Journal of Nanoparticle Research 1: 439–458, 1999.

© 2000 Kluwer Academic Publishers. Printed in the Netherlands.

Review paper

Role of nanoparticles in photocatalysis

D. Beydoun1 , R. Amal1,∗ , G. Low2 and S. McEvoy3

1
Centre for Particle and Catalyst Technologies, School of Chemical Engineering and Industrial Chemistry, The
University of New South Wales, Sydney, N.S.W. 2052 Australia; 2 Environment Protection Authority, Analytical
Chemistry, Lidcombe, N.S.W. 2141 Australia; 3 CSIRO Division of Energy Technology, Lucas Heights Science
and Technology Centre, Lucas Heights, N.S.W. 2234 Australia; ∗ Author for correspondence (Tel.: 2 9385 4361;
Fax: 2 9385 5966; E-mail: r.amal@unsw.edu.au)

Received 22 February 1999; accepted in revised form 17 June 1999

Key words: nanoparticles, quantum size, photocatalysis, dopants, sensitization, nanocrystalline films

Abstract

The aim of this review paper is to give an overview of the development and implications of nanotechnology in
photocatalysis. The topics covered include a detailed look at the unique properties of nanoparticles and their relation
to photocatalytic properties. Current applications of and research into the use of nanoparticles as photocatalysts has
also been reviewed. Also covered is the utilization of nanoparticles in doped, coupled, capped, sensitized and organic–
inorganic nanocomposite semiconductor systems, with an effort to enhance photocatalytic and/or optical properties
of commonly used semiconductor materials. The use of nanocrystalline thin films in electrochemically assisted
photocatalytic processes has been included. Finally, the use of nanoparticles has made a significant contribution in
providing definitive mechanistic information regarding the photocatalytic process.

Background on photocatalysis
The photocatalytic process
Organic chemicals which may be found as pollutants
in wastewater effluents from industrial or domestic
sources, must be removed or destroyed before dis-
charge to the environment. Such pollutants may also be
found in ground and surface waters which also require
treatment to achieve acceptable drinking water quality
(Lindner et al., 1995). The increased public concern
with these environmental pollutants has prompted the
need to develop novel treatment methods (Zeltner et al.,
1996) with photocatalysis gaining a lot of attention in
the field of pollutant degradation.
Much of the natural purification of aqueous system
lagoons, ponds, streams, rivers and lakes is caused by
sunlight initiating the breakdown of organic molecules
into simpler molecules and ultimately to carbon dioxide
and other mineral products. There are various natural
sensitizers that accelerate the process. The utiliza-
tion of ‘colloidal semiconductors’ and the introduc-
tion of catalysts to promote specific redox processes
on semiconductor surfaces were developed in 1976
(Kalyanasundaram, 1983). Since then, laboratory stud-
ies have confirmed that naturally occurring semicon-
ductors could enhance this solar driven purification
process (Matthews, 1993).
The photocatalytic detoxification of wastewater is
a process that combines heterogeneous catalysis with
solar technologies (Zhang et al., 1994a). Semicon-
ductor photocatalysis, with a primary focus on TiO2 ,
has been applied to a variety of problems of environ-
mental interest in addition to water and air purifica-
tion. The application of illuminated semiconductors
for degrading undesirable organics dissolved in air or
water is well documented and has been successful for
a wide variety of compounds (Hoffmann et al., 1995).
440
Organic compounds such as alcohols, carboxylic acids,
amines, herbicides and aldehydes, have been photocat-
alytically destroyed in laboratory and field studies. The
photocatalytic process can mineralize the hazardous
organic chemicals to carbon dioxide, water and simple
mineral acids (Ahmed et al., 1984).
Many processes have been proposed over the years
and are currently used to remove organic toxins from
wastewaters. Current treatment methods for these con-
taminants, such as adsorption by activated carbon and
air stripping, merely concentrate the chemicals present,
by transferring them to the adsorbent or air, but they
do not convert them into non-toxic wastes. Thus, one
of the major advantages of the photocatalytic process
over existing technologies is that there is no further
requirement for secondary disposal methods.
Another advantage of this process is that when
compared to other advanced oxidation technologies,
especially those using oxidants such as hydrogen per-
oxide and ozone, expensive oxidizing chemicals are not
required as ambient oxygen is the oxidant (Matthews
et al., 1993). Photocatalysts are also self-regenerated
and can be reused or recycled.
Finally, the solar photocatalytic process can also be
applied to destroy nuisance odours, taste and odour
compounds, and naturally occurring organic mat-
ter, which contains the precursors to trihalomethanes
formed during the chlorine disinfection step in drink-
ing water treatment (Zhang et al., 1994b).
During the photocatalytic process, the illumination
of a semiconductor photocatalyst with ultraviolet (UV)
radiation activates the catalyst, establishing a redox
environment in the aqueous solution (Zhang et al.,
1994a). Semiconductors act as sensitizers for light-
induced redox processes due to their electronic struc-
ture, which is characterized by a filled valence band and
an empty conduction band (Hoffmann et al., 1995). The
energy difference between the valence and conduction
bands is called the band gap.
The semiconductor photocatalyst absorbs impinging
photons with energies equal to or higher than its band
gap or threshold energy. Each photon of the required
energy (i.e. wavelength) that hits an electron in the
occupied valence band of the semiconductor atom, can
elevate that electron to the unoccupied conduction band
leading to excited state conduction band electrons and
positive valence band holes (Schiavello, 1989).
The fate of these charge carriers may take differ-
ent paths (refer to Figure 1). Firstly, they can get
trapped, either in shallow traps (ST) or in deep traps
Figure 1. Processes involved in semiconductor particles upon
bandgap excitation. CB: Conduction Band, VB: Valence Band,
ST: Surface Traps, DT: Deep Traps, rec: recombination.
(DT). Secondly, they can recombine, non-radiatively
or radiatively, dissipating the input energy as heat.
Finally, they can react with electron donors or acceptors
adsorbed on the surface of the photocatalyst (Hoffmann
et al., 1995). In fact, it was recently shown that any
photoredox chemistry occurring at the particle surface,
emanates from trapped electrons and trapped holes
rather than from free valence band holes, and conduc-
tion band electrons (Serpone et al., 1996).
The competition between charge-carrier recombina-
tion and charge-carrier trapping followed by the com-
petition between recombination of trapped carriers and
interfacial charge transfer are what determine the over-
all quantum efficiency for interfacial charge transfer
(Hoffmann et al., 1995). Also of great importance are
the band positions or flat band potentials of the semi-
conductor material. These indicate the thermodynamic
limitations for the photoreactions that can take place
(Hagfeldt et al., 1995).
Photocatalysts
An ideal photocatalyst should be stable, inexpensive,
non-toxic and, of course, highly photoactive. Another
primary criteria for the degradation of organic com-
pounds is that the redox potential of the H2 O/• OH cou-
ple (OH− → • OH + e− ; E0 = − 2.8 V) lies within the
bandgap of the semiconductor (Hoffmann et al., 1995).
Several semiconductors have bandgap energies suffi-
cient for catalysing a wide range of chemical reac-
tions. These include TiO2 , WO3 , SrTiO3 , α-Fe2 O3 , ZnO
and ZnS.
TiO2 , the semiconductor most thoroughly investi-
gated in the literature, seems to be the most promis-
ing for photocatalytic destruction of organic pollutants
(Howe, 1998). This semiconductor provides the best

compromise between catalytic performance and stabil-
ity in aqueous media (Aruna et al., 1996). The anatase
phase of titanium dioxide is the material with the high-
est photocatalytic detoxification (Bahnemann et al.,
1993).
Binary metal sulphide semiconductors such as CdS,
CdSe or PbS are regarded as insufficiently stable for
catalysis, at least in aqueous media as they readily
undergo photoanodic corrosion (Howe, 1998; Fischer,
1989). These materials are also known to be toxic.
The iron oxides are not suitable semiconduc-
tors as they readily undergo photocathodic corrosion
(Hoffmann et al., 1995). The band gap for ZnO (3.2 eV)
is equal to that of anatase. ZnO however, is also unsta-
ble in water with Zn(OH)2 being formed on the parti-
cle surface. This results in catalyst deactivation (Howe,
1998).
Nanocrystalline photocatalysts
Nanocrystalline photocatalysts are ultrasmall semi-
conductor particles which are a few nanometres in
size. During the past decade, the photochemistry of
nano semiconductor particles has been one of the
fastest growing research areas in physical chemistry
(Henglein, 1997). The interest in these small semi-
conductor particles originates from their unique pho-
tophysical and photocatalytic properties (Bahnemann,
1993).
Several review articles have been published con-
cerning the photophysical properties of nanocrystalline
semiconductors (Henglein, 1988; 1989; Wang et al.,
1991; Bahnemann 1993; Zeltner et al., 1996; Levy,
1997). Such studies have demonstrated that some prop-
erties of nanocrystalline semiconductor particles are in
fact different from those of bulk materials.
Nanosized particles, with diameters ranging
between 1 and 10 nm, possess properties which fall
into the region of transition between the molecular
and the bulk phases (Bahnemann, 1993). In the bulk
material, the electron excited by light absorption finds
a high density of states in the conduction band, where
it can exist with different kinetic energies (Henglein,
1997). In the case of nanoparticles however, the parti-
cle size is the same as or smaller than the size of the
first excited state. Thus, the electron and hole gener-
ated upon illumination cannot fit into such a particle
unless they assume a state of higher kinetic energy
(Weller et al., 1995).
441
Hence, as the size of the semiconductor parti-
cle is reduced below a critical diameter, the spatial
confinement of the charge carriers within a potential
well (Serpone et al., 1996), like a ‘particle in a box’
(Hagfeldt et al., 1995), causes them to behave quantum
mechanically (Hoffmann et al., 1995). In solid state
terminology this means that the bands split into dis-
crete electronic states (quantized levels) in the valence
and conduction bands (Weller et al., 1995) and the
nanoparticle behaves more and more like a giant atom
(Henglein, 1997). Nanosized semiconductor particles
which exhibit size-dependent optical and electronic
properties are called quantized particles (Q-particles)
or quantum dots (Kamat, 1995).
The critical size and changes in properties
due to nanosize
Quantum-size (Q-size) effects occur when the size of
the semiconductor particles become smaller than the
Bohr radius of the first excitation state (Hagfeldt et al.,
1995). This has been stated by other authors as when
the particle size of the colloidal particle becomes com-
parable to the DeBroglie wavelength of the charge car-
riers (Henglein et al., 1987; Weller et al., 1995).
There seems to be discrepancy between the reported
critical size below which quantization effects are
observed. Many values have been quoted in the litera-
ture for the same semiconductor nanoparticles. There
are also discrepancies between the estimated critical
diameter and the actual diameters at which quantiza-
tion effects are observed. These predictions depend
critically on the effective masses of the charge carriers
(Serpone et al., 1996).
Kormann et al. estimated the excitation radii for tita-
nia particles to be between 7.5 and 19 Å. The exciton
radii were computed by using various literature values
and calculated by the equation put forward by Brus
(Kormann et al., 1988). Gratzel estimated an excitation
radius of ∼ 3 Å (Gratzel et al., 1989).
Kormann et al. reported quantization effects with
20–40 Å titania particles. Q-size effects were observed
during particle growth and at the final stage of synthesis
of these transparent colloids. The synthesized anatase
TiO2 particles resulted in a bandgap shift of 0.15 eV rel-
ative to bulk anatase TiO2 while the synthesized rutile
TiO2 , with d ∼ 2.5 nm, were blue shifted by 0.1 eV.
Anpo et al. (1987) reported excitation confinement
with 55–2000 Å rutile particles and up to 530 Å for
442
anatase particles. Kavan et al. (1993) reported blue
shifts with 25–100 Å particles. Weller et al. (1995) has
stated that size quantization effects for semiconductor
particles typically occur in a diameter range between 2
and 50 nm. In a recent review about photocatalysis, it
was stated that the critical diameter for TiO2 is 10 nm
(Howe, 1998). The same value was quoted by Martin
et al., 1995.
Recently, it has been proposed by Serpone et al. that
what had been taken in the past as observed size quan-
tization effects on 2 nm TiO2 particles, may in fact not
be a Q-size effect (Serpone et al., 1996). Their deduc-
tions were made from observations with spectroscopic
blue shifts in the effective bandgap of TiO2 with particle
sizes of 21, 133 and 267 Å. The study argued that some
of the bandgap shifts might simply reflect observations
of direct electron transition in an otherwise indirect
bandgap semiconductor such as TiO2 . When examin-
ing the absorption and photoluminescence of these par-
ticles, the authors found that an attempt to describe
the absorption coefficients by the indirect band gap
semiconductor relationship failed to give the expected
linear correlation. However, a linear correlation was
obtained with the relationship applicable to direct band
gap semiconductors. Their conclusions were that the
particle sizes examined seemed to affect charge carri-
ers relaxation dynamics, however, these did not appear
to be related to excitation confinement (Serpone et al.,
1996).
When considering semiconductors other than TiO2 ,
many reports have observed quantum size effects with
many different particles. For example CdS and PbS
a few nanometres in size have been found to exhibit
quantum mechanical effects (Gallardo et al., 1989).
Quantization effects have also been demonstrated with
nanoclusters of hexagonal MoS2 and several of its iso-
morphous Mo and W chalcogenides (with cluster size
down to ∼ 2 nm) (Wilcoxon et al., 1997).
Henglein also observed size quantization effects
with 1–10 nm CdS particles (Henglein et al., 1987). The
authors recognized that quantization effects become
evident when the particle size becomes comparable to
the DeBroglie wavelength of the charge carriers. Quan-
tization effects for an electron in an evacuated box were
estimated to become significant at box dimensions of
∼ 0.1 nm (using the ‘particle in a box’ model). How-
ever, in the colloidal particles the effects were seen at
much larger particle size. They found the reason to lie
in the fact that the effective mass of a charge carrier,
which moves in the periodic array of the constituents
of the crystal lattice, is generally much lower than the
mass of an electron in free space. This results in a larger
DeBroglie wavelength. The smaller the effective mass
of the charge carriers, the more pronounced are the
optical-size effects (Henglein et al., 1987).
Size quantization in semiconductor particles leads to
drastic changes in numerous important properties of the
material. Firstly, size quantization affects the electronic
properties of the semiconductor particle, with the ultra-
small crystallites composed of a few molecular units
maintaining their discrete HOMOs (Highest Occupied
Molecular Orbitals) and LUMOs (Lowest Unoccupied
Molecular Orbitals) (Serpone et al., 1996). This in turn
affects charge-carrier dynamics (Mimic et al., 1990;
Smith et al., 1997). For example, for aqueous gold
and silver colloids, spatial-size confinement was found
to cause substantially slower electronic relaxation due
to reduction of non-equilibrium electron transport and
weaker electron–phonon coupling (Smith et al., 1997).
Secondly, in the Q-size regime, the chemical and
physical properties, which are related to electronic
properties, strongly depend on the size of the nanopar-
ticles (Weller et al., 1995). The electronic properties
relate to the solid state physics aspects of the particles,
that is, band structures and band gap, as well as the
electrochemical positioning of the bandgap edge poten-
tial with respect to the Nernst potential of the solution
(Hagfeldt et al., 1995).
The band gap of the semiconductor becomes larger
with decreasing particle size, and is indicated by
an absorption shift to shorter wavelengths (Henglein,
1997). The band edges shift to yield larger redox poten-
tials (Howe, 1998). The levels of the valence band are
moderately shifted to lower energies, while those of the
conduction band are strongly shifted to higher energies
(Henglein, 1987).
For a size-quantized particle, the increase in bandgap
energy, 1EBG , varies with the radius of the particle,
Rpart , the reduced effective mass of the excitation, µ,
and the dielectric constant of the semiconductor, ε
(Serpone et al., 1996). The reduced effective mass of
the excitation, µ, is related to the effective masses of
the charge carriers (me , mh ) by the following expres-
−1
sion: µ−1 = m−1 e + mh . From Eq. (1) it can be seen
that 1EBG depends critically on the effective masses of
the electrons and holes:
1EBG = h2 /8µRpart
2
− 1.8e2 /εRpart . (1)
As a result of the change in electronic properties,
quantization effects also have a pronounced effect

on spectral properties of semiconductors (Bahnemann
et al., 1984). For instance, with decreasing particle size,
the energy of the optical transition increases and the
colour of the fluorescence light is blue shifted, that is, it
is shifted to a shorter wavelength (Henglein, 1987). The
Q-particles can have a different colour depending on
the particle size. For example Cadmium sulphide nor-
mally exists as a yellow material, but becomes colour-
less when the particle is smaller than 22 Å. Cadmium
phosphide, which is normally a black material, can be
made in various colours depending on the particle size
(Henglein, 1997a). Bahnemann et al. used a molecu-
lar orbital description to explain the optical properties
of semiconductor particles. During particle growth of
TiO2 particles from molecular to bulk sizes, molecu-
lar orbitals of an increasing number of molecules over-
lap. The energy gap between the HOMO and LUMO
decreases. These changes result in a red shift (longer
wavelength) of the accompanying optical transition
(Bahnemann et al., 1987).
Activity of nano-photocatalysts
One of the main advantages of the application of
Q-sized particles is the increase in the bandgap energy
with decreasing particle size. As was mentioned earlier,
as the size of a semiconductor particle falls below the
critical radius, the charge carriers begin to behave quan-
tum mechanically and the charge confinement leads to
a series of discrete electronic states. As a result there
is an increase in the effective band gap and a shift of
the band edges. Thus by varying the size of the semi-
conductor particles, it is possible to enhance the redox
potential of the valence-band holes and the conduction-
band electrons (Hoffmann et al., 1992b).
However, the solvent reorganization free energy
for charge transfer to a substrate, remains unchanged
(Martin et al., 1995). The increasing driving force and
the unchanged solvent reorganizational free energy are
expected to lead to an increase in the rate constants for
charge transfer at the surface (Hoffmann et al., 1995).
Thus, the use of size-quantized semiconductor parti-
cles may result in increased photoactivity for systems in
which the rate-limiting step is interfacial charge trans-
fer (Martin et al., 1995).
Hence nanosized semiconductor particles can pos-
sess enhanced photoredox chemistry, with reduction
reactions, which might not otherwise proceed in bulk
materials, being able to occur readily using sufficiently
443
small particles (Serpone et al., 1996; Nedeljkovic et al.,
1986). Another factor which could be advantageous is
the fact that the fraction of atoms that are located at
the surface of a nanoparticle is very large (Henglein,
1997). Q-sized particles also have high surface area to
volume ratios, which further enhances their catalytic
activity (Hoffmann et al., 1992b). One disadvantage of
nanosized particles is the need for light with a shorter
wavelength for photocatalyst activation. Thus a smaller
percentage of a polychromatic light source will be use-
ful for photocatalysis.
The first account of light driven redox reactions in
nanocrystalline systems was published in 1981. Since
then, nanocrystalline semiconductor systems which
have been well studied include oxides, sulphides and
selenides, such as TiO2 , ZnO, WO3 , V2 O5 , Ag2 O,
ZnS, CdS, PbS, Cu2 C, MoS2 , and CdSe (Hagfeldt,
1995).
While some studies have found that nanoparticles
have enhanced photoactivities over their bulk-phase
counterparts, (Hoffmann et al., 1994; Anpo et al., 1987;
Nedeljkovic et al., 1986; Nosaka et al., 1990), others
have found the contrary to be true (Lepore et al., 1993;
Hoffmann et al., 1992a; Martin et al., 1995). In cases
where the activity of the nanoparticles was found to be
lower than that of their bulk counterparts, it is thought
that the positive effects of increased photo-potentials
were offset by unfavourable surface speciation and sur-
face defect sites on the size-quantized semiconductor
particles, due to the preparation method (Hoffmann
et al., 1995).
Wang et al. (1997) demonstrated that there exists
an optimal particle size in nanocrystalline TiO2 sys-
tems for maximum photocatalytic efficiency. In their
experiments which involved the decomposition of
chloroform, they observed an improvement in activ-
ity 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.
Martin et al. (1995) saw the variation in the photo-
efficiencies of different forms of TiO2 as being fun-
damentally related to their charge-carrier dynamics.
The authors studied the charge-carrier dynamics of Q-
TiO2 and Degussa P25 (made up of 20–35 nm pri-
mary particles, the size of the aggregates is 50–200 nm)
by time-resolved microwave conductivity. They found
that the resultant interfacial electron transfer appeared
to be faster for P25 than for Q-TiO2 . The slower
444
electron-transfer rates observed for Q-TiO2 were con-
sistent with the lower steady-state quantum yields.
This was supported by Zhang et al. (1998) who gave
the following explanation for these observations. They
suggested that in large TiO2 particles, volume recom-
bination of the charge carriers is the dominant process,
and can be reduced by a decrease in particle size. This
decrease also leads to an increase in the surface area
which can be translated as an increase in the available
surface active sites. Thus a decrease in particle size
should also result in higher photonic efficiencies due
to an increase in the interfacial charge-carrier transfer
rates. However, as the particle size is lowered below a
certain limit, surface recombination processes become
dominant since firstly, most of the electrons and holes
are generated close to the surface, and secondly since
surface recombination is faster than interfacial charge-
carrier transfer processes. This is the reason why there
exists an optimum particle size for maximum photo-
catalytic efficiency.
The first accurately determined quantum yields of
polycrystalline TiO2 were provided by Lepore et al.
(1993). The authors compared the photochemical and
photophysical behaviour of polycrystalline, optically
transparent TiO2 suspensions (with a 62 nm average
effective radius, prepared by successive centrifugation
of P25 slurries) with quantum-sized (∼ 2.4 nm) TiO2
solutions, as well as P25 slurries. The quantum yields
obtained with the centrifuged suspensions were similar
to those of P25, but were higher than those obtained
with the quantum-sized TiO2 .
This difference was explained in terms of a longer
lifetime of the charge carriers in the centrifuged sam-
ples and the P25 slurries, compared to the quantum-
sized (∼ 2.4 nm) TiO2 solutions. Also, from their
findings, the authors suggested the lack of surface-
trapped electrons in P25 samples as a possible factor
responsible for their higher photoactivity (Lepore et al.,
1993).
The first results demonstrating the enhancement
of photoredox produced by size-quantization effects,
were reported by Nedeljkovic et al. (1986). The
nanocrystalline semiconductors studied were HgSe,
PbSe, and CdSe colloids. For diameters less than 50 Å,
the optical absorption edge of HgSe and PbSe was
blue shifted by several volts. The enhancement effects
of the photoredox chemistry of Q-size semiconductor
particles were demonstrated with the evolution of H2
with aqueous colloids of HgSe and PbSe (d < 50 Å).
The nanocrystalline CdSe particles (d < 50 Å) were
studied for CO2 reduction (to formic acid) since they
have greater stability against photocorrosion compared
to HgSe and PbSe. Large particle-sized CdSe colloids
did not yield formic acid under the same experimental
conditions.
Anpo et al. (1987) synthesized extremely small TiO2
particles and investigated their use for the photocat-
alytic hydrogenation reactions of CH3 CCH with H2 O.
They found the activity to increase as the diameter of
the TiO2 particles decreased, especially below 100 Å.
Absorption and photoluminescence spectra of these
particles had exhibited blue shifts below 100 Å, sug-
gesting a size-quantization effect. The authors sug-
gested that the dependence of the yields on the particle
size arose from the differences in the chemical reactiv-
ity not the physical properties, such as the surface area,
of these catalysts. The authors recognized the presence
of quantization effects in the systems they were study-
ing, although they did not provide an explanation as to
why these effects led to increased activity. The photo-
catalytic activity of Q-TiO2 particles was also demon-
strated by Kormann et al. (1988).
Henglein et al. (1989) studied the photochemistry
of AgI nanoparticles. The absorption threshold of the
prepared colloids was blue shifted, which is indicative
of quantization effects. These AgI particles were found
not to be photoactive with respect to the formation of
silver or iodide. However, it was found that silver metal
was deposited on the surface of the AgI colloids when
the solution was de-aerated and sodium sulphite added.
The fluorescence of these particles, which occurs close
to the absorption threshold, was found to be quenched
by the small amounts of deposited silver, believed to be
acting as a charge scavenger. The scavenging process
did not result in an increase in the reaction yield, with
the silver deposit acting as a mediator for the recom-
bination of charge carriers. Hoffmann et al. (1992a)
showed that polymerization of methyl methacrylate
readily occurred when using Q-sized ZnO semiconduc-
tors as photointiators. The quantum yields decreased as
particle size decreased, due to either increased surface
defects or enhanced rates of competing electron–hole
recombination. Under the same experimental condi-
tions, no polymerization occurred with bulk-size par-
ticles as photoinitiators.
The same group also studied the efficiency of
photoinitiation of polymerization of several vinylic
monomers using both bulk and quantum-sized CdS,
ZnO and TiO2 . The authors found that the Q-sized
semiconductors demonstrated significantly higher

yields than their bulk counterparts. They attributed
this to the greater total reactive surface area of the
Q-particles.
Also, when comparing the efficiencies of the three
photocatalysts tested, they found that there was a corre-
lation between the semiconductor photoinitiation effi-
ciency and the reduction potential of its conduction
band electrons. A comparison of the quantum yields for
polymerization revealed that the rates increased in the
following order: TiO2 , ZnO, CdS. This order paralleled
an increase in the conduction-band potential (−0.1,
−0.2, −0.4 V versus SCE, respectively) (Hoffmann
et al., 1992b) (The potential of the SCE relative to the
SHE is 0.2444 V at 25◦ C).
Another area where photocatalysis is being applied
is in the photocatalytic reductions of CO2 . Kanemoto
et al. (1992) suggested the importance of the surface
structures of the nanocrystallites in CO2 photoreduc-
tions. They deduced this from surface modification
studies, which involved the addition of Zn2+ to a sys-
tem of ZnS nanocrystallites. This addition resulted in
product switching from formate to CO without loss in
efficiency. In 1997, the same group carried out an inves-
tigation of a CdS photocatalytic system for CO2 reduc-
tion, which examined the role of the surface structures
of the CdS nanocrystallites. They observed a marked
improvement of photocatalytic activity through the for-
mation of sulphur vacancies. They proposed that the
CO formation process occurred via adsorption of CO2
to a Cd atom in the vicinity of a sulphur vacancy
(Fujiwara et al., 1997).
The application of nanoparticles in photocatalysts
became a reality with the introduction of the now
commercially available HombiKat UV 100 from
Sachtleben Chemie GmbH. This novel photocatalyst
consists of 5 nm TiO2 anatase particles forming micron-
sized aggregate structures. The activity of this novel
material was investigated using dichloroacetic acid
(DCA) as the model organic compound, by Lindner
et al. (1995). The high photocatalytic activity exhib-
ited by this new photocatalyst, compared to another
commercially available catalyst, was explained by its
very high surface area (> 250 m2 /g). The authors found,
however, that higher concentrations of Hombikat UV
100 (5g/L) were required to reach its optimal perfor-
mance as compared with 0.5 g/L of the other photocat-
alyst. They attributed this to the slightly blue shifted
spectral response of this novel photocatalyst caused by
its very small primary particles, although no explana-
tion was provided regarding this conclusion.
445
Sato et al. (1996a) studied the photochemical
reduction of nitrate to ammonia with and without
methanol using layered hydrous titanate/cadmium sul-
phide (H2 Ti4 O9 /CdS) nanocomposites. The addition of
methanol was found to be useful for the promotion of
this reduction. Doping with Pt particles in the interlayer
was also found to greatly increase the catalytic activ-
ity of the nanocomposites. This group has also looked
at the photocatalytic properties of layered hydrous tita-
nium oxide/CdS–ZnS nanocomposites incorporating
CdS–ZnS into the interlayer. The hydrogen production
activity, which was observed for these nanocomposites
following irradiation with visible light, was found to be
higher than that of unsupported CdS–ZnS (Sato et al.,
1996b).
Another area where considerable interest has been
shown is the application of photocatalysis to sil-
ver recovery, for example from waste photographic
effluents. Recently Sahyun et al. (1997) studied the
photocatalytic deposition of silver from a silver salt
ethanol solution onto TiO2 nanoparticles prepared with
a chemisorbed surface alkoxide. From picosecond-
resolved transient absorption spectroscopy, the authors
deduced that the rate of formation of the colloid sil-
ver deposit is determined by the reduction of Ag(I) by
surface-trapped photoelectron states (Ti(III)).
Size-quantized CdS (∼ 20 Å) nanocrystals have
been used as photocatalysts for nitrate reduction
(Korgel et al., 1997). Due to the effects of quantum
confinement on electron and hole redox potentials, the
nitrate reduction rates were found to depend strongly
on the apparent particle size, with the fastest reduction
rates being observed with the smallest nanocrystals. In
the absence of an electron donor other than water, rapid
photocorrosion was observed; therefore, formate was
used as the sacrificial electron donor.
Ogura et al. (1997) carried out tests using series
of hexatitanates, M2 Ti6 O13 (M denotes Na, K, or Rb).
The authors compared the photocatalytic activity of the
hexatitanates supported on RuO2 , with the efficiency
for the production of photoexcited charges. The test
reaction was water decomposition. The hexatitanates
showed high photocatalytic activities and high pho-
toexcited radical formation (followed with ESR mea-
surements). The results indicated a close relationship
between the photocatalytic activity and the efficiency
of electrons and holes production.
The use of iron oxides as photocatalysts has been
given particular attention due to their absorptivity in
the visible region, abundance, and low cost. Faust et al.
446
(1989) examined the suitability α-Fe2 O3 as a photo-
catalyst by studying the kinetics and mechanisms of
the photocatalytic oxidation of sulfur dioxide in aque-
ous colloidal suspensions of 3–25 nm α-Fe2 O3 . The
results showed that the small hematite crystals pos-
sessed photocatalytic activity for the oxidation of sul-
fite (S(IV)), which readily depleted when the colloidal
solutions containing 1 mM S(IV), and 0.1 mM of the
nano α-Fe2 O3 particles were illuminated with light, of
λ = 320 nm, in the presence of air.
Kormann et al. (1989) also examined the suitability
of α-Fe2 O3 as photocatalysts using transparent α-Fe2 O3
3–20 nm in size. They also compared the photocatalytic
activity of hematite to the activities of colloids and sus-
pensions of ZnO and TiO2 . While ZnO and TiO2 were
found to be quite active photo-oxidation catalysts in the
formation of hydrogen peroxide and in the degradation
of chlorinated hydrocarbon molecules, only negligible
photocatalytic activity was found for α-Fe2 O3 .
Bahnemann (1993) has also carried out several tests
to compare the efficiencies of several semiconductors
as photocatalysts. This work involved the comparison
of ultrasmall zinc oxide, titanium dioxide, hematite
and titanium/iron mixed oxide particles. Q-size effects
were observed during particle growth and at the final
stages of synthesis of all of the oxides studied. While
zinc oxide, titanium dioxide and titanium/iron mixed
oxide particles exhibited considerable photocatalytic
activity, hematite particles were only found to oxi-
dize S(IV), with the quantum yields (φ) obtained
being < 0.3. An explanation involving surface-bound
molecules and free radical intermediates was provided
to account for these differences in reactivity.
In 1998, Cherepy et al. carried out ultrafast kinetic
studies of photoexcited charge carriers dynamics in
γ - and α-Fe2 O3 semiconductor nanoparticles using
femtosecond laser spectroscopy. The aim of this work
was to explain the observed low photoactivities of
these iron oxide semiconductors (Cherepy et al., 1998).
The results showed that the visible/near UV light
induced charge separation of the photoexcited elec-
trons in Fe2 O3 nanoparticles was very short-lived and
the decay was primarily non-radiative. A power depen-
dence, which reveals the relaxation mechanism for the
early time decay, was also found to be very different
from that in other semiconductor nanoparticles such as,
CdS or TiO2 . The authors saw these results as providing
some insight into the poor efficiency of Fe2 O3 as a pho-
tocatalyst. They also proposed that the identification
of materials, which have an intrinsically slow decay
of photoexcited electrons, would help in the search of
high-efficiency photocatalysts and photoelectrodes.
Enhancement of photoactivity of
nano-photocatalysts
Under bandgap excitation, metal oxide semiconduc-
tor particles behave as short-circuited electrodes, with
both oxidation and reduction processes occurring on
their surfaces (Kamat, 1995). Thus two critical pro-
cesses determine the overall quantum efficiency for
interfacial charge transfer. These are the competition
between the recombination and the trapping of the
charge carriers, followed by the competition between
the recombination of the trapped carriers and the inter-
facial charge transfer (Hoffmann et al., 1995). At least
in colloidal sols of TiO2 , it was found that the charge
carriers undergo 90% recombination ∼ 1 ns after exci-
tation (Serpone et al., 1996). The authors concluded
that the quantum yields of any surface photoredox reac-
tion could not be greater than ∼ 10%.
In order to enhance the photoactivity of bulk and
colloidal TiO2 particles, interfacial charge-transfer
reactions need to be enhanced. Improved charge sepa-
ration and inhibition of charge carrier recombination is
essential in improving the overall quantum efficiency
for interfacial charge transfer (Bedja et al., 1995). This
can be achieved by modifying the properties of the par-
ticles by selective surface treatment (Hoffmann et al.,
1995).
Several approaches have been taken to achieve this.
These have included surface modification of the semi-
conductor particles with redox couples or noble metals
(Choi et al., 1994, Aruna et al., 1996). Bahnemann et al.
(1984) have shown that the efficiency of charge transfer
at the semiconductor–electrolyte can also be improved
by simultaneous scavenging of holes and electrons by
surface adsorbed redox species. Another approach has
involved the coupling of two semiconductor particles
with different electronic energy levels (Bedja et al.,
1995).
Metal ion dopants
Depositing or incorporating metal ion dopants into
the titanium dioxide particles can influence the per-
formance of these photocatalysts. This affects the
dynamics of electron:hole recombination and inter-
facial charge transfer. The largest enhancement of
photoactivity through doping was found in nanosized
particles, in which the dopant ions are located within

1–2 nm of the surface (Choi et al., 1994). Also, the
high surface areas characteristic of nanoparticles (100–
500 m2 /g) appear to enhance the deposition process
and the resulting activity of the catalyst (Zeltner et al.,
1996).
The work of Choi et al. involved a systematic study
of the effects of 21 different metal ion dopants on
nanocrystalline TiO2 . Chloroform oxidation and car-
bon tetrachloride reductions were used as photoreactiv-
ity tests. Their results showed that some doped Q-TiO2
particles had much greater photoactivity than their
undoped counterparts. Doping with Fe(III), Mo(V),
Ru(III), Os(III), Re(V), V(IV) and Rh(III) at the
0.5 at% level in the TiO2 matrix, significantly improved
the photoreactivity for both oxidation and reduction.
Choi used laser flash photolysis and time-resolved
microwave conductivity measurements to correlate the
effects of metal ion dopants to the lifetime of the pho-
toexcited electron. In the Fe(III), V(IV), Mo(V) and
Ru(III) doped samples, the lifetime of the generated
electron was found to have increased to 50 ms com-
pared to < 200 µs with the undoped Q-TiO2 . There was
also an apparent linear correlation between the oxida-
tion quantum yield (of chloroform) and the reduction
quantum yield (of carbon tetrachloride) regardless of
the nature of the dopant.
This ion doping of large bandgap semiconductor
colloids might not always be effective in lengthening
the lifetime of the generated charge carriers. Recently,
Smith et al. (1998) showed that in Ru(III) doped
TiO2 colloids, the electronic decay was as fast as or even
faster than in undoped TiO2 . The difference between
the studies carried out by Smith et al. and those car-
ried out by Choi et al., was the higher dopant level of
Ru (III) of 3 at% used by Smith et al., compared with
the 0.5 at% dopant level used by Choi et al.
There could be several reasons for the variations in
the reported effects of the dopant ions. One reason for
these variations is the location and co-ordination of
the dopant ions. These depend critically on the meth-
ods of sample preparation and pre-treatment as well
as the concentration of the dopant ions. The dopant
ions may be adsorbed on the surface, they may be
incorporated into the interior of the particle on fir-
ing, or they may form separate oxide phases (Howe,
1998).
The dopant ions can function as both hole and elec-
tron traps or they can mediate interfacial charge transfer
(Choi et al., 1994). Once incorporated into the inte-
rior of the TiO2 , the dopant ions may occupy either
447
lattice (substitutional) or interstitial sites. Their ability
to function as trap sites and/or to mediate interfacial
charge transfer will depend on these factors (Howe,
1998).
When incorporated in the interior of the particles,
the d-electronic configuration of the dopant and its
energy level within the TiO2 lattice also seem to signifi-
cantly influence the photoactivity (Martin et al., 1995).
Finally, the site where the electron gets trapped greatly
influences the redox chemistry of the doped semicon-
ductor. A dopant ion might act as an electron trap, and
this might in fact lead to a lengthening in the lifetime of
the generated charge carriers, resulting in an enhance-
ment in photoactivity. However if an electron is trapped
in a deep trapping site, it will have a longer lifetime,
but it may also have a lower redox potential. This might
result in a decrease in the photoreactivity (Hoffmann
et al., 1995).
The work carried out by Zhang et al. (1998) shed
a new light on the role of dopant ions and their effect
on photoactivity. Firstly, these authors provided further
support for the existence of an optimum dopant con-
centration. Their main finding however was that this
optimum concentration is particle-size dependent and
decreases with an increase in size. The system they
studied was Fe3+ doped TiO2 for the photocatalytic
degradation of CHCl3 . They observed that for 6 nm
particles, the optimum Fe concentration was 0.2 at%,
while for 11 nm particles, the optimum concentration
was 0.05 at%. They provided the following explanation
for their observations.
Their first explanation was with regards the exis-
tence of an optimal Fe3+ dopant concentration. Fe3+
ions serve as shallow trapping sites for the charge car-
riers and increase the photocatalytic efficiency by sep-
arating the arrival time of e− and h+ at the surface. If
Fe3+ can act as a trap for both e− and h+ , at high dopant
concentration, the possibility of charge trapping is high,
and as such, the charge carriers may recombine through
quantum tunneling. If Fe3+ acts as a h+ trap only, the
recombination of the charge carriers is not of great con-
cern at low dopant concentrations. At high concentra-
tions however, a h+ may be trapped more than once as
it tries to make its way to the surface. This hole which
had been ‘held back’, might then recombine with an
electron which is generated by a subsequent photon
before it can reach the surface (i.e. increased incidence
of volume recombination). Thus there exists an opti-
mum Fe3+ concentration whether the Fe3+ acts as an e−
and h+ trap or as a h+ trap only.
448
With regards to the optimum concentration depend-
ing on the particle size, Zhang et al. suggested that
when the particle size becomes larger, the average path
length of a charge carrier to the surface is longer. Thus,
for a constant dopant concentration, the longer the path
length which the charge carrier needs to travel, the
higher the probability of meeting a dopant ion, and
hence the greater the chance of multiple trappings. This
multiple trapping leads to increased volume recombi-
nation. A lowering in the dopant concentration reduces
the chance of multiple trappings for a larger particle.
Thus the optimal Fe3+ dopant concentration should
decrease with increasing TiO2 particle size.
Dual semiconductor systems
Another approach taken to modify the surface of semi-
conductor colloids, with an aim to improve charge
separation and minimize or inhibit charge-carrier
recombination, has been to dope with a second semi-
conductor. Excitation of these dual semiconductors
results in an electron injection into the lower lying
conduction band of the second semiconductor. In the
composite nanoparticles, no electric field is necessary,
as the charge separation is achieved by the tunneling
of electrons (Henglein, 1997). Recent studies of these
interparticle electron transfer occurs within 500 fs–2 ps
(Evans et al., 1994).
Henglein presented the first example in the literature
of composite particles when he found that when small
amounts of Cd2+ were added to ZnS, the ZnS bandgap
fluorescence was quenched (Henglein, 1984). Since
then there have been many papers published regard-
ing the optical properties of mixed systems. Some of
the systems studied include ZnS–CdS (Ueno et al.,
1985), CdS–Ag2 S (Henglein et al., 1987), CdS–Ag2 S
(Spanhel et al., 1987a), mixed crystals of Znx Cd1−x S,
CdS–ZnS (Youn et al., 1988), AgI–Ag2 S (Henglein
et al., 1989), ZnS–CdSe (Kortan et al., 1990) and CdS–
PbS systems (Zhou et al., 1993).
Reber et al. (1986) reported that modifying the sur-
faces of platinized CdS powders with silver ions could
activate these photocatalysts, which are otherwise inac-
tive with respect to H2 formation. The activation was
attributed to the formation of a heterojunction between
CdS and Ag2 S. It was also observed that the fluores-
cence of CdS was quenched by Ag+ ions, and that the
spectral response for H2 formation was extended to
wavelengths up to ∼ 600 nm where CdS itself does not
absorb.
Recently, emphasis has been placed on the devel-
opment of coupled and capped semiconductor systems
and their application in photocatalysis. Many papers
have been published regarding coupled semiconduc-
tors systems. These include CdS–TiO2 , CdS–ZnO
(Spanhel et al., 1987b), CdS–Ag2 S (Spanhel et al.,
1987), ZnO–ZnS (Rabani, 1989), ZnO–ZnSe (Kamat
et al., 1992), AgI–Ag2 S (Henglein et al., 1989) and
CdS–HgS (Haesselbarth et al., 1992).
The charge separation mechanism in both capped
semiconductor systems and coupled semiconductor
systems involves the photogenerated electrons in one
semiconductor being injected into the lower lying con-
duction band of the second semiconductor. However,
the interfacial charge transfer is significantly differ-
ent (Bedja et al., 1995). The charge-transfer processes
involved in capped and coupled semiconductor systems
are shown in Figures 2 and 3 respectively. In a coupled
semiconductor system the two particles are in contact
with each other and both holes and electrons are acces-
sible on the surface for selective oxidation and reduc-
tion processes. Capped semiconductors on the other
hand have a core and shell geometry. The electron gets
injected into the energy levels of the core semiconduc-
tor (provided it has a conduction band potential which
is lower than that of the shell). The electron hence
gets trapped within the core particle, and is not readily
accessible for the reduction reaction.
In 1995 Bedja et al. synthesized TiO2 -capped SnO2
(SnO2 @TiO2 ) and TiO2 -capped SiO2 (SiO2 @TiO2 )
nanocrystallites. The photocatalytic properties of the
capped semiconductor systems were tested for the oxi-
dation of I− and SCN− . The SnO2 @TiO2 colloids were
80–100 Å in diameter and exhibited improved photo-
catalytic efficiencies compared to the uncapped TiO2
colloid. The quantum efficiency for I− oxidation was
improved by a factor of 2–3 upon capping the SnO2
colloids with TiO2 . The improved charge separation
in the SnO2 @TiO2 system was confirmed by laser
flash photolysis experiments. The photocatalytic prop-
erties of SiO2 @TiO2 colloids were found to be sim-
ilar to those of uncapped TiO2 colloids (Bedja et al.,
1995).
Similar work is being carried out by Amal et al.,
with this group being involved in the development
of two novel photocatalysts. The first photocatalyst
is α-Fe2 O3 @TiO2 , with an aim to expand the cat-
alyst’s photoresponse into the visible region of the
solar spectrum (Penpolcharoen et al., 1998). The sec-
ond is Fe3 O4 @TiO2 , with an aim to enhance the cata-
lyst’s separation properties from the treated water by
imparting magnetic properties onto the photocatalyst
(Beydoun et al., 1998).

Figure 2. Charge transfer in a coupled semiconductor system.
Figure 3. Charge transfer in a capped semiconductor system.
The development of these heterogeneous semicon-
ductor systems is very promising and has the potential
to contribute significantly to the area of photocatalysis.
By changing certain parameters, such as the thick-
ness of the shell or the particle radius of the core, this
approach may allow the tailoring of important proper-
ties, such as photocatalytic, optical, and magnetic prop-
erties, of the photocatalyst. It may also be important in
addressing problems such as photodissolution, which
might otherwise occur in an ‘unprotected’ photocata-
lyst such as iron oxide (Hoffmann et al., 1995).
In capped systems, if the thickness of the shell
deposited is sufficiently thick, relative to the core
radius, the individual identity of the two semiconduc-
tors can be maintained (Bedja et al., 1995). In these
systems, only the holes are accessible at the surface
of the photocatalyst. This allows for selective interfa-
cial charge transfer, and improves the efficiencies of
the oxidation reactions. However, one disadvantage of
this approach is the fact that the reducing charge car-
riers (the electrons) are not being utilized during the
449
photocatalyic reaction, since they are being accumu-
lated within the core semiconductor. Therefore these
photocatalysts cannot be used for photoreduction reac-
tions or reactions in which superoxide radicals (formed
by the reduction of oxygen molecules) play an impor-
tant role.
Three-layered colloidal particles are another devel-
opment in the field of surface-modified semiconductor
nanoparticles. These consist of a quantum-sized semi-
conductor particle as the core, covered by several layers
of another semiconductor material, onto which several
layers of the core material are then deposited, and act as
the outermost shell. These particles are called quantum
dots or wells (Weller et al. (1995). The first example
described in the literature was the system CdS–HgS–
CdS (Mews et al., 1994).
Another recent development in the application of
nanoparticles in photocatalysis has been the emergence
of organic–inorganic nanostructured composites. Inter-
actions between organic and inorganic molecules are
being used to generate a range of materials for cat-
alytic technologies. Published work by Braun et al.
(1996) describes the synthesis of stable semiconductor-
organic superlattices based on cadmium sulphide and
cadmium selenide. By incorporating organic molecules
in an inorganic lattice the authors anticipate that the
electronic properties of this type of materials can
be tailored. Therefore, these novel organic–inorganic
nanostructured composites may be suitable for pho-
tocatalytic applications. Tenne et al. (1996) have also
been working on the preparation of inorganic com-
pounds, namely WSe2 and PtS2 , with a crystal struc-
ture similar to graphite. These compounds can be
used to construct fullerene-like structures and nano-
tubes with potential applications in photocatalysis and
nanoelectronics.
450
Sensitization of TiO2
Despite titanium dioxide being the most promising
photocatalyst, it can only be activated by light of
wavelength 390 nm or lower. The UV region (below
390 nm) constitutes only ∼ 4% of the energy available
within the solar spectrum. Thus considerable research
is being carried out to extend this photocatalyst’s
response into the visible part of the solar spectrum.
The sensitization of TiO2 with a second component
to enhance activity and shift the wavelength of irradia-
tion into the visible region is a goal that has been eagerly
pursued. Again, several approaches have been taken.
The first involves the sensitization of TiO2 with organic
and organometallic dyes, these however are seen to be
are less likely to succeed in photocatalysis due to their
instability (Howe, 1998).
Another approach has been to utilize narrow-
bandgap semiconductors to photosensitize TiO2 . The
sensitizer has a high cross section for the absorption of
visible light and injects electrons into the lower con-
duction band of the wide-bandgap semiconductor. The
separated charge carriers can be used to initiate the
chemical reactions. This principle has been used to con-
struct photoactive layers, in which charge separation is
achieved with an efficiency of 80% (Henglein, 1997a).
Nanocrystalline, narrow-bandgap semiconductors
can be used as sensitizers. These semiconductors can
be tailored to suit specific purposes since changing their
size can shift their electronic bands (Q-size effects).
This concept is seen as more attractive alternative
for TiO2 sensitization since they are more stable than
organic dye (Howe, 1998).
Sensitizing TiO2 with Q-sized narrow-bandgap
semiconductors PbS and CdS was carried out by Vogel
et al. (Vogel et al., 1994). These systems however,
demonstrated a loss in efficiency, with photocorro-
sion of the narrow-bandgap semiconductors in aque-
ous media, under illumination with 460 nm light, also
being a problem. Howe suggested the possibility of
using such semiconductor sensitized nanocrystalline
TiO2 for gas-phase photocatalysis (Howe, 1998).
A different approach was taken by Bahnemann et al.
in 1993 in order to synthesize particles which utilize
parts of the visible solar spectrum when acting as pho-
tocatalysts. This approach involved the preparation of
a mixed Ti(IV)/Fe(III) oxide catalyst. Not only did this
photocatalyst have increased activity for the destruc-
tion of DCA (dichloroacetic acid), it also showed a
photoresponse to 450 nm light. The prepared particles
contained between 0.05 and 50 at% Fe(III) in their
matrix, and had particle diameters between 4 and 6 nm.
The photoresponse shifted to longer wavelengths with
an increasing content of ferric ions.
However, this novel photocatalyst also suffered from
the problem of a partial reductive dissolution upon illu-
mination. This cathodic corrosion competes with the
electron transfer to oxidants such as oxygen found in
the system. In order to alleviate the problem of pho-
todissolution, the authors suggested the introduction of
H2 O2 , as an electron acceptor, into the system. H2 O2
being a better electron acceptor than O2 can be used
to compete more efficiently with the photocatalyst’s
dissolution (Bahnemann et al., 1993).
Nanocrystalline films
Another area of research that links the nanotechnol-
ogy with heterogeneous photochemistry has been the
development of semiconductor nanocrystalline films.
Nanocrystalline semiconductor films constitute a net-
work, in which electronic conduction can take place.
The films are highly porous, and the pores between
the particles are filled with a conducting medium such
as electrolyte or semiconductor, forming junctions of
extremely large area contact (Henglein, 1997). The thin
films exhibit interesting photocatalytic and photoelec-
trochemical properties that are inherited from the native
colloids (Kamat, 1995). Chemical vapour deposition
or molecular beam epitaxy has been the preferred tech-
nique for depositing thin semiconductor films.
The nanosized particles from which the films are
made are in electronic contact allowing for electric
charge percolation through such films. This charge
transport is highly efficient, with the quantum yield
being practically unity (Hagfeldt et al., 1995). One
of the major advantages of nanocrystalline semicon-
ductors is their high porosity. This facilitates surface
modification with sensitizers, redox couples, and other
semiconductors. Using nanocrystalline semiconductor
films also allows the manipulation of the photocatalytic
process by electrochemical methods (Kamat, 1995).
Dye sensitization. Nanostructured films made up of
wide bandgap semiconductors, such as TiO2 , respond
only in the UV region. Sensitizing with dyes that absorb
strongly in the visible spectrum, has been one method
to extend the photoresponse of such films. In a porous
film consisting of nanometre-sized TiO2 particles, the
effective surface area can be enhanced 1000-fold, thus
making light absorption efficient even with only a dye
monolayer adsorbed on each particle (Hagfeldt et al.,

1995). Once photoexcited, the dye molecules inject
electrons into the semiconductor’s conduction band.
Recent developments in nanocrystalline electro-
chemical photovoltaic devices has meant that vast
research efforts have been invested into optimising the
properties of such films. O’Regan and Gratzel identi-
fied the improvement of light harvesting as the key to
improving the efficiency of the photoelectrochemical
cell. On a smooth surface, a monomolecular layer of
sensitizer absorbs less than 1% of incident monochro-
matic light (O’Regan et al., 1991).
O’Regan and Gratzel’s efforts led to the development
and commercialization of a device capable of harvest-
ing 46% of the incident solar energy flux. It was based
on a 10 µm thick, optically transparent semiconduc-
tor film consisting of nanocrystalline TiO2 particles,
coated with a monolayer of a Ru-based sensitizer dye.
The absorption onset was shifted to 750 nm, with the
light harvesting efficiency reading almost 100% in the
whole visible region below 550 nm. Efforts have con-
tinued to try and improve the quantum yield of current
photoelectrochemical devices. Recently, Salafsky et al.
(1998) found that in the presence of an electron donor
to the dye cation (I− /I3− redox couple), the injected
charge is prevented from directly recombining with the
cation and thus has a longer lifetime.
External bias/photoelectrochemical devices. Illumi-
nated semiconductor particles behave as short-
circuited electrodes, with the interfacial charge transfer
competing with the charge recombination process. The
high rate of recombination between the charge carriers
is a major problem in the photocatalytic degradation
of organics and is a limiting factor in controlling the
photocatalytic efficiency.
During the past few years, considerable effort has
been made in the preparation of nanoparticle films and
their application in photoelectrochemical devices. In an
electrochemically assisted photocatalytic process, the
thin nanocrystalline semiconductor film is coated on a
conducting glass surface, with the generated electrons
being driven via an external circuit to a counter elec-
trode by applying a positive bias. This leads to better
charge separation and the problem of charge recombi-
nation is easily overcome (Kamat, 1995).
In most of the photocatalytic reactions oxygen is
essential for scavenging electrons from the irradi-
ated semiconductor particle (Vinodgopal et al., 1996).
Thus, an advantage of an electrochemically assisted
451
photocatalytic process is that oxygen is no longer
required as an electron scavenger. This makes it
possible to carry out the photocatalytic reaction under
anaerobic conditions (unless O2 plays a role in the reac-
tion mechanism of organic degradation (Schwitzgebel
et al., 1995)). Another advantage is that the anodic and
cathodic processes are separate. Photoelectrochemical
devices can thus allow the isolation of the various reac-
tions occurring in photocatalytic systems and provide a
means to carry out selective oxidation and reduction in
two separate compartments (Kamat, 1995, Viodgopal
et al., 1996).
Several people have studied the preparation of pho-
toelectrochemically active thin films, using a number
of different semiconductor materials. Films have been
prepared from colloidal suspensions of ZnO (Spanhel
et al., 1991), TiO2 (O’Regan et al., 1991), WO3 (Bedja
et al., 1993; 1994a) and SnO2 (Bedja et al., 1994b). In
1997, Fu et al. studied the structure and electrochemi-
cally assisted photocatalysis of nanosize TiO2 /Pt/glass
thin films prepared by the sol–gel process. Their
results showed that a higher photocatalytic activity was
obtained when an anodic bias is applied, with the activ-
ity becoming stronger with increasing anodic bias. The
interlayer Pt and intensity of light source were also
shown to affect the photocatalytic activities of the films
(Fu et al., 1997).
The effectiveness of the electrochemically assisted
photocatalytic process have also been tested for the
degradation of using 4-chlorophenol and Acid Orange
7 in aqueous solutions by Viodgopal et al. (Viodgopal
et al., 1995; 1996). The semiconductor films used were
SnO2 , TiO2 and a SnO2 –TiO2 nanoclusters. The authors
found that combining photocatalysis and electrochem-
istry leads to improved photocatalytic degradation rates
(even in the absence of oxygen). The highest rates
were observed with the SnO2 /TiO2 coupled semicon-
ductor films, with a ten-fold enhancement in the degra-
dation rate being observed at an applied bias potential
of 0.83 V versus SCE. The role of the coupled semicon-
ductor was to further improve the charge separation.
The development of multicomponent nanocrys-
talline semiconductor films is recognised as being of
extreme importance to research in photoelectrochem-
istry (Kamat, 1995). These systems can serve two pur-
poses. The first purpose is to allow the extension of
the photoresponse of a wide-bandgap semiconductor
by coupling it with a narrow-bandgap semiconductor.
The second purpose is to inhibit (or slow down) the
charge-carrier recombination, with enhanced charge
452
separation upon the injection of electrons from the
conduction band of the narrow-bandgap semiconduc-
tor into the lower conduction band of the wide-bandgap
semiconductor (Bedja et al., 1995). Coupled semicon-
ductor systems in which increased photocurrent gener-
ation has been demonstrated include TiO2 –CdS (Vogel
et al., 1994), ZnO–CdS (Hotchandani et al., 1992),
TiO2 –CdSe (Liu et al., 1993) and TiO2 –SnO2 (Bedja
et al., 1995).
Hinogami et al. (1997) studied the modification of
semiconductor surfaces with ultrafine metal particles
for the efficient photoelectrochemical reduction of car-
bon dioxide. A p-type silicon was modified with small
metal (Cu, Au and Ag) particles. The holes generated
enter into the interior of the particle, while the pho-
togenerated electrons come out to the surface. These
electrons then transfer into the metal particles which
reduce CO2 with the aid of their catalytic activity. The
electrode has both high activity and very low surface
recombination rate (Hinogami et al., 1997).
Using nanoparticles to study the mechanisms of
photocatalytic reactions
Interest in the detailed mechanism of illuminated semi-
conductor reactions arises from their intensive use in
the photodegradation of organic pollutants (Rabani
et al., 1998). Mechanistic studies of photocatalysed
reactions are of paramount importance both for a fun-
damental understanding of the nature of heterogeneous
photocatalysis and for optimizing its efficiency (Lepore
et al., 1993).
The electronic states of molecules play an impor-
tant role in photochemistry. The population and life-
time of the charge carriers and the time scale of
the interfacial charge-transfer process determining
the overall efficiency of heterogeneous photocatalysis
(Colombo et al., 1996). Thus, for a clear understand-
ing of the redox processes across semiconductor–
electrolyte interfaces, it is highly desirable to obtain
detailed information on the dynamics of the photoin-
duced electron transfer by fast kinetic spectroscopy
(Kalyanasundaram, 1983). Time-resolved optical spec-
troscopy and quantum yield measurements are usually
the most useful sources of information in mechanistic
photochemistry.
Optical methods are difficult to employ when study-
ing heterogeneous photocatalytic slurries. Due to the
light scattering in these opaque systems, it is not easy
to determine accurately the irradiation light intensity
absorbed by the particles. This makes it difficult to
obtain accurate measurements of both the absorption
spectra and photochemical quantum yields (Lepore
et al., 1993). Another problem is the complexity of such
a small-scale photoelectrochemical system. This has
meant that details of the underlying reaction mecha-
nisms of photocatalysis have not been well understood
(Bahnemann et al., 1997). The use of nanoparticles
has lead the way in the approaches taken to provide
more definitive mechanistic information, particularly
for TiO2 photocatalysts.
Nanosize semiconductor particles have diameters
smaller than the wavelength of the incident light. Their
dispersions are optically transparent with the dimen-
sions of the particles being small enough to render
scattering of light negligibly small. Thus nanosize
semiconductor particles have the added advantage of
providing transparent solutions for detailed mechanis-
tic studies of photoredox processes by laser photolysis
techniques.
Due to the quantum effects, the luminescence of col-
loidal semiconductors is strongly influenced by parti-
cle size. Typically, a broad emission is observed which
blue shifts with decreasing radius of the particle. Lumi-
nescence analysis provides an important tool to study
the dynamics of charge-carrier recombination in such
colloidal semiconductors (Hagfeldt et al., 1995).
Thus, with nanosize semiconductors, it is possible to
directly monitor, by flash photolysis, the charge injec-
tion into or from the semiconductor to reagents present
in solution (Kalyanasundaram, 1983). This makes it
possible to obtain absorption spectra of the material
and, therefore, the kinetics of processes taking place
can be recorded, if they are reflected in a change of
the absorption (Bockelmann et al., 1996). This enables
elementary steps involved in the catalytic process to be
conveniently analysed (Hagfeldt, 1995).
Many mechanistic and spectroscopic studies have
used optically transparent solutions of colloidal TiO2 .
These investigations have led to a detailed understand-
ing of the nature and reactivity of charge carriers in
these colloidal particles (Lepore et al., 1993). Laser
flash photolysis technique has been used to quantify
the kinetics of various mechanistic steps (Howe, 1998)
and has allowed the identification of factors that govern
the dynamics of interfacial electron and hole transfer
reactions (Hagfeldt et al., 1995).
Early studies in 1985 used pico and nanosecond tran-
sient absorption measurements to monitor the fate of

photo-produced holes and electrons. Electron trapping
was reported to be faster than 30 ps, the time resolu-
tion of the laser system used. The trapping of holes
was estimated to occur within < 250 ns. Electron:hole
recombination was estimated to occur within 30 ns
(Rothenberger et al., 1985).
It is important to note that early flash photolysis stud-
ies suffered from the problem of a large number of
electron–hole pairs being generated in each TiO2 per
laser pulse (Bahnemann, 1997). In 1995, using nano-
sized TiO2 , Skinner et al. were able to employ experi-
mental conditions that ensured that on the average less
than one electron–hole pair was formed per semicon-
ductor cluster during each light pulse. The authors car-
ried out femto spectroscopic measurements, and under
the well-defined experimental conditions, this research
group found that electron-trapping time was approx-
imately 180 ± 10 fs. They also found that the elec-
tron:hole recombination occurred on a picosecond time
scale rather than nanosecond, with the mean lifetime
for the electron–hole pair was found to be 30 ps not
30 ns as reported earlier (Skinner et al., 1995).
Serpone et al. (1996) carried out a picosecond study
on colloidal solutions TiO2 . They reported a rapid trap-
ping of electrons and holes in less than 30 ps. The
second-order kinetics measured in their experiments
revealed two decay processes. A fast decay, which was
assigned to recombination of charge carriers in shal-
low traps. The longer decay occurred on a much longer
time scale, with the recombination occurring at times
greater than 20 ns. This decay was attributed to deeply
trapped charge-carrier recombination. Serpone et al.
proposed that it is the longer decay which determines
the photocatalytic activity.
Colombo et al. (1996) examined the charge-carrier
dynamics suspensions of Degussa P25 TiO2 , which
they probed with femtosecond time-resolved diffuse
reflectance spectroscopy. They also studied transient
events in dry P25 TiO2 powders. They compared the
electron trapping in both systems (wet and dry pow-
der) to electron trapping in quantum sized TiO2 . In all
three systems the electron trapping was very rapid and
occurred in less than 200 fs.
Colombo et al. also examined the interfacial hole-
transfer dynamics with P25/SCN− complexes being
probed as a function of thiocyanate ion concentra-
tion. The presence of thiocyanate adsorbed to the
surface of the P25 nanocrystalline particles dramati-
cally influences the recombination kinetics. Both an
increase in signal strength, which meant an increase
453
in the population of trapped charge carriers, and the
much slower decay in the transients indicated this. This
demonstrated the hole-scavenging ability of the SCN− .
It also demonstrated that the interfacial charge transfer,
of an electron from the SCN− to a hole on the photo-
excited TiO2 , effectively competes with electron–hole
recombination.
It is known that it is the number of holes avail-
able for the interfacial reaction, which ultimately deter-
mines the efficiency of a photocatalytic process. Thus,
this study presented a major finding which can have
significant implications on photocatalysis. The authors
showed that it was possible to adsorb species with
electron-scavenging ability such that the hole-transfer
reaction can successfully compete with the picosecond
electron–hole recombination process.
Nosaka et al. (1990) studied the electron transfer
from a laser-excited CdS colloid particle to surface-
adsorbed viologens (organic reducing agents). The
quantum yield of the photoinduced electron transfer
in CdS and In2 S3 semiconductor particles to surface-
adsorbed violgen molecules, was measured as a func-
tion of the density of adsorbed photons in the particles.
The authors found that at a lower photon density, the
quantum yields became constant, with the smaller par-
ticles having a lower quantum yield. The authors pre-
sented a kinetic model, which explained the decrease
of quantum yield with the decreasing diameter of the
particle. In their model, the ratio of the rate constant for
the electron–hole pair recombination (Kr) to the rate
constant for photoinduced electron transfer (Ke) was
found to be dependent on the size of the semiconductor
particle. For CdS particles the value of Kr/Ke increases
by a factor of about 20 with doubling of the radius. For
In2 S3 the dependence of Kr/Ke on the radius was found
to be very weak. Kr/Ke increases only by two times
with doubling of the radius. From their kinetic model
the authors proposed that when the electron-transfer
rate (Ke) does not increase much with decreasing
size, the value of the quantum yield decreases because
the electron–hole recombination rate (Kr) probably
increases largely.
As was previously mentioned, Lepore et al. (1993)
were the first to provide accurately determined quan-
tum yields of polycrystalline TiO2 (with an aver-
age radius of 62 nm). The quantum yields obtained
with these samples were similar to those of P25, but
higher than those obtained using the quantum-sized
(∼ 2.4 nm) TiO2 . A longer lifetime of the charge car-
riers in the polycrystalline samples and the P25 slur-
454
ries, compared to the quantum-sized TiO2 solutions,
was found to be the reason behind this. Martin et al.
(1995) studied the charge-carrier dynamics of Q-TiO2
and Degussa P25 using time-resolved microwave
conductivity. They found that the resultant interfa-
cial electron transfer was faster for P25 than for
Q-TiO2 .
Schwitzgebel et al. (1995) studied the role of oxygen
and the generated electrons in photocatalysed oxida-
tion of organics. The organics oxidized were n-octane,
3-octanol, 3-octanone, or n-octanoic acid, with the
oxidation carried out using buoyant nanocrystalline
n-TiO2 -coated glass microbubbles. The effect of dis-
solved Fe3+ ions on the reaction was also studied.
Their results showed that both the photogenerated
holes and electrons participate in the oxidation reac-
tion. They also found that molecular oxygen has two
roles. Firstly it accepts the electron and is reduced
to a superoxide radical (O2 •− or HO2 • ). Secondly it
combines with the organic radical, generated upon
the reaction between the organic and the hole or OH
radical reaction. This produces an organoperoxy rad-
ical (ROO• ). The superoxide radical, which is a rela-
tively ineffective oxidizing agent, combines with the
organoperoxy radicals to form an unstable tetraoxide
that decomposes to give CO2 . The effect of the dis-
solved Fe3+ ions was to reduce the CO2 yields in the
photocatalytic air oxidation of the four reactants. This
was due to the fact that they competed for the pho-
togenerated electrons and oxidized the superoxide to
O2 . In reactions that do not involve the superoxide
radical, for example the photocatalytic air oxidation
of n-octanal, the oxidation reaction was not inhibited
by Fe3+ .
Bockelmann et al. (1996) performed detailed pho-
tophysical and photochemical investigations of col-
loidal Ti/Fe mixed oxide suspensions using a flash
photolysis apparatus for time-resolved measurements.
In their efforts to understand the process of pho-
todissolution of this mixed semiconductor, they found
that during photodissolution the photogenerated elec-
trons are not mainly captured at Ti4+ centres but in
fact reduced Fe3+ centres within the microcrystals
forming Fe2+ .
More recently, in 1997, Bahnemann et al. car-
ried out time-resolved laser flash photolysis under
well-defined experimental conditions, which resemble
the steady-state irradiation conditions in photocataly-
sis. Bahnemann et al. used nanosized TiO2 particles,
of mean diameter 24 Å, to investigate the details of
the photocatalytic oxidation of the model compounds
DCA− and SCN− . The authors found that in the absence
of hole scavengers, the electrons were trapped instan-
taneously (i.e. within the duration of the laser flash).
The group suggested that at least two different types of
hole traps need to be considered. Deeply trapped holes,
which are long-lived and unreactive, and shallowly
trapped holes, which exhibit a very high oxidation
potential. The traps are interstitial atoms, impurities,
dislocations, and defects. (Weller et al. (1995) sug-
gested that traps in nanosized particles were found
mainly on the surface as a result of the large surface-
to-bulk ratio).
In the same study Bahnemann et al. also inves-
tigated the electron transfer kinetics to donors and
acceptors. They found that the adsorption of the
model compounds DCA and SCN on the TiO2 sur-
face prior to the bandgap excitation, was a prerequi-
site for an efficient hole scavenging (Bahnemann et al.,
1997).
Smith et al. (1997) have also studied the ultra-fast
dynamics of photoinduced electrons in several metal
and semiconductor colloidal nanoparticle systems
using femtosecond laser spectroscopy. For aqueous
gold and silver colloids, they found that spatial size
confinement caused slower electronic relaxation due
to reduction of non-equilibrium electron transport and
weaker electron–phonon coupling. The effect of sur-
factant on the electron dynamics in CdS colloids was
also examined and found to be significant. The authors
put forward that this finding may provide evidence to
suggest that the electrons were dominantly trapped at
the liquid–solid interface.
Rabani et al. (1998) studied nanosecond kinetics of
dry TiO2 using pulsed laser photolysis. They used lay-
ers of closely packed 5 nm titanium dioxide nanocrys-
tallites. Pulsed laser photolysis was carried out in the
presence and absence of added reactants. Their results
showed that TiO2 layers immersed in liquids (acidic
or alkaline water, CCl4 , CCl4 /CBr4 mixture, cyclohex-
ane) have the same absorption versus time profiles as
the dry layers.
Murakata et al. (1998) studied the effect of the sol-
vent in which the particles are dispersed on their photo-
catalytic properties using ESR spectra measurements.
The dependence of activity upon kind of solvent was
found to be due to the different concentrations of Ti3+
formed with the different solvents (these are respon-
sible for the reductive catalytic activity of the TiO2
particles).

Conclusions
Considering the topics covered in this review, it is evi-
dent that the emergence of nanotechnology is bound
to have significant implications in the research field of
photocatalysis. First, the nanostructure their remark-
able properties will prove invaluable in the develop-
ment of novel photocatalysts and the enhancement of
existing ones. In areas such as doping, coupling, cap-
ping and sensitizing, benefits have already been seen
with enhanced photocatalytic and optical properties.
Secondly, the use of nanocrystalline thin films in
electrochemically assisted photocatalytic processes is
another area where nanoparticles will be very useful.
Finally, the use of nanoparticles for providing mech-
anistic information will continue to make significant
contributions in enhancing the understanding of photo-
initiated processes in semiconductor materials.
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