Titanium Dioxide

Nanomaterials

see A14

Potential applications due to its semiconducting

properties: dynamics of electrons and holes
Catalysis

Dye sensitized
solar cells

Sensor technology

1972 Fujjshima:
photocatalytic water splitting

Self cleaning glass

Li-ion-batteries

Titania Bulk phases

Rutile is the thermodynamically stable TiO2 phase in standard

conditions. The transformations from anatase to rutile has been deeply
studied, because the TiO2 phase is one of the most critical parameters
determining the use of this oxide as a photocatalyst. Anatase is
metastable, i.e., its transformation into rutile reaches a measurable
speed only at T > 900 K. This temperature can be lowered by the
presence of foreign atoms which catalyze the transformation.

Crystal structures of a) anatase b) rutile and c) brookite TiO2 using a

condensed polyhedra view.
The different phases share the distorted octahedra in different ways.
Rutile: slight orthorhombic distortion, each octahedron in contact with 10
neighbor octahedrons (2 edge sharing, 8 corner sharing)
Anatase: highly distorted octahedrons (symmetry lower than orthorhombic)
each octahedron in contact with 8 neighbor octahedrons (4 edge sharing, 4
corner sharing)
Ti-Ti distances larger and Ti-O shorter in anatase,

The relative bulk phase stability is reversed by the particle size

of the oxide: anatase is most thermodynamically stable at grain
sizes smaller than 11 nm, and rutile is most stable at sizes
greater than 35 nm.

size

Titania B: a further bulk like phase

The TiO2(B) phase is observed

as a lamellae in anatase
natural samples and it has still
largely unexplored properties
(its photocatalytic properties
seem to be rather interesting
and are now much
investigated)

Related Titanate phases: layered solids

TiO2 Anatase

TiO6 octahedra sharing corners form (0 01) planes.

They are connected with their edges with the plane
of octahedra below.
space group I41/amd
a=b=0,3782 nm, c=0,9502 nm

Titanate structures

TiO6 octahedra sharing edges to form

corrugated ribbons. They are connected by
corners.
space group P21/M(11)
a=0,8998 nm, b=0,3764 nm, c=0,9545 nm, =102,65

Titania at Nanoscale: a really populated zoo

nanotubes

nanocrystals

Titanate

nanosheets

Bulk
TiO2

(e.g. Na2Ti3O7 )

nanowires

Titania nanoparticles

Titania 1D and 2D nanostructures

The lepidocrocite-like bilayer:

a nanosheet obtainable from wet chemistry

Cs0.7Ti1.825O4

Ti0.91O2

brookite
rutile

anatase

lepidocrocite

Crystal size
reduction

Titania nanotubes
TNT

see A15

alumina anodic membrane

hydrothermal method
The hydrothermal method has been widely used to prepare TiO2 nanotubes since it was
introduced by Kasuga et al. in 1998. Briefly, TiO2 powders are put into a highly
concentrated NaOH aqueous solution and held at 20-110 C for several hours in an
autoclave. TiO2 nanotubes are obtained after the products are washed with a dilute HCl
aqueous solution and distilled water.

TiO2 anatase

Na-titanate
nanowires

10M NaOH
48h, 110C,
Reflux

H-titanate
nanotubes

SBET= 131 m2g-1

SBET= 280 m2g-1

HCl
1M, aq

SBET= 83 m2g-1
500
nm
500 nm

NaOH,
10M, aq

500 nm

500 nm

50 nm

stacking of layered titanates

TiO2 anatase
10M NaOH
48h, 110C,
Reflux

Na-titanate
nanowires

H-titanate
nanotubes
HCl

500nm
nm
500

NaOH

Hypothetical mechanism for

formation process of TiO2
nanotubes
the TiO2 nanotubes are formed in the stage of the
acid treatment following the alkali treatment.
When the raw TiO2 material was treated with
NaOH aqueous solution, some of the Ti-O-Ti
bonds were broken and Ti-O-Na and Ti-OH bonds
were formed. The Ti-OH bond could form a sheet.
When the material was treated with an aqueous
HCl solution and distilled water, new Ti-O-Ti
bonds and Ti-O-H-O-Ti hydrogen bonds were
generated.
The bond distance from one Ti to the next Ti on
the surface decreased. This resulted in the
folding of the sheets and the connection between
the ends of the sheets, resulting in the
formation of a tube structure.

Nanobowl arrays

Electronic structure
of titania

Occupied levels
(from UPS) :
O 2p localised

Electronic structure
of titania

Empty levels (from XAS):

Ti (2p) Ti 3d transition

Changes due to size:

XAS spectra

the metal (titanium) or the nonmetal (oxygen)

component can be replaced in order to alter
the materials electronic properties.

3d Metal doped titania (substitutional on Ti sites)

the metal (titanium) or the nonmetal (oxygen)

component can be replaced in order to alter
the materials electronic properties.
Doping of titania: Anions
3d Metal doped titania
on Ti sites)
Ti(substitutional
1-x AxO2
A=F,C,N,P,S

Anion doping vs cation doping of

titania

It appears easier to substitute the Ti4+ cation in TiO2 with other

transition metals, and it is more difficult to replace the O2anion 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

Light activated titania

Absorption of a photon with enough energy leads to a charge separation

due to an electron promotion to the conduction band and a generation
of a hole (h+) in the valence band.
The photogenerated electronhole pair (eh+) induces new properties to
the titania sample and in fact several different processes related to the
existence of electrons and holes can take place concomitantly on the
same TiO2 surface.

Photocatalysis is a well-known process and is mostly employed to degrade or transform (into less
harmful substances) organic and inorganic compounds and even microorganisms.
If the electrons are used in an outer circuit to perform work, we speak about a photovoltaic solar cell.
The recently discovered wettability, termed by Fujishima as superhydrophilicity, presents a large
range of applications in cleaning and anti-fogging surfaces.

Milestones of photocatalytic properties of titania

see A16

Photoexcitation and possible follow-up

The charge carriers can recombine, nonradiatively or radiatively (dissipating
the input energy as heat or photons), or get trapped and react with electron
donors or acceptors adsorbed on the surface of the photocatalyst.

with h> EBg

Recombination

Surface reaction
A-

PL=

h
heat

photoluminescence

Photocatalytic activity of a semiconducting

material

Energy scheme of a semiconductor particle in which an electron is excited

by light absorption. Located now in the conduction band it is capable of
reducing species A (in most cases just oxygen from air). When excited by
absorbing a photon h there remains a positive charge (defect electron or
hole) in the valence band capable of oxidizing species D.
In TiO2 the oxidizing power of such a hole is very high.

A good photocatalyst is characterized by its capability to adsorb simultaneously two

reactants, which can be reduced and oxidized by a photonic activation through an efficient
absorption (h Eg).

bottom of CB
effective in reducing water

top of VB
effective in oxidizing water

The ability of a semiconductor to undergo photoinduced electron transfer to an adsorbate is

governed by the band energy positions of the semiconductor and the redox potential of the
adsorbates.
The energy level at the bottom of conduction band is actually the reduction potential of
photoelectrons. The energy level at the top of valence band determines the oxidizing ability
of photoholes, each value reflecting the ability of the system to promote reductions and
oxidations.

For a semiconductor photocatalyst to be efficient, the different

interfacial electron processes involving e and h+ must compete
effectively with the major deactivation processes involving eh+
recombination, which may occur in the bulk or at the surface

Light harvesting from titania

There are several ways to increase light absorption:

-using nanostructured TiO2 nanomaterials
- bulk doping TiO2 with other elements can alter the optical
properties of TiO2 materials.
- sensitizing TiO2 with other colorful inorganic or organic
compounds can improve its optical activity in the visible light
region.
- using metal-TiO2 nanocomposites which couple collective
oscillations of the electrons in the conduction band of metal
nanoparticle surfaces to those in the conduction band of TiO2
nanomaterials to improve performance.

Effect of the nanostructure on the

light absorption
The main mechanism of light absorption in pure semiconductors is direct
interband electron transitions.
This absorption is small in indirect semiconductors, e.g., TiO2, where the direct
electron transitions between the band centers are prohibited by the crystal
symmetry.

An enhancement of light absorption in small TiO2 crystallites is expected due to

indirect electron transitions with momentum non-conservation at the interface.
This effect increases at a rough interface.

Considerable enhancement of the absorption is expected in small TiO2

nanocrystals, as well as in porous and microcrystalline semiconductors

Effect of the nanostructure on the

e-h+ dynamics
In general, semiconductors lack a continuum of interband states to assist the
recombination of electronhole pairs, which assure a sufficiently long lifetime
of eh+ pair to diffuse to the catalysts surface and initiate a redox reaction
However, the hole-electron dynamic is strongly dependent on
the dimensionality , shape and defectivity of the material

As the size of a particle decreases, a gradual transition from semiconductor

properties to molecular properties is expected and a lower level of defectivity is
observed.
In quantum-sized particles, the wave functions of the charge carriers spread over the
whole semiconductor particle. Thus, charge carriers do not need anymore to diffuse to
the surface to accomplish reactions with species present at the surface and, as a
consequence, it is possible to obtain quantum yields approaching unity.

Bulk doping

Cr implanted titania

Cr doped titania (wet chemistry)

Figure 55. Schematic diagram to illustrate the photoexcitation

process under visible light of metal-doped 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.

non metal doped titania Ti1-x AxO2

A=F,C,N

Substitutional sites introduce deep states in the gap

Titania Sensitization: using a dye

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.
A 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 structures 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.

Titania Sensitization: using a metal

nanoparticle
After the Ag nanoparticles are photoexcited due to
plasmon resonance, charge separation occurs by
the transfer of photoexcited electrons from the Ag
particle to the TiO2 conduction band with the
simultaneous transfer of compensating electrons
from a donor in solution to the Ag particles.

Photocatalytic Water Splitting

The photogenerated electrons and
holes cause redox reactions.
Water molecules are reduced by the
electrons to form H2 and oxidized by the
holes to form O2, leading to overall
water splitting.
The potential of the band structure of
TiO2 is just the thermodynamical
requirement. Other factors such as
charge separation, mobility,
and lifetime of photogenerated
electrons and holes also
affect the water splitting efficency.
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

Use of TNTs

highly ordered TiO2 nanotube arrays

have superior electron lifetimes and
provide excellent pathways for
electron percolation in comparison to
nanoparticulate systems.

Photovoltaic use of Titania

use of the photo-induced e-h+ charge separation to produce an

external work

Dye sensitized
solar cells

photovoltaic solar cell

(Dye Sensitized Solar Cell , DSSC)

CELLE
DI GRTZEL
sensitizer

see A17
tesina
Quintavalle

The basic element of a DSSC is a

nanostructured material, an assembly of
titanium dioxide nanoparticles about 20 nm
diameter, well connected to their neighbors

The electrons are first injected from dye

molecules that cover the TiO2 particles. The
dye is sensible to the visible ligth. The
nanoparticulate semiconductor functions as
the transporter of light induced electrons
towards the external contact, a transparent
conductor that lies at the basis of the TiO2
film.
Because the dye attaches well to the whole
TiO2 surface, the nanostructure enhances the
area that is used for collecting photons by a
factor 100-1000, with respect to the device
area.

When a dye molecule injects an

electron, it becomes oxidized. It is
very rapidly regenerated by a hole
transporting material, usually a
redox electrolyte.

In the complete DSSC, electrons and

holes created at the dye molecules,
are
successfully
transfered,
separately,
to
the
external
electrodes,
and
electricity
is
generated from sunlight. Maximum
conversion efficiencies are currently
about 10%, but long term stability
needs to be improved.

ee

he

eh

eh

h
e

Vetro TiO
2
conduttore

3II3-

Fattori che influenzano lefficienza complessiva:

- Velocit di trasporto degli elettroni attraverso lanodo;
- Caratteristiche del dye:
coefficiente di estinzione ;
velocit del trasferimento di carica;
- Caratteristiche dellelettrolita:
velocit nel trasporto di lacune;
cinetica di rigenerazione del dye;
- Ricombinazione degli elettroni nel semiconduttore con il dye ossidato (eq 5);
- Intercettazione degli elettroni da parte dellelettrolita (eq 6).

Efficienza di conversione della radiazione solare:

J sc Voc FF
=
Pin
dove JSC la corrente di cortocircuito, VOC la differenza di potenziale tra gli
elettrodi a circuito aperto (ovvero la forza elettromotrice), FF il fill factor, ovvero il
rapporto tra la potenza massima erogata dalla cella ( J max Vmax ) e il prodotto di JSC e VOC.

FF =

J max Vmax
J SC VOC

e Pin la potenza della radiazioincidente

pu essere incrementata aumentando VOC, JSC o FF; tuttavia il fill factor, influenzato
dalle varie resistenze presenti nelle celle come quella degli elettrodi, del semiconduttore,
al trasferimento di carica, non ha modo di andare oltre lo 0,85, e non c spazio per
ulteriori miglioramenti.
Pertanto le vie pi sensate sono quelle che mirano ad alzare VOC e JSC.

Prospettive delle DSSC

Lefficienza migliore (11%) quella ottenuta con il prototipo originale del 1993.

La cinetica dei processi coinvolti fondamentale.

Oltre al miglioramento delle propriet di cascun componente, si devono trovare
combinazioni che diano risultati soddisfacenti.

Visti gli ultimi sviluppi nella ricerca in questo settore, alcuni autori ritengono che
a breve sar possibile raggiungere unefficienza del 16%.

Photon induced Super Hydrophilicity (PSH)

involves reduction of Ti(IV) cations to Ti(III) by electrons and simultaneous trapping of
holes at lattice sites (usually bridging oxygen) or close to the surface of the
semiconductor. Such trapped holes weaken the bond between the associated titanium
and lattice oxygen, allowing oxygen atoms to be liberated, thus creating oxygen
vacancies (photostimulated oxygen desorption).
The subsequent dissociative adsorption of water at the site renders it more
hydroxylated. An increased amount of chemisorbed OH leads to an increase of van
der Waals forces and hydrogen bonding interactions between H2O and OH. Water can
easily spread across the surface and hydrophilic properties will be enhanced

see A18
tesina
Bovo

Self-cleaning glass is a specific type of

glass with surface which keeps itself free of
dirt through natural processes.
The first self-cleaning glass was based on
thin film titanium dioxide coating.
The glass cleans itself in two stages:
-The 'photocatalytic' stage of the process
breaks down the organic dirt on the glass
using ultraviolet in sunlight (even on
overcast days) and makes the glass
hydrophilic (normally glass is hydrophobic).
-During the following 'hydrophilic' stage rain
washes away the dirt - leaving almost no
streaks, because hydrophilic glass spreads
the water evenly over its surface.
Titanium dioxide is a material of choice
because it is characterized by high
photocalytic properties, chemical stability
and low price. Its anatase phase is most
photocalytic.