it is possible that we can make nanoplate

(b)

Rate of H2 evolution (mol/(gcalh))

Degree of decolourization (%)

(a)

1
2
3

1
2
3

Time (min)

Time (min)

Fig. 10
(a) Degree of decolourization of MO solution and (b) rate of H2 evolution with the role of La2Ti2O7 samples
(synthesized by (1) hydrothermal, (2) SSR) and (3) Degussa P25 under UV light. Reproduced with permission from Ref. [66],
2006 IOP Publishing, Ltd.
(b)

(c)

(3)

CH4 (ppm)

(a)

(2)

(1)
Time (h)
Fig. 11 (a) and (b) FESEM images of ultra-thin nanosheet-scaffolded microspheres. (c) CH4 generation over various
ZnGa2O4 samples as a function of irradiation time: (1) bulk ZnGa2O4 (obtained by the solid state), (2) mesoporous ZnGa2O4, and
(3) nanosheet-scaffolded microspheres ZnGa2O4. Reproduced with permission from Ref. [64], 2014 American Chemical
Society.

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Nanoplates (pH 6.15)


Nanorods (pH 7.0)

C/C0

Dark Light on

Nanoplates (pH 6.15)


Nanorods (pH 7.0)

Fig. 12 (a) SEM and (b) TEM images of m-BiVO4 nanoplates. (c) SAED pattern recorded from the white framed area
indicated in (b). (d) Schematic illustration of the crystal orientation of the nanoplate. (e) PC degradation of RhB and (f) PC O2
evolution from an aqueous AgNO3 solution over nanoplates, nanorods, and various m-BiVO4 microcrystals prepared at
different pH values under visible light irradiation. Reproduced with permission from Ref. [13], 2010 Royal Society of
Chemistry.

photocatalyst with high surface energy facet exposed


through choosing proper surfactant. Xi and Ye [13]
reported the synthesis of well-defined m-BiVO4
nanoplates with certain exposed facets by a
straightforward hydrothermal route in which no
template or organic surfactant was used so that most of
facet active sites can be maintained (Figs. 12(a)12(d)).
These nanoplates show considerable PC activity for the
degradation of RhB and the evolution of oxygen, better
than other m-BiVO4 microcrystals (Figs. 12(e) and
12(f)).
In summary, the advantages of high surface area,
much more reactive facets exposed, photo induced
carriers being able to survive longer on the nanosheets
contribute to the high PC activity, making nanosheet

PCs become more popular. To further investigate the


surface of nanosheets, more effort should be applied to
the construction of parent compounds with suitable
layered structures.
4. 2

Films

Conventional PCs are usually utilized as suspended


powders which are difficult to recollect and cause great
loss, while thin film PCs are more recyclable. Also,
thin film is easier made into electrode, which is
necessary in PC water decomposition. Thus using thin
film PCs is a tendency. Moreover, abnormal properties
can be induced by the heterointerface in thin film.
Previous studies have shown that the nature of the

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substrate can influence on crystal phase and optical or


PC properties of thin film, like the band gap shift or
phase change, which could be used to modify the PC
properties of the films [6,6871].
Compared to the powder or bulk samples which can
be dispersed in solutions to do experiments of
photocatalysis, PC properties of films can be tested by
gaseous PC experiment in a gas system. For instance,
the TiO2 and WO3/TiO2 films were tested as PCs for
the decomposition of 2-propanol and benzene in the
gas phase [72]. The gas reactor system used for this
reaction is shown in Fig. 13. 2-Propanol (or benzene)
and water vapor were added in the vacuum reactor. The
gas mixtures in the reactor magnetically convected
during the irradiation. After irradiation at regular
intervals, a bit of gas sample in the reactor was
automatically picked up and sent to a gas
chromatograph by using an auto sampling valve
system. CO2, reactants, and other intermediates were
detected and measured in gas chromatography (GC)
system. WO3/TiO2 compositions can also be made into
porous structure. Pan and Lee [73] prepared highly
ordered cubic mesoporous WO3/TiO2 films by spin
coating via an evaporation-induced self-assembly
process. The mesoporous film structure TiO2 can be an
efficient photocatalyst due to their ultra-high surface
area and greatly organized pore structures.
Actually, even though thin films do show some PC
capability and are sensitive to light irradiation in small
devices, the PC ability is relatively weak because of
the low concentration of PCs. Therefore, we need to
find a way to improve the PC ability of thin films, like
increasing surface areamaking porous thin films.
Besides WO3/TiO2 films, porous TiO2, Bi2WO6, and
BFO thin films on solid supports have been developed
and researched [74,75]. Bi2WO6 is one of the new
ternary metal oxide semiconductors showing great
potential in the utilization of solar energy. Zhang et al.
[76] synthesized the porous Bi2WO6 thin films as
efficient visible light active PCs using carbon-sphere

Fig. 13
films.

template. Ordered porous Bi2WO6 films with the


average size of the open pores varied from 290 to
320 nm exhibit a much higher PC activity and
photocurrent conversion efficiency than nonporous
Bi2WO6 films (Fig. 14). Their stability experiment
indicated that the porous Bi2WO6 film is fairly stable
under the studied conditions. The porous films can
be synthesized by template method and chemical
solution deposition. After the calcining process, we
can get the well crystalline, continuously porous
films. The process is shown in Fig. 13. The sphere
templates can be Pluronic block copolymer P123
((EO)20(PO)70(EO)20, EO is ethylene oxide and PO is
propylene oxide), carbon-sphere, and poly styrene
sphere. To increase the connectivity between the
spheres and the substrate, the template should be kept
at a proper temperature for a while. Besides the porous
films mentioned above, discontinues nanoporous films
constructed by particle-like units are also studied. Chio
et al. obtained nanoporous morphology (specific
surface area of 31.8 m2/g) of BiVO4 electrode (Fig. 15).
They applied electro deposition method to make a
template (BiOI), and then added V2O5 solution to
converse BiOI to BiVO4 through heating process. They
found that this kind of structure effectively suppresses
bulk carrier recombination without additional doping,
manifesting an electronhole separation yield of 0.90
at 1.23 V versus the reversible hydrogen electrode
(RHE), being beneficial to the PC performance
[77,78].
In the future, people are supposed to keep looking
for other novel 2-D PCs with high PC efficiency.
Cooperating with computational strategy, people can
predict or explore more novel highly efficient 2D
materials for PC materials [79].

Composites

To prevent the recombination of electronhole pairs,

Left: the gas reactor system used for this PC reaction. Right: an illustration of the process of fabricating porous thin

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Fig. 14 (a) SEM image of a porous Bi2WO6 film synthesized with 390 nm carbon spheres. (b) Photo degradation of MB in
the presence of porous Bi2WO6 films with pore sizes of 290 and 320 nm under visible light irradiation; the nonporous film
was studied for comparison. (c) Potentiodynamic scans under chopped illumination for porous and nonporous Bi2WO6 films.
(d) Action spectra of porous and nonporous Bi2WO6 film electrodes. Reproduced with permission from Ref. [76], 2009
WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fig. 15 Morphologies of nanoporous BiVO4 electrodes: (a) SEM image of BiOI, (b) top-view of BiVO4, (c) and (d)
side-view of BiVO4. Reproduced with permission from Ref. [78], 2014 American Association for the Advancement of
Science.

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the approach that has generally been applied is to load


co-catalysts such as Pt, Pd, NiO, and RuO2 on the
semiconductor surface. Lots of experiments have
proved that, compared to the composites with
components simply mixed, those with components
intimately attaching each other are more efficient in
photocataysis. The heterojunctions formed between the
host semiconductor and the co-catalyst provide an
internal electric field that facilitates separation of
the electronhole pairs and induces faster carrier
migration. Furthermore, these co-catalysts exhibit
better conductivity, lower overpotential, and higher
catalytic activity than the host. Enlightened by this,
people make kinds of composites to construct internal
electric field induced by the bend of electric energy
band, or modify the surface acidity. The internal field
is the origin force for the separation of photo induced
eh, which is important in improving the efficiency of
utilization of carriers involved in the reaction and
enhancing the PC efficiency [10].
The most typical internal field is that in pn junction,
which is the foundation for conventional photovoltaic
solar energy conversion. When p-type and n-type
semiconductors contact each other, charges transfer
because of the concentration difference of holes and
electrons so that the Fermi levels can equilibrate. The
charge redistribution creates an electric field in the
space charge region from n-type side to p-type side,
which helps to separate photo generated charge carriers
and improve the efficiency of PC reactions. At phase
boundaries, the difference in the positions of band
edges can create an internal field and thus separate
charges. The photo induced electrons always transfer
through the interface (junction) from higher conductive
band to the lower one, while the holes from lower
valence band to the higher one. Besides, the transfer
rate of holes (14 ps) is much faster (40 times) than
that of electrons (40160 ps). Theoretically, three kinds
of junction constructions are able to improve the
efficiency of PC activity (Fig. 16). This is the
separation caused by the band bending and the open

circle potential (OCP) of which should be smaller than


the band gap of the photocatalyst. Meanwhile, the OCP
arised from ferroelectric phenomena could be much
larger than the band gap of the material, and this is the
reason why ferroelectric materials with small band gap
are now widely researched [80].
Internal electric field in ferroelectric compositions
(capacitors) can be classified as two independent
components and written as
E Ebi Ep
where Ebi represents the built-in field and Ep is the
depolarization field:

2 F / d
P
Ep

0 F 2 F / d e /
where F is the relative dielectric constant of the
ferroelectric thin film; e relative of the electrode
layer; the screening length; P the polarization
value; d the ferroelectric film thickness [81]. The
depolarization field Ep is proportional to the strength
of polarization; the built-in field Ebi originates from
boundary contact. Especially in the film photocatalyst,
the equation helps people design high-efficiency
structure.
The composite PCs could be constituted by
two different semiconductors or two different
nanostructures of one semiconductor. In this review,
we present some examples, classifying them into 00,
01, 02, and other composites.
5. 1

00 composites

00 composites indicate PCs composed with two or


more 0-D structures which are very common,
including oxideoxide nanoparticle composites,
quantum
dots/nanoparticle
noble
metal,
or
sulfideoxide composites.
For the oxideoxide, we take TiO2 for example.
People have tried to composite it with other oxides like
ZrO2, WO3, BFO, etc. TiO2ZrO2 nanocomposite
synthesized by hydrothermal method was observed a

Fig. 16 Three types of band bending for the carrier transferring.

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shift in the absorption edge towards longer wavelength,


which indicates the sub band gap absorption arises
from surface states of the TiO2ZrO2 material [82].
BFO/TiO2 coreshell structured nanocomposites
(Figs. 17(a) and 17(b)) have good visible light
absorption properties (Fig. 17(c)), which should be
induced by Fe or Bi/Ti inter diffusion in interfaces and
the band bend in the boundary (Fig. 17(d)) [83]. Other
oxide composites have also been extensively
investigated. n-Type NaTaO3 loaded with p-type
co-catalyst NiO, synthesized by heated mix of NaTaO3
powders and aqueous Ni(NO3)26H2O solution, shows
enhancement water splitting activity under UV
illumination [84].
Among quantum dot (or nanoparticle) noble metal
(or nonoxide semiconductor)oxide types, the widely
used CdS, CdSe, or other sensitizing dye molecules

can strongly increase solar conversion efficiency. Ag,


Pt, and Au are popular noble metals in decorating PCs
to enhance the PC activity remarkably [85,86]. BFO
particles with surface decoration of Ag nanoparticles
displayed enhanced PC activity (Fig. 18(a)). The TEM
image shown in Fig. 18(b) reveals that Ag
nanoparticles with size of 620 nm are uniformly
deposited on the surface of BFO crystals. Ag has a
Fermi level of 0.4 V versus normal hydrogen electrode
(NHE), which is positive to the CB potential of BFO
(0.1 V vs. NHE) (Fig. 18(c)). Compared to bare BFO
particles, in the Ag decorated samples, the photo
generated electrons are thermodynamically favorable
to transfer from the CB of BFO to Ag nanoparticles,
consequently benefiting the PC process [87].
To clearly explain the internal electric field that
facilitates separation of the electronhole pairs and

Fig. 17 (a) TEM and (b) HRTEM images of BFO/TiO2 nanocomposites. (c) Normalization concentration of CR in the
solution with different PCs versus the exposure time under visible light irradiation: (1) without catalysts, (2) pure TiO2, (3) pure
BFO, BFO/TiO2 nanocomposites with mass ratios of (4) 1:2, (5) 2:1; and (6) 1:1. (d) Schematic illustration for the calculated
energy level diagram of TiO2 and BFO. Reproduced with permission from Ref. [83], 2009 AIP Publishing LLC.

Fig. 18 (a) PC ability of bare BFO and Ag decorated BFO. (b) TEM image of Ag decorated BFO. (c) Schematic illustration
of the PC mechanism of Ag@BFO photocatalyst toward the degradation of RhB. Reproduced with permission from Ref.
[87], 2014 Springer Science+Business Media New York.
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induces faster carrier migration formed in noble


metaloxide heterojunctions, we take the n-type
TiO2Pt photo electrochemical cell for example, which
is similar to nanoscale powder photocatalyst
(Fig. 19(a)). If the ECB is higher than the hydrogen
evolution potential, photo generated electrons can flow
to the counter electrode and reduce protons, resulting
in hydrogen gas evolution without an applied potential,
although there should be big enough value versus the
standard hydrogen electrode. The remaining holes in
the valance band (VB) are active on the TiO2, available
for oxidation reactions [88].
In the noble metal loaded system, besides the low
electronhole recombination, the effective light
absorption by noble metal like Au and Ag which
subsequently inject the generated hot electrons to the
CB of semiconductors is believed another main reason
for the enhanced photocatalysis, called plasma
resonance enhancement of photocatalysis [89]. The
practical performance of plasmon-exciton strongly
depends on the mutual arrangement, particle size,
shape of the metal and semiconductor, and the
electronic structure of metal [90]. To load these noble
metals on PCs, people choose several methods. For
example, Au can be added with coprecipitation,
electrochemical deposition, chemical vapor deposition,
laser vaporization, modified impregnation, and photo
deposition method [91]. Among these methods, photo
deposition method is facile, common, and widely
applicable [77,92,93].
Sometimes, people make one low-dimension
structure with two or more different materials, called
poly-component 1-D, 2-D, or hybrid nanostructures,
like bicomponent nanosheets, but we still classify them
as 00 type because the components attach each other

in 0-D form. With two or even more components


assembling into an integrated heterostructure, the
internal field built in heterojunction and the transfer of
the photo induced electronsholes could be more
favorable for the conversion of visible light than the
single phase alone. Several approaches could be used
to fabricate 1-D hybrid nanostructures [9499].
5. 2

01 composites

Besides the nanoparticles, 1-D or 2-D structure


composites also occupy an important position. 01 PC
composites come from decorating 0-D semiconductors
or noble metals on 1-D PCs, e.g., CdSe QDs/ZnO
nanotubes, CdSe QDs/ZnO nanowires, CdS QDs or
Ag/TiO2 nanotubes, Pt/WO3 nanotubes [100104].
These 01 PCs show incredibly enhanced visible light
PC performance. And like that in the 00 type, special
methods like solvothermal technique and sequential
chemical bath deposition could be used to obtain
composites with intimately attached boundary rather
than simple mixture.
The bonding 01 composites have the advantages of
0-D and 1-D structures, and junction forms around the
boundary. The TiO2 nanoparticles (with uniform
diameter 5 nm) with single-walled carbon nanotube
attached exhibit higher PC activity than that of
Degussa P25 when photo degrading RhB aqueous
solution under UV light. The excellent PC activity
could be attributed to larger surface area, and
especially the ester bonds formed at the junction [103].
Cu2O/TiO2 nanotube array (NTA) photo electrodes
prepared by the ultrasonication-assisted S-CBD, made
of n-type TiO2 NTAs with Cu2O nanoparticles on them
(Figs. 20(a) and 20(b)) exhibit more effective photo
conversion capability than TiO2 nanotubes alone.

Fig. 19 (a) Schematic representation of powder photocatalyst. (b) Schematic representation of photo electrochemical water
electrolysis using illuminated oxide semiconductor electrode.

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Cu2O/TiO2 composite photo electrodes possess


superior photo electrocatalytic activity and stability in
the degradation of RhB (Figs. 20(c) and 20(d)) [105].
The composites always display a better PC
performance than the individual part, and modulating
the properties of the components in the composites

may further improve the PC efficiency. For example, in


the composites of Cu2O nanoparticles/ZnO NR arrays
(Figs. 21(a)21(c)), the samples with Cu2O prepared in
stronger alkaline solution have the highest PC
efficiency due to higher carrier concentrations
(Fig. 21(e)). In Cu2O (pH = 11.0)/ZnO NR arrays, the

Fig. 20 (a) SEM image and (b) low magnification TEM image of Cu2O/TiO2 NTAs (top view). The inset in (a) is the
close-up. (c) Photo response of Cu2O/TiO2 NTAs prepared for (1) 4 min, (2) 9 min, (3) 1 min, (4) 19 min, and (5) TiO2
NTAs. (d) PC degradation rates of RhB under visible light irradiation for TiO2 NTAs and Cu2O/TiO2 NTAs prepared for
different time. Reproduced with permission from Ref. [105], 2013 Royal Society of Chemistry.

Fig. 21 (a) SEM and (b) and (c) TEM images of Cu2O/ZnO NR arrays. (d) Light intensity dependent surface photo
voltage (SPV) of Cu2O/ZnO NR arrays at 532 nm. (e) Concentrations of methylviologen reduzate formed over different
Cu2O/ZnO NR arrays under visible light ( > 400 nm) irradiation. Reproduced with permission from Ref. [37], 2013
Royal Society of Chemistry.
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higher carrier concentration was believed to generate a


more positive Fermi level, leading to photo induced
charge carriers being separated quickly and efficiently
under the largest interfacial electric field (Fig. 21(d))
[37].
Usually, the metal part in 01 composites works as
0-D shape, quantum dots or nanoparticles, but 0-D
oxide compositing with 1-D metal has also been
studied, and their PC enhancement mechanisms are
consistent. Zhou et al. [106] coated uniform TiO2 on
Au NRs and Au/Ag coreshell NRs, and evaluated
their PC activities by the degradation of MB under
visible light irradiation. They observed that the
presence of plasmonic metal NRs enhances the PC
activity of TiO2, especially the bimetallic Au/Ag NRs.
5. 3

02 composites

02 composites indicate that 0-D organic molecules or


premade semiconductor nanocrystals are grafted or
deposited onto the surface of beforehand 2-D
PCs. Lots of teams have been studied, like WO3 or
MoO3 nanocrystal/TiO2 films, CdS nanoparticle/
TiO2 nanosheet, Pt-loaded WO3-sodium titanate
(NaxH2x)Ti2O4(OH)2 network film, CdS or CdSe /TiO2
mesoporous thin films (Fig. 22(b)) [106108].
02 type shares some similarities with 01 type, also
combining the advantages of 0-D and 2-D structures,
and junction forms around the boundary together. Here
we present two examples of nanoparticles/mesoporous
film PCs. The PC activity of highly ordered
cubic mesoporous film composites WO3/TiO2 was
2.2 times higher than a mesoporous TiO2 film and

6.1 times higher than a nonporous TiO2 film in photo


decomposing 2-propanol in the gas phase [106].
Meanwhile, the presence of WO3 strengthens the
stabilization of the mesoporous structure. In this case,
it was also believed the enhanced PC activity of
WO3/TiO2 is ascribed to the increase in surface acidity
induced by the WO3 present on the surface of the
mesopores [73]. Bartl et al. [107] synthesized
CdS/TiO2 mesoporous thin films by thermally
post-treated Cd2+-doped TiO2 films with sulfur vapor,
and the structure shows an enhanced sensitivity to
visible light. In Fig. 23, by switching from UVVis to
Vis-only illumination (right part of curves), the pure
anatase titania mesoporous films fail to produce a
measurable I ph , whereas the composite CdSanatase
titania mesoporous film is still able to generate a clear
on/off I ph response, which is around 25% of the total
UVVis I ph . These discoveries imply that making 02
structure broadens photo response band.
Although the 0-D particles used to decorate 2-D PC
are usually noble metals or semiconductors, loading
0-D PC on non-PC with 2-D structure like graphene
(Fig. 22(a)) is also effective [109,110].
5. 4

Others (11, 12, 22)

There are other combination types apart from those


mentioned above, such as 11, 12, 22, and even
012.
The nanotree-like CdS/ZnO nanocomposite is one
typical 11 structured photocatalyst, with ZnO NRs on
the surface of CdS nanowires [111]. This kind of
spatially branched hierarchical structure was proved

Fig. 22 (a) SEM image of BFOgraphene nanohybrids. Reproduced with permission from Ref. [109], 2012 Royal
Society of Chemistry. (b) TEM image of CdSe/cubic mesoporous titania. Reproduced with permission from Ref. [107],
2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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Fig. 23 Periodic on/off photocurrent I ph response curves of (a) nanocrystalline pure anatase titania and (b) nanocrystalline
composite CdS/anatase titania cubic mesoporous films illuminated with a periodically light/dark modulated Xe lamp. Arrows
indicate the switching from UV and visible photons simultaneously (left side of the arrow) to illumination with visible photons
only (right side of the arrow). Reproduced with permission from Ref. [107], 2004 WILEY-VCH Verlag GmbH & Co. KGaA,
Weinheim.

with high light harvesting efficiency, which also boosts


charge separation and fast charge transport.
An intriguing structure was fabricated by Yang et
al. [112]. They synthesized CdS/ZnO core/shell
nanofibers, one of the 11 types (Figs. 24(a) and 24(b))
by one-pot single-spinneret electro spinning. The
CdS/ZnO core/shell nanofibers display high H2
production efficiency (Fig. 24(c)). An et al. [113]
studied the WO3 NRs/graphene composites (could be
classified to 12 type) (Fig. 25(a)), and the composites
display high-efficiency visible-light-driven PC ability
(Fig. 25(b)). Sun et al. [114] composited ordered
m-BiVO4 nanotubes and 2-D graphene (Fig. 25(c)),
and found the composites exhibit unprecedented
visible-light-driven PC activities, over 15 times faster
than that of commercial P25 or bulk BiVO4
(Fig. 25(e)). The improvement may be due to the
efficient electron transport along the axial direction of
nanotube, decreasing aggregation, and easy aqueous
dispersion. The synergistic effects between the

microscopic crystal structure and macroscopic


morphological features of 1-D quantum tubes2-D
sheets composites help provide increased PC reaction
sites, enhanced charge transportation, and separation
efficiency simultaneously.
Last but not the least, we can make PCs by
combining three dimensions together according to the
need of the materials, which is the 012 type. Xie and
his co-workers [115] coated TiO2 ultra-thin layers
made with ALD method in different thickness on the
TiO2 NRAs/CdS QDs, and observed that 2 nm thick
TiO2 thin layer covered by TiO2 NRAs/CdS QDs
(Figs. 26(a) and 26(b)) enhances the degradation rate
of MO under visible light compared to the samples
without TiO2 thin layer cover (Fig. 26(c)). The
remarkable PC ability is due to the enhancement of the
separation of eh and the reduced photo-corrosion of
the CdS QDs induced by the introduction of the
ultrathin TiO2 top layer.

Fig. 24 (a) TEM image of the samples (CdS)1/(ZnO)1. (b) HRTEM image of the interface between core CdS and shell ZnO.
(c) PC H2 production efficiency of (CdS)x/(ZnO)y. Reproduced with permission from Ref. [112], 2013 Royal Society of
Chemistry.

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Fig. 25 (a) TEM image of WO3 NRs/graphene composites. (b) Visible-light-driven photo degradation of RhB by
WO3/graphene composites and other WO3-based PCs. Reproduced with permission from Ref. [113], 2012 Royal Society of
Chemistry. (c) High magnification TEM image for ordered m-BiVO4 quantum tubesgraphene nanocomposites. The inset is a
schematic illustration of 12 type. (e) RhB concentration changes over several PCs under visible light irradiation.
Reproduced with permission from Ref. [114], 2012 Royal Society of Chemistry.

Fig. 26 (a) SEM and (b) HRTEM images of TiO2 NRAs/CdS QDs coated with ALD TiO2 with 60 cycles. The 2 nm coating
layer can be clearly seen. (c) Visible light ( > 420 nm) degradation behavior over MO of the TiO2 NRAs/CdS QDs coated
with different cycles of ALD TiO2, and the samples with 60 cycles did the best. Reproduced with permission from Ref. [115],
2014 Elsevier Ltd.

Conclusions

In this review, we have selectively discussed and


summarized the recent progress in the field of
low-dimensional PCs. These PCs with special

structures possess excellent optical and PC properties


due to high eh separation efficiency and large surface
area, representing an encouraging prospect in the
realization of a sustainable society. By applying the
advanced low-dimensional PCs, people could convert

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light energy to other forms, which is useful in


decomposing harmful substances, producing storable
fuels, and detecting light signals. In the future, these
PCs are supposed to be dedicated to more practical
real-life applications, including being used to treat
factory pollutant, purify the air, design indoor
degerming or self-cleaning household items, make
photoelectric sensors, and manufacture novel batteries
and hydrogen generator.
The promising opportunities offered by the
low-dimensional structures are outstanding. On one
hand, we can make delicate structure via those
advanced methods mentioned before to take the place
of the traditional bulk materials. On the other hand, we
can carry out modification on the base of the
low-dimensional structures. In addition to the structure
construction, people have learnt that energy band
configuration of a photocatalyst affects greatly the
utilization of light and determines the redox potentials,
that is why energy band engineering plays a significant
role in the field of looking for high-efficiency PCs. As
mentioned above, the band gap of a photocatalyst may
vary with the morphology, size, dimension, but doping
elements is the main method to achieve band gap
modification. For the single phase PCs, people prefer
those with small band gaps. According to the orbit
hybridization and band theory, doping proper both
non-metal and metal elements in photocatalyst can
narrow the band gap. Introducing non-mental anions
(e.g., N, C, S, P, B, F) on the O sites could raise the
VBM, extending the light absorption region toward
visible light region. Doping metal elements (e.g., Bi,
Co, Ce, Mn) can either lower the conduction band
minimum (CBM) or raise the VBM, and thus improve
the PC ability. The relationship between doping
concentration and PC efficiency is not liner, but the
optimal value exists. Comparing to non-metal doping,
metal doping obsesses more choices. People have tried
almost every possible metal element to dope the PCs,
including 3d-transition elements, p-block cations with
d10 configuration, d-block cations that have a d0
electronic configuration, etc. Designing proper band
combination via band modification that benefits carrier
separation the most is worth considering. Considering
the band modification and structure construction
together, we can combine the element doping with the
structure configuration, such as manufacturing
element-doped nanotube oxide PCs loaded with noble
metal quantum dots. In this way, the eh can be highly
efficiently separated; the band gap can be narrowed

simultaneously, which are two of the key issues in


photocatalysis. In the case of Ag loaded N-doped TiO2
nanotubes, the sample has higher light adsorption
and better degradation of acid orange-II than both
N-doped TiO2 NTs and Ag loaded TiO2 nanotubes
[102].
Although we have incredible opportunities,
challenges in the areas of materials science and
engineering still exist. For example, theoretical
prediction to the activity or explanation for the
performance of PCs with various structures need
develop. More specifically, although a number of
theories have been proposed to explain the PC
selectivity along different crystal orientations, like
theories based on facet surface energy, polarization
state, and effective mass, no satisfactory and
comprehensive understanding of mechanisms involved
has yet been arrived at. Moreover, from the point of
view of industrialization and commercialization, how
to get sophisticated structures much more efficiently
remains a question. In the future, with a more complete
theory system established and technical hurdles
addressed, high efficient and low-cost low-dimensional
PCs are expected to be developed.
It hopes that this review will provide useful
information in the utilization of low-dimensional
nanostructures for versatile PC applications, and
inspire growing efforts in the area of low-dimensional
nanostructure based photocatalysis.
Acknowledgements
This work was supported by the National Natural
Science Foundation of China (Nos. 51272121,
51221291, 51328203, and 51025205).
Open Access: This article is distributed under the terms
of the Creative Commons Attribution License which
permits any use, distribution, and reproduction in any
medium, provided the original author(s) and the source
are credited.
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