Photochemical Applications of Solar Energy - Photocatalysis and Photodecomposition of Water

Photochemical applications of solar energy:
photocatalysis and photodecomposition of

water
K. Kalyanasundaram
Downloaded by University of Lancaster on 17/01/2015 22:25:39.
Published on 31 October 2013 on http://pubs.rsc.org | doi:10.1039/9781849737722-00182
DOI: 10.1039/9781849737722-00182
Two main aspects of solar energy applications are reviewed, viz. photocatalysis
and the photodecomposition of water into hydrogen and oxygen. In most of the
cases solid phase photocatalysts are used and this topic is often referred to as
heterogeneous photocatalysis.
Introduction and scope
This review covers the research publications that appeared during the years
2011 and 2012 in two major research areas: photocatalysis and the photodecomposition of water to hydrogen and oxygen using semiconducting
materials such as TiO2 and related oxides. Majority of the catalysts used are
solid phase catalysts dispersed as particulates or as electrodes and hence
these studies are referred to as heterogeneous photocatalysis. Intense
research activity is underway in both the areas discussed here as evidenced
by over 500 publications appearing during the two-year review period.
Several review publications have appeared capturing the highlights on
photocatalysis120 and photochemical water splitting.2129 On the photocatalysis front, several new photocatalysts have been identied, with which
many of the photoreactions catalyzed by titania (TiO2) in the UV can now
be sensitized with visible light with high eciency.
The eld of articial photosynthesis has beneted with the crystal
structure reports at 1.9 A resolution of the photosynthetic water oxidation
complex of Photosystem II.30 The oxygen evolving complex (OEC) involved
in the water splitting consists of 4 Mn atoms and 1 Ca atom and is located
near the lumenal surface of photosystem II. At 1.9 A resolution, it is
possible to place the coordinated water molecules and this has facilitated
design of suitable model complexes. There have been several reports
identifying a growing number of homogeneous and heterogeneous water
oxidation catalysts whose mode of operation resemble more closer to the
currently accepted models on how water oxidation to molecular oxygen
takes places in natural photosynthesis.
Studies of photodecomposition of water using semiconductor electrodes
and particle photocatalysts now use water oxidation or reduction as
additional co-catalysts. The rates and the quantum eciency of water
oxidation and reduction processes are enhanced in the presence of these
redox catalysts. Few photocatalytic systems have been identied, which for
the rst time eect complete decomposition of water to H2 and O2 in a
Laboratory for Photonics and Interfaces, Institute of Chemical Sciences and Engineering, Swiss
Federal Inst. of Technology (EPFL), Station 6, EPF-Lausanne, CH-1015, Lausanne,
Switzerland. E-mail: k.kalyanasundaram@ep.ch
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The Royal Society of Chemistry 2013
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sustained manner with reasonable eciency. These studies are reviewed in

the second part of this chapter.

Photocatalysis
Titania still remains as the most extensively studied photocatalyst material in

various morphological forms and photocatalysis studies using TiO2 are rst
reviewed. This is followed by studies on other oxide and non-oxide semiconductors including many that are active under visible light irradiation.
2.1 Titania (TiO2 ) based photocatalysis
Photocatalysis refers to the process of using solar energy to eect chemical
conversion of organic and inorganic molecules and in the removal of toxic
pollutants and wastes present in water and in air. Photoinduced generation
of strong oxidants and/or reductants is achieved via light absorption by an
organic molecule, inorganic metal complex or a semiconducting material. In
a seminal paper published in 1972 Fujishima and Honda31 reported on
possible photodecomposition of water through bandgap excitation of oxide
semiconductors such as TiO2.
Fig. 1 shows conceptually various processes that take place following
optical excitation with photons of energy EZEbg. Photo excitation of
semiconducting oxides such as TiO2 leads to generation of holes in the
valence band and electrons in the conduction band. While a good part of the
photogenerated charge carriers recombine, they also diuse apart to reach
the surface rapidly where they can trapped or transformed to other reactive
intermediates (equations 18):
TiO2 ! h vb e cb
h vb ! h tr ; e cb ! e-tr
Fig. 1 Schematic representation of various processes that take place following optical excitation of a wide bandgap oxide semiconductor with photons of energy EZEbg. (Adapted with
permission from: T. Ochiai and A. Fujishima, J. Photochem. Photobiol., 2012, 13, 247.)
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H2 O ! OH H
h tr RH ! R H
h tr O2 ! 1 O2
e tr H2 O2 ! OH OH
e tr O2 ! O2
e tr R H ! RH

tr
In a sequence of steps, the electrons and holes can oxidize and reduce
surface-adsorbed molecules through interfacial charge transfer. Hydroxyl
radicals have been identied as one of the most active and nonselective
initiators of photocatalytic oxidation of organic substrates, particularly
in relation to weakly adsorbing species such as alcohols and aromatics.
Secondary radical formation from the oxidation of organic substrates often
increases the complexity in working out mechanistic details. Thermodynamic limits of photooxidation or photoreduction are set by the relative
disposition of the energy levels of valence and conduction band of the
semiconductor. Most active photocatalysts used are TiO2, ZnO, WO3 and
recently other oxides such as BiVO4.
TiO2 as a white pigment has been used in the fabrics and paint industry
for a long time. Earlier studies have shown that, in addition to water oxidation, other industrially and environmentally useful photooxidations can
be carried out using this photocatalyst. A few publications have appeared
tracing the history of photocatalysis as practiced today.32 Keidel in his
paper33 invoked the photosensitivity of TiO2 as a possible cause of the
degradation of paints and degradation of fabrics as early as 1929. However
there are reports that the term photocatalysis was rst used as early as
1910 in a Russian textbook on photochemistry by J. Plotnikov34 and a few
years later by Landau in 1913.35 Eibner reported results of his studies on the
degradation of inorganic and organic paints via photolysis in the presence of
ZnO as a catalyst.36 It was reported that UV absorption produces active
oxygen species on the TiO2 surface, causing the photobleaching of dyes. In
addition to the early work of Landau and Plotnikov, Terenin and coworkers studied in 1930s several photochemical reactions in solution and in
heterogeneous media There was a report on the photobleaching of dyes by
TiO2 both in vacuum and in oxygen in 1939.37 Though the term photocataysis was known, the process was referred to as photosensitization.
Markham discussed some of these early studies on the photocatalytic
properties of oxides such as TiO2 , ZnO and Sb2O3 in a review paper.37
Studies on photocatalysis using titania and related oxide semiconductors
can be broadly grouped in three main categories: i) preparation of alternate
versions of TiO2 photocatalysts in dierent electronic content, morphological forms with additional facet control; ii) ecacy of standard titania
based photocatalysis for photodegradation of various industrial and
general toxic wastes and iii) development of novel/new applications of
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semiconductor-based photocatalysis. TiO2 occurs in three stable polymorphic forms: anatase (tetragonal), rutile (tetragonal) and brookite
(orthorhombic). Anatase (band gap energy Ebg=3.2 eV) is considered as the
most photoactive forms, (in particular certain crystallogrpahic planes) than
the rutile form (Ebg=3.0 eV). The most widely used form of TiO2 is as
aqueous suspensions of P-25 particulates (prepared originally by Degussa
through aerosol process, now sold under the name Aeroxide P25). P25 is a
mixture composed of approximatively 75% anatase and 25% rutile. P-25
has fairly high surface area (BET), 54 m2/g with an average particle diameter of ca. 20 nm. Due to its smaller bandgap, rutile can be photoactivated
using near UV photons of the solar radiation (ca 4% of solar radiation).
Nearly all photochemical studies report some sort of comparison of the
catalyst eciency. Quantitative comparison of catalyst eciency amongst
various photocatalysts is dicult and complex for several reasons. The
dierences in morphology, surface structure and surface chemistry (which
depends often on the pre-treatment history) and preferential adsorption of
substrates on one form of photocatalyst over the other are some of the
factors that are dicult to quantify. Since P25 is a readily available commercial powder, it has been used as a standard photocatalyst. Synergistic
eect in catalysis refers to the situation where the photocatalytic activity of
a mixture exceeds the sum of activities of the components. It is generally
accepted that this P25 exhibits better catalytic eciency and there have been
a lot of speculations on this synergistic enhanced.
2.1.1 Titania photocatalyst in dierent morphologies - nanostructuring.
Advances in nanoscience and nanotechnology permit today synthesis of
photocataysts tailored to any specication (size and architecture) dened at
nanometric scale. Eciency of catalytic reactions can then be optimized.
Synthesis of catalyst materials can be approached in two dierent ways:
start with macro-sized larger materials and process them (cleaving and
polishing) to get particles of lower dimensions (top-to-bottom approach).
Alternatively, one can start with simple atoms and molecules and use various assembling procedures to make larger nanoparticles (bottom-up
approach). Nanostructured materials that are zero-, one- and two-dimensional have been prepared and found to have their own unique properties.
Spherical nanoparticles, nanocrystals and quantum dots are examples of
zero-D materials. Nanorods/nanowires/nanobres and nanotubes are 1-D
materials. Nanosheets and nanoribbons have 2-D morphology. Sol-gel and
hydrothermal followed by high temperature sintering (calcination) are most
common methods.
Hierarchical structures are systems of relatively large dimensions composed of smaller building blocks connected together in a repetitive, often
highly periodic, manner. 1D nanostructure can be used as template to grow
one- or two-sided comb-like structures or even brush-like hierarchical
architectures. Hierarchical systems can be fabricated in principle by
combing 0D, 1D, and/or 2D nanoparticles to form a wide range of
architectures. Electrochemical anodization and electrospinning are also
being used extensively to prepare organized nanostructures for photocatalysis applications.3841
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Photocatalysis studies using particulates (slurry systems) is the simplest and

common approach. Studies using larger electrodes in photoelectrochemical
cells have added advantage that oxidation and reduction processes can be
spatially separated and quantitative studies on factors that aect the performance (role of added co-catalyst layers for example) are feasible. Recently
there have been a number of studies of thin lm electrodes fabricated using
nanoparticles and they try to integrate the advantages of nanoparticles in
increasing the collection eciency of photogenerated charge carriers.
Two key factors that control the catalytic performance of any photocatalyst are the intrinsic electronic and surface properties. For particulate
systems and mesoporous lms, the particle size, surface area, porosity/pore
volume, pore size, crystallinity and types of facets exposed at the surface are
some of the key parameters that are to be controlled. Nanostructuring of
the photocatalyst in dierent morphologies such as nanorods, bers, tubes,
sheets and interconnected architectures is one viable approach. In the last
decade there has been a phenomenal growth in the experimental method
for the preparation and characterization of nanostructures in zero, one,
two and three dimensions. Catalysts in the form of spheres are of zerodimension oering very high surface area. One dimensional tubes and bers
oer short distances for photogenerated charge carriers to escape and reach
the surface rapidly. Two dimensional sheets and lms provide additional
control on substrate distribution/adsorption. One and two-dimensional
nanostructures can be used as templates to grow larger hierarchical 3-D
structures which allow the architecture control even further.
2.1.1.1 Photocatalysis using P25 and sol-gel derived Titania nanoparticles.
Controlled hydrolysis of suitable precursors and solvent composition is a
method well known as sol-gel process for the preparation of nely
divided monodispersed form of colloidal metals and metal oxides. A
number of studies have used this method to prepare photocatalysts.4245
TiO2 sols can be prepared via hydrolysis and polycondensation reactions of
Ti-alkoxides Ti(OR)n in aqueous solutions. The solvent from the as
prepared colloidal solutions can be removed to prepare dry powders. Alternatively the sol solution, after suitable concentration can be coated onto
conductive glass and other substrates to form thin lms. Doctor blading and
screen printing are the common methods for planar/at surfaces.
For conformal lm deposition on non-planar structures (steps, stacks or
trenches), spray coating is preferable. Sol-gel route is a powerful technique to
prepare thin lms or large homogeneous (monodisperse) concentration and
stoichiometric control. The method also permits facile co-doping of other
materials, non-metals such as boron or nitrogen in particular.
One other fundamental problem to face in the quantitative analysis of
photocatalysis studies is the manner in which various modications of
the photocatalyst are performed. Other materials are introduced in/onto the
pristine catalyst using dierent procedures. Metal ions and anions can be
readily adsorbed on to the photocatalyst by stirring the TiO2 particles in an
aqueous solution containing these salts. When the additives are introduced
during the sol-gel hydrolysis process itself, the additives can form an inner
or outer shell over that of the pristine titania particles. The term doping is
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often used in a loose manner, though usage of the terms such as core-shell
systems may be more appropriate. Akpan and Hameed44 have reviewed
recent studies of sol-gel method for doping TiO2 photocatalysts.
In principle, doping refers to the introduction of foreign elements in the
host matrix of the parent/pristine semiconductor, at suciently low concentration (o1%) so as not to disturb the crystallographic phase. For
titania, there is the creation of additional conduction electrons by the
addition of heterovalent cations having a valency higher than that of Ti4
(V5, Nb5, Ta5, Mo6, W5, etc) (n-type doping) or the creation of holes
by heterovalent cations having a valency smaller than 4 (Al3, Ga3, Cr3)
(p-type doping). Doping is resorted to for two main reasons: to improve the
separation of photogenerated charge carriers and to improve the visible
light (solar radiation) response of the photocatalyst. TiO2 by itself is a wide
bandgap semiconductor and harvest hardly 3% of the solar radiation
reaching the earths surface. There have been several cases of anion- and
cation- doping of titania resulting in materials that show enhanced light
absorption in the visible light region.
The spectroscopic origin of the new absorption in the visible region has
not been unambiguously established in many cases, due to lack of any
photocatalytic activity for photoexcitation in the visible light region. In
some case studies of photodegradation of organic dyes, dye oxidation
proceeds only for a limited period of time. On the contrary even deposition
of noble metal ions and inorganic anions (such as phosphate or uoride) on
the surface of the photocatalyst has been found to aect charge recombination by rapid trapping of one of the charge carriers and thereby enhance
the photocatalytic activity.
The TiO2 and the P-TiO2 transparent lms that strongly adhere to the
surface of fused-silica substrate were prepared by the sol-gel method and
spin-coating process. The eects of calcination temperature and phosphorus
dopants on the properties of the photocatalyst have been studied. In the
pristine TiO2 case, anatase-to-rutile phase transformation was observed
above 900 1C with pure rutile form obtained at 1000 1C. But after introducing
phosphorus atoms into the Ti-O framework, the anatase-TiO2 can withstand
temperature up to 900 1C, without the formation of rutile-TiO2. As expected,
the average size of the titania crystallites increased with calcination
temperature. After exposing to 365-nm UV light for 12 h, the P-TiO2 lms
calcined between 600 1C and 900 1C can photocatalytically decompose at a
higher rate.44b Thin lms of TiO2 have been prepared42 on borosilicate glass
via a sol-gel dip coating method, with and without polyethylene glycol. The
photoactivity of textile dyes such as congo red has been studied.
Malengreaux et al.43 prepared TiO2 thin lms by a dip-coating process
using a non-aqueous sol-gel method. This study investigated the inuence of
the operating variables such as nature of the substrate, sol concentration,
withdrawing speed of the dip-coater and number of layers on the physicochemical properties of the lms. Photocatalytic activity of the lms was
evaluated by following the degradation of methylene blue under articial
UV light at 25 1C. Plantard et al.45 have compared the photocatalytic
properties of sol-gel method derived TiO2 lms with that of a commercial
P-25 powders.
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2.1.1.2 Spherical nanoparticles of titania, hollow spheres. Historically

nanosized particulates have been used in photocatalysis for many decades.
Commercially available Degussa P25 particle is one common catalyst
sample used worldwide. In addition to aerosol-derived anatase-rutile mixture P25, sol-gel hydrolysis route has been used to prepare monodisperse
particles of dierent sizes. Sol-gel derived particles and mesoporous lms
are to be annealed at higher temperature to improve the crystallinity of the
material (though such treatments reduce the surface area available).
Crystallinity is important for ecient generation of charge carriers.
An important extension of the spherical particles is hollow spheres,
prepared via a templating procedure.4654 In addition to providing higher
surface area, hollow structures permit multiple refractions and reections of
light, assisting the light harvesting process. Hollow spheres are prepared by
sol-gel hydrolysis in the presence of well dened polystyrene beads and the
template removed subsequently through calcination. There have been a
number of reports on the synthesis of hollow spheres of titania and assays
on their performance as photocatalysts. Flower-like anatase TiO2
hierarchical spheres assembled from nanosheets as substrates in a hydrothermal growth process in the presence of glycine. These ower-like spheres
are about 2 um in diameter with sheet thickness about 20 nm.
Jiao et al.46 have reported the use of phosphate as a morphology
controlling agent to prepare hollow anatase TiO2 single crystals and meso
crystals. Hollow and mesocrystals show enhanced catalytic activity for
water and CO2 reduction. Hollow mesoporous titania microsphere (HTS)
was fabricated49 in a sol-gel process by alternatively coating of titania
precursor Titanium tetrabutoxide (TBOT) and polydimethyl-diallylammonium chloride (PDDA) polyelectrolyte onto cationic polystyrene sphere
(PS) template, followed by calcination. The resultant uniform mesoporous
HTS (diameter 1.22 mm) features a low shell thickness/diameter ratio
(B2%) and a high specic surface area (B77.5 m2/g), and thus leads to a
high photocatalysis. The porous TiO2 hollow spheres were obtained by
using TiOSO4 as a titanium source and carbon nanospheres as a sacricial
template. Their particle size, diameter and morphology can be readily
controlled by varying growth parameters, including reaction temperature,
time and reagent concentration.51
Leshuk et al.52 have reported on the synthesis of robust, monodisperse,
mesoporous titanium dioxide (TiO2 ) submicrometer hollow spheres through
a single step hydrothermal silica etching reaction under mild conditions. The
resulting processing conditions yielded TiO2 hollow spheres with a surface
area of B300 m2/g and anatase phase crystallization, which exhibit enhanced
photodegradation of methylene blue. A template-free solvolthermal route for
the preparation of anatase TiO2 hollow spheres using TiCl4 and a mixture of
acetone-alcohol mixtures has also been reported.50 Control of the hollow
spheres size was achieved by adjusting the ratio of alcohols to acetone. The
as-prepared TiO2 hollow nanostructures exhibited good photocatalytic
activity for the degradation of phenol compared to Degussa P25.
2.1.1.3 Titania as thin lms. Thin lms of photocatalysts can be deposited from nanoparticles or deposited by other chemical methods.5559
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Procedures have been developed using Atomic Layer Deposition method

(ALD) for the preparation of highly photoactive organic-inorganic hybrid
titanicone lms using TiCl4 and ethylene glycol.56 Lyandres et al.58 have
used substrate RF bias and reactive gas partial pressure to control preferred
orientation and photoreactivity of TiO2 lms by reactive direct current
(DC) magnetron sputtering and studied the eciency of the lms for the
photooxidation of acetaldehyde. They observe an optimum RF bias of
50 V at which the lms exhibit biaxial texture with the c-axis parallel to
the surface with maximum crystallinity and degree of orientation, corresponding to a maximum in the reactivity as well.
2.1.1.4 Facet control of the photocatalysts. In light activated semiconductor oxides, the electrons and holes are intimately linked to the surface species. Dierent surface sites are exposed depending on the exposed
crystal facet in solution. Some of the facets can be strongly oxidizing while
some others can exhibit reducing tendency. Association of facet control
with catalytic selectivity has been studied extensively in conventional
catalysis and the methods have since been exported to photocatalysis.
Photocatalysts in the form of 3D structures (cubes, pyramids, spinel and
other anisotropic structures) have several unique crystal facets exposed.
There have been a number of studies with targeted synthesis of titania
photocatalysts with one or more facets.6065
Ohno et al.60 demonstrated the preferential reductive and oxidative facets
on TiO2 crystals using the photocatalytic reduction of H2PtCl6 and oxidation of Pb(NO3)2 probes, respectively. They identied rutile {110} and
anatase {011} as the reductive sites, whereas rutile {011} and anatase {001}
acted as the oxidative sites. The reductive anatase {011} was further conrmed visually by single particle uorescence spectroscopy. Whereas the
photocatalytic activity of faceted catalysts can (and should) be substratespecic in nature, it is thought that a balance between redox reactions, for
example, facets targeting oxidation of organic compounds and those targeting reduction of molecular oxygen, needs to be achieved for optimal
photocatalytic activity.
The inherent mechanisms of facet nucleation and morphology evolution
of anatase in the presence of uoride ions has been studied recently.63
Simply tuning the Ti/F ratio in the synthetic mixture leads to single anatase
crystal exposed with dierent facets like {001}, {010}, or {110}. And complex sphere structure exposed with {001} facets can be formed by secondary
nucleation and growth. Prolonging the hydrothermal treatment time causes
selective etching on {001} facets, whereas deuorination via thermal calcination produces many pores on the surface. The photodegradation of
positively and negatively charged, and zwitterionic dyes indicates that the
type of reactant, adsorption mode and surface area play signicant roles in
photocatalysis. In a related study, Wang et al.64 have successfully prepared
anatase TiO2 hollow microspheres with (001) facets in a one-step process in
the presence of H2O2 and HF solution. The product exhibited enhanced
performance in the photodegradation of methylene blue. A mechanism for
formation of the TiO2 hollow spheres with exposed {001} facets by
dissolution-recrystallization and Ostwald ripening is proposed.
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Hollow anatase TiO2 single crystals and mesocrystals with dominant

{101} facets have been prepared65 by a new route with PO43/F as
morphology controlling agent and they have been used to study the extent
of bulk recombination of charge carriers in faceted photocatalysts. It was
found that with respect to solid crystals, being hollow crystals and
mesocrystals can substantially improve photocatalytic activity (O2/H2
evolution from water splitting, CH4 generation from photoreduction of
CO2) as a result of the synergistic eects of shortened bulk diusion length
of carriers for the decreased bulk recombination and increased surface area.
2.1.1.5 Nanotubes and nanober form of titania photocatalysts. Nanotubes and nanobers represent the two-dimensional morphological forms.
They are readily prepared principally via electrochemical anodic oxidation,
sol-gel template methods and hydrothermal methods. A number of reviews
have appeared on the synthesis and catalytic properties of titania nanotube
arrays.6673 Anodic oxidation is a versatile method permitting the preparation of either compact or porous nanotubes, depending on the nature of
the electrolyte medium. Electrochemical oxidation route permits synthesis
of nanotubes of tunable length, The formation of nanotubes takes place via
electric eld assisted dissolution of Ti metal ions, electric eld assisted
oxidation of Ti metal to form TiO2 and dissolution of Ti and TiO2 due to
etching by uoride ions. The relative rates of these control the length and
the aspect ratio of the nanotubes. The aspect ratio can also be controlled
with change in the composition of the electrolytes present and the solvent
(DMSO, ethylene glycol, N-methylformamide, etc.)
Ti-containing precursor reagents undergo sol-gel hydrolysis. The TiO2
formed is allowed to polymerize or deposit onto the template. Subsequent
removal of the template material and calcination yields crystalline TiNT.
The literature reports a wide variety of templates. Advantages of this
approach include tight control over the size and morphology of the TiNT
based on the geometry of well-understood template materials. Hydrothermal process employs high temperature and pressure under alkaline
conditions to generate single layer nanosheets of titania which self-assemble
(roll) into tubes due to the high surface energy of sheets.
Fang et al.74 prepared highly ordered titanium oxide (TiO2 ) nanotubes by
electrolytic anodization of titanium electrodes. Morphological evolution and
phase transformations of TiO2 nanotubes on a Ti substrate and that of freestanding TiO2 membranes during the calcinations process were studied. Sun
et al.75 prepared TNT via hydrothermal route and used them to construct a
novel photocatalytic membrane reactor for the photodegradation of brilliant
blue dye. The activity was 45 times higher in the membrane reactor for all
TNT samples tested. Hydrogen treatment of titania particles under high
pressure (200 barH2) at 200 1C for 5 days in a stainless steel container leads to
the formation of a Black hydrogenated form of titania. These black particles
show enhanced visible light response, possibly due to the introduction of
disorders in the surface layers. Danon et al.76 prepared black TiO2 nanotubes
and examined their activity towards acetaldehyde oxidation under visible light.
2.1.1.6 Photonic crystals - improving the light harvesting capacity of
photocatalysts. Photonic crystals are a class of opto-electronic material
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designed to conne, control and manipulate photons so as to increase the

light harvesting properties. They are three-dimensional periodic dielectric
composites with lattice parameters on the order of the wavelength of light.
There are three basic requirements for the design of photonic crystals:
lattice parameters in the range of several tenths of mm to several mm
refractive index ratio between the air and the material should be high while
the optical absorption is low and ability to form well-ordered lattice. titania
with a high refractive index (2.6 at 500 nm for anatase) and a wide bandgap
of 3 eV is well suited as a substrate. Since the eciency of any photocatalysts
depends on the extent of light absorption, there have been several attempts
to improve the light absorption properties of titania-based catalysts. Being a
wide bandgap material (with a bandgap in the range of 3.03.2 eV), TiO2
absorbs only 3% of the solar radiation. Use of photonic crystals and surface
plasmonic eects using noble metal deposits are some of the methods
examined.
Procedures have been developed for the preparation of photonic crystals
of titania using polystyrene latex beads as templates during sol-gel hydrolysis of titanium alkoxides followed by calcinations to remove the carbon
template. There have been few studies of photonic crystals in photocatalysis
and dye-sensitized solar cells.7784 Wu et al.79 for example used colloidal
templating to prepare three-dimensionally ordered macroporous titania
with a range of pore diameters. Calcination at dierent temperatures to
remove the templates resulted in dierent crystalline phases. The structural
and photonic properties were characterized and their eects on photocatalytic activity are presented as well. A strong eect of the pore diameter
on the photocatalytic activity was observed and correlated with the photon
energy involved in the photodegradation process of organics.
2.1.2 Bulk doped titania catalysts. Dopants are external components
added to a host lattice and they can be present as interstitially dissolved
foreign atoms or by substitutional dissolution. Dierence in sizes of the
foreign atom with respect to the native atom can introduce strain in the
lattice. Aliovalent doping refers to the situation where the dopant ions have
dierent valency as compared to those in the host lattice. In these case, their
eective charge will aect the electroneutrality condition and thereby aect
the defect equilibria. Nonstoichiometric oxides with excess metal in the
form of predominating interstitial metal ions exhibit the same qualitative
eects of aliovalent foreign cations.
2.1.2.1 Reduced titania (blue) via hydrogenation or F, Nb doping.
Heating of titania samples in hydrogen atmosphere at elevated temperature
leads to the formation of reduced form of titania which is black in
color.85 Excess of metal compared to oxygen stoichiometrically results in
the formation of formally Ti3 ions. But this can be pictured either as an
O-vacancy as in TiO2x or as interstitial Ti as in Ti1 xO2. F and Nb doping
of stoichiometric TiO2 also leads to lattice Ti3 ions in a pseudo-octahedral
environment. Experimental evidence for the formation of reduced titania
comes from various data: absorption bands in the visible light region
responsible for the dark color; occurrence of new state in the bandgap at
about 0.8 eV below the CB of TiO2 attributed to reduced Ti3 ions; shift in
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the core level binding energies of reduced form of Ti-atoms in the XPS and
iv) the presence of more than one EPR signal associated with dierent types
of paramagnetic Ti3 ions in the lattice.
2.1.2.2 Metal ions doping of titania. There have been several reports on
metal ion-doped titania photocatalysts with enhanced visible light absorption properties.86103 In many cases catalytic activity upon irradiation in the
visible light absorption bands is poor or non-catalytic (turnover with respect
to the catalyst o1). Depending on the redox state and the energy level of the
dopants, they may function as electron- or hole-acceptors. The inserted
energy levels provide photons of sub-bandgap energy to create charge
carriers through additional channels (e.g., dopant d-band to CB or VB to
the dopant d-band). Application of high energy routes such as high energy
RF and magnetron sputtering can introduce novel tetravalent dopants
(Fe4, Cr4, V4) that match the valency of Ti4 in TiO2 . Co-doping with a
conjugate metal ion such as Rh3 or Sb5 can preserve the charge equality
of the doped photocatalysts, resulting in improved photocatalytic activity.
Doping in general can create structural and aliovalency defects that are
dicult to circumvent and they can become potential sources for charge
recombination. In such cases, introduction of dopants can lead to a decrease
in the photocatalytic eciency.
Herrmann86 has elaborated on why the Cr(III) doping of TiO2 is in
general catastrophic for photocatalysis. Although Cr-doped (0.85 at%)
TiO2 absorbs in the visible region, it only becomes a photoconductor
through band-gap illumination and the doping causes a considerable
decrease in photoconductivity by three orders of magnitude. Correspondingly, its photocatalytic activity is diminished, as can be noted in ve
dierent reactions representative of various media in which titania is active.
There have been few reports of enhanced photocatalytic activity of titania
in the presence of Cr(VI) ions as surface adsorbed species. Cr(VI) ions can
desorb and get reduced to Cr(III). Since uoride ions are known to
enhance surface adsorption, immobilization has been explored using urochromate(VI) K[CrO3F] instead of K2Cr2O7.91 Wang and coworkers87
have compared the eect of chromium on photo-oxidation of propan-2-ol,
for which hydroxyl radicals are the catalytically active intermediates, and
stearic acid oxidation which proceeds mainly via direct hole transfer. The
Cr/TiO2 samples were prepared by co-precipitation from aqueous TiCl4
solutions. The photo-oxidation of liquid propan-2-ol oxidation to acetone
was followed by gas chromatography. The oxidation of stearic acid to
carbon dioxide on irradiation of a pressed disc of stearic acid/TiO2 was
followed by using FTIR spectrometry of the product CO2.
Modication of the pristine TiO2 photocatalyst with metal ions, particularly d metal ions such as Fe(III), Cr(III), Ru(IV), Mo(VI) results in the
insertion of impurity energy levels between the parent valence and conduction bands. Rauf et al.101 have reviewed studies of photodegradation of
azo dyes in the presence of TiO2 doped with selective transition metal ions
(Cr3, Fe3 and Cu2). At chromium concentrations below 1% (typical for
ion doping without altering the crystal lattice), both the lifetime and photocatalytical activity were reported to decrease drastically to a nearly
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constant low level. At much higher concentrations employed (1015%),

Cr-ions are possibly present as surface adsorbed ions. Surprisingly
Rhodamine B underwent 25% more degradation in the presence of such a
high concentration of Cr(III) ions.
Single molecule uorescence microscopy has been used to study photodegradation of uorescent dye resourun on Sb-doped TiO2 nanorods.103
Two potential oxidants (OHd, and O2d radicals) can oxidize the dye
causing a decrease in the uorescence intensity. Using two distinct
quenchers (Superoxide dismutase for OHd and DMSO for O2d radicals) to
remove selectively one of the two oxidants, authors can follow the specic
sites where each of the two oxidants operates. Enhanced photodegradation
of organic dyes in the presence of Cu(II) ions arise from scavenging of the
electrons to form Cu . In the case of low levels of Fe3, Fe3 traps photo
generated holes and forms Fe4 which reacts with the surface adsorbed
hydroxyl ions to produce hydroxyl radicals and O2 on the surface lattice of
doped TiO2.
Visible light induced photocatalytic activity of synthesized materials was
studied for 4-chlorophenol (4-CP) oxidation.97 A considerable photocatalytic activity was observed in the case of F-Cr(VI)@TiO2 and TiO2
@MCrO4 type materials, M= Mn2, Ba2, CO2, Cr3). Besenbacher and
coworkers102 prepared high-quality polycrystalline Fe-doped TiO2 (FeTiO2) porous lms via one-step electrochemical oxidation. Properties such
as the impurity concentration and the microstructure inuence the performance of the material for photovoltaic and photocatalysis applications and
they have been controlled by adjusting the electrolyte composition.
The eciency of ethidium bromide photodegradation has been studied
using a series of ve Fe-doped TiO2.95 The photocatalysts were prepared
using a combined sol-gel/reverse microemulsion method and the iron
content varied from 0.5 to 5%. The initial amorphous oxide was overnight
dried at 100 1C and then calcined at 450 1C for 2 hours. The photodegradation was studied in the presence of oxygen or H2O2.
The mechanism of enhanced photocatalysis of TiO2 with Fe3 was
studied by Zhang et al.96 using Sulfadiazine (SD) as the model compound
under dierent photolysis conditions. The results are interpreted with a
mechanism of enhanced photocatalysis of TiO2 by Fe3 in the present
study. Both oxygen and Fe3 act as the electron acceptors of TiO2.
A study has been reported investigating the photocatalytic activity of
TiO2 samples enriched with several percentages of Mn for the degradation
of gaseous acetaldehyde in the presence of both O2 and UV-visible light at
atmospheric pressures and room temperature.98 Mn doped TiO2 samples
were prepared by a modied sol gel method. The photocatalyst was
obtained by precipitating titanium dioxide on a sol of manganese dioxide.
Photolysis was carried out using dierent light sources in the UV and visible
light region. At low loading, as in the case of 0.1% Mn doped TiO2 , the
sub-band-gap response was present in the whole range from 3.15 eV to
almost 2 eV demonstrating that the introduction of Mn in the TiO2 lattice
does increase signicantly the material sub-band-gap absorption. Doping
of TiO2 samples with higher levels than 1% of Mn, although it results
in higher absorbance in the visible, it leads to substantial lower
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photocatalytic decomposition yields of CH3CHO under both UV and

visible irradiation.
An eective co-doping approach is described to modify the photoelectrochemical properties of anatase TiO2 by doping with nonmetal (N or C)
and transition metal (Nb or Ta) impurities.104 Here, compensated and
non-compensated co-doped TiO2 systems are constructed with dierent
proportions and dopant species, and then their dopant formation energies
and electronic properties are calculated to study the stability and visiblelight photoactivity by rst-principles density functional theory incorporating the LDA U formalism, respectively.
2.1.2.3 Plasmonic eects of noble metal ions loaded titania photocatalysts.
Metal nanoparticles in the size regime 110 nm exhibit characteristic size and
shape dependent properties due to better charge transfer that cannot occur in
bulk materials because the exposed surface atoms are 50 times less than
quantum size particles . Noble-metal nanoparticles (NPs) such as Au and Ag
can respond to visible light due to the localized surface plasmon resonance
(LSPR), which is produced by the collective oscillations of the surface electrons, exhibiting great potential for extending the light absorption range of
wide band gap semiconductors. This surface plasmon resonance eect has
been studied in various forms of titania photocatalysts.105117
Lu et al.105 prepared photonic crystals of TiO2 using 240 nm polystyrene
beads and then inltrated 15 nm Au nanoparticles (NP) into photonic crystals
of TiO2. The light absorption by Au NP was amplied. Rate constant for the
photodegradation of 2,4-dichlorophenol was 2.3 times faster as compared to
the reference catalyst made using mesoporous lm (TiO2 MP/Au NP).
Kochaveedu et al.106 decorated Silica-TiO2 core shell particles (SiO2@TiO2 )
with Au nanoparticles to examine plasmonic eects. An optimized system
employing Au NP arrays with 15 nm size and 700/mm2 density showed best
catalytic eciency due to a synergistic eect of the rm contact between Au
NPs and TiO2 . Kaur and Pal108 reported results on the eect of supported
Au nanoparticles of various sizes and shapes on its cocatalytic activity
imparted to TiO2 during photocatalytic oxidation of salicylic acid.
Vertically oriented TiOxNy nanopillar arrays with embedded Ag nanoparticles have also been examined for photocatalysis in the visible light
region.113 N-doped titania nanopillars were prepared by reactive DC
sputtering to produce TiN followed by high temperature oxidation
(450800 1C) in the presence of oxygen. By controlling the oxidation
conditions, the band gap of the prepared TiOxNy can be tuned to dierent
wavelength within the range of visible light. Higher temperature oxidation
(>800 1C) leads to rutile formation. Surface plasmon eects of Au nanoparticles deposited on N-doped titania in the photocatalytic reduction of
Cr(VI) has also been reported.110
Shiraishi et al.107 found that Pt nanoparticles supported on Anatase
TiO2 also exhibit absorption in the visible light region assigned to surface
plasmon resonance SPR. The intensity of these SPR band however was
weak as compared to that obtained with Au nanoparticles. Ag nanoparticles
decorated SiO2 nanospheres were also found to exhibit remarkable
surface plasmon mediated photocatalytic activities.109 The as-prepared
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Ag-decorated SiO2 NSs showed a signicantly red shifted and relatively

broad SPR absorption when compared with the individually dispersed Ag
nanoparticles. Owing to the considerably broad SPR absorption that
spanned from the visible to the near-infrared region, Ag-decorated SiO2 NSs
surpassed N-doped P-25 TiO2 powder and individually dispersed Ag nanoparticles in photocatalytic activity. Facile synthesis of a variety of metaldecorated TiO2 nanoparticles using a novel photoirradiation approach has
been reported,111 wherein polyoxometalate (POM) molecules sandwiched
between TiO2 and metal nanoparticles were employed as UV-switchable
agents to control the metal loading onto TiO2 surface. A TiO2 /POM/metal
nanocomposite essentially act as a cocatalytic system, wherein not only the
photocatalytic eciency of this system is signicantly improved, this composite also showed good activity for visible light photocatalysis.
Cao et al.,116 found that, for the methyl orange photodegradation, a
composite photocatalyst AgI/AgCl/TiO2 showed much higher photocatalytic activity than AgCl/TiO2 and AgI/TiO2 under visible-light irradiation (lW400 nm). When the molar percentage of AgI to initial AgCl is
20% (sample SE-20%), the maximal degradation eciency of MO reached
85.8% after irradiation for 120 min. The enhancement of photocatalytic
activity of the composite photocatalyst AgI/AgCl/TiO2 will be attributed to
its good absorption in the visible-light region. Photoluminescence studies
using terephthalic acid as a probe has been used to probe the mechanistic
details. The detection of reactive species by radical scavengers displays that
O2d and H2O2 are the main reactive species for the degradation of MO
under visible-light irradiation.
The role of ionic silver, Ag, and metallic silver, Ag0, on the potential
photocatalytic activity of a titanosilicate ETS-10 semiconductor has
been studied.117 Unlike as-synthesized ETS-10 and Ag-ETS-10 samples,
Ag0-ETS-10 samples showed absorbance in the visible region. The
absorption bands at B350 nm and B460 nm observed for Ag0-ETS-10 were
attributed to the surface plasmon resonance of Ag0 nanoparticles on the
surface of ETS-10 crystals. In contrast to as-synthesized silica sample, which
was essentially inactive in this illumination range, all Ag and Ag0 samples
supported on titanosilicate showed apparent enhanced activity for the
degradation of MB under visible light (420630 nm) irradiation.
2.1.2.4 Anion doping of titania. Anionic doping has been a recent new
innovative concept associated with the narrowing of the band gap energy
obtained by substituting foreign anions to O2 anions. In a pioneering
paper, Asahi et al.,118 reported on the preparation of visible light active
photocatalysts, N-doped TiO2 prepared via sputtering of TiO2 in N2/Ar gas
mixture and subsequent annealing in N2 atmosphere at 550 1C. Visible light
active N-doped titania catalysts have also been prepared via ammonialysis
(high temperature treatment with NH3 gas). Nitrogen-doped TiO2 nanocatalysts with a homogeneous anatase structure were successfully synthesized through a microemulsion-hydrothermal method by using some
organic compounds such as triethylamine, urea, thiourea, and hydrazine
hydrate. During the last two years, several papers appeared dealing with
anion-doped titania photocatalysts.119130
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For nitrogen doping (N-doping dierent from n-type doping), according

to the valence induction law, it should be proved (i) that nitrogen is
really present in the nitride state N3, (ii) that N3 anions are in O2 lattice
bulk positions and (iii) that, under oxidizing working conditions, titania
has no tendency to perform self-cleaning by expulsion of N3 anions
from the anionic sub-lattice via their oxidation with a favorable
progressive decrease of the ionic radius of element N from 1.71 A to 0.55,
0.25, 0.16 and eventually to 0.13 A, corresponding to the progressively
increasing oxidation states of N equal to 3, 0, 1, 3 and 5,
respectively.)
The visible light response and enhanced catalytic activity can arise from
the substitutional doping (Ti-N-Ti) or via interstitial N impurities (Ti-O-N
or Ti-N-O). The N3 anions can go at the lattice bulk positions of O2
causing a bandgap narrowing driving by mixing of N 2p states with the O 2p
states.129 Umezawa and coworkers130 have made Density Functional Theory (DFT) Calculations to determine the deep impurity states in N-doped
anatase. Hybridization of N p with Ti d states of Ti is believed to give rise to
a new band at the valence band edge. A plausible mechanism for the visible
light absorption of the catalyst has been proposed.
Rice grain-shaped Nitrogen-doped titanium dioxide (N-TiO2 ) nano/
mesostructures were fabricated through a combination of sol-gel and electrospinning methods.127 The bers formed initially are continuous but
break up into rice grain-shaped nanostrucutures upon thermal treatment at
500 1C for 1 hour. The average size of the particles is in the range of
5080 nm. The presence of N in the TiO2 lattice was conrmed by X-ray
photoelectron spectroscopy (XPS). The band-gap of TiO2 reduced from
3.19 eV to 2.83 eV upon increasing doping level of N from 0% to 5%(w/w),
respectively. The N-TiO2 rice grains showed an enhanced UV light-assisted
photocatalysis compared to pure TiO2 in the photodegradation of Alizarin
Red S dye, an industrially important anthraquinone dye.
Wang et al.131 have reported on the eects of annealing temperature on
the photocatalytic activity of nitrogen-doped (N-doped) titanium oxide
(TiO2) thin lms deposited on soda-lime-silica slide glass by radio frequency
(RF) magnetron sputtering. As-deposited N-doped TiO2 thin lms have
been found to be nearly amorphous. The rutile and anatase phases coexisted
when the N-doped TiO2 thin lms were annealed at 623 and 823 K for 1 h,
respectively. Chi et al.123 have used micro-arc oxidation method to prepare
N-doped and N-Eu co-doped titania catalysts and studied their photocatalytic performance.
Photodegradation of the antibiotic Cefazolin has been found to occur at
enhanced rate when N-doped TiO2 catalysts are employed as compared to
Degussa P25.122 The decomposition of 3-chlorophenol on N-modied TiO2
photocatalyst has also been reported.121 Selvam and Swaminathan125 have
developed the visible light photolysis of N-doped TiO2 in the presence of
nitrobenzene as a synthetic method for quinaldines.
2.1.3 Surface modications of titania photocatalysts. Titania dispersed
as particulates in aqueous solutions expose a large surface area. Being an
amphoteric oxide, the surface is lled with hydroxyl groups and its partially
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ionized forms. It has been found that simple adsorption of ions to the
surface can inuence signicantly the photocatalytic properties.
2.1.3.1 Superhydrophilic and superhydrophobic titania photocatalysts for
air cleaning. Depending on the method of preparation and thermal treatments, titania can have isoelectric point anywhere between 4 to 6. In the
presence of moist air/humidity, acids or bases, the surface hydroxyl groups
can undergo reversible protonation, deprotonation. Wetting of the surface
depends critically on the surface properties. Freshly calcined TiO2 sample
surface is very hydrophilic, as indicated by low contact angle measured for
wetting by water droplets. Upon free standing in air, the surface becomes
partially hydrophobic. The hydrophobicity can be increased signicantly by
adsorption of long chain fatty acids. Thus, with suitable acid/base treatment
and additives adsorption, it is possible to tune the hydrophobic/ hydrophilic
properties of titania. Such super hydrophilic materials nd applications
in air-cleaning and as window coatings.132139 Fujishima and coworkers
have exploited this tenability to make Self-cleaning windows. Adsorbed
organic products (dirts) are photodegraded by the titania pigments of the
window glasses, leaving the surface superhydrophilic. Simple washing of
the window glass removes the degraded organics leaving a clean surface.
Self cleaning windows are available commercially from Pilkington, SaintGoban and other glass companies. Fujishima and others have recently
reviewed new photocatalysis applications of this kind.132134
Using long chain fatty acids, it is possible to prepare TiO2 surfaces that
are hydrophobic or superhydrophobic. Fujishima and coworkers have used
hydrophobic compounds such as octadodecylphosphonic acid (ODP),
octadecyl-trimethoxysilane (ODS), or uoroalkylsilane.
Photodecomposition of the adsorbed layer using photocatalysts converts
these surfaces to be hydrophilic and even superhydrophilic. Using patterning photomasks, it is possible to make wettability patterns on a selfassembled monolayer of hydrophobic molecules such as ODS. Wettability
patterns are used in many elds such as oset printing and in uid
microchips.
Ramakrishna and coworkers135 have used electrospinning method to
prepare rice-shaped nano/mesostructures deposited on glass substrates. The
water contact angle decreased with increase in the lm thickness resulting in
superhydrophilic transparent coatings for possible use in air cleaning and in
window coatings. The self-cleaning property of the TiO2 lm consisting of
rice-shaped nano/mesostructures is compared with that of commercially
available Degussa P-25 in the photodegradation of Alizarin red dye and
found to be more eective. Xi et al.136 have used a adsorptive self-assembly
method to prepare TiO2 thin lms for self-cleaning applications. By tuning
the number of process cycles (i.e., adsorption-then-heating) of TiO2 colloidal suspension, we could facilely prepare large-area TiO2 lms at a
desired thickness and with uniform crystallite morphology. As-prepared
anatase TiO2 thin lms also display superhydrophilicity and excellent
photocatalytic activity for self-cleaning application.
Verma et al.136 have reported on a solution-based adsorptive selfassembly approach to fabricate anatase TiO2 thin lms on dierent glass
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substrates such as simple plane glass and patterned glass at variable

compositions (normal soda lime glass or solar-grade borooat glass).
As-prepared nanostructured TiO2 thin lms on glass substrates do not cause
deterioration in optical transmission of glass. The lms display superhydrophilicity and excellent photocatalytic activity for self-cleaning application. Photocatalytic degradation of methyl orange indicates that these
thin lms are indeed highly eective, in comparison to other commercial
TiO2 thin lms under identical testing conditions. Mesoporous titania-silica
composites that have photocatalytic activity have been synthesized by
mixing ethoxysilane oligomers and titanium dioxide nanoparticles in the
presence of a nonionic surfactant (n-octylamine).139,140 The resulting
nanomaterials create eective adhesive and crack-free coatings for stone.
These coatings give self-cleaning properties to stone and improve its
mechanical resistance.
2.1.3.2 Surface modication with adsorption of anions. Phosphate anions
are known to adsorb strongly on titania surfaces. A simple strategy to
greatly increase the thermal stability of nanocrystalline anatase has been
described through this adsorption by Jing et al.141 Ecient TiO2-based
photocatalysts prepared under ultraviolet irradiation, via the surface
modication with phosphate anions. Compared to un-modied TiO2, the
modied TiO2 calcined at high temperature (over 700 1C) exhibits much
high photocatalytic activity for degrading Rhodamine B (or phenol) solution, even superior to the commercial P25 TiO2. In a related study these
authors142 prepared nanocrystalline TiO2 lms by a doctor blade method
followed by post-treatment with sodium orthophosphate solution.
Phosphate-modied TiO2 was eective for the photodecomposition of
water . Zhu et al.143 prepared a multilayer photoactive coating containing
surface uorinated TiO2 nanoparticles and hybrid matrices by sol gel
approach based on renewable chitosan was applied on poly(lactic acid)
(PLA) lm by a step wise spin-coating method. The photocatalytic activity
of resulting highly transparent lms has been studied for the degradation of
Methyl orange as a pollutant.
2.1.3.3 Titania photocatalysts on various supports (zeolites, clays, etc).
To improve the surface area, titania photocatalysts have been deposited on
a number of high surface area support materials such as Zeolites and clay
minerals.144152 TiO2 hybridized with HZSM-5 zeolites has been prepared
by a simple solid state dispersion method and studied the photocatalytic
oxidation of NOx over TiO2 /HZSM-5 having dierent Si/Al radios and at
dierent humidity levels.146 Co impregnation has been examined in Zeolite
supported TiO2 photocatalysts for photoinduced water splitting reaction.
Dierent sources of Co (as nitrate or chloride) and zeolites (Na-Y and
Na-Mordenite) have been studied. Although nitrate based catalyst showed
increased visible light absorption, they produced 30% lower H2 rate in
comparison to chloride salts.144 Verbruggen et al. report145 on a fast, low
cost immobilization method involving a one step suspension coating of
pre-synthesized colloidal TiO2 particles and titania nanotubes on glass
beads and studied the eciency of the supported catalyst in the gas phase
photodegradation of ethylene.
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Vermiculite is a layered magnesium aluminium silicate with 2:1 crystalline

structures. It consists of two silica tetrahedral sheets and one magnesium
octahedral sheet. Heat treatment at high temperatures enables it to become
a highly porous exfoliated material with high adsorption and selective
ion-exchange capabilities. TiO2 photocatalyst was incorporated into acidtreated vermiculite and the photocatalytic activity of TiO2/vermiculite
composites was evaluated by removal of methylene blue (MB).148 Fly
ash cenospheres, a low cost alumino-silicate rich by-products generated
in coal-red power plants has been used to support hollow sphere TiO2.149
The polypyrrole-sensitized TiO2 layer on y ash cenosphere (PPy-TiO2/
FAC) was successfully used as a photocatalyst for methylene blue
photodegradation.
TiO2/y-ash cenosphere substrate has also been used150 to prepare
photocatalysts modied with heteropolyacid by sol-gel followed solvothermal method at 40 1C. The modied catalyst was found to be very
eective in causing photodegradation of ciprooxacin antibiotic. The
molecular/ions surface imprinted TiO2/y-ash cenospheres photocatalyst
has been prepared by molecular imprinted technology with coordination
compounds of La3 and oxytetracycline as molecular template. This
photocatalyst showed preferential selectivity in the photodegradation of
antibiotics. For example, the relatively coecient of selectivity degradation
on oxytetracycline could reach 4.5146 compared with the ciprooxacin.
Aluminum silicate ber is a re-resistant and thermal insulation material
and has been widely used in industry and building. A novel TiO2 -aluminum
silicate ber (TAS) nanocomposite, synthesized by a sol-gel method, is
proposed to use as a photocatalyst for the removal of multiple pollutants.
The TAS nanocomposite has excellent mechanical and thermal properties
and high corrosion resistance. The TAS calcined at 500 1C exhibited the
biggest BET surface area and highest photocatalytic activity for the removal
of) in a simulated coal combustion ue gas SO2, NO and also elemental
mercury.151
There are few studies on nanocomposite titania photocatalysts with
conducting polymers.153,154 Liao et al.153 have described the synthesis of
polyaniline (PANI) modied core-shell mesoporous TiO2 photocatalyst
(PANI/m-TiO2) by hydrothermal synthesis followed by chemisorption.
PANI/M-TiO2 possessed a unique core-shell structure allowing multiple
reection or scattering of light in the photocatalyst and led to the increase of
optical path length. Hence increasing loading of PANI and associated path
length increase leads to signicant enhancement in the visible light absorption
of the photocatalyst. For the photodegradation of Rhodamine B dye, the
catalytic activity increased with increasing amounts of PANI, with optimal
performance obtained at 6%. In addition to Rhodamine, the photodegradation of 4-chlorophenol has also been examined. In a related work
conducting polymer of polyaniline PANI -TiO2 nanocomposites were synthesized via a hydrothermal method154 and followed by a low-temperature
calcination treatment process. It was found that such a PANI/TiO2 nanocomposite exhibits higher photocatalytic activity and stability than bare TiO2
and TiO2 xN(x) toward the liquid-phase degradation of methyl orange (MO)
under both UV and visible light (420 nmolo800 nm) irradiation.
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2.1.3.4 Nanocomposites of photocatalysts and Carbon allotrophs. In

recent years procedures have been developed for the synthesis and
characterization of various allotrophic forms of carbon, particularly as
nanostructures. There have been several studies of dispersing titania on
various allotrophic forms of carbon, on graphene in particular.155168
Graphene can be viewed as one atom thick sheet of graphite. Few- and
single-layer transferable graphene nanosheets are usually obtained by
mechanical exfoliation (Scotch-tape method) of bulk graphite and by
epitaxial chemical vapor deposition. Graphene oxide graphite (also referred
to as reduced graphene oxide rGO) is one that has been oxidized to intersperse the carbon layers with oxygen molecules, and then reduced, to
separate the carbon layers completely into individual or few layer graphene.
Carbon nanotubes, graphene and graphene oxide, C60 and related
materials have been found to be good support materials and even as templates for titania-based photocatalysts. They all exhibit excellent charge
carrier mobility, a large surface area and good electrical conductivity. Used
as a template, graphene can help control the morphology of the TiO2
nanoparticle by controlling the nucleation and growth processes. In nearly
all cases, photocatalytic performance improves signicantly when the TiO2
photocatalyst is dispersed as nanocomposites with dierent carbon allotrophs. A one-step colloidal blending method has been used to prepare a
TiO2-graphene oxide composites for the photocatalytic degradation of
methylene blue dye.165 Remarkable improvement in the dye degradation
was found with the GO nanocomposite as compared to the parent Degussa
P25 catalyst.
Several studies have indicated TiO2-CNT (carbon nanotube) nanocomposites to exhibit enhanced photocatalysis compared to pure TiO2 for the
oxidation of organic compounds. Eder has provided a recent review on the
synthesis, properties of CNT-inorganic oxide photocatalysts.155 The CNTs
have superior electronic properties such as large electron storage and can
accept photons and excited electrons in mixtures with TiO2 and hence
retarding recombination of the charge carriers. Two possible mechanisms
have been discussed in the literature: a photoinduced transfer of electrons
from TiO2 to the CNT thereby enhancing the charge separation or CNT itself
acting as a sensitizer pumping electrons into the conduction band of TiO2.
Electrospinning technique has been used to prepare Anatase-multiwall
carbon nanotube (MWCNT) composites with negligibly small percentage of
rutile and brookite polymorphs. The nanocomposites are obtained by high
temperature sintering of as-spun composite bers. Enhanced photocatalysis
was conrmed for the nanocomposite as compared to pristine TiO2 rice
grains and P25 particulates for Alizarin Red oxidation.158,159
The role of dimensionality of the substrate and hosts as nanotubes
or nanosheets on the photocatalytic activity has been examined recently.
Carbon nanotube-titania nanosheet and graphene-titania nanosheet
composites with low carbon defect densities are compared.156 The resulting
2D-2D graphene-titania nanosheet composites yield superior electronic
coupling compared to 1D-2D carbon nanotube-titania nanosheet composites, leading to greater enhancement factors for CO2 photoreduction
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157
under ultraviolet irradiation. Kim et al.

prepared Graphene/Carbon
composite nanobers (CCNF) with attached TiO2 nanoparticles and
studied their performance in the photodegradation of methylene blue dye.
A signicant increase in the reaction rate was observed with TiO2-CCNF
materials under visible light. This increase is due to the high migration
eciency of photoinduced electrons and the inhibition of chargecarrier recombination due to the electronic interaction between TiO2 and
graphene.
The eect of activated carbon on the structural and photocatalytic
properties of titania has been studied using a series of catalysts prepared by
hydrothermal and reux methods. Hydrothermal method gave catalysts
with mesoporous structures while reex method yielded micropores with
decreased mesoporosity. The photocatalyst prepared via reex method
showed a better performance for the light induced removal of Rhodamine B
dye.160 Hierarchical porous TiO2-carbon hybrid composites (TiO2@C)
with a hollow structure have been successfully fabricated by a one-pot
low-temperature solvothermal approach in the presence of dodecylamine.
The hybrid hollow sphere catalysts exhibited enhanced activity for the
photodegradation of Rhodamine B dye.167 Ravindrananathan Thampi
et al.162 prepared a series of C-doped, W- doped and C, W-codoped TiO2
samples using modied sol-gel techniques in the presence of Melamine
Borate. Visible light-induced photocatalytic activity of C-doped material
was superior to that of an undoped catalyst.
A series of TiO2-reduced graphene oxide RGO nanocomposites have
been prepared by one step hydrothermal reaction using TiCl4 and graphene
oxide without any reducing agents. The synthesized nanocomposites of
biphasic TiO2 with RGO showed enhanced catalytic activity compared to
conventional TiO2 photocatalyst, P25. The photocatalytic activity is
strongly aected by the concentration of RGO in the nanocomposites,164
TiO2 nanoparticles supported on two dierent forms of activated carbon
(Darco G60 and Norit SA UF) have been prepared and tested for the
degradation of Acid Red 88 dye.168
2.1.4 Applications. Degradation of toxic and industrial waste organic
compounds to small (C1) chemicals has been the major application of
heterogeneous photocatalysis. While Degussa P25 particulates are used as
standard or reference photocatalyst, organic dyes Methylene Blue,
Methyl Orange, Eosin and Rhodamine B are often used as bench mark
reference dyes. Herein we review some recent studies on the photodegradation of simple organic molecules as well larger organic dyes.169180
2.1.4.1 Photodegradation of organic molecules. Li et al.169 have used a
combination of experimental techniques to study the mechanism of
photodegradation of methyl orange on TiO2, whether the primary oxidation
step involve direct electron transfer between the substrate and positive holes
or secondary active species. Active species such as holes, electrons, hydroxyl
radicals (dOH), and superoxide radicals (O2d) involved in the photodegradation process of methyl orange (MO) over TiO2 photocatalyst were
detected by several techniques. Using dierent types of active species
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scavengers, the results showed that the MO oxidation was driven mainly by
the participation of O2d, holes and dOH radicals.
The degradation pathways for citric acid degradation by
TiO2-heterogeneous photo-catalysis were studied through the analysis of its
degradation intermediate products.178 The most important product formed
was 3-oxoglutaric acid, but several other compounds, like acetoacetic,
lactic, pyruvic, malic, glyoxylic, acetic and formic acids plus acetone were
found. While citric acid is present, the intermediates cannot be photocatalytically degraded. Degradation of nitrophenol has been studied using
TiO2 photocatalysts (commercial P25) and sulphuric acid-treated activated
carbon catalysts.180
2.1.4.2 Photodegradation of toxic pollutants (drugs, bacterial, industrial
wastes, etc). Removal of bacterial and pathogenic microorganism contaminants in drinking water and waste water is one of the major objectives
of photocatalysis. A number of publications appeared in this area.181192
Photocatalysis and other toxic waste removal schemes attempt to
convert toxic pollutants to smaller components which are biodegradable.
Biodegradation is a natural process carried out by microorganisms using
oxygen and Sturm test is often used to determine if a given chemical is
biodegradable or not. In a recent report, the use of photocatalysis to eect
biodegradability of the antibiotic Tetracycline was investigated using Sturm
test to assess the biodegradability. Tests showed that the byproducts are not
biodegradable.190
UV-irradiation is generally used to destroy the pollutants. Photolysis is
usually carried out using entire UV-light (200400 nm, labeled as UV-C
radiation) or limited to near UV region (above 340 nm, labeled as UV-A).
Increasingly UV-A light is used for the removal of bacteria, viruses and
protozoan cysts. Two reports have appeared recently examining the
relative eciency of these two types of irradiation on the bacterial model
Escherichia coli (E. coli) and Degussa P25 as the photocatalyst.184 Total
destruction is not feasible and often the bacteria can repair some of their
DNA damages, becoming more resistant to such treatments. Cyanobacteria
are known to produce a group of potent toxins (neurotoxins and hepatotoxins). Vielela et al., have tested a at plate glass reactor coated with
Degussa P25 TiO2 to follow the degradation of the [D-Leu]-Microcystin-LR
toxin. 150 min. photolysis was necessary to reduce the toxin level to WHOs
guidelines for the drinking water.185
Lanao et al.186 studied disinfection of another bacteria, Enterooccus sp.,
using a combination of TiO2 and H2O2 and UV-B range photolysis. Only
radiation in the UV-B range was eective in the inactivation.
The presence of pharmaceutical waste is another major health hazard
concern in the environmental protection. Drugs are designed to have a
physiological eect on humans and animals at very low/trace levels. Often
they are often non-biodegradable and hence remain in the environment for
a long time. Photocatalytic degradation of drugs has been shown to be
eective in several cases.187192
The UV-A/TiO2 photocatalysis has been used to study the degradation of
the antibiotic Amoxicillin in aqueous suspensions.187 Eight dierent
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commercial titania samples were tested and Degussa P25 was found to be
most active, giving 93% mineralization. Similarly Ioannou et al.191 found
P25 was eective to photodegrade (to 80% level) Atenolol and Propranolol
(b-blockers used for high blood pressure control) in aqueous solutions. The
ecacy of photolysis in the visible light region using doped titania catalysts
such as carbon-doped titania has been tested for the photodegradation of
the antibiotic Noroxacin.189 The inuences of catalyst dosage, initial probe
compound concentration and solution pH levels on the decay performance
and reaction kinetics were investigated and optimized.
2.1.4.3 Photocatalysis and atmospheric pollution. TiO2 for air purication.
There is increasing awareness and concern that the atmosphere above the
earth is getting polluted increasingly with increasing number of gaseous and
particulate wastes coming from combustion and other human activities. UN
agencies have identied ve greenhouse gases (CO2, CH4, N2O, Chlorourocarbons (CFCs) and SF6) as chemical agents that cause signicant climate changes, including a decrease in the ozone layer of upper atmosphere.
Few review publications have appeared on this topic.193195 Photo- and
electrocatalysis studies are being employed and to x CO2 in the form of
useful C1 chemicals such as methanol and reforming gas (CO H2),196210 to
decompose nitrous oxide (N2O) and to oxidize methane gas.
CO2 reduction has an important role. Depending on the photocatalyst
and experimental conditions, photoreduction of CO2 in aqueous solutions
can give rise to one or more of the following products: CO, CH4, CH3OH,
HCHO, and HCOOH (equations 915):
2CO2 2e ! CO CO3 2
CO2 2H 2e ! CO H2 O
CO2 2H 2e ! HCOOH
Eo 0:53V
Eo 0:61V
9
10
11
CO2 4H 4e ! HCHO H2 O
Eo 0:48V
12
CO2 6H 6e ! CH3 OH H2 O
Eo 0:38V
13
CO2 8H 8e ! CH4 2H2 O
Eo 0:24V
2CO2 12H 12e ! C2 H4 4H2 O
14
15
One of the products, CO, can be combined with H2 gas produced from
water reduction to form the syn-gas and further reductions to methanol or
methane. Sustained photoreduction with high turnover numbers (TON) and
turnover frequency rates (TOF) are important for practical applications.
Titania photocatalyst carrying various metal deposits such as Pd, Rh, Pt,
Au, Cu, or Ru.as co-catalysts have been tested for the reduction of CO2.
Various aspects of the photocatalytic reduction of CO2 with water on
various types of active TiO2 photocatalysts have been reviewed.196199
Photoreduction under heterogeneous gas-solid conditions produce methane
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as the main product while methanol also forms as a predominant product

on highly dispersed TiO2 catalysts anchored on zeolites and mesoporous
silica.200210
In 1987, Thampi, Kiwi and Graetzel203 reported the photo-methanation
of CO2 at room temperature and atmospheric pressure using dispersed
ruthenium and ruthenium oxides loaded onto TiO2. This work was followed
up by Anpo and coworkers,204,205 who reported on the formation of
methanol and CO. Ogura et al.206 found H2 and CH4 as reduction products
when CeO2-TiO2 photocatalyst was irradiated by visible light. Rajalakshmi
et al.207 have reported results of their recent studies on the photoreduction
of CO2 on three dierent TiO2 catalysts (including P25) in aqueous alkaline
solutions. Methane, methanol and ethanol are observed as the major
products. Activity in terms of total hydrocarbons production and (methane
methanol) yields during six hours run follows the order: P-25>RM-TiO2W
UV-100. Ethanol is formed in signicant amounts in the case of UV-100
and RM-TiO2 but not with P-25. Probable reaction pathways that lead to
the formation of these products have been proposed.
The mechanism of photocatalytic reduction of CO2 with H2O in the gas
phase over PtTiO2 lms produced by the solgel deposition over glass
beads was investigated.208 Accumulation of Hydrogen gas had an inhibitive
eect on the photoreduction process, as seen in the slower rate of methane
formation in the presence of added H2. A binary co-catalyst of Pt and Cu2O
with a core-shell structure has been found to be eective for the
photoreduction of CO2, water mixture to methane and CO.209 It has been
proposed that Cu2O shell provides sites for the preferential activation of
CO2 while Pt core extracts the photogenerated electrons from TiO2. The
same binary catalyst is also active for the photoreduction of water to H2.
There have been a number of reports on the photoreduction of CO2
using various transition metal complexes, particularly metal-carbonylpolypyridines. A few review publications have appeared summarizing the
research progress in this area.200,201 Ishitani and coworkers have reported211
on the photoreduction of CO2 using a number of polypyridyl carbonyl
complexes of Ru and in particular on the selective formation of formic acid
as the reduction product. HCOOH is an important industrial chemical and
also used as a preservative and an insecticide. a trinuclear complex with two
photosensitizer units and one catalyst unit photocatalyzed CO2 reduction
(F(HCOOH)=0.061, TON(HCOOH)=671) with the fastest reaction rate
(TOF(HCOOH)=11.6 min1).
Methane is an important green house gas, whose concentration in the
atmosphere has to be reduced. It is preferable that the conversion of
methane yields other industrially useful chemicals along with H2 gas.212 In
steam reforming methane is converted to H2 and CO2. Taylor213 has
reported on the oxidation of methane in the presence of water to H2 and
methanol using WO3 and TiO2 as photocatalysts. With WO3 visible light
irradiation is possible. The photocatalyst with the highest level of conversion of methane was found to be the lanthanum-doped tungsten oxide.
Photocatalytic steam reforming of methane was examined recently by
Shimura et al.,214 using metal-loaded K2Ti6O13 photocatalysts. Although
the production rate was improved by loading Pt cocatalyst on the K2Ti6O13
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photocatalyst, unfavorable formation of CO and gradual deactivation of

photocatalyst were observed. On the other hand, a Rh-loaded K2Ti6O13
sample showed two times higher activity than the Pt-loaded one did,
and promoted the selectively without deactivation for many hours. The
Rh-loaded titanate catalyst was also tested for the photoredcution of water
to H2.
A novel air-cleaner based on photocatalysis coupled to plasma assisted
catalysis with a TiO2 impregnated Ti-mesh lter has been developed by
Fujishima and coworkers.215 The air-cleaners were tested by the tobacco
smoke deodorization tests according to both the standard test method
for air cleaner and the proposed test method. In the standard test method,
80100% decrease of the concentrations of gaseous compounds in tobacco
smoke in 1 m3 box has been achieved for 30 min by the air-cleaner. In a
related work, N-doped titania has been tested as a photocatalyst for air
purication.216 Since N-doped TiO2 absorbs in the visible region, ambient
uorescent lamp light can be used as the light source. A N-TiO2 photocatalyst prepared via sol-gel process was loaded with Pt catalyst and the
Pt/N-TiO2 successfully tested in a closed reactor containing a mixture
of volatile organic compounds (VOC) Acetone, ethanol, 2-propanol, TCE,
n-hexane and toluene.
Likewise important is nitrous oxide N2O pollutant removal. This is a very
stable greenhouse gas. With a lifetime of over 100 years, it is 200 times more
harmful than CO2. Because of its stability it migrates to the stratosphere
were N2O is involved in reactions leading to stratospheric ozone reduction.
The main source of Nitrous oxide is soil, coming from synthetic nitrogen
fertilizers used in agriculture. Other sources are fossil fuel combustion,
ammonia from livestock manure and from industrial production of nitric
acid and in adipic acid synthesis for use in nylon industry. There has been a
sustained interest to nd suitable thermal and photocatalysts to decompose
N2O. Various metals supported on pure and mixed oxides and zeolite
systems have been studied.217220
A review from Matsuoka and Anpo193 reported that transition metal
oxides (Ti, V, Mo, Cr) incorporated within the framework of zeolites as well
as transition metal ions (Cu, Ag, Pr3) exchanged within the zeolite
cavities exhibited high and unique photocatalytic activities for various
reactions such as the decomposition of N2O into N2 and O2 or the reduction
of CO2 with H2O to produce CH4 and CH3OH. According to Anpo and
Matsuoka, the use of zeolites is one of the most promising approaches in
designing ecient photocatalytic systems to eliminate global air and water
pollution. Firstly because their physicochemical properties such as pore size
diameter or channel structure allow to control the photocatalytic activity, as
well as the selectivity of the reaction product. Then because transition metal
ions can be introduced in the zeolites frameworks by simple methods
(ion exchange or hydrothermal synthesis) and the obtained mono-atomic
dispersion of metal oxides or ions, results in remarkable enhancement of the
photocatalytic performance as compared with corresponding bulk metal
oxides such as TiO2.
Toma et al.210 studied photocatalytic removal of nitrogen oxides on
Degussa P25 as a function of catalysts concentration, catalyst morphology
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and exposed surface area and temperature. The conversion rates increased
until an optimal value of TiO2 by weight 35% for NO concentration and
around 20% for NOx decomposed. The decomposition increased proportionally to the geometric surface exposed to irradiation,. Recently
photocatalytic reduction of nitrous oxide has been studied211,212 on Ag-,
Cu- or Au-supported titania catalysts. In the presence of methanol and
water vapor, these catalysts eciently reduced N2O to N2.
2.1.4.4 Wastewater treatment. Water pollution is a major environmental
problem in nearly all industrialized countries. A wide range of industrial
wastes and redundant chemicals such as pharmaceuticals, pesticides, ame
retardants, personal care products, fragrances, detergents, plasticizers and
so on are being discarded. Many of these chemicals are non biodegradable
and they remain as an environmental hazard for many years. River water
and other natural resources get contaminated. Growth of pathogenic
microorganisms and their mutation to chemically resistant strains is another
threat. Goals of heterogeneous photocatalysis are to decompose totally or
at least degrade them to small fragments which are bio-degradable. Most
often, a combination of chemical and photochemical degradation processes
are applied.
In addition to photocatalysis, electrochemical oxidation, electrical
discharges, Fentons Reagent, Ozone, ultra-ltration and sonolysis are
employed. Such a collection of degradation pathways is referred as
Advanced Oxidation Processes (AOP). A number of reports have
appeared on waste water treatment using photocatalysis in combination
with other water purication methods.221234 Chemical Oxygen Demand
(COD) is one of the important water quality parameters and is widely
employed to assess the total organic pollution level, especially for heavily
polluted industrial wastewaters. Analytically, the COD value can be used to
represent the total of all chemically degradable organic pollutants in
water and wastewaters. The oxygen demand is determined via chemical
degradation of organic compounds by strong oxidizing agents such as
dichromate. The extent of degradation is determined by the amount of
electrons transferred to the chemical oxidizing agent during chemical
degradation, which is indirectly quantied by measuring dichromate
depletion via titration or spectrophotometry.
Estrogens are chemicals that are used for treatment on animals for the
diseases of their reproductive tract. Human exposure to estrogens as
contaminants of plant soils can pose medical problems such as infertility
and nymphomanic activity. Chlorophenols are known broad spectrum
fungicides with long time in water (up to 1700 h). Since they are not
bio-degradable, photocatalysis has been tested as a method to degrade the
toxic pollutant. Andreozzi et al.233 have shown that a homogeneous photocatalysis route using Fentons reagent can be used eectively to degrade 2,4and 3,4-dichlorophenols in aqueous solution. The results show that the best
working conditions, for both compounds, are found for pH=3.0 and initial
Fe(III) concentration equal to 1.5.10e4 mol-1. Bisphenol-A (BPA) is a
common raw material in the manufacture of polycarbonate plastics and
epoxy resins. Due to its widespread usage, its presence has been detected in
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drinking and waste water resources. TiO2-based photocatalysts immobilized

on various solid supports have been used to degrade BPA.234 Photoelectrochemical oxidation using immobilized Ti/TiO2 lms has been found to be
eective.
Terpenes such as pinene, careen and limonene are found in the waste
waters of citrus transformation factories. Gas chromatographic analysis of
the eluent water after Solid phase microextraction method used for the clean
up showed incomplete removal of the terpenes. A titania-based photocatalysis applied permits complete degradation of the pollutants to acceptable levels.230 TiO2-based heterogeneous photocatalysis has been applied to
the oxidation of benzalkonium chloride (BKC), a bactericide widely used in
pharmaceutical and cosmetic formulations and risky for the biota.227 In a
related study, Sousa et al.226 described a titania-based photocatalytic
treatment system to treat municipal waste water containing pharmaceuticals
such as diclofenac.
The viability of using hollow ber ultraltration membranes along with
photocatalysis has been studied to remove organic dyes from waste
waters.232 The solution pH was proved to be the predominant force that
controlled the interactions by changing the surface charge characteristics of
TiO2 and altering the size and fractal dimension of TiO2 aggregates which
determined the property and structure of deposit layer. Falaras and
coworkers229 described composite TiO2 photocatalytic-ultraltration
membrane set up for waste water treatment. Ultra-ltration membranes
were coated nanoparticles of TiO2 without aecting the ltration process.
CuO has been deposited on to nanosized particles TiO2 (CuO-TiO2) for use
as a photocatalyst to degrade pollutant dyes of sea water.228 Methylene blue
degradation has been studied as a model system. At 2.5% loading the
photocatalyst was very eective for the dye degradation and for water
decomposition as well.
Bilgewater, a polluted euent with a smell of hydrocarbons and rotten
eggs is a corrosive mixture from the bilge of ships that mainly originates
from seawater inltration and leakage of engine oil and fuel. In a recent
study, Cazoir et al.231 have described methods based on TiO2-based
photocatalysis and air-stripping to reduce the amount of hydrocarbon levels
in the waste water to accepted levels. Air-stripping is a method by which
volatile impurities are purged out by purging through an air stream.
2.2 Oxides other than titania and titanates as photocatalysts - ZnO,
WO3, Fe2O3, etc.
During the last few years a large number of oxide and non-oxide
semiconductors-based photocatalysts have been discovered, many of them
operating in the visible light region. Table 1 gives the bandgap energies for
some of the popular ones currently being examined. Most of them are based
on single material. Binary and ternary semiconductors prepared as alloys,
solid solution or as nanocomposites are also being explored as
photocatalysts.
ZnO is a wide bandgap semiconductor (Eg=3.37 eV) with several properties suited for photocatalytic applications: high redox potential, an
extremely large excitation binding energy of 60 meV, good chemical stability
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Table 1 Bandgap energies of popular semiconductors used in photocatalysis studies.

Semiconductor
Ebg, eV
Semiconductor
Ebg, eV
Semiconductor
Ebg, eV
TiO2 (rutile)
TiO2 (anatase)
N-doped TiO2
ZnO
WO3
Fe2O3
SnO2
Bi2O3
Ta2O5
Cu2O
BiVO4
3.0
3.0
2.4
3.23.37
2.7
LiNbO3
NaTaO3
LaFeO3
SrTiO3
In2O3
ZnS
ZnSe
ZnTe
CdS
CdSe
CdTe
4.0
4.0
2.07
3.3
3.6
3.54
2.7
2.25
2.42
1.741.84
1.441.49
GaN
GaP
InP
GaAs
CuInSe2
Bi2S3
PbS
PbSe
FeS2
MoS2
Ta3N5
3.44
2.25
1.35
1.43
1.0
1.7
0.37
0.27
0.95
1.7
2.1
3.6
2.8
3.36, 4.3
2.17
2.4
and non-toxicity. Some of the recent studies of ZnO as a photocatalyst

are reviewed here.235245 Drawing on the earlier observations that thermochromism exhibited by ZnO (turns from white to yellow at high temperature) is due to an increase in the oxygen vacancies, Wang et al.235 have
reported synthesis of yellow ZnO by annealing of ZnO2 under dierent
atmospheres. The absorption edge of this material is shifted to longer
wavelengths and spectroscopic studies conrmed a decrease in the concentration of oxygen vacancies. The ZnO with oxygen vacancies are found
to be ecient for photodecomposition of 2,4-dichlorophenol under visible
light irradiation.
The ower-like ZnO materials were hydrothermally synthesized using
citric acid as the template directing agent with and without additional
ultrasonic treatment.236 The photoluminescence spectra have identied
several kinds of defects in as-synthesized ZnO materials, such as oxygen
vacancy (Vo), zinc vacancy (VZn) and interstitial zinc (Zni). The relative
content of oxygen vacancy is signicantly reduced by the ultrasonic treatment as reected by the suppression of green emission. On the contrary, the
ZnO materials synthesized without ultrasonic treatment possess more
oxygen vacancies and show more obvious green emission, which determines
their better activity for the photodegradation of Rhodamine B.
Due to the higher surface-to-volume ratio of nanosized particles, there
have been eorts to prepare nanosized quantum dots of ZnO for photocatalysis studies.
Nanocomposites of ZnO quantum dots-SiO2 nanotubes (ZnOqd-SNT)
have been prepared by direct heat treatment of electrospun Zinc acetate/
tetraethyl orthosilicate TEOS/polymer nanotubes NT.237 ZnO quantum
dots (ZQDs) with diameter about 35 nm were highly dispersed on the SiO2
nanotubes (SNTs). The photocatalytic studies revealed that the ZQDs-SNT
nanocomposite exhibited high photocatalytic activity to degrade Rhodamine B (RB) under ultraviolet (UV) light irradiation, which might be
ascribed to two reasons.
Hierarchical ower-like ZnO nanostructures with controlled
morphology and dimensions have been synthesized on Zn sheets by solution
phase approach and functionalized by Au nanoparticles (Au-NPs) by
electrodeposition.238 The Au-NPs on the surface of the ZnO structure
increases the absorption coecient of the Au-ZnO hybrid nanostructure in
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the visible region because of strong surface plasmon resonance (SPR) of the
Au NPs. The hybrid nanostructure combines the large specic surface
area, stability and catalytic activity of small AuNPs, and exhibit higher
photocatalytic activity (for Rhodamine B degradation) than that of pure
ZnO.
Hybrid ZnO nanostructures decorated with noble metal nanoparticles
(e.g. Au, Ag, Pt) have been prepared using pre-synthesized gold nanoparticles (GNP) capped with a dithiolate diethylentriaminepentaacetic acid
derivate (DTDTPA).239a The capping agent played a crucial role as a
directing and stabilizing medium in the dispersion of GNP uniformly on the
ZnO support. The photodegration of methyl orange was studied as a model
system, along with photoelectrochemical decomposition of water. As with
many of the modied catalysts, Au-capped ZnO exhibits enhanced photocatalytic and photo-electrochemical performances in comparison to pure
ZnO. In a related study worm-like Ag/ZnO core-shell heterostructural
composites have been fabricated by a two-step chemical method.239b Singlecrystal Ag nanowires were rst synthesized by the polyol process. Highly
dense ZnO particles were then grown on the lateral surfaces of Ag nanowires by an ultrasonic assisted aqueous solution method. Photocatalysis test
results show that Ag/ZnO core-shell heterostructural composites exhibit
higher photocatalytic activities in comparison with pure ZnO particles; in
particular, samples prepared with 2.8 atom % Ag have the highest photocatalytic activity.
A series of NiCo@Pt nanoalloys from icosahedrons to hollow spheres
have been prepared by Wen et al.240a through the element lithographic
process, in which a magnetic NiCo alloy hollow core is included in platinum
nanoshells. As prepared hollow spheres were than mixed with ZnO nanoparticles at room temperature under ultrasonic treatment to get compound
alloy semiconductor catalyst NiCo@Pt/ZnO. Photodegradation of model
dye methylene blue was examined using this photocatalyst. UV- and visiblelight-driven synergistic photocatalysis for ZnO toward the degradation of
dye wastewater has been reported.
ZnO/carbon quantum dots (ZnO/CQDs) nanocomposites have been
prepared by a one-step hydrothermal reaction and examined them as
photocatalysts for the degradation of toxic gas (benzene and methanol)
under visible light at room temperature.241a The nanocomposites exhibit
higher photocatalytic activity (degradation eciency over 80%, 24 h)
compared to N doped TiO2 and pure ZnO nanoparticles under visible light
irradiation. Ren et al.242b have used a wet chemical synthesis procedure to
grow conformal ZnO nanowire arrays on the surface of various magnetic
core-shell particles of FexOy@SiO2. The introduction of the silica layer in
the g-Fe2O3@SiO2ZnO koosh ball stabilizes the magentic core from
dissolution. This design also alleviates the electron-hole recombination at
the interface, as evidenced by the enhanced rate of Rhodamine B photodegradation by ZnO.
As with titania, there have been several attempts to modify ZnO via
transition metal and anion doping so as to increase the visible light harvesting properties. Mg-doped ZnO (ZMO) has been prepared recently
through an oxalate co-precipitation of ZnO and MgO and the bandgap
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242
values tuned by varying the Mg content. ZMO alloys can exist as either
hexagonal or cubic crystals due to structural dissimilarity between ZnO and
MgO. The activity of ZMO particles were examined for methylene blue
photodegradation. Wurtzite phase ZMO samples exhibited a blue-shift in
the near band edge photoluminescence (PL) emission, reduced PL intensities, and enhanced sunlight-induced photocatalytic activities compared to
undoped ZnO, whereas the ZMO composition 0.2-MgZnO containing MgO
secondary phase showed the highest PL intensity and lowest photocatalytic
activity. The most active sample 0.1-MgZnO obtained at 600 1C showed a
2-fold enhancement in the sunlight-induced photocatalytic decomposition
of methylene blue.
Xiao et al.243 have used a two-step anodization combined pyrolysis
strategy to prepare a highly ordered ZnO/TNTs hybrid nanostructure.
Structural studies indicated that in situ formed ZnO phases were uniformly
grafted to TNTs framework giving rise to hybrid nanostructure. ZnO
nanocrystals distributed on the TNTs could serve as favorable hole channels
and receptors for ecient separation of photoexcited charge carriers, which
results in signicantly enhanced photocatalytic performances of ZnO/TNTs
heterostructure in comparison with pure TNTs, ZnO lm, and P25 particulate lm. Furthermore, it is found that the hybrid photocatalyst
demonstrated excellent photostability.
In a related work,244 heterostructure ZnO/TiO2 corebrush nanostructures were synthesized on glass substrates by a combination of aqueous
solution growth and magnetron sputtering method. The heterostructure
corebrush shows the single crystal ZnO nanorod as the core and polycrystalline TiO2 nanowires as the brush-like outer layer. The photocatalytic
activity of the ZnO/TiO2 corebrush nanostructure was evaluated by the
decomposition reaction of Bromo-Pyrogallol Red dye under UV (245 nm)
and visible-light (450 nm) irradiation. The results revealed that the core
brush structure exhibited much higher photocatalytic activities than that of
a TiO2 lm and a TiO2/ZnO composite lm.
Porous ZnO nanostructures have been prepared by a microwave assisted
hydrothermal reaction.245 A nanocomposite ZnO-ZnSe subsequently was
prepared using these nanoparticles in a microwave assisted dissolutionrecrystallalization in an aqueous solution containing selenium ions. The
porous ZnOZnSe nanocomposites showed absorption bands in the visible
region and much higher activities than the porous ZnO nanostructures.
Tin Oxide (SnO2) and In2O3 are direct wide bandgap semiconductors
with similar bandgap energies (Eg=3.6 eV), both exhibiting excellent chemical stability and gas sensing properties. Cheng et al.246 have reported on
the synthesis of SnO2 nanorods with large aspect ratio by solvothermal
route and using Polyethylene glycol (PEG) as the template directing agent.
SnO2 nanorods exhibiting rutile phase have an average diameter and
length of 13 nm and 550 nm, respectively, presenting a mean aspect ratio of
42. As-prepared SnO2 nanorods present excellent photocatalytic degradation of Rhodamine B (RhB), causing total degradation of RhB in less than
45 minutes. Glucose has been used as a structure-directing agent in the solgel hydrolysis of stannous chloride to make large (ca 50 nm diameter)
nanospheres of SnO2 by self-assembly of nanoparticles.247 The nanospheres
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of SnO2 have high surface area (160 m /g) and exhibited elevated
photocatalysis activity toward methyl orange degradation with good
recyclability.
It was mentioned earlier that nanostructured hollow spheres of oxide
semiconductors can be prepared via hydrothermal routes with hard templates such as polystyrene latex particles, carbon particles or colloidal Silica
or soft templates such as micelles, vesicles or microemulsion droplets and
even without these templates. Hollow spheres of In2O3 have been prepared
from Indium chloride and nonporous polymeric templates by sol-gel
hydrolysis using carbonaceous spheres or sulfonated polystyrene particles
as the sacricial templates, followed by calcinations to remove the template.248a The hollow In2O3 particles have high surface area (260 m2/g) and
an enhanced photocatalytic eciency (up to Bone-fold increase) against
methylene blue (MB). In a related work, a combination of electrospinning
and solvothermal growth has been used to prepare one-dimensional In2O3TiO2 heterostructures with high visible-light photocatalytic activity.248b
Structural analysis indicated that the secondary In2O3 nanostructures were
successfully grown on the primary TiO2 nanobers substrates. The catalyst
showed enhancement of the visible-light photocatalytic activity to degrade
Rhodamine B (RB) because of the formation of heteroarchitectures and
recycling without the decrease in the photocatalytic activity
Reactive DC magnetron sputtering (5100 kHz range) has been used to
prepare Ta2O5 thin lms on quartz and conducting glass TCO substrates.249
The eect of pulsing parameters (reverse time and reverse voltage and pulse
frequency) on the thin lm properties has been studied. The optical bandgap
of the oxide varied with the pulsing frequency, Eg=4.30 and 3.36 eV on
quartz and ITO respectively. The pulsed-Ta2O5 thin lms were compared
with continuous DC-Ta2O5 lms. The sample prepared at 50 kHz pulsing
frequency shows high photocatalytic activity for the photodegradation of
Rhodamine B.
A wide band gap Ta2O5 semiconductor nanoparticle was prepared by the
hydrothermal method.250 A noble metal (Auo) deposited on by a deposition
precipitation. The photocatalytic potential of AuTa2O5 semiconductor
was investigated by degrading Methyl Orange in the presence and absence
of electron acceptors by illuminating with visible light.
Suzuki et al.251 have used hydrothermal method with carbon reinforcement to prepare mesoporous Ta2O5 spheres of particles with diameter
100500 nm range with large surface area (up to 105 m2/g) and controllable
pore diameter. A N-doped version was prepared subsequently by ammonia
treatment with retention of mesoporosity and morphology. The N-doped
Ta2O5 exhibited good photocatalytic activity for CO2 reduction.
Anodization of Ta in a K2HPO4 containing glycerol electrolyte at elevated
temperatures (180 1C) has been used to prepare nanoporous Ta2O5.252
Under optimized conditions, uniformly over the entire anodized surface,
self-organized porous Ta2O5 structures can be formed, that consist of highly
aligned pores of 25 nm diameter and several tens of micrometers in length.
Synthesis of Ta2O5 thin lms in the forms of three-dimensionally ordered
macroporous (3-DOM) materials by aqueous organic gel process guided by
polystyrene (PS) colloidal templates has also been reported.253
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254a
An et al.
have reported on the synthesis of uniform nanospheres
of core-shell Fe3O4@SiO2 nanocomposites by a combination of polyol,
sol-gel processes and then use them to prepare ferromagnetic Fe3O4@SiO2@AgCl:Ag plasmonic nanoparticles via polyol precipation followed by
photoreduction. The as-achieved nanophotocatalysts exhibit excellent performance in the decomposition of organic pollutants, such as Rhodamine B
(RhB) under visible-light irradiation. Moreover, the catalysts can be
recovered easily by applying an external magnetic eld. These features mean
the present magnetic nanophotocatalysts have promising applications in
environmental remediation and water disinfection elds.
A series of heterostructures of zinciron mixed oxide photocatalysts have
been fabricated by solutioncombustion method using urea as the fuel, and
nitrate salts of both iron and zinc as the metal source.254b The synthesized
photocatalysts were tested towards photodegradation of 4-chloro-2-nitro
phenol (CNP), Rhodamine 6G (R6G), and photocatalytic hydrogen production under visible light (lZ400 nm). The photocatalyst having zinc to
iron ratio of 50:50 showed best photocatalytic activity among all the synthesized photocatalysts. Layered titanates modied with molecular level
iron oxide were synthesized by a reaction between K0.7Ti1.73Li0.27O4 and
Fe(III) acetylacetonate complex using the dodecylammonium-exchanged
layered titanate as intermediate.254c The iron oxide-modied layered titanates were used as catalysts for selective oxidation of cyclohexane with
molecular oxygen under sunlight irradiation. The catalysts produced
cyclohexanone and cyclohexanol with high selectivity up to 100%. The
cyclohexane conversion over the iron oxide-modied layered titanates was
substantially improved with 100% selectivity maintained by conducting the
reaction under a CO2 atmosphere.
Cuprous oxide (Cu2O) is a p-type semiconducting material with a
moderate bandgap of 2.17 eV with a high optical absorption coecient.
There have been many reports on its possible usage in photodecomposition
of water and in photocatalysis. As with other semiconducting oxides, the
properties of the copper oxide depend on the morphology and microstructure. As with titania and ZnO, Cu2O synthesis in dierent morphologies - nanowires, hollow spheres, nanotubes and nanocubes as well as
hierarchical structures derived from these. Recently Meng et al.255 has
reported on the synthesis of novel hierarchical bow-like Cu2O at room
temperature using Polyvinylpyrrolidone PVPV as the structure directing
agent in the presence of NaBH4. Details of the growth mechanism also
investigated. The prepared hierarchical bow-like Cu2O crystals exhibited
a higher photocatalytic activity for photodegradation of Rhodamine B
aqueous solution under visible light illumination than the other prepared
Cu2O crystal samples with dierent morphologies (nanoparticles and
octahedra) because of its large surface area and specic hierarchical bowlike structure.
Manganese oxides nanomaterial (MnOx) with crystalline phases of
MnOOH nanorod and Mn3O4 octahedron-like were synthesized by
hydrothermal method based on the redox reaction between MnO4 and
HCHO at 120 1C and 200 1C for 10 h, respectively.256 The material was
active to catalytic degrade alizarin yellow R in aerated aqueous solutions
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under visible light irradiation. Manganese oxide catalyst has also been
prepared from several mineral resources such as Birnessite and Todorokite
and their eciency for the photocatalytic degradation of phenol studied.257a
The photocatalytic disinfection of Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) was investigated systematically with polythiophene/MnO2 (PTh/MnO2) nanocomposite photocatalyst under solar
light irradiation.257b The inuence parameters of disinfection by PTh/MnO2
nanocomposite, such as irradiation time and concentration of photocatalyst
were studied. Almost all (99.9%) of the initial bacteria were killed after 6 h
incubation at 37 1C in the presence of 1 mg/mL PTh/MnO2 photocatalyst
under solar light irradiation.
Novel Ag3VO4/TiO2 nanocomposites photocatalysts with high
eciency and broad spectral response have been prepared by a facile and
low-cost coupling method.258a The samples performed high photocatalytic
activity and stability in decomposing continuous-ow gaseous benzene with
high toxicity and stability under both visible and simulated solar light
irradiation. The conversion and mineralization rate was nearly two times
higher than that of nitrogen-doped TiO2 (TiO2xNx), Nussbaum and Paz258b
reported a study on the photocatalytic degradation of contaminants
(salicylic acid and stearic acid) on titanium dioxide lms overcoated with a
few monolayers of silica. A rather uncommon situation was observed,
where the presence of the thin silica layers decreased the degradation rate
of stearic acid while increasing that of salicylic acid. The eect explained
in terms of gradual changes in the isoelectric point. If optimized, this
eect can be utilized to precisely control adsorption or desorption and
accordingly to induce specicity in the photocatalytic degradation of
contaminants.
2.3 Chalcogenides based photocatalysts
2.3.1 Metal chalcogenides photocatalysts. After titania and related
titanates, metal chalcogenides such as CdS are the most extensively studied
family of photocatalysts. One major attraction of metal chalcogenides such
as PbSe, PbS, CdSe or CdS is the potential to tune the bandgap energy
through size quantization eects. The visible light response of the photocatalysts can be tuned through the entire visible light region and even into
the infra-red. A major problem of CdS as a photocatalyst in aqueous
solution is its photocorrosion. They corrode rapidly due to the autooxidation of the semiconductor by the photogenerated holes. A common
protection procedure is to employ redox mediators such as polysuldes or
polyselenides to rapidly extract the holes and transfer them to the solution
phase. Various nanostructures (nanowires, nanospheres and nanotubes of
CdS have been prepared towards increasing the photoreactivity and
improved stability.259269
Many of the techniques that been developed for titania photocatalysts
(such as metal ions doping) are being extended to metal chalcogenide
semiconductors as well. Luo et al.259 have reported on the synthesis
of hollow spheres of CdS and Ni-doped CdS via a simple tempate
free one pot method. As prepared CdS and Ni-doped CdS hollow spheres
showed superior photocatalytic activity for the degradation of
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Rhodamine B and phenols under visible light. The unique hollow spheres
structure may favor the harvesting of exciting light due to multiple
scattering within the interior space, and the doping of Ni2 may
facilitate the generation of electrons and holes pairs and inhibit their
recombination rate by act as a temporary trapping sites of photoinduced
electrons.
Vela et al.260 have reported on the controlled fabrication of colloidal CdSPt hybrid nanostructures via site-selective metal photodeposition. Careful
selection of synthetic conditions allows deposition of Pt and Pd particles on
CdS and CdS0.4Se0.6 nanorods with a high degree of selectivity (9095%
surface-bound obtained photochemically) over the formation of freestanding metal particles (7094% unattached under thermal conditions).
In addition, metal photo deposition occurs on specic segments of
CdS0.4Se0.6 nanorods with compositional anisotropy by taking advantage of
the band gap dierential between dierent nanodomains.
Irradiation at short wavelengths favors formation of Pd nanoparticles on
the large band gap CdS-rich region of the nanorods (57% and 55% at 350
and 420 nm, respectively), while irradiation at longer wavelengths favors the
formation of Pd nanoparticles on the small band gap CdSe-rich region of
the nanorods (83% at 575 nm). These specially decorated metal (M=Pt, Pd)
islands on the semiconductor (SC) surface signicantly enhance activity and
selectivity and also greatly stabilize the SC against photoinduced etching
and degradation. Under selected conditions, CdS-Pt favors dehydrogenation (H2) over hydrogenolysis (toluene) 8 : 1, whereas CdS0.4Se0.6-Pd favors
hydrogenolysis over dehydrogenation 3 : 1.
In-situ preparation of metal chalcogenides in the presence of noble
metal salts permit synthesis of novel photocatalyst systems of metal
core@semiconductor shell architectures. Kamats group has carried out
signicant research on such core-shell nanocomposites, including the study
of photogenerated electrons behavior using the spectroscopic techniques
and the photocatalytic activity. In a recent publication Xu et al.261
described a method to fabricate the Pd@CdS nanocomposite with a novel
coenocytic, i.e. multi-Pd core@CdS shell structure via a L-cysteine-assisted
hydrothermal treatment. Its photocatalytic activity is evaluated using
selective oxidation of alcohols to corresponding aldehydes as testing reactions under mild conditions. The activity of the coenocytic catalyst is much
higher than that of blank CdS prepared in the absence of Pd colloids as
seeds.
Hybrid nanoparticles containing the semiconductor CdS and the
palladium compounds PdO or Pd4S were produced by Banin et al.262
through two dierent synthetic mechanisms. The hybrids CdS-Pd4S and
CdS-PdO underwent photoinduced charge separation, as demonstrated by
their activity in the photoreduction of water. Pak et al.263 have reported on
the synthesis of PbSe/CdSe/CdS core/shell/shell heterostructure nanocrystals with type II or quasi-type II band osets. Varying deposition
rates of the CdS shell result in nanocrystals of diverse morphologies
ranging from spheres to pyramids to tetrapods. The faceted shapes
enable the selective growth of Au tips, which help increase photocatalytic
activity since the Au tips serve as an electron sink.of water.
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Photodegradation of methylene blue dye has been studied using these

nanocrystal materials.
A novel heterostructure consisting of a metal Cd core and a ZnO-CdS
heterostructural shell, (ZnO nanoparticles are embedded in a CdS shell) has
been prepared and tested for photoreduction of water. Photocatalytic
hydrogen evolution is greatly improved due to the metal Cd core, which
provides a charge-carrier transport channel for enhancing the recombination of photoexcited electrons from ZnO and holes from CdS based on Zscheme co-operation.264 Gao et al.265 prepared Graphene Oxide-CdS-Pt
(GO-CdS-Pt) nanocomposite with dierent amount of Pt via formic acid
reduction followed by two-phase mixing method. Photocatalytic studies
showed that the GO-CdS-Pt composite containing 0.5 at% of Pt exhibits
the highest hydrogen evolution rate of 123 mL h1 g1 with strong photostability, which is about 2.5 times higher than that of GO-CdS and 10.3
times higher than that of CdS.
Reli et al.266 have examined photoreduction of CO2 to CH4 and CO on
ZnS particles deposited on Montmorillonite under dierent photolysis conditions. The addition of Na2SO3 improved methanol yields due to the oxidation prevention of incipient methanol to carbon dioxide. The gas phase
yields were decreased by the Na2SO3 addition. The best tested reaction
medium for the photocatalytic reduction of CO2 was the solution of sodium
hydroxide. Sulfur oxide (SO2) is one of the important air pollutants, which
mainly originates from the combustion of coal and fuel derived from petroleum. Flue gas desulphurization (FGD) is considered as one of the
most eective ways to control emissions of SO2 from the combustion of fossil
fuels. Ammonia-based wet ue gas desulfurization has drawn increasing
attention because of its lower investment, higher desulfurization eciency,
and useful byproducts. CdS loaded with Pt was selected as the model
photocatalyst to study photocatalytic ue gas desulphurization.
2.3.2 Binary nanocomposites of titania and metal chalcogenides. To
improve the spectral response, a combination of two or more photocatalysts
has also been examined. The two catalysts can be present as independent
particulates suspended in solution or the two integrated into a single device.
Several congurations of catalysts integration such as alloys, solid solutions,
core-shell system and as nano-composite heterostructures have been examined.270277 Hydrothermal growth and electrochemical deposition using one
of the two photocatalyst as a template are possible approaches. Inter-particle /
inter-semiconductor electron-hole transfer processes in such binary semiconductor systems depend on the relative disposition of the valence and
conduction band-edges of the two semiconductors. Relative dispositions of
two well studied heterostructures are schematically shown in Fig. 2.
In Type I case, the semiconductor 2 has a larger bandgap and its Ecb(2),
Evb(2) lie above and below the Ecb(1) and Evb (1) levels respectively. In
Type II case, the semiconductor 1 and 2 can have similar bandgaps with
Ecb(2) placed above Ecb(1) as in Type I but Evb(2) is more positive with
respect to Evb(1). Since this disposition permits ow of electrons and holes,
type II heterojunciton functions similarly as in a p-n junction, but without
special doping of one or the other semiconductor to shift the band edge
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Fig. 2 Relative dispositions of valence and conduction bandedge positions in binary Type I
and Type II heterostructure systems.
Table 2 Data on the eective bandgap energies and location of eective valence band maximum for some binary heterostructures formed by semiconductors.
Heterostructure
VBmax
Location
Eective
Bandgap
(eV)
ZnO
ZnO
ZnO
ZnO
ZnO
ZnS
ZnSe
ZnTe
CdS
CdSe
2.07
1.84
1.17
2.17
1.73
ZnS
ZnSe
ZnTe
CdS
CdSe
Heterostructure
VBmax
Location
Eective
Bandgap
(eV)
CdS ZnSe
CdSe CdTe
CdSe ZnTe
GaN GaP
ZnSe ZnTe
ZnSe
CdTe
ZnTe
GaP
ZnTe
2.05
1.16
1.07
0.87
2.07
positions. In addition, Type II heterojunctions can reduce substantially the

bandgap so as to eciently harvest more light.
Table 2 lists data for the eective bandgap energy and the location of
valence band maximum of some of the heterostructures studied. Such Type
II heterostructures have been studied for possible use in Dye-sensitized solar
cells and in quantum dot solar cells. Such heterostructures have been prepared using nanoparticles, compact electrodes made out of these nanoparticles and even with nanowires.
A nanocomposite of CdZnS grown on titania nanotubes (Cd0.5.Zn0.5S/
TiNT) has been prepared in an one-step process by Chen and Guo.270 CdZnS
nanoparticles of 90 nm size are surrounded by the network of titania nanotubes. Under visible light irradiation Cd0.5.Zn0.5S/TNTs displayed improved
activities compared to the single Cd0.5.Zn0.5S for hydrogen evolution. The
highest apparent quantum yield of 38.1% at 420 nm achieved is among the
highest eciencies for the noble-metal free photocatalysts ever reported.
2.4 New photocatalysts
2.4.1 Graphene, graphene oxide, graphene nitride (g-C3N4). In recent
years several synthetic procedures have been developed for the preparation
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and characterization of various allotrophic versions of carbon. Carbon

nanotubes, graphenes, graphene nitride are some nanostructured materials
showing great promise in several applications. Some of the attractive features of carbon allotrophes are their chemical inertness, low toxicity, ease of
preparation and electrical conductivity. Graphene is an important material
for diverse applications in photonics, optoelectronics and energy storage.278282 Graphene in addition to providing a large surface for dispersing
the photocatalyst can act as electrically conducting substrate. Graphene
oxide, the precursor material for the preparation of graphene also has been
tested.
Graphene Quantum Dots also received attention as possible alternatives
to oxide and chalcogenide-based semiconductors. Quantum dots of carbon
have been prepared by a number of methods (laser ablation, electrochemical
oxidation of graphite, thermal oxidation of carbon precursors, vapor phase
deposition of soot and microwave synthesis) and tested for photocatalysis
applications.283289 Top-down approaches such as cutting of graphene
sheets or ribbons have also been described.
Pan et al.283 have reported a method for the fabrication of water-soluble
and well-crystallized graphene quantum dots with lateral size about 3.0 nm
by a hydrothermal cutting method. A facile hydrazine hydrate reduction of
graphene oxide (GO) with surface-passivated by a polyethylene glycol
(PEG) method for the fabrication of graphene quantum dots (GQDs) with
frequency upconverted emission has been reported.284 The upconversion
luminescence is believed to be due to the anti-Stokes photoluminescence
(ASPL), where the dE between the p and s orbitals is near 1.1 eV. A facile
one-step alkali-assisted electrochemical synthesis of high-quality CQDs
with sizes of 1.23.8 nm has been reported,285 which exhibit stable and
strong photoluminescence (quantum yield about 12%). By combining free
dispersion in water, size-dependent optical properties, and upconverted PL
properties, CQDs may provide a new type of uorescent markers as well as
a new approach to high-eciency catalyst design for applications in
bioscience and energy technology.
A series of TiO2-reduced graphene oxide (RGO) nanocomposites were
prepared by simple one-step hydrothermal reactions using the titania precursor, TiCl4 and graphene oxide (GO) without reducing agents.287
Hydrolysis of TiCl4 and mild reduction of GO were simultaneously carried
out under hydrothermal conditions. In addition, the photocatalytic activities of the synthesized composites were measured for the degradation of
Rhodamine B dye. The catalyst also can degrade a colorless dye such as
benzoic acid under visible light. The synthesized nanocomposites of
biphasic TiO2 with RGO showed enhanced catalytic activity compared to
conventional TiO2 photocatalyst, P25. The photocatalytic activity is
strongly aected by the concentration of RGO in the nanocomposites, with
the best photocatalytic activity observed for the composite of 2.0 wt %
RGO.
Graphene-TiO2 (G-TiO2) composites have been prepared through a onepot solvothermal reaction by using graphite oxide (GO) and tetrabutyl
titanate as starting materials.288 TiO2 particles with anatase phase and a
narrow size distribution were dispersed on the surface of graphene sheets
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uniformly. The product prepared with 30 mg of GO and 8 h of reaction time

exhibited excellent photocatalysis to methylene blue (MB) degradation
under irradiation of simulated sunlight
Graphitic carbon nitride is a Carbon-derived photocatalyst showing great
promise. The material, actually a polymer, poly(tri-s-triazine), g-C3N4
derived from cyanamide has been known since 1834 under the name
melon. It is the most stable allotroph of carbon nitride. The aromatic
nature of the s-triazine ring in the condensation polymer, g-C3N4 confers
exceptional thermal stability (up to 600 1C even in air) and resistance to
chemical attacks (acid, base and organic solvents). Studies have established
that GCN is an indirect semiconductor with a bandgap of 2.7 eV, corresponding to optical absorption threshold of 460 nm. A number of photocatalytic processes have been found to occur on graphene nitrides.289299
For the water photodecomposition to H2 and O2, the band edge positions of
valence and conduction bands of GCN are placed signicantly above and
below the H/H2 and O2/H2O redox potentials. Mesoporous g-C3N4 with
high surface area has been prepared via nanocasting or replication of
mesoporous silica matrices
Wang et al.289 rst predicted that g-C3N4 is capable of photo-splitting
water thermodynamically under light irradiation in neutral solution as well
as under acidic or basic conditions. Their proof-of-concept studies revealed
that bulk g-C3N4 can successfully catalyse two parts of the water splitting
cycle with visible light, namely, the water-reduction half-cycle to produce
H2 and the water oxidation half-cycle to form O2 under visible light irradiation (lW420 nm). This redox reaction can occur in the presence of a
proper sacricial electron acceptor or donor, respectively, even without
addition of precious metal co-catalysts.
Apart from C-H and O-H oxidation, N-H oxidation can also be carried
out using GCN.290 For example, light-excited mesoporous g-C3N4 can
activate molecular oxygen for the oxidation of alcohols to aldehydes/
ketones with high selectivity. Mesoporous mgp-C3N4 catalyzes the oxidation of benzyl alcohol to benzaldehyde with >99% selectivity and 57%
conversion under visible light irradiation for 3 h at 100 1 C. Under optimized
conditions, complete conversion of benzylamine into Nbenzylidene
benzylamine was obtained in 3.5 h. Latter one is a rare catalytic reaction, as
these heteroatoms usually poison most metal catalysts. Specically, a simple
and ecient synthesis of benzoxazoles, benzimidazoles, and benzothiazoles
could be realized through a one-pot synthesis by this photocatalytic cascade
reaction with notably high yields.
Oxidative coupling reactions can also carried out using GCN and O2.
Oxidative coupling of N-phenyl-1,2,3,4-tetrahydoisoquinoline with nitromethane in the presence of mpg-C3N4, visible light, and oxygen can achieve
100% conversion to the condensation product with a high isolated yield
(92%). Oxidative coupling reactions of various tetrahydroisoquinolines
with nitroalkanes have also been demonstrated.
2.4.2 New photocatalysts - metal-organic frameworks and polyoxometalates. Metal-Organic Frameworks (MOF) are crystalline compounds consisting of metal ions or clusters coordinated to often rigid
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organic molecules to form one-, two-, or three-dimensional structures that

can be porous. Long et al.300a have prepared amine-functionalized zirconium metalorganic framework (MOF) (UiO-66-NH2)4) and tested its
ability as a photocatalyst. The material showed light absorption in the bluegreen region, permitting excitation of the photocatalyst with visible light.
The MOF has been shown to work as a visible-light photocatalyst (420 nm
light) for selective aerobic oxygenation of various organic compounds
including alcohols, olens and cyclic alkanes, at high eciency and high
selectivity.
Wen et al.300b have prepared ve new metalorganic frameworks
[M(btec)0.5(bimb)]n1 (M=Co (1), Ni (2), Cu (3), Zn (4)) and [Cd(btec)0.5(bimb) 0.5]n5, by reactions of the conjugated 1,2,4,5-benzenetetracarboxylic
acid (H4btec) and 4,4 0 -bis(1-imidazolyl)biphenyl (bimb) with corresponding
metal salts under hydrothermal conditions, respectively. Compounds 1, 2,
and 5 proved to be good MOFs-based visible-light-driven photocatalysts
for the oxidation of an anionic organic dye X3B with good stability toward
photocatalysis. In a related work, Fu et al.300c have reported on successful
photocatalytic reduction of CO2 to HCOO in acetonitrile under visible
light irradiation over a photoactive Ti-containing MOF, NH2-MIL-125(Ti),
which is fabricated by a facile substitution of ligands in the UV-responsive
MIL-125(Ti) material. Two limitations of the current photocatalytic system
are the low eciency of the MOF catalyst and the usage of TEOA as the
sacricial electron donor. Proposed mechanism involves optical excitation
of LMCT band leading to electron transfer from the organic ligand to Ti4.
When CO2 is introduced into the suspension, the reduction of CO2 by Ti3
to HCOO occurs.
Transition metal oxyanions readily link together to form larger polyoxometalates (POM) with a 3-dimensional framework structure.301304
Group 5 and 6 transition metals in their high oxidation state such as V(V),
Nb(V), Ta(VI), Mo(VI) and W(VI) form readily polyoxymetalates. Keggin
anion such as [PW12O40]3 and Wells-Dawson polyoxometalate, K6[aP2W18O62].14H2O are best known examples of phosphotungstate POMs.
Phosphotungstate anion [PW12O40]3 for example is composed of a framework of 12 octahedral tungsten oxyanions surrounding a phosphate
group. Recent attraction has been the ease of synthesis of dierent polyoxometalates. Oxygen anions are generally inert, making these robust
materials for catalytic studies.
Photocatalytic H2 evolution activity under UV irradiation has been
reported with various Keggin structured XW12O40n clusters (X = Si, P, B,
Ge, Fe, Co or H2). A tin(II) tungstosilicate derivative K11H[Sn4(SiW9O34)2] 25H2O with four sandwiched Sn2 cations has been prepared by
reaction of SnCl2, KCl and Na10[a-SiW9O34] xH2O.302 This material shows
visible light absorption, with the bandgap energy estimated to be ca 2.0 eV.
Notable feature of this POM is photocatalytic H2 evolution under visible
light irradiation with Pt nanoparticles as co-catalyst and methanol as
sacricial agent.
Huang et al.303 have reported on the synthesis of three novel polyoxoniobates by a self-assembly procedure: KNa2[Nb24O72H21] 38H2O (1),
K2Na2 [Nb32O96H28] 80H2O (2), and K12[Nb24O72H21]4 107H2O (3).
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UV-light photocatalytic H2 evolution activity was observed for these

compounds with Co(III)(dmgH)2(py)Cl as a cocatalyst and TEA as a
sacricial electron donor. A complex of polyoxoniobate with copper(II)
ethylenediamine, [Cu(en)2]11K4Na2[KNb24O72H9]2 12 H2O (1) has been
synthesized and systematically characterized.304 The Cu(II)en complex
presents a strong adsorption in the visible light region, permitting an
extension of the spectral response of [Nb6O19]8 to the visible region. Visible
light photocatalytic H2 evolution activity was researched with 1 as the
visible-light photosensitizer and catalyst, cobaloximes [Co(III)(dmgH)2pyCl] as the co-catalysts, and triethylamine (TEA) as the sacricial electron
donor.
2.4.3
oxides
New photocatalysts - perovskites and other layered perovskite
2.4.3.1. Bismuth based photocatalysts (tungstate, vanadate and molybdates). Bi2WO6 absorbs in the visible light region up to 460 nm and hence
can be a good photocatalyst for visible light.305311 Zhang et al.305 reported
the identication of ower-like Bi2WO6 as a highly selective visible-light
photocatalyst toward aerobic selective oxidation of glycerol to dihydroxyacetone using oxygen as oxidant in water at room temperature and
atmospheric pressure. Ag-loaded Bi2WO6 catalyst has been found, as
expected, to show enhanced photocatalytic activity due to surface plasmon
resonance eects.306
Hydrangeas-like Bi2WO6 powders were synthesized successfully by saltultrasonic assisted hydrothermal process.307 The band gap was estimated to
be 2.56 eV from the onset of UV-Vis absorption spectra of the catalyst. The
photocatalyst found to eciently cause degradation of Rhodamine B under
visible light irradiation. In a related work,308 nanostructured Bi2WO6 with
dierent hierarchical morphologies were synthesized via a warmly hydrothermal route and examined for their relative performance to photodegrade
Rhodamine B. The nest-like Bi2WO6 exhibited superior photocatalytic
eects compared with other three Bi2WO6 morphologies. The Mo-doped
Bi2WO6 three-dimensional (3D) hierarchical microspheres from nanoplates
have been synthesized by a hydrothermal route and found to be more
eective than the pristine catalyst for the photodegradation of Rhodamine
B dye.309
BiVO4 with monoclinic sheelite-like structure is a visible light-responsive
compound active in photocatalytic processes.312318 Sol-gel hydrolysis of a
mixture of Bismuth nitrate and ammonium vanadate followed by calcinations gives active BiVO4 photocatalyst.312 Control studies of photodegradation of methylene blue using visible light have shown that most
active form of the catalyst is formed only when the pH of the precursor
solution is kept around pH 7. Chen et al.313 prepared BiVO4 by hydrothermal method using Bi(NO3)3 and NH4VO3 and found the photocatalytic
eciency of BiVO4 depended on the preparation conditions. Photoreduction of CO2 to methane was studied under visible light. Best results are
obtained with materials hydrolyzed at pH 7 followed by calcination at
195 1C for 6 hours. In a related study, visible-light irradiation to monoclinic
scheelite BiVO4 (m-BiVO4) in a solution of copper acetylacetonate
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314
(Cu(acac) 2 led to its decomposition and Cu recovery.

The photonic
eciency at l=440 15 nm reaches 3.4%, exceeding the value for the TiO2
photo-catalyzed reaction at l=355 23 nm (2.0%).
The inuence of hydrothermal synthesis, thermal post-treatment at 500 1C
and Mo content on a series of Bi1-x/3V1-xMoxO4 (0.02oxo0.15) photocatalysts was investigated for methylene blue (MB) degradation and O2
evolution.312a Mo incorporation stabilized the tetragonal scheelite phase of
BiVO4, thereby inducing a small blue shift of the band gap. This adverse
eect could be partially compensated by incorporation of lower Mo amounts
(up to ca. 4%), which, stabilized the particle morphology upon calcination.
Both BiVO4@TiO2 and BiVO4:Mo@TiO2 heterojunction composites with
TiO2 particle coatings in the 10 nm range were newly synthesized and displayed promising photocatalytic performance in MB degradation.
Gawande and Thakare315 prepared a graphene-wrapped BiVO4 by sol-gel
hydrolysis method in the presence of graphene and found the derived GWBiVO4 photocatalyst showed enhanced activity for the photodegradation of
methylene blue. Photoluminescence and trapping experiments showed that
the direct hole oxidation of BiVO4 was responsible for the observed photodegradation. Using citric acid or polymethylmethacrylate PMMA as
structure directing agent during hydrothermal synthesis, Liu et al.316 have
prepared 3-D macroporous BiVO4 with high surface area (1824 m2/g).
Photodegradation of phenol was studied by using this photocatalyst with
added H2O2 as a co-oxidant. Measured bandgap energies of the BiVO4
photocatalysts are in the range of 2.502.55 eV, which are comparable with
those (2.482.55 eV) of monoclinic BiVO4 reported previously. Among the
as-prepared BiVO4 samples, the one with a surface area of ca. 24 m2/g
showed the best visible light-driven photocatalytic performance for phenol
degradation (phenol conversion of ca. 94% at phenol concentration=
0.1 mmol/l and in the presenceof 0.6 mL H2O2.
A one-step template free hydrothermal synthesis method has been
examined to prepare binary BiVO4-TiO2 photocatalyst using Bismuth
nitrate and (NH4)2TiF6 as precursors and glucose as the structure guiding
agent.317 Analysis of the product showed formation of hollow microspheres
containing BiVO4 and TiO2 nanocrystals. The binary catalyst showed good
activity for the photodegradation of acetic acid under visible light irradiation. Bi2S3 is a low bandgap semiconductor (Eg=1.3 eV) with good photocatalytic properties. A binary nanocomposite of Bi2S3 and BiVO4 has
been tested. Well-dened olive-shaped Bi2S3/BiVO4 microspheres were
synthesized through a limited chemical conversion route (LCCR), where
olive-shaped BiVO4 microspheres and thioacetamide (TAA) were used as
precursors and sulfur source, respectively.318 The composite catalyst
showed better performance for the photodegradation of Rhodamine B and
for refractory oxytetracycline.
Mesoporous bismuth molybdenum oxide (Bi2MoO6) microspheres have
been fabricated via a template-free solvothermal process using bismuth
nitrate Bi(NO3)3 and ammonium molybdate ((NH4)6Mo7O24) in the presence of ethylene glycol.319 Structural characterization showed that the
microspheres were composed of nanosheets with diameter of 0.51.0 um,
specic surface areas of about 50.86 m2/g, and a band gap energy of about
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2.59 eV. The photocatalyst showed much better performance for Rhodamine B photodegradation with visible light as compared to degradation
using titania. In a related work, Bi2MoO6 hollow microspheres were modied by depositing TiO2 nanoparticles through a simple hydrothermal
method.320 The prepared TiO2/ Bi2MoO6 composite catalyst was tested for
Methylene Blue degradation under visible light. The photocatalysts based
on nanostructured Bi2MoO6 and TiO2 exhibit much higher photocatalytic
activity than the single-phase Bi2MoO6 or TiO2 and the mechanical mixture
of Bi2MoO6 and TiO2 for degradation of MB under the same conditions.
Bismuth Oxide (Bi2O3) quantum dots decorated anatase TiO2 with
exposed {001} high energy facets has been prepared on graphene sheets by a
simple and feasible strategy using the hydrouoric acid.321 During the
synthesis process, TiO2 nanosheets were homogeneously decorated with
surface enrichment of Bi2O3 quantum dots and graphene was uniformly
covered with a large number of Bi2O3/TiO2 composites. The Bi2O3/TiO2/
graphene hybrids could be used as a stable photocatalyst for the highest
photocatalytic activity for Rhodamine B degradation.
2.5 Advanced oxidation processes (AOP)
It was mentioned earlier that Advanced Oxidation Processes refer to protocols where more than one of degradation methods, chemical, photochemical, sonolysis, ozonolysis, and ultraltration using special membranes
is used to obtain maximum eciency. Here we briey mention some of the
studies using ultraltration,322,323 ozonolysis,324,325 sonolysis326329 and
Photo-Fenton330334 processes. Synergistic role of multiple oxidation
pathways is a question that is also addressed in these studies.
2.5.1 Hybrid photocatalysis ultraltration. While immobilization of
the photocatalyst facilitates its ready separation, there can be some loss of
activity as well - reason most studies still use aqueous particulate suspensions. Photocatalytic Membrane Reactor (PMR) is another concept that
involves coupling of photocatalysis with a physical membrane ltration
process. Microltration (MF), ultraltration (UF) and reverse osmosis
(RO) are some of the processes of interest. Membrane ltration permits
separation of the degraded products by retaining the photocatalyst.322,323
The problem of membrane fouling that causes a decrease in the ux through
the membrane (caused by the adsorption and re-precipitation of organic
and inorganic compounds) has still to be solved.
A hybrid photocatalysismembrane separation process (in a laboratoryscale pilot system) has been successfully tested for the degradation of Humic
Acids (HAs).322 A photocatalytic Membrane Reactor (PMR) employing an
Ultraltration (UF) submerged module was operated in continuous mode
with TiO2 catalyst concentration 0.75 g/L and UV-A radiant ux 15.1 J/s,
treating feed water with HA concentrations 5.0 and 10.0 mg/L. The overall
process removal eciency (comprising both HA oxidation and UF membrane rejection) was even higher, as a result of the synergistic eects of
photocatalytic oxidation and membrane ltration. A combination of photocatalysis and ultraltration has been examined for eective removal of
azo dyes in the waste water treatment.
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2.5.2 Hybrid photocatalysis ozonolysis. Ozone is known to react

directly and selectively with many organic compounds with unsaturated
bonds via cycloaddition reactions. Decomposition of ozone generates
hydroxyl radical, a good non-selective oxidant. In view of these two benecial factors, photocatalysis studies are often carried out in the presence of
added ozone (ozonolysis). The synergistic action of the two processes has
been examined by Mena et al.324 in the oxidation of methanol. Three main
processes are considered during photocatalytic ozonation: direct ozonemethanol reaction, indirect ozone reactions and photocatalytic reactions.
The presence of ozone exerts a positive eect in the reaction rate of oxidizing species formation due to light induced reactions also enhancing the
quantum yield from 0.34 to 0.80. Combined ozonolysis and TiO2-based
photocatalysis have been successfully used to degrade sulfamethoxypyridazine in aqueous solutions.325
2.5.3 Hybrid photocatalysis sonolysis. Sonication is another degradation method used along with photocatalysis to enhance the rate of
decomposition of organic compounds. The penetrating ability of ultrasound is very strong even for the opaque wastewater medium and its
penetrating depth can ordinarily attain 1520 cm. Dual frequency (20/
40 kHz) or multiple frequency sonolysis is often employed. Sonolysis in
the presence of H2O2 has been reported to produce more hydroxyl (dOH)
and hydroperoxy (dOOH) radicals. In the degradation of phenol, Wang
and Yu326 have observed a synergistic eect of sonolysis and ZnFeO4/
TiO2 hybrid photocatalytic degradation. A study of dual frequency
ultrasonic assisted photocatalysis of methylene blue degradation has been
reported.327 Neppolian and coworkers328 have used ultrasound-assisted
method to prepare nanosized Pt-graphene oxide GO-titania photocatalysts. The photocatalytic and sonophotocatalytic degradation of a
commonly used anionic surfactant, dodecyl-benzenesulfonate (DBS), in
aqueous solution was found to be 3 times more ecient with the PtGO
TiO2 nanoparticles as compared to that obtained with standard P25
titania particles.
2.5.4 Fenton and photo-fenton reactions. Advanced Oxidation processes
(AOP) refer to the combined use of chemical, photochemical and electrochemical techniques to bring about chemical degradation of organic dyes.
The popular chemical route involves the use of Fe(III) ions and H2O2 as the
source of the reactive hydroxyl radical (dOH) to trigger the degradation
process of organic compounds. UV-light irradiation is also used with the
chemical oxidant and the combined process is known as Photo-Fenton
reaction. A few reports have appeared on photodegradation using the
combined photocatalysis routes.330334
The photodegradation of the dye Direct Yellow DY12 by photocatalytic
reactions of ZnO has been studied in the presence of Fe3 salts.330
A comparison of electro-Fenton (EF), UV/ZnO, Photoelectro-Fenton
(PEF) and PEF/ZnO processes for decolorization of DY12 solution was
performed. Results showed that color removal follows the decreasing order:
PEF/ZnO/PEF/EF/UV/ZnO.
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333
Liu et al.
prepared Fe/TiO2 nanocomposites in a two step process,
preparation of nanoparticles of titania by sol-gel hydrolysis-calcination
followed by chemical reductive deposition of Fe. Analysis showed that the
loaded forms of iron include Fe, Fe2 and FeOOH due to the reaction with
oxygen. The Fe/TiO2 catalyst has signicantly increased optical absorption
than TiO2. In a test reaction of photodegradation of 2,4-dichlorophenol,
the Fe/TiO2 composite was more eective than Fenton-reaction or TiO2
alone.
3
Photodecomposition of water
Since the reports by Fujishima and Honda on possible photodecomposition

of water to H2 and O2,31 there have been a number of photochemical and
photoelectrochemical studies on this topic.335338 Water decomposition is a
dicult process to achieve for two main reasons: i) Whatever photoactive
materials are employed, they should be able to generate suitable redox
active species that are capable of oxidizing water (anodes) and reducing
water (cathode process). For semiconductors as light absorbers, primary
charge carriers produced upon light absorption are electrons in the conduction band and holes in the valence band respectively. So the band-edge
positions of the semiconductor must traverse these thermodynamic
energy limits. ii) The generation of molecular H2 and O2 as products involve
multi-electron transfer processes (H2 reduction involve 2 electron reduction
of protons while oxidation to O2 is a 4-electron transfer process (reactions
1618).
Anode :
Cathode :
Overall :
2H2 O 4h ! O2 4H ;
4H 4e ! 2H2 ;
Eo 1:23 V vs: NHE
Eo 0 V vs: NHE
2H2 O ! O2 g 2H2 g;
DG 237 kJ mol=l
16
17
18
Fig. 3 shows schematically ideal dispositions of the valence and conduction bands of a semiconductor for eective photodecomposition of
water to H2 and O2.
Most of the photoactive materials are not good electrocatalysts for H2
and O2 evolution reactions. Hence the multi-electron transfer processes
are to be promoted using suitable redox catalysts. Several electrocatalysts
for H2 and O2 evolution reactions have been identied recently. Thermodynamically both reactions require some over-voltage as driving force.
Numerous studies have shown that at least 200 mV driving force
must be allowed for each of these two reactions to occur cleanly and
quantitatively without involving one-electron or hole transfer processes.
Thermodynamic requirement for water decomposition to H2 and O2 is
1.23 eV. With the minimal overvoltage losses for the two processes, photodecomposition of water using solar radiation is feasible at energies
>1.7 eV. When the overvoltage requirements are high in cases where the
semiconductor is a poor catalyst, then energy requirements go up, resulting
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Fig. 3 Schematic diagram showing the ideal disposition of bandgap positions of oxide
semiconductors to achieve photodecomposition of water to hydrogen and oxygen.
in need to use photons of increasingly higher energy (lesser solar energy

harvesting).
As a wide bandgap material, TiO2 has a large bandgap energy of 3.0 eV.
There have been numerous attempts to increase the visible light response by
various methods, principally via doping. iii) With semiconductor materials
as photosensitizers, light induced generation of charge carriers is accompanied by rapid recombination of electrons and holes, a reaction that
kinetically competes with the escape of these reactive species to the surface
from the bulk. There have been numerous studies addressing this issue using
nanostructured materials of dierent morphologies (1-, 2- and 3-dimensional materials) and with nanocomposites prepared with suitable materials
that can enhance the charge separation process.
In the absence of total decomposition of water, for charge balancing,
studies of photoreduction of water to H2 need to use sacricial electron
donors such as EDTA, ascorbic acid or triethanolamine to reduce the holes.
Similarly photooxidation studies for O2 evolution, use sacricial electron
acceptors such as persulphate. Photocatalysis studies have been reported
using semiconductors as dispersions (particulates) and also as macroelectrodes in photoelectrochemical solar cells.
There are practical problems of photodecomposition of water in particulate systems. One is eventual separation of the two gaseous products.
Second is possible recombination of H2 and O2 (products) on the redox
catalysts limiting the overall eciency. Production of the two gases at different sites is ideally preferred as it happens in photoelectrochemical cells.
There has been a tremendous progress in all of the above areas listed above.
Chen et al.335 have provided recently a comprehensive review of various
semiconductor based catalysts for the photocatalytic hydrogen generation.
Performances of various oxide semiconductors under UV-light irradiation
as well as modied oxides that are active under visible light irradiation are
discussed.
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3.1 Catalytic photoreduction of water to H2 (half cell systems)

3.1.1 Hydrogen evolution studies in particulate suspensions of titania
3.1.1.1 Hydrogen evolution under UV irradiation. There have been
a number of studies of photoinduced H2 evolution using various morphological forms of titania, coated with a H2-evolution co-catalyst such as
Pt.339344
Nickel sulde345 and Co(II)-ions346,347 have also been used as co-catalysts
for photoreduction of water on titania. Towards design of a water
decomposition system with collection of gaseous products in geometrically
dierent zones, Tsydenov et al.340 examined a membrane photocatalytic
system (MPS), Pt/chemically loaded TiO2/ltration loaded TiO2/porous
polymer membrane/support. Chemical bath deposition of TiO2 followed by
aging was found to be essential for mechanical stability and high activity in
hydrogen production. Photodehydrogenation of ethanol was observed on
Pt-loaded titania with high quantum eciency of 13%. Self-organized TiO2
nanotube arrays allow more uniform distribution of the Pt co-catalyst and
overall improvement in the H2 production eciency.343 Similarly Pt-loaded
on to nanotubes of TiO2 prepared by rapid breakdown anodization technique showed better performance.344
A novel titanate-zirconate solid solution with controllable nanoleaf/
microsisal-like three-dimensional morphology, Na2(Ti0.75Zr0.25)4O9, has
been grown on the surface of a Ti-based bulk metallic glass by a combination of hydrothermal and dealloying processes.341 The as-synthesized
nanoleaf/microsisal-like material was found to be a good photocatalyst for
hydrogen from a methanol/water solution and the measured rates were
better than a commercial TiO2 (Degussa P25) lm and undoping titanate
nanotube lm.
Wu et al.342 have reported on photocatalytic hydrogen evolution from
water using Pd-loaded titania (P25) particulates. The Pd-loading was carried out in the presence of Gardenia leaf extracts. The Pd-Gardenia-TiO2
catalyst exhibits good photocatalytic activity for H2 evolution at rates much
higher than that of Pd photodeposited on TiO2. Since the photolysis has
been carried out for limited time it is not clear if surface-bound Gardenia
itself gets decomposed in a catalytic manner.
Nanocomposites of NiS/TiO2 photocatalyst have been prepared by a
solvothermal synthesis method and tested for photoinduced hydrogen
production in aqueous solutions containing lactic acid as the sacricial
agent.345a The structure and amount of co-catalyst play important role in
improving the photocatalytic activity of the nanocomposite. The rate of H2
evolution was increased up to about 30 times than that of TiO2 alone. TiO2
and ZnO has been prepared by sol-gel method and tested for photoreduction for water.345b In aqueous ethanol solutions, photocatalytic H2 evolution was observed, six times more eective than TiO2 alone as
photocatalyst.
3.1.1.2 TiO2 on carbon supports. There have been a number of water
photodecomposition studies on titania modied with dierent Carbon
allotrophs. Carbon-modied TiO2 photocatalyst has been prepared via
hydrothermal synthesis route, using sucrose as the carbon source.348 For the
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photogeneration of H2 from aqueous methanolic solutions, an improvement was achieved from no gas evolution at all with the bare TiO2, to an
evolution of 0.21 mL g1 h1 from a composite material modied with an
optimum carbon loading of 3.62%.
Nanotubes of titania with dierent structural features have been prepared
by anodic oxidation of Ti-foil in ethylene glycol solutions containing
ammonium uoride, followed by annealing at 400 1C. Carbon was introduced into the nanotubes by having them in the precursor materials.349
Photoelectrochemical studies of water oxidation using the C-modied TiO2
anodes showed that the eciency depended strongly on the properties
(aspect ratio, wall thickness and pore size) of the titania nanotube arrays
used.
Cheng et al.350 prepared TiO2 (P25)-graphene hybrids by solvothermal
reaction of graphene oxide and P25 using ethanol as the solvent. P25-GR
nanocomposites possessed enhanced light absorption ability and charge
separation eciency. As photocatalysts, P25-GR hybrids were much better
than the bare P25, for the hydrogen evolution from aqueous methanol
solution under Xe-lamp illumination. In a related study, TiO2-graphene
sheets have been prepared by hydrothermal method and their performance
as photocatalyst for water decomposition studied.351 The fabrication process features the reduction of graphene oxide and formation of TiO2
simultaneously leading to the well dispersion of generated TiO2 nanoparticles on the surface of GS. Resulting TiO2-graphene nanocomposite
showed better performance as compared to that of Degussa P25 dispersions.
Fan and coworkers also prepared352 nanocomposites of titanium dioxide
(P25) and reduced graphene oxide (RGO) using several techniques
(including UV-assisted photocatalytic reduction, hydrazine reduction, and
hydrothermal method) and studied as photocatalysts for the evolution of
hydrogen from alcohol solution under UV-Visible light irradiation. Kamat
and co-workers have demonstrated earlier that the photogenerated electrons from UV-irradiated TiO2 can be transferred to graphene oxide (GO),
reducing GO to RGO.353 Under optimal conditions, the rate of H2 evolution over the P25-RGOcomposite can be an order of magnitude higher than
that over pristine TiO2 P25.
A composite photocatalyst of TiO2 has been prepared via sol-gel
hydrolysis route, using zeolites and heteropolyacids as the support medium
and CO2 ions as the catalyst for H2 evolution. Two dierent
zeolites and two dierent Co(II) precursors have been examined. Nitrate
salts of Co (not chlorides) gave samples with enhanced visible light
absorption and possible formation of N-doped titania has been invoked.
photocatalysis studies indicated a lower activity for photolysis in the visible
light region.
3.1.1.3 Visible light-doped titania. It was mentioned earlier that doping of
titania with nitrogen by calcinations in the presence of ammonia introduces
sub-bandgap states and visible light response. Similarly noble-metals
deposited on to TiO2 photocatalyst can introduce additional visible light
absorption due to surface plasmon resonance eects. There have been
few studies of such doped catalysts for Hydrogen evolution using these
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354360
visible-light response photocatalysts.

It may be noted that, with
N-doped titania, photocatalytic reduction of water to H2 occurs eciently
even without the addition of co-catalysts such as Pt.
Dierent versions of N-doped titania catalyst was prepared by sol-gel
hydrolysis in the presence of chitosan and subsequent thermal treatment in
the presence of ammonia.355 This photocatalyst is active in visible range
with band gap energy of 2.65 eV. The eciency of the N-doped catalyst to
evolve H2 from water under visible light illumination was 16 times better
than that obtained with Degussa P25 samples. N-doped titania samples
have also been prepared via Pluronic 123 template based sol-gel hydrolysis.356 A sample with moderate N-doping (3.46 at.%) and surface area
(67 m2/g) of mesoporous TiO2, were found to possess surpassing photocatalytic activities of hydrogen production as compared to P25 samples.
Ramakrishna and coworkers prepared354 N-TiO2 nanostructures using
sol-gel and electrospinning methods followed by post annealing of the
composite bers. The electrospun bre form of N-doped titania evolved H2
from water under visible light photolysis in photoelectrochemical cells. In a
related work, Fe and Ni co-doped TiO2 nanoparticles have been prepared
by alcohol-thermal method with tetrabutyl titanate as the Ti source.360 The
codoped TiO2 exhibits a good absorption of visible light, and the optimal
molar ratio of Fe and Ni to Ti is 5.0% and 4.0%, respectively. The nano
TiO2 samples possess pure anatase phase and doping TiO2 with metal ions
can suppress the crystal growth of the particles. Photocatalytic activity of
the material for hydrogen evolution from aqueous ethanolic solutions studied under visible light radiation.
Loading TiO2 with noble metals (e.g. Pt, Au, and Pd) is an eective way
to enhance the photocatalytic eciency of TiO2 by reducing the fast
recombination of the photogenerated charge carriers and also increase the
visible light response via plasmon enhance surface resonance eects. The
mesoporous Au-TiO2 nanocomposites with dierent Au concentrations
were prepared via a co-polymer assisted sol-gel process.359 The prepared Au
TiO2 nanocomposites exhibit remarkable visible-light activity for H2 evolution from photocatalytic water reduction in the presence of ascorbic acid
as the electron donor. Plasmonic eects on the photocatalytic water splitting have also been studied on Au/TiO2 prepared by the photodeposition
method.357 Photodeposition of Au nanoparticles on P25 titania particles
was carried out using HAuCl4 solution. Simultaneous evolution of H2 and
O2 was studied under UV- and combined UV-Visible light radiation. The
two gases were found to evolve in stoichiometric amounts. Interestingly, no
H2 production was observed on Au/TiO2 under the irradiation of visible
light alone.
The mechanistic details of visible light response via plasmonic eects in
noble-metal loaded titania have been investigated using dierent photolysis
wavelengths (532 nm laser light or polychromatic light, l>400 nm).358 The
eciency and operating mechanism were found to be dierent, depending
on whether excitation occurs on the titania semiconductor (gold acting as
electron buer and site for gas generation) or on the surface plasmon band
of gold (photoinjection of electrons from gold onto the titania conduction
band and less oxidizing electron hole potential of about 1.14 V). For the
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novel visible light photoactivity of Au/TiO2, it has been determined that

gold loading, particle size and calcination temperature play a role in the
photocatalytic activity. The samples under study containing gold nanoparticles were found also to exhibit photocatalytic activity for O2 generation
from water under both UV and visible light.
3.1.2 Photogeneration of hydrogen using other semiconducting materials.
ZnRh2O4 photocatalyst has been prepared by a conventional solid state
reaction using commercial ZnO and Rh2O3 powders and tested as a H2evolution photocatalyst.361 The oxide has signicant light absorption in the
visible light region, extending into the infra-red. It is believed to be an
indirect bandgap material with estimated Eg in the range of 1.21.6 eV.
Upon visible light photolysis, the oxide evolves H2 eciently in the presence
of HCHO but only scarcely in the presence of CH3OH indicating that the
potential of the valence band top of ZnRh2O4 lies at w0.1 V (vs. SHE). The
quantum eciency for H2 evolution was high, ca 25% even at 770 nm
region.
A three dimensional branched ZnO/Si heterojunction nanowire array has
been prepared by a two-step, wafer-scale, low-cost, solution etching/growth
method and its use as photoelectrode in a photoelectrochemical cell for high
eciency solar powered H2 generation examined.362 It is shown that the
branched nanowire heterojunction photoelectrode oers improved light
absorption, increased photocurrent generation for photoreduction of water
due to the eective charge separation in Si nanowire backbones and ZnO
nanowire branching, and enhanced gas evolution kinetics because of the
dramatically increased surface area and decreased radius of curvature. In a
related work, mixed oxides of barium zirconate (BaZrO3) is a perovskite
material with a cubic structure and this has been reported to be a good
photocatalyst to evolve H2 from water.363
A Ta-doped version of this photoanode has been prepared in homogeneous solution using ZrOCl2 8H2O and BaCl2 2H2O and tantalum
pentaethoxide Ta(OEt)5 added with continuous stirring and the resulting
white precipitate calcined to get BaZr1-xTaxO3. Highest H2 production rate
(180 mmol/h) was achieved with the catalyst of the composition BaZr0.96Ta0.04O3. Bismuth sodium titanate Bi0.5Na0.5TiO3 is another perovskite
type photocatalyst reported to be a photocatalyst for water reduction.364
Microspheres of this catalyst showed modest H2 evolution rate of
325.4 mmol h1g cat1 under the irradiation of a 500 W xenon lamp. In a
related work, solid solutions of this photocatalyst has been prepared by
spray pyrolysis and the catalyst examined for H2 evolution from aqueous
methanolic solutions under visible light irradiation (l>415 nm).365 NiO has
been found to be a good co-catalyst to increase the rate of hydrogen
production.
3.1.3 Photocatalytic production of H2 using metal chalcogenides. Chalcogenide based semiconductors such as CdS, CdSe and PbSe have received
scrutiny as possible photocatalysts for water reduction to water. Chalcogenides have inherent stability problem due to the rapid reactions of
photogenerated holes with the semiconductor itself (photocorrosion). So
suitable redox mediators in large excess have to be used so as to rapidly
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scavenge the holes to the electrolyte phase. This then will permit sustained
reduction of water using the photogenerated electrons. Rapid recombination of charge carriers in the bulk of the semiconductor is another factor
that can limit the quantitative use of electrons and holes in the water
decomposition process.
Han et al.366 have described a homogeneous system for light induced
reduction of water to H2 in a sustained manner. The system is based on
CdSe nanocrystals capped with dihydrolipoic acid (DHLA) as the light
absorber and a soluble Ni2 1-DHLA catalyst for proton reduction and
ascorbic acid as the electron donor at pH 4.5. Visible light irradiation of the
system evolves H2 from water reduction with turnovers >600,000. The
photosystem functioned without any diminution in activity for over 15 days
and the quantum yield for water reduction at 530 nm estimated to be 0.36.
For semiconductors generated as nanoparticles by sol-gel processes,
Graphenes serve as a useful support medium. They provide very high theoretical specic surface area, high mobility of charge carriers and good
mechanical strength. Pt-loaded CdS nanoparticle based catalyst supported
on graphene oxide (GO) has been found to evolve H2 at much higher rates
(4.87 times) as compared to that of pure CdS nanoparticles.367 An apparent
quantum eciency (QE) of 22.5% at wavelength of 420 nm has been
measured for the H2 evolution process. In a related study,368 CdS-graphene
(GR) and CdS-Carbon nanotubes (CNT) have been made by a hydrothermal process and tested for photoreduction of water. The photocatalytic
activities improved on the carbon support and depended on the mass ratio
of CdS :GR or CdS :CNT in the nanocomposites. Under optimized mass
ratios, the CdS-GR was more ecient than the CdS-CNT.
A series of N-doped Graphene (N-GR)/CdS nanocomposites also have
been prepared by calcinations and their eciency for photoreduction of
water under visible light irradiation (l>420 nm) studied.369 As in the studies cited above, photocatalyst performance improved on the graphene
substrate and at the optimal loading of 2 wt% N-GR, the catalyst showed
highest activity. Graphene and graphene oxides were also examined as
support and following relative eciency order has been measured: N-graphene/CdS W graphene/CdSWGO/CdSWCdS.
In a related work, graphene oxide supported ZnxCd1-xS nanocomposite
has been prepared by a coprecipitation-hydrothermal reduction strategy.and tested for its eciency for water photoreduction.370 A high H2
production rate was observed (450% higher as compared to pristine
Zn0.8Cd0.2S catalyst ) and with an apparent quantum eciency of 23% at
420 nm.
Liu et al. examined possible use of inorganic molecular sieves with different metal ions M(x)-MCM-41 (M=Zr, Ti) for dispersing CdS photocatalyst.371 Supported catalysts were prepared by hydrothermal, ionexchange and suldation process. Photoreduction of water was studied
under visible light irradiation (l >430 nm) in aqueous solutions containing
triethanolamine as the sacricial donor. Two catalysts, CdS/Zr(0.005)MCM-41 and CdS/Ti(0.02)-MCM-41 showed the highest hydrogen evolution activity. Polymeric graphene nitride (g-C3N4) has shown promise as a
photocatalyst for water decomposition, albeit with low yields. Hence a
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nanocomposite of g-C3N4 with CdS quantum dot particles has been prepared via a chemical impregnation method.372 The eciency of the catalyst
has been studied at dierent CdS loading using Pt as the co-catalyst in
aqueous methanolic solutions. A synergistic eect of g-C3N4 and CdS has
been noted with H2 evolution rates 9 times higher than that of pristine
graphene nitrite.
ZnS is a semiconductor that is resistant to photocorrosion and with its
conduction band placed favorably negative with respect to the redox
potential of H2O/H2. An organic-inorganic hybrid of ZnS prepared via
surface modication with organics such as ethylene diamine (en) has been
reported to be a good catalyst for H2 evolution in aqueous methanolic
solutions.373 Hexagonal ZnIn2S4 photocatalysts with 3D-hierarchical persimmon-like shape have been synthesized via an oleylamine (OA)-assisted
solvothermal method.374 After Pt-loading, the material exhibited good H2
production activity, with a quantum yield of 13.6%. Crystal facet control
was also examined. It was found that an increase in the [006] facets terminated by metal ions is the most active one. ZnS-AgIn5S8/uoropolymer
ber composites have been made and tested for their performance for H2
evolution.375 The composites showed higher photocatalytic activity than
that of powders.
MoS2 is a low bandgap material (Eg=1.7 eV) with good performance as
an electrocatalyst for the H2-evolution reaction. Bulk MoS2 occurring
in nature as Molybdenite is a layered material with S-Mo-S sheets
held together in stacks. Chorkendor has reviewed extensively376 photocatalytic and photoelectrochemical studies on hydrogen evolution using
MoS2. Two strategies for designing photocatalysts using MoS2 are indicated:
use MoS2 both as a semiconductor and as hydrogen evolving catalyst HEC
or use MoS2 as HEC with some other photocatalyst such as CdS or p-Si.
3.1.4 Photocatalytic reduction of water using p-type semiconductors in
PECs. Gallium Phosphide (GaP) is one of the early, well character sized
examples of semiconductor with a bandgap of 2.3 eV. Used as a p-doped
material it can catalytically reduce water to H2 under visible light illumination. Photoelectrochemical studies showed that the onset for H2 evolution occurs at more positive potentials than at bandedge levels (OV vs NHE)
indicating that the semiconductor by itself is a poor electrocatalyst for H2
evolution. Deposition of Pt-nanoparticles on the surface improves signicantly the catalytic photoreduction process. In recent studies on p-GaP
electrodes,377 showed no benecial eects of electrodeposited Pt. However
Pt deposited via PVD improved the photocurrent by 25%. Simple etching of
the photoelectrode itself improved the cathode performance. Presumably
substrate dissolution and redeposition produces insulating oxides on the
surface and these can be removed by the etching process.
Copper Oxide is another promising material. It is a p-type semiconductor
with a bandgap of 2.2 eV. Zhang and Wang378 prepared highly ecient and
stable copper oxide composite photocathode materials by a facile two-step
electrochemical strategy, which consists of electrodeposition of a Cu lm on
an ITO glass substrate followed by anodization of the Cu lm under a
suitable current density and then calcination to form a Cu2O/CuO
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composite. The synthesized Cu2O/CuO composite was composed of a thin

layer of Cu2O with a thin lm of CuO on its top as a protecting coating. The
best photocathode material among all materials prepared was the Cu2O/
CuO composite with Cu2O in (220) orientation, which showed a highly
stable photocurrent of 1.54 mA cm2 at a potential of 0 V vs. reversible
hydrogen electrode at a mild pH under illumination of AM 1.5G. This
photocurrent density was more than 2 times that generated by the bare
Cu2O electrode ( 0.65 mA cm-2) and the stability was considerably
enhanced to 74.4% from 30.1% on the bare Cu2O electrode.
Copper oxide is very susceptible to photocorrosion via anodic or cathodic
pathways. A two stage protection scheme has been successfully tested by
Graetzel and coworkers.379 Electrodeposited Cuprous oxide was rst prepared. Few nanometer-thick layers of Al2O3 and of TiO2 (or ZnO) put over
followed by electrodeposition of Pt nanoparticles. The roles of the dierent
surface protection components were investigated, and in the best case
electrodes showed photocurrents of up to 7.6 mA/cm2 at a potential of
0 V versus the reversible hydrogen electrode at mild pH.
In 2004, Kudo and coworkers reported380 an important discovery that
doping of wide bandgap semiconductor SrTiO3 with noble metals such as Ru,
Rh, Ir and Mn turns these materials highly colored with intense absorption
bands in the visible light region. Mn- and Ru-doped SrTiO3 showed photocatalytic activities for O2 evolution from an aqueous silver nitrate solution
while Ru-, Rh-, and Ir-doped SrTiO3 loaded with Pt cocatalysts produced
H2 from an aqueous methanol solution under visible light irradiation
(lW440 nm). The Rh(1%)-doped SrTiO3 photocatalyst loaded with a Pt
cocatalyst (0.1 wt %) gave 5.2% of the quantum yield at 420 nm for the H2
evolution reaction. There are several subsequent studies on the nature of
the doping process involved.381383 Rh-doped SrTiO3 (Rh:SrTiO3) behaves
like a p-type material. The Rh doping results in a large decrease of
the bandgap energy, turning it to a p-type material, a visible-light-driven H2evolving photocatalyst in a solar water splitting reaction.381 Recently
epitaxial Rh-doped SrTiO3 thin lm photocatalysts were fabricated by pulsed
laser deposition under various deposition conditions.383 Cyclic voltammetry
measurements in a K2SO4 solution conrmed that Rh-doped SrTiO3 thin
lm is a highly ecient hydrogen-producing photocathode with a characteristic p-type behavior under visible light irradiation.
Wang et al.384 studied nanostructures formed using n-type ZnO and p-type
Si with and without metal layers as photocathodes for H2 evolution, Si|ZnO
electrodes showed increased cathodic photocurrents due to improved charge
separation by the formation of a p/n junction, and Si|ZnO:Al (n -ZnO) and
Si|ZnO(N2) (thin lms prepared in N2/Ar gas) lead to a further increase in
cathodic photocurrents. A thin metal coating on ZnO showed increased
photocurrent due to a catalyzed hydrogen evolution reaction and Ni metal
showed comparable catalytic activities to those of Pt and Pd.
3.2 Catalytic photoxidation of water to O2 (half-cell systems)
3.2.1 Photocatalytic oxidation of water to O2 using n-type TiO2 electrodes. With the advent of nanotechnology and several procedures available
to make nanostructured thin lms starting from nanoparticles, novel
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nanostructured photoanodes have been made for many oxide and nonoxide semiconductor photocatalysts. In nearly all cases, the photoelectrochemical performance of these nanostructured thin lm anodes is much
better than anodes prepared from bulk materials or by conventional
methods.
TiO2 is a wide bandgap material (with bandgap energies 3.0 and 3.2 eV
for rutile and anatase respectively), absorbing only ca. 3% of the solar
radiation. Photooxidation of water to O2 using dierent preparations of
TiO2 electrodes has been studied by several authors.385389 Earlier we
indicated several attempts to improve the light harvesting properties of
titania. Doping with non-metal ions such as C, S and N has been widely
studied. The valence band of TiO2 is largely composed of oxygen 2p states.
Possible hybridization of p-states of these non-metal ions can give rise to an
upward shift of the valence band. Other possibility is for the p-states of
these dopants form impurity states above the valence band. In both case
there will be a narrowing of the bandgap energy. Recently it has been
reported that hydrogen doping of TiO2 produce similar eects. In addition
to improved light harvesting in the visible light region, such doping also
increase the quantum eciency for light energy conversion.
The photoelectrochemical cell performance of anodes made of rutile TiO2
nanowires of dierent lengths (0.28 to 1.8 um) grown on F-doped conducting glass substrates depend strongly on the nanowire length and surface
properties (Hwang et al.389). The photocurrents increase with length, with a
maximum photocurrent measured for 1.8 mm long nanowires). While the
incident photon to current conversion eciency (IPCE) increases linearly
with photon absorbance for near band gap illumination (l=410 nm) case, it
decreases severely at shorter wavelengths of light for longer nanowires due
to poor electron mobility. Atomic layer deposition (ALD) was used to
deposit an epitaxial rutile TiO2 shell on nanowire electrodes which enhanced
the photocatalytic activity by 1.5 times.
Wang et al.388 for example, prepared hydrogen-treated rutile TiO2
(H:TiO2) nanowires by annealing the pristine TiO2 nanowires in hydrogen
atmosphere at various temperatures in a range of 200550 1C. In comparison to pristine TiO2 nanowires, H:TiO2 samples show substantially
enhanced photocurrent in the entire potential window. Under optimal
conditions, max. photocurrent density obtained corresponds to a solar-tohydrogen (STH) eciency of 1.63%. It has been proposed that hydrogen
treatment increases the donor density of TiO2 nanowires by 3 orders of
magnitudes, via creating a high density of oxygen vacancies that serve as
electron donors. Similar enhancements in photocurrent were also observed
in anatase H:TiO2 nanotubes.
In a related work, Hoang et al.386 used hydrothermal synthesis route to
prepare single crystal TiO2 nanowire arrays (5 nm diameter, 4.4 um ) on
F-doped SnO2 electrodes. Annealing of the sample in owing NH3 gas leads
to ecient nitridation (N-doping) of the titania. The visible light absorption
of the N-doped TiO2 is improved signicantly in the visible light region
(threshold at 520 nm, corresponding to a modied bandgap of 2.4 eV.
Co-treatment of the N-doped titania improved the UV-light absorption,
leading to further improvement in the PEC performance of the doped
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titania electrode. It has been proposed that the cobalt treatment enhances
PEC performance via two mechanisms: passivating surface states on the
N-modied TiO2 surface and acting as a water oxidation cocatalyst.
In a further follow up of this work,387 the photoelectrochemical cell
performance of TiO2 nanowire electrodes doped both with hydrogen and
nitrogen was examined. and found the co-dopants were found to exhibit a
synergistic eect. TiO2 nanowire electrodes were prepared via hydrothermal
synthesis followed by annealing at 500 1C in air (pristine TiO2), a mixture of
H2 and Air (5% of H2) for H-TiO2 and in NH3 for N-TiO2, The visible light
(>420 nm) photocurrent of the cotreated TiO2 is 0.16 mA/cm2 and
accounts for 41% of the total photocurrent under simulated AM 1.5 G
illumination.
In view of the minimal lattice mismatch between SnO2 and TiO2,
Sn-doping has been examined in TiO2 nanowire for possible applications in
photoelectrochemical splitting of water.388a Sn dopants are incorporated
into TiO2 NWs by a one-pot hydrothermal synthesis with dierent ratios of
SnCl4 and tetrabutyl titanate, and a high acidity of the reactant solution is
critical to control the SnCl4 hydrolysis rate. PEC measurement on Sn/TiO2
NW photoanodes with dierent Sn doping ratios shows that the photocurrent increases rst with increased Sn doping level to >2.0 mA/cm2 at 0 V
vs Ag/AgCl under 100 mW/cm2 simulated sunlight illumination up to 100%
enhancement compared to our best pristine TiO2 NW photoanodes and
then decreases at higher Sn doping levels. Annealing of Sn/TiO2 NWs in H2
further improves their photoactivity with an optimized photoconversion
eciency of 1.2%. Electrochemical impedance measurement reveals that the
density of n-type charge carriers can be signicantly increased by the Sn
doping.
3.2.2 Photooxidation of water using other n-type oxide semiconductors.
ZnO, WO3 and Fe2O3 (haematite) are other widely studied semiconductor
photocatalyst for water decomposition. The light harvesting capacity of
ZnO is nearly the same as titania (Eg=3.2 eV) while the other two have
smaller bandgap (Eg (WO3)=2.7 eV). Monoclinic tungsten trioxide (WO3)
is considered as a promising photocatalyst, particularly for oxygen evolution in the presence of an electron acceptor (i.e. AgNO3), due to its very
deep VB maximum. Synthesis of WO3 photoanodes with signicant visible
light response has been a challenge. Reported bandgap energies of various
nanostructured WO3 anode preparations are in the range of 2.9 to 3.25 eV.
While photoresponse in the UV region is always high (>50%), visible light
response appear to depend strongly on the preparation methods.
3.2.2.1 Tungsten Oxide WO3 photoanodes. Long term stability of the
photoanode is an important issue to be addressed in the performance of
various semiconductor based photocatalysts and this is related to the nature
of the electrolyte employed. Augustynski et al.390 found that nanostructured
WO3 anode showed excellent stability in the presence of methane sulfonic
acid as support electrolyte during photooxidation of water. Large, stable
photocurrents were obtained in this solvent. The dynamics of charge carrier
dynamics on mesoporous WO3 during water splitting has been studied using
transient absorption spectroscopy. The photogenerated electron (and holes)
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decays very slowly (ms-s timescale) in the presence of (degassed) methanol

solutions.391 The measured rates are quite comparable to those measured
for TiO2 and a-Fe2O3. In these materials, the rate-limiting step in photochemical water oxidation was shown to be a very slow hole transfer into
solution (a-Fe2O3 (tE3s) and TiO2 (tE30300 ms)).
Thin lms of crystalline WO3 nanosheets oriented perpendicular to
tungsten substrates have been grown by a surfactant-free hydrothermal
method, followed by sintering.392 The lms exhibit photoelectrochemical
oxygen evolution at low overpotential. Modest photocurrent (2.0 mA/cm2
at 1.0 V vs. NHE) has been measured for these thin lms (50200 nm) during
water oxidation. Ohtani et al.393 have prepared a vertically arrayed
ake lm, ake-wall lm, of monoclinic tungsten oxide (WO3) on a
transparent conductive glass by controlling anisotropic crystal growth and
self-arrayed growth of WO3 hydrate with a layered crystal structure. The
WO3 ake-wall lm exhibited superior performance for photoelectrochemical water oxidation under visible-light irradiation (photocurrents upto
1.8 mA/cm2 at 1.2 V vs NHE) compared to that of a lm consisting
of horizontally laminated WO3 akes. Redox catalytic reactions involving
co-catalysts invariably are slow and hence it is desirable that the lifetime of
photogenerated charge carriers also are comparably long for ecient
interception.
Liu et al.394 examined photodecomposition of water (as two half cell
reactions) on Tungsten oxide dispersed on silica (WO3/SiO2) prepared via
sol-gel hydrolysis and annealing at 600 1C. Photocatalytic O2 evolution was
examined in the presence of iron(III)sulfate and photocatalytic H2 evolution
using platinized WO3-SiO2 particles (Pt-WO3-SiO2) in aqueous methanol
solutions. Photooxidation of water on silica supported tungsten oxide
improved signicantly as expected. Surprising, however, is the signicant
photoinduced evolution of H2 using this photocatalyst, since it is known
that the conduction band of WO3 is situated well below the chemical
potential of (H/H2). The photocatalyst prepared via sol-gel route is made
of nanosized particles. Larger bandgap (3.3 eV instead of 2.6 eV) with
corresponding shifting of conduction band to more negative potential have
been proposed to explain the experimental results.
WO3 photoanodes have been reported to produce peroxo species as well
as O2 during photooxidation reactions, and the accumulation of peroxo
species on the surface is known to cause a gradual loss of photoactivity of
WO3. Seabold and Choi396a have examined possible improvements to water
oxidation to O2 on WO3 using the Co-Phosphate as co-catalyst. The Co-Pi
catalyst improved the quantum eciency for O2 generation from 61%
measured on pristine WO3 to 100%. In addition formation of peroxide
has been suppressed, leading to improved stability of the tungsten oxide
photoanode. In a related study, oxidation of water to O2 has been examined
in a photoelectrochemical cell using a modied WO3 anode. To assist
water oxidation to O2, a manganese (III/IV)oxo-terpyridine dimer.
[Mn(III)(O)2Mn(IV)(H2O)2(Terpy)2](NO3)3, was deposited on the anode.
There have been few reports of binuclear Mn complexes acting as redox
catalysts to promote water oxidation to O2. Visible light photolysis in
aqueous solutions led to evolution of H2 and O2 in near stoichiometric
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amounts. As in the case of SiO2-supported WO3, the origin of H2 evolution

is not clear.
Bignozzi and coworkers397 have used potentiostatic anodization of
metallic tungsten in various solvents/electrolytes to prepare WO3 photoanodes for use in water oxidation. Anodization in the NMF/H2O/NH4F
solvent mixture was found to yield highly ecient WO3 anodes. The use of
such electrodes results in high water electrolysis yields of between 70 and
90% in 1M H2SO4 under a potential bias of 1 V versus SCE and close to
100% in the presence of methanol. Xie et al.396b deposited boron oxynitride
B2O3-xNx nanoclusters on the surface of WO3 particles by a combination of
thermal oxidation of tungsten boride (WB) in air and the subsequent
nitriding process in gaseous ammonia. The resultant nanoclusters are found
to improve the photocatalytic oxygen evolution of WO3.
3.2.2.2 Fe2O3. Leite et al.398 have used colloidal dispersions of nanoparticles as a precursor to make hematite Fe2O3 photoanodes for water
photolysis studies. The photoelectro-chemical characterization shows that
the colloidal approach used to process an undoped hematite photoanode
produced a high-performance electrode for water photooxidation with an
onset potential as low as 0.8 V (RHE). Photocurrents for pure hematite thin
lms reach 1.1 mA/cm2 at 1.23 vs. NHE with back-side illumination. In a
related work,399 templated sol-gel hydrolysis method has been used to
prepare transparent a-Fe2O3 mesoporous lms, followed by annealing
at various temperatures from 350 1C to 750 1C in air. A Cobalt-phosphate
(Co-Pi) catalyst was then deposited via impregnation or electrodeposition
method. The hematite lms heat-treated at relatively low temperature
(500 1C), and therefore devoid of any extrinsic dopant, achieve light-driven
water oxidation under near-to-neutral (pH=8) aqueous conditions after
decoration with a Co catalyst.
Wang et al.400 used a slightly dierent procedure, using sol-gel hydrolysis
with iron(III) chloride as the Fe precursor, followed by annealing at 550 1C
in air to prepare transparent a-Fe2O3 lms. The lms were subsequently
doped with Ti using Ti-butoxide as the precursor. Compared to the
undoped sample, the photocurrent onset potential of Ti-doped a-Fe2O3 for
water oxidation is shifted about 0.10.2 V to lower potential, thus
improving the photocurrent and incident photon to current conversion
eciency (IPCE) at lower bias voltages. In a related work, same group
prepared Sn-doped hematite nanostructured photoanode using
Sn(IV)chloride as the precursor. The hematite nanowires sintered at 800 1C
yielded a pronounced photocurrent density of 1.24 mA/cm(2) at 1.23 V vs.
RHE, which is the highest value observed for hematite nanowires.
3.2.2.3 Nanostructured ZnO photoanodes for water splitting. There is
growing interest to prepare ZnO photoanodes using one and two-dimensional nanomaterials. Weintraub et al.403 have reviewed some early work in
this area. Yu and Cao404a have reported synthesis of ZnO photoanodes for
water splitting using ZnO nanorods of diameter 4050 nm and length
400800 nm. Mott-Schottky measurements give a at-band potential
of 0.10 V, a carrier density of 3.7 10.17 cm3, and a space-charge layer
of 26 nm. The photocurrent of 800 nm-long nanorods shows 10 times higher
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than that of 400 nm-long ones, and an encouraging maximum

photoconversion eciency of 0.25% is obtained under illumination of
100 mW/cm2 (AM 1.5), which is among the highest reported for an undoped
ZnO photoelectrode to date.
Wei et al.,404b have used V-grooved Si(100) as the template to grow ZnO
nanorod arrays via a hydrothermal method and examined the light trapping
and photoelectrochemical properties of this nanostructured ZnO photoanode. Photolithography followed by reactive ion etching was used to
prepare the V-grooved template. The bridged ZnO nanorod arrays showed
increased photocurrents 0.73 mA/cm2 and half time of 1500 sec. These are 4
and 10 times superior to the values obtained for ZnO nanorods grown on
at substrate. In a related work, patterned ZnO nanorod arrays with different densities and spacing distances on silicon (Si) substrate have been
grown by electron beam lithography (EBL) method combined with the
subsequent hydrothermal reaction process.
A dense array of vertically aligned ZnO-ZnGa2O4 core-shell nanowires
was synthesized by Zhong et al.406 on a large scale on an a-plane sapphire
substrate by a simple two-step chemical vapor deposition method. The coreshell anode was tested in photoelectrochemical water splitting. A stable and
large photocurrent of 1.2 mA/cm2 was obtained with the ZnO-ZnGa2O4
core-shell nanowire array when used as a photoanode at an applied bias
of 0.7 V (versus Ag/AgCl) under a 300 W xenon lamp illumination.
3.2.2.4 SrTiO3. Various transition-metal- doped SrTiO3 photocatalysts
have been developed by Kudo and coworkers for H2 and O2 evolution in the
presence of reducing and oxidizing reagents, respectively, under visible-light
irradiation.408 Among them, Rh-doped SrTiO3 (SrTiO3:Rh) is a highly
active oxide photocatalyst for sacricial H2 evolution under visible-light
irradiation. An electrode version of the catalyst has been prepared by
pasting SrTiO3:Rh powder onto a transparent indium tin oxide electrode.
PEC studies indicate a cathodic photocurrent under visible-light irradiation
(lW420 nm), indicating that the SrTiO3:Rh photocatalyst electrode possessed p-type semiconductor character. The cathodic photocurrent
increased with an increase in the amount of doped Rh up to 7 atom %. The
incident-photon-to-current eciency at 420 nm was 0.18% under an
applied potential of 0.7 V vs Ag/AgCl for the SrTiO3:Rh (7 atom %)
photocatalyst electrode. The photocurrent was conrmed to be due to water
splitting by analyzing the evolved H2 and O2. The water splitting proceeded
with the application of an external bias smaller than 1.23 V versus a Pt
counter electrode under visible-light irradiation and also using a solar
simulator, suggesting that solar energy conversion should be possible with
the present photoelectrochemical water splitting.
Kim and coworkers409 prepared a new series of photocatalysts based on
SbMO4 (M=Nb, Ta) by conventional solid state reactions and studied their
photocatalytic water splitting performance.. Diuse reectance analysis
showed that both compounds have moderate band gaps of 3.7 eV for
SbTaO4 and 3.1 eV for SbNbO4 (cf. 3.0 eV for TiO2). Mott-Schottky
analysis reveals that their conduction-band edge potentials are higher
than the water reduction (hydrogen evolution) potential (0 V vs. RHE),
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indicating both compounds can generate hydrogen from water splitting.

After loading RuO2 as a co-catalyst, both oxies showed photocatalytic H2
production from water under UV irradiation.
Since the atomic radii of Zn(II) and Cu(II) are similar, there have
been attempts to introduce Cu2 in the ZnO as a lattice substituent. Ternary
Zn1-xCuxO nanorods with a controllable optical band gap were fabricated
by a simple electrochemical route.410 The at-band positions have been
estimated based on Mott-Schottky plots for pure ZnO, Zn0.96Cu0.04O and
Zn0.92Cu0.08O to be 0.27 V, 0.37 V and 0.39 V, respectively. Photoelectrochemical (PEC) measurements revealed that the Zn-Cu-O nanorods
increased the photoconversion eciency to 2 times that of pure ZnO, and
they exhibited a greater photoresponse to visible light because of the band
gap narrowing eect.
3.2.2 Perovskite
decomposition
oxide
materials
as
photocatalysts
for
water
3.2.2.1 Perovskite oxides as photocatalysts. Depending on the composition, Oxides exhibit rich and diverse form of crystalline structures: Perovskites (BaTiO3, KNbO3), Pyrochlores (Cd2Nb2O7), Tungsten-bronzes
(PbNb2O6, PbTa2O6), Illmenites (LiTaO3), layered perovskites (Sr2Nb2O7)
and Aurivillious compounds (Bi4Ti3O12, PbBi2Nb2O9). A common feature
of these dierent structural forms is the presence of small size ions with high
charges (Ti4, Nb55, Ta5, . . .) inside an oxygen octahedron that shares
corners to form oxygen-metal-oxygen chains.
Perovskites are a group of oxide materials of ABX3 group where A and B
are two cations of very dierent sizes, and X is an anion that bonds to both
(oxygen). The A atoms are larger than the B atoms. The ideal cubic-symmetry structure has the B cation in 6-fold coordination, surrounded by an
octahedron of anions, and the A cation in 12-fold cuboctahedral coordination. (A=La, Sr, Ca; Ba; B=Mn, Co,Fe, Nb, Ta, ). Oxynitride perovskites with general formula ABO2-xN1 x are derived in general from
perovskite Oxides ABO3 and have been further widely investigated by
several groups. They generally form by early transition metals occupying
the B sites (V, W, Ta, Nb, Zr, Mo and Ti) and alkaline earth and rare earth
metals in the A sites.
The layered perovskite type materials of the tantalates and niobate family
((Sr2Ta2O7, Ca2Ta2O7, Rb4Ta6O17, Ba5Ta4O15, Sr2Nb2O7 and Ba5Nb4O15)
are attractive alternatives to titania and Titanate semiconductors in showing high quantum yields for the photodecomposition of water. Most of
them are wide bandgap materials with Eg >3.5 eV and bandgap engineering
is essential for their use as photocatalysts working under solar radiation.
Nisar et al.411 have used DFT theoretical calculations to follow bandgap
changes upon anionic, mono and co-doped Sr2Nb2O7 semiconductor.
Calculations indicate that doping S, N-N and C-S in the oxide can increase
substantially visible light absorption and hence photocatalysis using visible
light.
Rubidium niobate (Rb4Nb7O17) is another layerd oxide that has shown
promise as a photocatalyst for water decomposition. Arney and Maggard412
prepared layered RbLaNb2O7 photocatalyst in platelet-shaped
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morphologies using a RbCl ux and with a modulation of the particle

morphologies using hydrothermal route. Further, the silver-ion exchanged
AgLaNb2O7 product could be prepared by reaction of the RbLaNb2O7
particles within a AgNO3 ux at 250 1C for 24 h. Ag-ion exchanged catalyst showed signicant visible light absorption due to surface plasmon
resonance eects. Photocatalytic hydrogen evolution from aqueous
methanol was observed using these catalysts under UV and visible light (for
the Ag-exchanged catalysts) irradiation.
3.2.2.2 Layered bismuth oxides of Aurivillius oxide family. Bismuth
Vanadate, BiVO4 with monoclinic scheelite type structure is a visible lightresponsive compound showing excellent photocatalytic properties. The
physicochemical property of BiVO4 strongly depends upon its crystal
structure, surface area, particle size and particle morphology, factors which
are determined by the method of preparation. Since compact (non-porous)
form of the oxides show poor catalytic activity, research eorts are focused
on the preparation of hollow or porous form of the material with high
surface area.
Three-dimension ordered macroporous (3D-OM) bismuth vanadates
with a monoclinic crystal structure and high surface area (1824 m2 g1)
have been prepared by Liu et al.413 using ascorbic acid (AA)- or citric acid
(CA)-assisted poly(methyl methacrylate) (PMMA)-templating strategy with
bismuth nitrate and ammonium metavanadate as the metal sources, HNO3
as the pH adjuster and ethylene glycol and methanol as the solvent. One of
he BiVO4 catalyst preparation with surface area of ca. 24 m2 g1 showed the
best visible light-driven photocatalytic performance for phenol degradation.
In recent years bismuth tungstate Bi2WO6, the simplest Auivillius
(layered) Oxide has been found to exhibit excellent photocatatalytic properties. Bare Bi2WO6 presents photoabsorption properties from UV light to
visible light with the threshold wavelength at 450 nm. Towards improving
the visible light response of Bi2WO6 via surface plasmon resonance eects,
Ag-loaded Bi2WO6 catalyst was prepared.414 A study of photodegradation
of phenol showed that the Ag-loaded catalyst performed better than the
pristine oxide and a higher temperature is benecial for the catalyst
performance.
Towards improving the visible light response of the Bi2WO6 catalyst,
Zhang et al. have prepared a binary nanocomposite Bi2S3/Bi2WO6 by
hydrothermal route. Bi2S3 is a narrow bandgap semiconductor
(Eg=1.7 eV). The electrons excited by the visible light can be transferred to
Bi2WO6 from the narrow bandgap Bi2S3. For the photodegration of phenol,
the binary catalyst exhibits much enhanced photocatalytic activity than
bare Bi2WO6. In a related work, Ma et al.415 prepared olive-shaped Bi2S3/
BiVO4 microspheres using thioacetamide and sulfur sources. Compared
with pure BiVO4 microspheres and Bi2S3 nanorods, the Bi2S3/BiVO4 products showed obviously enhanced photocatalytic activity for the degradation of Rhodamine B (Rh B) in aqueous solution under visible-light
irradiation (lW400 nm). In addition, the Bi2S3/BiVO4 composite microspheres showed good visible-light-driven photocatalytic activity for the
degradation of refractory oxytetracycline (OTC) as well.
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Bi2MoO6 is a related layered oxide of the Aurivillius family. Synthetic

studies of Bismuth molybdate have shown that hydrothermal, sol-gel or
coprecipation methods require treatment at very high temperature
(400700 1C) to improve the crystallanity of the catalyst. In a recent
work,416 Bi2MoO6 microspheres have been prepared via a facile template
free hydrothermal method and the performance of the catalyst for the
photo-degradation of standard Rhodamine B dye examined. Bismuth
oxyhalides are compounds analogous to the layered oxides of Aurivillius
family, with intervening layers composed of [Bi2O2]2 layers. Jiang et al.417
prepared visible-light-responsive BiOBr photocatalysts with Ti doping
and Ag decorating were prepared by three methods (chemical reduction,
photoreduction, and thermal reduction). The as-prepared 3% Ag/Ti-doped
BiOBr photocatalysts exhibited the owerlike microsphere structures that
assembled by nanoplates, and showed higher photocatalytic activity for
Rhodamine B degradation and excellent durability.
3.2.2.3 BiVO4 as a photocatalyst. Bismuth vanadate is one of recently
identied semiconductor photocatalyst suitable for water decomposition.
With a direct bandgap of 2.4 eV, it has appropriate valence band position
for water oxidation to O2. Its conduction band edge position and at band
potential are fairly negative, just short of the thermodynamic level for H2.
As a result, complete water splitting with BiVO4 requires only a small
amount of external bias. Seybold and Choi418 prepared lms of BiVO4 by a
simple electrodeposition and annealing procedure and studied its ability to
oxidize water to O2 under visible light.
Much higher photocurrents measured in sulte as compared to that
obtained in water suggested that BiVO4 to be a poor electrocatalyst to assist
in the formation of molecular oxygen. Introduction of a iron-oxyhydroxide
Fe-O-OH thin lm as a co-catalyst on BiVO4 improved the photoanode
performance signicantly. FeOOH is known to be a good electrocatalyst for
evolving O2 from water at moderate overpotentials, In particular, the
BiVO4/FeOOH photoanode showed an outstanding performance in the low
bias region (i.e., E o 0.8 V vs RHE).
3.2.2.4 Niobates. Few niobates have been identied as photocatalysts for
water decomposition, even though Nb2O5 is not a photocatalyst by itself.
Miseki and Kudo419 have prepared single phases of KM2Nb5O15 and
K2LnNb5O15 by solid-state reaction and polymerizable complex methods.
The band gaps of these niobates were estimated to be 3.13.5 eV. These
metal oxides loaded with an activated NiOx cocatalyst showed photocatalytic activities for water splitting into H2 and O2 under UV irradiation.
When K2LnNb5O15 was doped with Rh ions, a new visible-light absorption
band was observed around 400500 nm in addition to the band gap
absorption band of the K2LaNb5O15 host. K2LaNb5O15:Rh showed photocatalytic activities for H2 or O2 evolution from an aqueous solution
containing a sacricial reagent under visible-light irradiation.
A related photocatalyst is layered material, K4Nb6O17 with a bandgap of
3.5 eV. Ion-exchange and exfoliation methods have been used to separate
out nanosheets and Pt and IrOx (x=1.52) nanoparticles photochemically
deposited onto the surface of the nanoscrolls to produce two- and
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420
three-component photocatalysts.
Under UV irradiation, the nanostructures produced H2 from pure water and aqueous methanol, with
turnover numbers ranging from 2.3 and 18.5 over a 5 h period. Interestingly
from water, no oxygen is evolved. Instead, the formation of surface-bound
peroxides in a 1:1 stoichiometry with H2 is observed. Nishiyama et al.421
have identied few sodium, niobium, and tantalum phosphate bronzes
Na4M8P4O32 (M = Nb, Ta) photocatalysts for the total decomposition of
water. Addition of RuO2 as a co-catalyst to these bronzes leads to high,
stable activity in the stoichiometric production of H2 and O2 under UV
irradiation.
3.2.3 Nitrides and oxynitride photoelectrodes for water oxidation.
Numerous metallo nitrides and oxynitrides have been reported in recent
years as ecient photoanodes for the oxidation of water to oxygen in
electrochemical cells.422,423 Tantalum nitrile (Ta3N5) is a promising nitride
semiconductor for use as a photocatalyst in water splitting studies: It has a
moderate bandgap of 2.1 eV, with its conduction and valence band edges
located at ca. 0.4 and 1.7 V vs. NHE respectively.
In a recent work,422 nanostructured Ta3N5 photoanodes were synthesized
via a two-step process: rst, nanocolumnar Ta2O5 lms were deposited by
evaporation of tantalum metal in a vacuum chamber in a low pressure
oxygen ambient followed by heating in an ammonia gas ow to convert
Ta2O5 into orthorhombic Ta3N5. Under Xe lamp irradiation (73 mW/cm2),
a 100 nm nanoporous Ta3N5 electrode achieved an anodic photocurrent of
1.4 mA/cm2 at 0.5 V versus Ag/AgCl in 1 M KOH solution. The photocurrent yields drop to 0.4 mA/cm2 when thicker lms were used, illustrating the practical advantages of using nanoparticulate mesoporous lms.
Ta3N5 lms however suered from inherent self-oxidation under light
illumination, and application of a cobalt cocatalyst layer was found to
improve the stability as well as photocatalytic activity of the Ta3N5 lms.
SrNbO2N is a perovskite-type oxynitride semiconductor with a relatively
narrow bandgap of 1.8 eV.424 Recently SrNbO2 powders have been found to
eciently oxidize water to O2 under visible light in the presence of AgNO3 as
the electron acceptor. These niobium oxynitrides were prepared by heating the
corresponding oxide precursors, which were synthesized using the polymerized
complex method, for 15 h under a ow of ammonia. Used a photoelectrode in
a PEC, it acts as an active anode for water oxidation even without any
applied potential. Nearly stoichiometric amount of H2 and O2 was observed
during the photoelectrolysis of water in a neutral aqueous solutions when a
potential of 1.0 to 1.55 V vs. NHE was applied. In a related work, colloidal
iridium oxide IrOx was shown to be a good co-catalyst to assist water oxidation on SrNbO2N particles coated on FTO glass as a photoelectrode.425
3.2.4
Multicomponent systems as photocatalysts
3.2.4.1 Solid solutions of two photocatalysts. Solid solution of two catalyst materials is being investigated as another approach for bandgap engineering. In view of the fact that two ecient photocatalysts NaTaO3 and
LaFeO3 crystallize in the same phase group with very similar lattice parameters, the two form an ideal pair to form solid solutions.426 The solid
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solution based on these photocatalysts showed absorption of visible light

extending up to 450 nm. Upon loading of platinum nanoparticles cocatalyst,
the photocatalytic hydrogen evolution was obtained for 2% doping of
LaFeO3 in NaTaO3, under visible radiation (l W 390 nm; 20% methanol
solution). The photocatalytic properties of the solid solution were found to
be better than Fe doped NaTaO3 compounds on account of the suitable
band structure.
Domen and coworkers have developed solid solutions of GaN and ZnO
(denoted as GaN:ZnO) as visible-light-driven photocatalysts for overall
water splitting.4-9 Upon modication by suitable co-catalysts, GaN:ZnO
becomes active for the reaction. In a recent report,427 the authors have
prepared solid solutions of GaN:ZnO modied with Rh2-yCryO3 nanoparticles as H2 evolution co-catalysts under visible light (400500 nm range).
The rate of visible light water splitting remained unchanged for 3 months
(2160 h), producing H2 and O2 continuously at a stoichiometric amount.
After 6 months of operation, a 50% loss of the initial activity occurred.
Bismuth vanadate BiVO4 has been found to be an excellent photocatalyst
for oxidation of water to O2 but it cannot reduce water to H2 because of the
low lying nature of its conduction band with respect to that of H2O/H2.
Solid solution approach has been explored to reduce the bandgap and shift
the band-edge positions of this oxide. With this in mind a series of solid
solution photocatalysts Bi1xDyxVO4 (BDV) were synthesized by partial
substitution of Dy3 for Bi3 in BiVO4 and discovered to have photocatalytic activities when BDV were loaded with cocatalyst. BDV (x=0.3,
0.5) were discovered to split water into H2 and O2.428
Among these catalysts, Bi0.5Dy0.5VO4 showed the best photocatalytic
activity for water splitting under UV light irradiation. In addition, several
other solid solutions of the type Bi0.5M0.5VO4 (M = La, Sm, Nd, Gd, Eu,
Y) with tetragonal structure were synthesized and their photocatalytic
activities were discussed and compared with the photocatalytic property of
Bi0.5Dy0.5VO4. In a related work,429 a series of mixed oxide (BYV) photocatalysts BixY1xVO4 were prepared by solid state reaction. When the
composition was below x=0.65, BYV were of single phase and of zircontype structure and can be regarded as solid solutions of YVO4 and BiVO4
within the same structure. All the BYV solid solutions were proved to be
eective photocatalysts for overall water splitting under UV light.
3.2.4.2 Heterostructures and interpenetrating networks. Hara and Irie430
have reported results on complete decomposition of water using a mixture
of two dierently modied SrTiO3 particulate systems, one loaded with InV and the other with Bi-Ga (In,V@SrTiO3, Bi, Ga@SrTiO3)..Pristine
SrTiO3 was prepared by a solid state reaction and was mixed with oxides of
surface modifying catalysts (Bi, Ga, In and V) by ball-milling followed by
annealing at high temperature (750 1C.). Pt co-catalyst was also added on by
photodecomposition method. Photolysis of the mixed powder of these
modied SrTiO3 catalysts with visible light in the presence of (I/IO3) as
the redox mediator, lead to steady evolution of H2 and O2 in stoichiometric
amounts. A Z-type scheme coupling the two photocatalytic system has been
proposed to explain the results.
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3.2.5 Photoelectrochemical oxidation of water assisted by OEC. An

important breakthrough in our attempts to oxidize water to molecular
oxygen (O2) occurred about ve years ago with the reports of Nocera and
coworkers that Co(II) and phosphate ions in aqueous solution formed a
black thin lm on electrodes and this serves as an excellent catalyst to
mediate water oxidation to O2. The Cobalt-Phosphate catalyst system
Co-Pi is remarkable for several reasons: i) the lm forms in situ in mild
conditions (pH 7.0 at room temperature); ii) a variety of Co(II) precursors
(chloride, nitrate, sulphate,. . .) can be used; iii) the catalyst is self healing
through a series of linked electron/proton transfer processes and iv) catalyst
maintains high activity even in chloride-rich salt solutions, opening venues
for water oxidation of river and sea waters and v) the catalyst preserve its
ability for several thousand redox cycles, electrolysis extending to 8 hours or
more.
Nocera et al. have successfully integrated the Co-Pi water oxidation
catalyst into a Si solar cell.431433 Deposition of Co-Pi on ITO-passivated
p-side of a p-n Si junction solar cell enables the majority of the voltage
generated by the solar cell to be used for the water splitting reaction. In a
follow up work, a photoelectrolysis cell for total decomposition of water has
been reported. The cells consist of a triple junction, amorphous silicon
photovoltaic interfaced to hydrogen- and oxygen-evolving catalysts made
from an alloy of earth-abundant metals and a cobalt-borate catalyst,
respectively. The devices described here carry out the solar-driven watersplitting reaction at eciencies of 4.7% for a wired conguration and 2.5%
for a wireless conguration when illuminated with 1 sun.
A notable advance has been that the Co-Pi catalysts deposited on to
semiconductor photoelectrodes such as ZnO, WO3, Fe2O3 and BiVO4 can
assist ecient and sustained photooxidation of water to O2.434438 Photooxidation of water using WO3,396 Fe2O3 402,434438 and ZnO407 photoanodes
assisted by homogeneous Co-Pi catalyst of Nocera has been studied by
several research groups. On pristine WO3 photoanodes peroxo species as
well as O2 are produced during photooxidation of water, and the accumulation of peroxo species on the surface is known to cause a gradual loss
of photoactivity of WO3. The presence of the co-catalyst increases the
photocurrent for O2 generation from approximately 61% to approximately
100%. The complete suppression of peroxo formation provided the WO3/
Co-Pi OEC photoelectrode with long-term photostability. a-Fe2O3 lms
used in this study were prepared by electrodepositing Fe lms in nonaqueous solutions, followed by thermal oxidation at 500 1C. Photodeposition of Co-Pi OEC was carried out by using photogenerated holes in the
valence band of a-Fe2O3 to oxidize Co2 ions to Co3 ions in a phosphate
buer solution, which resulted in the precipitation of Co-Pi OEC on the
a-Fe2O3 surface. Co-Pi cocatalyst improved the photocurrent of a-Fe2O3
electrodes more than CO2 ions simply adsorbed on the a-Fe2O3 surface
and the Co-Pi deposited under short circuit conditions resulted in the most
pronounced photocurrent enhancement.
Wang et al.407 used photochemical deposition method to load cobalt
based oxygen evolution catalysts (CoPi) on the surface of ZnO in a neutral
phosphate buer solution containing Co2 ions. The CoPi phase formed
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was amorphous and was deposited on the surface of ZnO uniformly as a

layer of nanoparticles. The enhanced activity for oxygen evolution was
directly observed from photocatalytic water oxidation over CoPi loaded
ZnO. The oxygen produced in the rst hour was more than 4 times of that
obtained over ZnO alone.
Light induced oxidation of water to O2 has been studied on W-doped
BiVO4 photoanode in the presence of dierent water oxidation catalysts.439
IrOx, Pt and Co3O4 catalysts were deposited on a drop cast lm of BiVW-O
anode on uorine doped Conducting glass electrode FTO or by photodeposition method. Visible light irradiation of the anode in aqueous sodium
phosphate buer solutions showed pronounced catalytic evolution of O2
with Pt and Co3O4 catalysts but the metal oxide IrOx was found to be
ineective. In a related work, Li and coworkers report440 that introduction
of Co-Pi water oxidation catalyst to BiVO4 anode improves signicantly the
light induced oxidation of water to O2. They found that this tendency is true
for BiVO4 loaded with a series of dierent electrocatalysts as the cocatalysts. By depositing the Co-Pi as the oxidation cocatalyst and Pt as the
reduction cocatalyst on an yttrium-doped BiVO4 (Bi0.5Y0.5VO4), overall
water splitting reaction to H2 and O2 was realized.
3.3 Cyclic decomposition of water without addition of sacricial donors or
acceptors
3.3.1 Possible approaches. If the semiconductor photocatalyst has its
valence and conduction band positions suitably placed so as to bracket the
redox potentials required for water oxidation to H2 and O2, then simultaneous evolution of O2 and H2 can be achieved. Only few semiconductor
systems have been identied that meets these conditions and TiO2 is one of
them. Even in these most-favorable conditions, use of co-catalysts that
promote water oxidation or reduction improves the catalyst performance
(turnovers as well quantum eciency for the generation of H2 or O2). In the
absence of complete decomposition of water to H2 and O2, for charge
balancing, half-cell reactions leading to H2 or O2 evolution use sacricial
electron donors or acceptors. Majority of photocatalysis of water decomposition fall under this group. In solvent systems such as aqueous alcohol
mixtures, the solvent itself can act as a sacricial donor. Total decomposition of water has been claimed explicitly or implicitly but only in few
cases, experimental data on the quantities of H2 and O2 gases evolved has
been presented. Most often photocatalytic reactions are carried out only for
short period of time when the turnover number is still low and possible
involvement of the components of the photocatalytic system being consumed as sacricial donors or acceptors cannot be ruled out.
Most often the valence band is located at very positive potentials to
permit water oxidation to O2 to occur without any additional energy
requirements. Oxide semiconductors such as SrTiO3, WO3, Fe2O3 and
BiVO4 can eciently oxidize water to O2 but the conduction band positions
are not adequately placed cathodically to permit direct reduction of water to
H2. With a small amount of applied bias, the conduction band electrons
can be upgraded in energy to eect water reduction to H2. These are
cases referred to as photo-assisted electrolysis of water. Similarly there
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are p-type semiconductors such as p-GaP, p-Cu2O that are capable of

reducing water to H2 without concomitant oxidation of water to O2.
Recently Rh-doped SrTiO3 (Rh:SrTiO3) has been found to exhibit p-type
behavior and the doped electrode capable of reducing water to H2
catalytically.
Two parallel developments have advanced signicantly the research for
the identication of suitable photosystems that achieve total decomposition
of water simultaneously to H2 and O2. One is identication of growing
number of homogeneous and heterogeneous catalysts for the production of
H2 and O2 in recent years. Second is electrochemical studies on bulk/
electrode version of potential photocatalysts that help quantify in an elegant
manner the overvoltage requirements as well as quantum eciency for the
generation of molecular H2 and O2 under visible light irradiation. Through
a judicious combination of results from these two approaches (increasing
use of co-catalysts deposited on to semiconductor photocatalysts) has
permitted identication of photosystems that carry out total decomposition
of water simultaneously.
Semiconducting particulate systems are easiest to assemble and explore
but they have the inherent problem of production of a explosive mixture of
the gases (H2 and O2). The gases have to be separated at a cost in a secondary process. An added complication is that many of the co-catalysts
employed to promote water oxidation or reduction can also promote
recombination of H2 and O2. Such recombination process leads to slow
cessation of reactions of interest, viz. water decomposition. Surprisingly few
semiconductor particulate systems with co-catalysts have been identied
recently that exhibit sustained decomposition of water to H2 and O2. These
are described as nanoscale photochemical diodes where the co-catalysts
deposited on to the semiconductor photocatalyst presumably forms
Schottky junctions.
3.3.2 Total decomposition of water in particulate suspensions. Lithium
Niobate LiNbO3 is a very wide bandgap (Eg=4.0 eV) but it has its valence
and conduction bands ideally placed to oxidize and reduce water concurrently. In a recent study, Saito, Koga and Kudo441 found that with the
deposition of a co-catalyst RuO2 on LiNbO3, the photocatalyst particulates
splits water to H2 and O2 (O2 yields slightly in excess to stoichiometric
amounts), albeit with a low quantum eciency (0.7% at 254 nm). In a
related study, RuO2-loaded Zn2GeO4 semiconductor (bandgap energy EgW
4.5 eV) has been found to eect cyclic decomposition of water, with stoichiometric amounts of H2 and O2 evolution under deep UV-irradiation of
the particulate suspensions.442 In both cases cited above, due to the large
bandgap, deep UV radiation (o300 nm) has to be employed. This is a
serious limitation of these photocatalysts.
Among the various photocatalysts studied so far, NaTaO3 is one of the
most ecient photocatalysts for the water-splitting reaction under UV
radiation. NaTaO3 has a large band gap value (Eg 4.0 eV) and so bandgap
engineering has to be applied to introduce visible light response. Studies on
modied NaTaO3 illustate nicely the case on how doping can alter profoundly the ability of the alkali metal tantalates ABO3 to eect total
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decomposition of water to H2 and O2. Kato, Kudo and coworkers made

some important observations on how the presence of excess alkali metal
ions (A= Li, Na and K) during the synthesis of alkali metal tantalates.443,444
ATiO3 aects the photocatalytic properties of these materials.
When the alkali tantalates were prepared in the presence of excess alkali,
their activities were increased by 1 to 2 orders of magnitude. A LiTaO3
photocatalyst showed the highest activity among the naked alkali tantalate
photocatalysts prepared in the presence of excess alkali. On the other hand,
the activity of a NaTaO3 photocatalyst was increased by 1 order of magnitude when a NiO cocatalyst was loaded. The NiO (0.05 wt %)/NaTaO3
photocatalyst produced H2 and O2 from pure water with rates of 3.39 and
1.58 mmol h-1, respectively. The apparent quantum yield was 20% at
270 nm. Suggestions have been made that the valence band of NaTaO3 is
mainly formed by the Ta 5d orbital and doping at the Ta site would signicantly alter the band structure, while codoping at the Na site would help
maintain the ionic charge balance.
NiO-loading on NaTaO3 produced even more favourable results.445 NiOloaded NaTaO3 doped with lanthanum showed a high photocatalytic
activity for water splitting into H2 and O2 in a stoichiometric amount under
UV irradiation. The photocatalytic activity of NiO-loaded NaTaO3 doped
with lanthanum was 9 times higher than that of non-doped NiO-loaded
NaTaO3. The maximum apparent quantum yield of the NiO/NaTaO3:La
photocatalyst was 56% at 270 nm. Structural studies showed NiO cocatalysts were loaded on the edge of the nanostep structure of NaTaO3:La
photocatalysts as ultrane particles. The H2 evolution proceeded on the
ultrane NiO particles loaded on the edge while the O2 evolution occurred
at the groove of the nanostep structure. Thus, the reaction sites for H2
evolution were separated from those of O2 evolution over the ordered
nanostep structure. The small particle size and the ordered surface nanostep
structure of the NiO/NaTaO3:La photocatalyst powder contributed to the
highly ecient water splitting into H2 and O2.
SrTiO3, a wide band gap (3.2 eV) semiconductor is another case that has
been found to catalyze the overall water splitting reaction under UV light
irradiation in the presence of a NiO cocatalyst. Co-catalyst NiO-loaded
SrTiO3 evolves H2 and O2 in stoichiometric ratio under UV illumination
(>3.2 eV). It was mentioned earlier that Rh-doping of SrTiO3 introduces
sub-bandgap states, resulting in a large decrease in the bandgap energy. The
doping turns the photocatalyst to a p-type material capable of evolving H2
from water upon visible light photolysis. BiVO4 similarly is a photocatalyst
capable of evolving O2 from water upon visible light irradiation.
A tandem device composed of a p-type cathode capable of photoreduction of water to H2 coupled to a n-type Oxide capable of oxidation of water
to O2 can exhibit sustained complete decomposition of water to H2 and O2.
Kudo et al.446 demonstrated one such system recently, composed of p-type
Rh:SrTiO3 and BiVO4 photoanode. Townshed et al.447 compared the water
oxidation eciency of bulk SrTiO3 anodes with similar anodes prepared
using nanoparticles. Water oxidation reaction persists in nanoscale particles
of the material, although the process is less eective at the nanoscale.
Decreased eciency is attributed to an increase of the water oxidation
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overpotential for the smaller particles and reduced light absorption due to a
quantum size eect.
Dierent morphological forms of titania photocatalyst has been examined
for the photocatalytic production of H2 from water. The N-doped titania for
example has signicant visible light absorption. Ramakrishna et al.448 examined photocatalytic H2 evolution under simulated solar light irradiation on
electrospun TiO2 nanostructures coated FTO glass plates as photoanodes. in
aqueous solutions. Under illumination, at 1 V, the current densities for water
oxidation were 1.4, 0.6 and 0.2 mA/cm2 for the 5%, 3% and 0% N-TiO2,
respectively. The photoconversion eciency was determined to be 0.8% and
0.5% and 0.1%, respectively for above doped samples. Mesoporous titania
thin lms (MTTFs) with two dierent structures (pillar and and tubular
structures) have been deposited on Ti-foil through an evaporation-induced
self-assembling process in the presence of a surfactant as a structure-directing
agent.449 Under visible light photolysis in photoelectrochemical cells, H2 and
O2 gases evolved in stoichiometric ratio and mesoporous lms of tubular form
showed better performance than the pillar form.
A novel plasmonics based water splitting photoelectrochemical cell has
been reported recently.450 A dense array of aligned gold rods are capped
with TiO2, forming a Schottky/metal semiconductor interface that is illuminated above a Pt counter electrode. Visible light irradiation of this device
leads to photogenerated electrons collecting at the dark Pt electrode where
H2 gas evolves. The resultant positive charges in the Au rods function as
holes and are extracted by an oxidation catalyst which electrocatalytically
oxidizes water to O2 gas.
3.3.3 Total decomposition of water in photoelectrochemical cells
(photoassisted). It was mentioned earlier that the conduction bandedge
position of some of the photocatalysts used in water decomposition are not
suciently cathodic for water reduction to H2 to take place. In such cases,
additional voltage bias has to be applied on the cathode and the process
labeled as photoasssited.451458 Ecient TaON and Ta3N5 photoanodes
for water splitting were fabricated on conducting glass support (FTO) by
Domen and coworkers.451,456458 Several dierent co-catalysts to assist
oxygen evolution were tested. Noceras Co-oxide CoOx was deposited on to
a TaON photoanode coupled to a Pt counter electrode in a photoelectrochemical cell. Since the conduction band of TaON is not suciently
cathodic, a small bias (0.6 V vs. Pt) has to be applied to assist H2 evolution
Addition of phosphate ions increases the photocurrent, possibly due to the
formation of Noceras Co-Pi catalyst phase on the electrode surface.
In a related work,456 loading of IrO2 nH2O nanoparticles as a cocatalyst
for water oxidation improved the photocurrent of the TaON (or Ta3N5)
photoanode. A colloidal solution of IrO2 was used to deposit a IrOx cocatalyst on the synthesized Ta0.9Co0.1Nx lms. The incident photon to
charge carrier eciencies (IPCEs) of the TaON and Ta3N5 photoanodes
were calculated to be ca. 76% at 400 nm and ca. 31% at 500 nm, respectively, at 1.15 V vs. reversible hydrogen electrode (RHE) in aqueous Na2SO4
solution. Overall water splitting into H2 and O2 under visible light was
demonstrated using an IrO2 nH2O-loaded TaON (or Ta3N5) photoanode
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combined with a Pt electrode under an externally applied bias (TaON: W

0.6 V, Ta3N5: W 1.0 V).
BiVO4 is another example of a photocatalyst where total decomposition
of water under applied bias has been demonstrated.418,452455 Earlier we
referred to a number of studies where O2 evolution has been shown to
occur. Jia, Iwashina and Kudo452 have described a simple method for the
preparation of BiVO4 electrodes as thin lms, by dipping an F-doped
conducting glass electrode FTO in an aqueous solution of Bi(NO3) 3 and
NH4VO3 followed by calcinations at 500 1C: Sponge-like orange colored
thin lms before calcinations, upon calcination sinter to form necked
nanoparticles. The BiVO4 thin lm electrode gave an excellent anodic
photocurrent with 73% of an IPCE at 420 nm at 1.0 V vs. Ag/AgCl.
Modication with CoO co-catalyst on the BiVO4 electrode improved the
photoelectrochemical property. Total decomposition of water to H2 and O2
can be achieved by applying a small external bias voltage.
Mullins and coworkers453 have synthesized nanostructured BiVO4
lms by coevaporation of bismuth and vanadium in an oxygen ambient, a
process referred to as reactive ballistic deposition (RBD). The lms were
tested in various electrolyte solutions to assess their activity for
photoelectrochemical water oxidation. Films deposited with excess vanadium
(V/Bi=2) and incident angles of deposition at 65 showed the highest initial
photocurrents with IPCE values above 21% for light wavelengths of
340460 nm (in 0.5 M Na2SO4 at 1.0 V vs Ag/AgCl). Stoichiometric BiVO4
lms remained stable under illumination but their photocurrents were limited
by surface reaction kinetics. The addition of cobalt as an electrocatalyst to the
surface of these lms increased their photocurrent by a factor of 3.
In a study of the visible-light-induced water oxidation of metal-iondoped BiVO4,454 W and Mo doping gave signicant enhancement of the
photo-oxidation activity of bare BiVO4. W- or Mo-doped (2 atom %)
BiVO4 photoanodes about 1 mm thick were fabricated onto transparent
conducting substrate by a metalorganic decomposition/spin-coating
method. Photoelectrochemical studies of W- and Mo-doped anodes showed
IPCE of 35 and 40% respectively Theoretical calculations indicated
both W and Mo to be shallow donors and Mo doping generated superior
conductivity to W doping. Using TiCl3 as the structure directing agent
in a hydrothermal synthesis of BiVO4, Wang et al.455 managed to optimize
the formation of monoclinic crystals with preferentially exposed (040)
facets. The photocatalytic activity of oxygen evolution on BiVO4 is
found to be proportionally correlated with the exposed surfaces of the (040)
facet. It is assumed that the active sites with a BiVO4 structure on the
exposed (040) facet is assigned to be responsible for the high activity of O2
evolution.
3.3.4 Total decomposition of water in PECs (unassisted). In a review
publication, Kudo and coworkers highlighted some possibilities. A NiO
(0.2wt%)/NaTaO3:La (2%) photocatalyst with a 4.1-eV band gap showed
high activity for water splitting into H2 and O2 with an apparent quantum
yield of 56% at 270 nm.459 Kanhere et al.460,461 studied recently the eect of
Bi3 doping of NaTaO3 powders. It was found that the Na/Ta molar ratio
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Fig. 4 A coupled semiconductor-based photoredox system for the total decomposition of

water. (Adapted with permission from: Y. Sasaki, A. Iwase, H. Kato and A. Kudo, J. Catal, B,
2008, 259, 133.)
of the starting materials aects the site occupancy of Bi at Na or Ta site in the

lattice, and thus the optical and photocatalytic properties are signicantly
altered. Under Na-decient conditions, Bi predominantly occupied Na site;
the sample did not show absorption in the visible region. While under
strongly Na-rich conditions, Bi occupancy at Ta site was predominant. These
samples showed visible light absorption up to 450 nm. The samples prepared
under mildly Na-rich condition, which leads to approximately equal occupancy of Bi at Na and Ta sites, showed visible light absorption up to 550 nm.
The Mott-Schottky plots revealed that the at band potential of the pristine
NaTaO3 is highly negative to the H2/H2O reduction potential (1.19 eV vs.
SCE, pH=7) and for all Bi doped NaTaO3 samples, the at band potential
was sucient for the hydrogen generation (cf. Fig. 4).
LaFeO3 with orthorhombic Perovskite structure has been prepared by
sol-gel hydrolysis route and found to be an excellent photocatalyst for water
decomposition. The material has an optical bandgap of 2.07 eV. Tijare
et al.462 observed photocatalytic evolution of H2 using Pt-loaded version of
this oxide (Pt-LaFeO3) in aqueous ethanolic solutions The oxide without
any co-catalyst was investigated by Parida et al. 463 under visible light
irradiation (lc420 nm). Total decomposition of water can be observed.
Highest amount of H2 and O2 evolved in 180 min over the LaFeO3 activated
at 500 1C was recorded to be 1290 mmol and 640 mmol, respectively having
apparent quantum eciency (AQE) 8.07%.
Protonated layered perovskite oxides H1.9K 0.3La 0.5Bi0.1Ta2O7
(HKLBT) and [H1.6K 0.2La 0.3Bi0.1Nb2O6.5] (HKLBN) have been prepared
and found to be good photocatalysts for water splitting under UV light
irradiation.464,465 Treatment of KLBT(N) with HCl leads to partial loss of
K and Bi w HKLBT(N) with replacement by protons to give HKLBT.
Bandgap energies for various photocatalysts have been estimated to be 3.22
(KLBN), 3.44 (KLBT), 3.49 (HKLBN) and 4.0 eV (HKLBT). Though the
bandgap of the catalyst increases by the acid treatment, the partially substituted showed considerably higher photocatalytic activity for H2 and/or
O2 evolution than KLBT(N) in the absence of sacricial reagents (90 and 25
Photochemistry, 2013, 41, 182265 | 249
View Online
times higher for the Ta and Nb-based perovskites respectively). Water

photodecomposition with concurrent evolution of H2 and O2 continues
over 20 hours without any sign of photocorrosion of the catalyst. It has
been suggested that inter layer modication via ion exchange is a potential
route to design more photocatalysts.

Concluding remarks
Both the areas of heterogeneous photocatalysis and photodecomposition of

water have seen signicant advances in several fronts. New catalysts that
permit photodegradation of organic pollutants and water decomposition
using visible light have been identied. Cyclic decomposition of water with
continuous evolution of H2 and O2 from water has been observed in select
photoelectrochemical cells and even in particulate aqueous suspensions.
Nanostructuring of the photocatalysts using 0-, 1- and 2-dimensional
morphologies and even hierarchical structures grown on these as templates
permit further enhancement of the catalysis eciency and in select cases
with added specicity/selectivity in the photoproducts formation. Several
applications such as air-cleaning, waste water and industrial eluents treatment have reached commercial levels. Clearly more exciting developments
based on recent advances bound to appear in the coming years.
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Photochemical Applications of Solar Energy - Photocatalysis and Photodecomposition of Water

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Photochemical Applications of Solar Energy - Photocatalysis and Photodecomposition of Water

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Photochemical applications of solar energy:

photocatalysis and photodecomposition of

Introduction and scope

182 | Photochemistry, 2013, 41, 182265

The Royal Society of Chemistry 2013

sustained manner with reasonable eciency. These studies are reviewed in

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Titania still remains as the most extensively studied photocatalyst material in

Photochemistry, 2013, 41, 182265 | 183

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Photocatalysis studies using particulates (slurry systems) is the simplest and

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2.1.1.2 Spherical nanoparticles of titania, hollow spheres. Historically

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Procedures have been developed using Atomic Layer Deposition method

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Hollow anatase TiO2 single crystals and mesocrystals with dominant

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designed to conne, control and manipulate photons so as to increase the

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constant low level. At much higher concentrations employed (1015%),

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photocatalytic decomposition yields of CH3CHO under both UV and

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Ag-decorated SiO2 NSs showed a signicantly red shifted and relatively

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For nitrogen doping (N-doping dierent from n-type doping), according

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substrates such as simple plane glass and patterned glass at variable

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Vermiculite is a layered magnesium aluminium silicate with 2:1 crystalline

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2.1.3.4 Nanocomposites of photocatalysts and Carbon allotrophs. In

200 | Photochemistry, 2013, 41, 182265

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under ultraviolet irradiation. Kim et al.

Photochemistry, 2013, 41, 182265 | 201

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CO2 4H 4e ! HCHO H2 O

CO2 6H 6e ! CH3 OH H2 O

CO2 8H 8e ! CH4 2H2 O

2CO2 12H 12e ! C2 H4 4H2 O

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as the main product while methanol also forms as a predominant product

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photocatalyst, unfavorable formation of CO and gradual deactivation of

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drinking and waste water resources. TiO2-based photocatalysts immobilized

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Table 1 Bandgap energies of popular semiconductors used in photocatalysis studies.

and non-toxicity. Some of the recent studies of ZnO as a photocatalyst

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