Documente Academic
Documente Profesional
Documente Cultură
copying and redistribution of the article or any adaptations for non-commercial purposes.
Review
pubs.acs.org/CR
Department of Chemistry and Materials Science and Engineering Program, University of California at Riverside, Riverside,
California 92521, United States
1. INTRODUCTION
1.1. Scope
Titanium dioxide (titania, TiO2) has been fervently researched
over the past few decades due to its potential applications
across many dierent areas. Thanks to its bulk properties,
CONTENTS including high refractive index and ultraviolet (UV) light
absorption, TiO2 has seen considerable use as a white pigment
1. Introduction 9853 in paint, food coloring, and personal care products and as a UV
1.1. Scope 9853 absorber in sunscreens.17 These applications utilize TiO2
1.2. Advantages of TiO2 Composites 9854 across a wide range of sizes from hundreds of nanometers to
2. Metal and Metal OxideTiO2 Composites 9855 several micrometers. Although these applications account for
2.1. Group I and II Metals 9855 the majority of global TiO2 consumption, its utilization in
2.2. Early Transition Metals 9856 nanoscale research has primarily focused on its near semi-
2.3. Middle Transition Metals 9858 conductor electronic properties. Beginning with the initial
2.3.1. Vanadium, Niobium, and Tantalum 9858 discovery of the production of hydrogen from a TiO2 anode
2.3.2. Chromium, Molybdenum, and Tungsten 9859 under UV irradiation,8 much work has been done, which has
2.3.3. Manganese and Rhenium 9860 expanded use of TiO2 to numerous new applications. These
2.4. Late 3d Transition Metals 9860 applications range from photovoltaic cells9 to photocatalysts for
2.4.1. Iron and Cobalt 9860 hydrogen production and environmental remediation10 as well
2.4.2. Nickel, Copper, and Zinc 9861 as photoelectrochemical sensors.11 Many other niche uses have
2.5. p-Block Metals 9864 also been studied, particularly in the medical and biological
2.6. Lanthanides 9866 elds, where TiO2-based nanomaterials have been investigated
3. Noble Metal and Metal OxideTiO2 Composites 9866 for in vivo imaging,12,13 cancer therapy,10,14 and protein
3.1. Ruthenium and Rhodium 9866 separation/purication1524 and as bactericides.2528 Although
3.2. Palladium 9866 applications as a pigment/UV absorber are typically possible
3.3. Platinum 9868 using pure TiO2, it has become clear that this is less feasible for
3.4. Silver 9869
applications utilizing photoelectrochemical properties as well as
3.5. Gold 9870
a number of biological applications. Thus, much research has
4. Nonoxide SemiconductorTiO2 Composites 9871
been dedicated to the construction of nanoscale TiO 2
4.1. Metal Pnictogenides 9871
composite materials.
4.2. Metal Chalcogenides 9872
Various excellent reviews have looked at TiO2 and its
4.2.1. Cadmium Chalcogenides 9872
applications to each of the aforementioned elds of study over
4.2.2. Other Single-Metal Chalcogenides 9873
the years and give a signicant amount of background for each
4.2.3. Semiconductor Alloy Chalcogenides 9873
TiO2 material.9,10,26,2941 However, many of these reviews look
5. CarbonTiO2 Composites 9873
at either a multitude of materials (i.e., not limited to TiO2
5.1. Carbon Nanotubes 9873
5.2. Graphene and Graphene Oxide 9873
composites) and/or a specic application of TiO2 materials
5.3. Other Carbon 9875 with a narrow focus. Thus, the intent of this review will be to
6. Templated Composites 9875 discuss the synthesis of TiO2 composite nanomaterials and
6.1. YolkShell and CoreShell 9875 their applications across a wide range of elds. To clarify the
6.2. Ordered Mesoporous Silica and Zeolites 9876 focus of this review, we will dene a composite as a
6.3. Anodized Aluminum Oxide (AAO) 9877 combination of one or more materials (metal, metal oxide,
7. Summary and Outlook 9877 metal sulde, etc.) with TiO2. These combinations may appear
Author Information 9879 in many forms such as layered or coreshell structures and can
Corresponding Author 9879 be produced by various methods including chemical synthesis,
Notes 9879 solution- or gas-phase deposition, and templated fabrication.
Biographies 9879
Acknowledgments 9879 Special Issue: 2014 Titanium Dioxide Nanomaterials
References 9879
Received: November 3, 2013
Published: July 11, 2014
2014 American Chemical Society 9853 dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889
Chemical Reviews Review
Figure 1. (a) General model of photocatalysis on TiO2. Reactions occur in three steps: (i) absorption of photons greater than the band gap energy to
produce an electronhole pair; (ii) separation of charges and migration to the surface; (iii) redox reactions with adsorbed reactants. (b) TiO2
composite structure exhibiting a heterojunction and charge trapping on TiO2 and the second component.
We do concede that many of the composite materials discussed detailed. It is also necessary to note that a number of
herein have shown little improvement in performance toward composites consist of multiple materials which span dierent
their applications and, as such, have been superseded by categories. In these cases the composite will be discussed in the
superior materials; however, in the interest of being section relevant to the specic component that is yielding the
comprehensive, they will be covered as well. Further, we greatest benet or is the most novel addition.
acknowledge that the utilization of TiO2 for the photocatalytic 1.2. Advantages of TiO2 Composites
degradation of dyes is only a model system to test
photocatalytic activity; however, especially with how ubiquitous The photoactivity of TiO2 has been shown to be dependent on
it is in the literature, this technique has become a useful tool for several key properties: crystal phase, surface area, exposed
determining and comparing the gross improvements of various crystal facets, uncoordinated surface sites, defects in the lattice,
composite materials. It is frequently included within this review and degree of crystallinity. Morphology control of TiO2 via
to make such comparisons, although we disregard the synthesis of composite materials has allowed for the improve-
likelihood of its extension to a commercial product. ment and ne tuning of many of these properties. Additionally,
Since the study of TiO2 has become such a widespread, TiO2 composite structures can create and tune other properties
multidisciplinary eld, a signicant amount of research has been such as mid-band-gap electronic states which can alter charge
dedicated to it over the last several decades. Consequently, a migration or produce a red shift in the absorption spectrum.
brief search of the literature in the SciFinder Scholar database Further, formation of heterojunctions between TiO2 and other
for TiO2 returns over 250 000 results. This can be narrowed materials can yield visible light absorption by the added
to just over 11 000 results when using TiO2 composite, material with charge separation facilitated by the TiO2. The two
although many composite materials that are not specically main polymorphs of TiO2 which show the highest photoactivity
labeled as such are left out. Thus, it becomes apparent that in are the anatase and rutile phases, which have typically reported
order to best review the state of TiO2 composite materials, band-gap values of 3.2 and 3.0 eV, respectively. Although the
criteria for separating types of composites must be determined. band gap of rutile is narrower, the anatase phase is typically
Here, we will rst organize composite materials by reviewing considered more favorable as it has a higher reduction potential
specic metal composites based on their positions in the and a slower rate of recombination of electronhole pairs.30,32
Periodic Table. Then, we will switch to categorization using Unfortunately, its wide band gap dictates that it will primarily
specic material types. The initial sections of the review will absorb UV radiation. Here the utility of mixed phase TiO2 must
look at metal and metal oxideTiO2 composites. Metals that be discussed. Optimization and control of the phase transition
are similar chemically or utilized for similar applications will be and its applications have been covered in detail elsewhere;4247
grouped together in order to make simpler comparisons. It is however, commercial Degussa P25, or simply P25 for short, is
worth noting that while there are numerous composites with one of the most commonly used mixed phase TiO2 composites.
dierent types of metals and metal oxides there are still some This mixed phase material allows for utilization of visible light
elements which are seldom used outside of doping, and as such, wavelengths through excitation of the rutile phase while also
a number of metals will not be considered. Following this we containing benets of anatase TiO2, such as a decreased
will discuss nonoxide semiconductorTiO2 composites, which recombination rate of charge carriers. The initial mechanism for
have been the subjects of signicant research in the elds of this enhancement was ambiguous; however, utilizing electron
photocatalysis and photoelectrochemical cells. CarbonTiO2 paramagnetic resonance (EPR), Hurum et al. studied the fate of
composites, which have been heavily researched due to the photogenerated charge carriers in order to shed light on the
recent increase in the production of carbon nanomaterials such mechanism.48,49 They found that electrons which were
as nanotubes and graphene, will then be discussed. The photogenerated by the rutile component were transferred to
subsequent section will discuss templated composites, which a previously proposed electron trap site in the anatase lattice
have seen an increase in study recently. The synthesis and which lies 0.8 eV below the anatase conduction band.50 Further,
utilization of complex TiO2 nanostructures using templates this is situated lower than the rutile conduction band. A
such as polystyrene, silica, zeolites, and aluminum oxide will be decrease in electronhole recombination is achieved since the
9854 dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889
Chemical Reviews Review
photogenerated holes remain within the rutile component and such, most of the metals below will be discussed as their metal
the electrons are spatially separated into the anatase oxides. Further, the most common oxide will be preferentially
component. It was later determined that the photogenerated discussed as other oxides are likely to be unstable and thus do
holes are preferentially trapped on the surfaces, whereas not form stable composites.
electrons become trapped within the lattice. As such surface 2.1. Group I and II Metals
electron trap sites increase the recombination rates, which
indicates that a composite with a second material which is Due to their high oxidation potentials and instability in aqueous
either a hole or an electron sink can further increase catalytic solutions, composites of the Group I and II elements are mainly
eciency. based on their oxides. Additionally, many of these elements are
Beyond the use of mixed phase TiO2, composites with non- also frequently used for formation of metaltitanate materials,
TiO2 materials are a very promising means to extend the which exceeds the scope of this review and will not be
usefulness of anatase into the visible wavelengths. Alternatively, specically discussed. The large majority of the Group I and II
for composites consisting of the rutile phase, inclusion of higher metal oxideTiO2 composites were initially studied as part of
work function materials can yield slower charge carrier more complex aluminosilicate and aluminotitanate glasses
recombination. Other methods to decrease charge carrier and ceramics for a variety of applications.5153 These
recombination include increasing crystallinity, which can be composites are not strictly TiO2 composites, however, as they
done by high-temperature calcination, addition of dopants, or are formed from melts of metal oxide mixtures and typically
specic synthetic protocols. Additionally, defects, which can result in titanate products. Lithium oxide specically has little
serve as charge carrier traps and reduce the recombination of use in composites besides as a component in glasses which,
photogenerated electronhole pairs, can also be either induced once melted, typically form lithium titanate materials.54,55
or stabilized by formation of a composite. Composites which Oxides of sodium, rubidium, and cesium have also seen a
can help to tune the grain size have also been shown, such as considerable portion of their usage as components in
metal oxide solgel precursors which can form composites with glasses.56,57
TiO2 and inhibit crystallinity. Interestingly, potassium oxide, as K2O, has seen interest as a
Figure 1a shows a general model for photocatalysis on component in composites for catalytic processes. In a system
anatase TiO2 in which light is absorbed to produce an containing a mixed composite of TiO2ZrO2, it was shown that
electronhole pair, charges migrate to the surface, and redox a mixture of K2O and CO2 can be benecial in increasing both
reactions occur. This ideal case assumes low charge the reactivity and the selectivity of the dehydrogenation of
recombination and easy charge migration to the surfaces. ethylbenzene to styrene.58 Conversion of ethylbenzene was
Charge separation can be enhanced by creation of features such increased from 60.59% to 71.95% with addition of 3 wt % K2O,
as surface defects where electrons and holes can be trapped to and the selectivity was increased from 97.04% to 99.63%. It is
prevent recombination or, as discussed earlier, in P25 where a worth noting that one previous study of the addition of only
natural electron trap exists below the anatase conduction band. K2O to the TiO2ZrO2 composite for this reaction reported
Figure 1b shows an improved case utilizing a TiO2 composite decreased activity due to K2O neutralizing the acidic sites on
heterojunction. In this case, a structure with a narrower band the TiO2ZrO2 composite,59 although it was shown that this
gap can utilize visible light to produce an electronhole pair. neutralization did have the added benet of increasing the
Assuming a favorable band oset, the electron can migrate to selectivity by suppressing the dealkylation products.60 The
the TiO2, while the hole is trapped in the second material. basicity of K2O has also been shown to inuence other
Redox reactions are now free to occur at the separate surfaces reactions as well. In one study, by again neutralizing the acidic
since the likelihood of charge recombination has been sites in a V2O5(WO3)/TiO2 composite, selective reduction of
diminished. A heterojunction composite structure can then be NO by NH3 was poisoned to nearly zero conversion with 1 wt
rationally designed in order to produce a favorable band oset % K2O.61 On the other hand, catalytic applications that can
and band positions in order to develop a catalyst for the needs utilize the basicity of K2O have also been studied with positive
of specic reactions, such as water splitting. results. Recently, Salinas et al. demonstrated the trans-
In addition to the improvement of photocatalysis, composite esterication of commercial canola oil over a K2O/TiO2
structures can yield other benets. Such advantages include the catalyst for production of biodiesel.62 The results show that a
ability to tune the surface properties, i.e., acidity/basicity or 20 wt % K2O/TiO2 catalyst can achieve total conversion to
open coordination sites, of the resultant materials, which is of methyl esters in reuxing methanol after 7 h of reaction time.
importance to the adsorption of molecules, a critical factor This compares favorably to other catalysts which utilize
relevant to catalysis, separation, and further modication. potassium in the forms of KOH, KNO3, or KI supported on
Numerous mixed metal oxide/TiO2 composites are benecial alumina, which have conversions of approximately 90% over
for stabilization of thermal catalysts where reactions such as reaction times ranging from 8 to 10 h for similar commercial
high-termperature NOx reduction are improved. Composites oils.6365 A follow up study on this system showed that upon
such as coreshell materials are also benecial toward the calcination above 600 C the composite formed an even more
stabilization of nanoparticles against phenomena such as active titanate catalyst which yielded total conversion in under 3
sintering or aggregation. Further, composites can be of great h.66
use to create highly porous materials, hollow shells, or In addition to K2O/TiO2 composites, MgO/TiO2 compo-
hierarchical structures by templating methods. sites have also seen use in biodiesel production with similarly
active catalysts being developed.67,68 After the work by Tanabe
2. METAL AND METAL OXIDETIO2 COMPOSITES et al. in 1978, which detailed the catalytic activity of composites
Most metals are either too chemically reactive, especially on the of MgO/TiO2 based on acidity/basicity,69 little research had
nanoscale, not having properties that can be taken advantage of been conducted until the past decade. Aside from the
readily, or unnecessary with regard to composites with TiO2. As production of biodiesel, recent work has been established
9855 dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889
Chemical Reviews Review
utilizing MgO/TiO2 composites for photocatalysis and photo- to a 0.35 Mg/Ti molar ratio; above this ratio the blockage of
electrochemical cells. One example of such work done by hole escape by MgO on TiO2 is thought to be excessive, and
Taguchi et al. utilized a thin layer of MgO over TiO2 for thus, the performance decreased. This recombination was
stabilization of solid-state dye-sensitized solar cells (DSSCs).70 previously studied by Bandara et al., whereby they monitored
Magnesium methoxide was deposited onto a TiO2/F-doped the degradation of various organic molecules under UV
SnO2 (FTO) cell in an ethanolic solution and then sintered to irradiation with TiO2 loaded with dierent amounts of
form a thin (0.25 nm) MgO layer. The cell was completed MgO.73 These catalysts consisted of clusters of MgO on the
with Ru 535 dye, CuI as a hole scavenger, and an Au-coated surface of TiO2, and the optimal catalyst was determined to
FTO slide. The role of MgO was to stabilize the cell and act as have a composition of 3 wt %. The MgO clusters act as
a physical barrier between TiO2 and CuI to prevent charge coordinately unsaturated defect sites where anion vacancies can
recombination and, most importantly, to prevent back electron eciently separate and trap electrons with the resulting holes
transfer between TiO2 and the dye molecules. Consequently, trapped in the TiO2, thus preventing recombination and
both the open-circuit voltage (Voc) and the short-circuit current allowing for optimal work to be done by the system. This
density (Jsc) improved from 430 to 510 mV and 8.38 to 8.74 charge separation was later conrmed by DFT simulation of
mA/cm2, respectively, and the eciency increased from 2.13% MgO clusters on a rutile TiO2 (110) surface. 74 The
to 2.90%. Additionally, the stability over time for both combination of these ndings has inspired new research into
parameters improved markedly with the MgO coating as these MgO/TiO2 composite structures as inexpensive materials
shown in Figure 2. The increase in Jsc was unexpected as the with improved catalytic performances.75,76
Whereas MgO has seen considerable research in composites
with TiO2 in recent years, the remaining Group II metals have
been little used, which is likely due to the abundance of
research on the more useful and interesting systems with
strontium and barium titanates. Some research has been
conducted utilizing CaO in a composite with TiO2 where a
basic oxide is needed for catalytic applications,77 akin to the use
of potassium oxide mentioned above. However, mixtures of
CaO and TiO 2 have seen more research as ceramic
materials,78,79 wherein again the titanate product is most
commonly formed.80 TiO2@SrO core@shell nanowires have
recently been prepared and their photocatalytic properties
tested for dye degradation.81 The composite was prepared by
dip coating TiO2 nanowires in an aqueous Sr(NO3)2 solution
for dierent times and then calcining the products in air to 450
C. The SrO coating, however, shows no well-dened SrO
peaks by X-ray diraction and appears to be amorphous under
the given conditions, although higher temperature calcination
may form a strontium titanate phase rather than SrO.82 It is
worth noting that compared to the pure TiO2 nanowires, there
was still an improvement in the rate of dye degradation when
the shell thickness was optimized. Barium oxide has seen recent
usage as part of TiO2 and/or Al2O3 composites for NOx
Figure 2. Stability of Voc (open square), Jsc (open triangle), ll factor
storage/reduction applications. Initial results out of the Toyota
(cross), and eciency (lled circle) of solid-state DSSCs (a) without Motor Corp. laboratories showed the ability of NOx to adsorb
MgO layer and (b) with MgO layer under continuous illumination. onto the basic barium oxide surface to form Ba(NO3)2, which
Adapted from ref 70 with permission from The Royal Society of stored the NOx as a nitrate for reduction at a later step.83
Chemistry. Adsorption of NO2 on BaO/TiO2 composites was improved
greatly when utilizing TiO2 as a support as compared to Al2O3,
which was attributed to the weaker surface Lewis acid sites of
MgO layer may reduce the eciency of electrons from excited TiO2 binding NOx as well, compared to limited binding by the
dyes being injected into TiO2; however, an unforeseen benet more acidic Al2O3.84,85 Andonova et al. additionally found that
of the MgO layer was an increase in dye adsorption of 20% as Ti-containing domains had a strong anity toward Ba-
compared to the TiO2 surface alone. containing domains, to the point that upon calcination at 600
Later work by Jung et al. also showed similar increases when C barium titanates and bariumtitaniumaluminates were
dye-sensitized solar cells (DSSCs) were fabricated from TiO2 formed as shown in Figure 3. They further determined that the
particles (Degussa, P25) which were predecorated with MgO.71 strong anity between Ti and Ba domains can be benecial for
They also found an optimal weight percentage to be 0.6 wt % inhibiting formation of BaSO4, which poisons the NOx uptake
MgO, which yielded an improvement from 3.1% to 4.5% in eciency.8587
their as-constructed cells. Construction of DSSCs for hydrogen
2.2. Early Transition Metals
production was also observed to show a minor increase in H2
production when a MgO/TiO2 composite cell was constructed Although oxides of scandium have not been commonly utilized
utilizing an overcoat of MgO on a TiO2:ITO cell.72 It was in composites with TiO2, other early transition metal oxides
found that under bias voltage the decrease in charge have seen considerable use. Here we will focus on the
recombination was benecial for MgO loading amounts of up utilization of yttrium, zirconium, and hafnium oxideTiO2
9856 dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889
Chemical Reviews Review
Figure 3. Illustration of the eect of calcination and BaO deposition on an Al2O3 substrate. Reprinted with permission from ref 85. Copyright 2009
American Chemical Society.
composites, where lanthanum will be reserved for the amount. At this concentration, the cell eciency was found to
lanthanides section later. Yttrium oxide has been most notably increase from 5.84% in the pure TiO2 cell to 7.00%, with
utilized in composites with TiO2 for enhancement of corresponding increases in Voc, Jsc, and the ll factor (FF).
upconversion particles. Lu et al. showed that Y2O3 doped Although the increase in eciency is modest, the benet of
with Tm3+ and Yb3+ (Y2O3:Tm3+,Yb3+), when coated with a converting infrared light into more usable wavelengths to
TiO2 layer, showed an upconversion emission intensity increase DSSC performance is notable.
enhancement of up to 5.4 times that of the uncoated sample.88 Zirconium oxide has seen considerable usage in TiO2
These core@shell structures were prepared by a modied composite materials. However, it is most frequently incorpo-
Stober process to coat the cores with TiO2 using tetrabutyl rated as part of a mixed oxide ceramic system or as a mixed
titanate in place of a silica precursor. The reaction was allowed oxide catalytic support system, although some more recent
to proceed for various times in order to tune the shell thickness. usage has focused on the interaction between ZrO2 and TiO2
The TiO2 layer showed an amorphous structure by X-ray for photocatalytic applications. The frequent use as a support
powder diraction, since the structure was not calcined post can be attributed to optimal surface acidity of the ZrO2/TiO2
synthesis and drying. The enhancement of the emission composite, 91 which can be ne tuned based on the
intensity was attributed to the TiO2 layer, which provides a concentration of ZrO2 within the composite as well as the
ligand eld for surface lanthanide dopant ions to convert from a calcination temperature and the synthetic conditions.92,93 The
dormant state to an active one. However, it is noted that in acidbase tunability of these supports can be utilized for the
composites where the TiO2 shells were too thick, absorption of catalytic, or photocatalytic, oxidation of organic molecules;9497
the incident light and reabsorption of the emitted light dehydrogenation reactions;59,98 and NOx reduction,99,100
increased to the point that the enhancement factor would among other reactions, which have been reviewed previ-
begin to decrease. Although optimal samples were denoted by ously.101,102 Also of interest recently is the utilization of ZrO2/
optimum coating time, statistical analysis for an optimized TiO2 composites for photocatalysis, which is tested by dye
thickness coating was not performed. degradation or water splitting.103106 Addition of ZrO2 to TiO2
In addition to the upconversion enhancement, composites of has been shown to retard or even prevent formation of rutile
lanthanide-doped Y2O3 and TiO2 have also been utilized for phase within TiO2 composites, which corresponds to a decrease
photocatalysis and DSSCs. Li et al. prepared a composite of in the growth of TiO2 grains in the microstructure and an
Y2O3:Tm3+,Yb3+/TiO2 by hydrolyzing TiCl4 in an ethanolic increase in the surface area,106109 although the robust nature
solution containing the upconversion particles, followed by of ZrO2 makes it dicult to remove from the TiO2 composite
calcination at 500 C.89 The optimal upconversion particle was unlike the case of SiO2. Chen et al. recently utilized this
found to have a Yb3+ concentration of 2 mol % with a xed increase in surface area to optimize ZrO2/TiO2 composite
Tm3+concentration of 0.5 mol %. They found that when microspheres for the adsorption of heavy metal oxides.110 They
compared to pure TiO2 prepared using the same methods there were able to reach a maximum surface area of 413 m2/g in a
was an increase in the degradation rate of methyl orange (MO) 30:70 Zr:Ti molar ratio composite, which compares favorably
by solar irradiation. Pure TiO2 degraded approximately 40% of to the pure phase surface areas of 108 and 104 m2/g for TiO2
the MO in 150 min, whereas the composite achieved 100% and ZrO2, respectively.
degradation. The photocatalytic enhancement was attributed to One recent study for the use of this system in a photocatalyst
infrared radiation in the solar spectrum being upconverted to was done by Li et al., who synthesized a series of composites
UV light, which could then be utilized by the TiO2 portion of containing ZrO2, CeO2, and TiO2.105 The composites were
the composite. Recently, Y2O3:Er3+ nanorods were utilized to prepared via the evaporation-induced self-assembly (EISA)
improve the eciency of a TiO2:FTO DSSC.90 The cells were method utilizing Pluronic P123 as a surfactant, Ce(NO3)3,
constructed by depositing a 12 m thick layer of a TiO2 colloid ZrOCl28H2O, and titanium n-butoxide in an ethanolic solution
onto FTO, then mixing the Y2O3:Er3+ nanorods with a separate followed by calcination at 500 C. The ZrO2-containing
TiO2 colloid solution and adding a 4 m thick layer of the composite consistently showed increases in surface area, pore
mixture on top, followed by sintering at 450 C. On the basis of diameter, and pore volume when compared to samples without
several trials, the optimum weight percent of the upconversion ZrO2, indicating the inuence of the ZrO2 on the micro-
particles was found to be 5 wt % compared to the overall TiO2 structure of the composite. The resistance to sintering provided
9857 dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889
Chemical Reviews Review
by the ZrO2 allows for stabilization of long-range, ordered materials. One study by Triyoso et al. showed that in an
pores throughout the microstructure. The photocatalytic optimum synthesis by atomic layer deposition the mixed oxide
activity was further tested via the visible light degradation of deposition is favorable when compared to alternating layers of
Rhodamine B (RhB). The mesoporous ZrO2CeO2TiO2 HfO2 and TiO2.112 The mixed oxides yield values of 38 at a
composite showed the highest photocatalytic activity when 10:1 HfO2/TiO2 ratio and 28 at a 1:2 ratio, as compared to
compared to the other catalysts including P25, as shown in values between 21 and 25 with layered structures. Other recent
Figure 4. studies have also shown improvement of the relative
permittivity of mixed oxide systems as compared to pure
HfO2, with better charge mobility and reasonable charge
leakage.113116
2.3. Middle Transition Metals
2.3.1. Vanadium, Niobium, and Tantalum. Much like
how ZrO2 has been utilized in composites with TiO2, vanadium
oxides in the form of V2O5 have seen frequent usage when
combined with TiO2 as a support material for reactions such as
the catalytic reduction of NOx117119 and oxidation of organic
molecules.120,121 Other applications of V2O5/TiO2 composites
which have seen some study are for use in gas sensors122,123 and
photocatalysis.124126
One recent study by Yang et al. found that nanotube arrays
consisting of a V2O5/TiO2 composite have benecial properties
in supercapacitor applications.127 The nanotube arrays, which
are shown in Figure 5af, were fabricated through anodization
of Ti:V alloy plates (Ti:V ratio ranging from 0.2 to 18 atom %)
in an electrolyte consisting of ethylene glycol and HF. It had
been shown previously that V2O5 demonstrated signicant Li+-
intercalation properties such as a high capacity and rate, which
is improved in the presence of TiO2.128 Pure phase V2O5
nanotubes could not be grown due to instability under typical
anodization electrolytes, so TiO2 nanotubes provided an
optimal and a stable structure to utilize for the composite. As
shown in Figure 5g, the cyclic voltammograms show the highest
current densities for nanotubes fabricated from the 18 atom %
vanadium alloy. Upon calcination, the nanotubes showed
improved performance until formation of the rutile phase,
which is considered to reduce the conductivity.129 Ultimately,
the optimized nanotubes showed specic capacitance values up
to 220 F/g with an energy density of 19.56 Wh/kg.
Additionally, other oxides of vanadium, most notably
Figure 4. Photocatalytic adsorption, degradation, and reduction of vanadium(IV) oxide, VO2, have been used in composites
total organic carbon percentages (a) and photodegradation kinetic with TiO2, although much of this research is limited due to the
curves (b) of RhB on P25, TiO2, CeO2TiO2, mesoporous CeO2 inherent instability of the lower oxides. However, because of
TiO2, and mesoporous ZrO2CeO2TiO2. Reprinted from ref 105, the considerable amount of research regarding the thermo-
with permission from Elsevier. Copyright 2013. chromic transition of VO2,130132 composites with TiO2 have
been investigated to enhance both the chemical stability of VO2
Hafnium oxide (HfO2 )TiO 2 composites have seen and the transmittance, with some good results to date,133136
extensive research recently as potential materials for applica- including a slight decrease in the transition temperature, though
tions as gate dielectrics due to the high relative permittivity it still remains too high for practical use.
(dielectric constant, ) of HfO2 and TiO2 compared to the Both niobium and tantalum oxides have not been frequently
standard gate dielectric, SiO2. The increase of the permittivity researched for use in composites with TiO2. Niobium(V) oxide
of the gate dielectric is of considerable importance since it Nb2O5 has seen some applications in photocatalysis for dye
allows for a higher capacitance with a smaller or equal thickness degradation,137,138 selective photooxidation of organic mole-
as compared to SiO2. TiO2 alone should be an ideal material cules,139,140 and DSSCs.141144 Nb2O5/TiO2 composites for
based on its permittivity measured in the range of = 80110 DSSC applications focus mostly on the use of Nb2O5 as a
as compared to SiO2, in which = 3.9. Unfortunately, due the blocking layer between the conducting electrode and TiO2 to
presence of stable Ti3+ within a TiO2 structure, oxygen reduce the recombination rate of the charge carriers, which has
vacancies at these reduced sites act as carrier traps and high- been recently shown to improve eciency in DSSCs.145,146
leakage paths.111 Thus, HfO2 ( = 25) is seen as a better Incorporation of Nb2O5 has been observed to improve the cell
alternative, especially when improved values with reduced eciency by between 22% and 35%, depending on the
current leakage can be found in HfO2/TiO2 composites. structure of the composite and the thickness of the Nb2O5
Additionally, composites of HfO2/TiO2 should also improve layer on the TiO2, where thicknesses on the order of a few
the charge mobility, which is one other drawback to pure HfO2 nanometers are optimal. In addition to its use as a blocking
9858 dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889
Chemical Reviews Review
Figure 8. (a) TEM images of -Fe2O3/TiO2 multiple-component clusters (red circles are used to highlight -Fe2O3 nanocrystals) and corresponding
primary -Fe2O3 nanocrystals (inset). (b) XRD pattern of composite sample ((*) anatase-phase TiO2, (#) maghemite-phase -Fe2O3). (c) MALDI
mass spectra of the tryptic digest of -casein (100 L, 108 M) after enrichment. Insets are photos of the composite sample dispersed in water before
and after exposure to external magnetic elds. (d) EDX analysis of the as-synthesized composite sample. Reprinted with permission from ref 20.
Copyright 2010 American Chemical Society.
Nickel supported on TiO2 has been of interest for decades for a for pseudocapacitive properties,232 and Wang et al. utilized
wide range of catalytic reactions such as hydrogenation,212214 NiO/TiO2 nanowire arrays to fabricate stable (to 600 cycles)
reforming,215 as well as others.216218 More recently, however, composites with a high areal capacity.233 While these studies
nickel oxide and hydroxide composites have been utilized in p can still benet from additional optimization, they have shown
n junction nickel oxide or hydroxide/TiO2 catalysts for promise for potential pseudocapacitor applications.
photocatalytic organic molecule degradation,219223 hydrogen Copper oxides have been heavily researched as composites
production,224226 and DSSCs.227230 In one recent report by with TiO2 recently due to their inherent p-type conguration.
Lin et al., TiO2 nanobelts were produced by hydrothermal The band gaps of CuO and Cu2O are 1.4 and 2.2 eV,
synthesis using P25 and NaOH, followed by treatment with respectively, which makes both materials promising for research
HCl to form protonated H2Ti3O7 nanobelts.222 The nanobelts in the conversion of solar radiation.35,234,235 Most composites
could subsequently be coarsened by hydrothermal treatment in featuring copper oxides have shown a considerable dependence
H2SO4. NiO was deposited on the nanobelts by wet on the copper oxide loading percent in order to create optimal
impregnation with Ni(NO3)2, followed by calcination at 600 catalysts. The photocatalytic degradation of organic molecules
C. The products of each step can be seen in the SEM images over Cu2O/TiO2 composites has been of particular interest,
in Figure 9ad, which clearly show both the coarsened especially to extend the activity of TiO2 to visible wavelengths.
nanobelts (Figure 9c) and the NiO deposited on the nanobelts In addition to visible light excitation, formation of a type II
(Figure 9d). The activity of the NiO/TiO2 composite heterojunction between the n-type TiO2 and p-type Cu2O leads
nanobelts was then tested by both UV and visible light to improved charge separation where photoexcited electrons
degradation of methyl orange (MO), as shown in Figure 9e and are passed from Cu2O to TiO2 and holes remain localized in
9f. It is apparent that addition NiO, as well as the coarsening of Cu2O. Initial studies utilizing composites of Cu2O/TiO2
the nanobelts, greatly improves the photocatalytic activity. showed that deposition of Cu2O onto P25 enhanced both
Yu et al. showed impressive results when making a simple the UV and the visible light degradation of dyes as compared to
mixture of Ni(OH)2 deposited on P25.224 At an optimized 0.5 bare P25.236239 Recently, other architectures have been
wt %, the evolution of H2 under UV irradiation was 3.056 considered as well, including Cu2O deposited on TiO2
mmol/h g in a 25 vol % aqueous methanol solution. DSSCs nanowires, Cu2O on TiO2 nanosheets, and Cu2O@TiO2
fabricated from deposition of NiO onto TiO2 have been studied core@shell structures, all of which showed improved organic
recently, and utilization of NiO produced up to a 16% increase molecule degradation under visible light when compared to
in cell eciency when compared to cells without NiO.229 pure TiO2.240242 Chu et al. prepared Cu2O@TiO2 coreshell
Additional studies on nickel/TiO2 composites have been done heterojunction composites by precipitation of Cu2O from
with applications in batteries.231233 Kim et al. recently CuCl, followed by direct coating with titanium(IV) n-
synthesized NiO/TiO2 nanotube arrays which were measured butoxide.241 Samples were subsequently calcined at 400 C
9862 dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889
Chemical Reviews Review
Figure 11. (a) Illustration of photoelectrochemical diode for water Figure 12. TEM images of (a) PS/ZnOTiO2 composite particles
splitting comprised of n-type TiO2 and p-type CuTiO nanotube and (b) ZnOTiO2 hollow spheres. Electron energy loss (c) Zn and
array lms, (b) lateral and (c) top view FESEM images of a CuTiO (d) Ti element mapping images of ZnOTiO2 hollow spheres.
nanotube array sample. Adapted with permission from ref 235. Reprinted with permission from ref 259. Copyright 2009 American
Copyright 2008 American Chemical Society. Chemical Society.
degradation of organic molecules.279284 Addition of In2O3, capacity. The large theoretical specic capacity for SnO2 (790
which has a band gap of 2.5 eV, allows for visible light mAh/g) as compared to TiO2 (170 mAh/g), combined with
absorption of In2O3/TiO2 composites. Further, since the the better structural and chemical stability of TiO2, suggests a
conduction band of In2O3 (0.63 V versus NHE) is oset promising candidate electrode material.303 Jeun et al.
higher than that of TiO2 (0.4 V versus NHE), an ecient synthesized hollow SnO2@TiO2 void@shell@shell nanotubes
heterostructure can be formed which supports ecient which show Li+ capacities higher than TiO2, with superior
separation of photogenerated charges.282,283 These benecial stability to pure SnO2.302 As shown in the scheme in Figure
attributes ensure that research on In2O3/TiO2 composites is 14a, the composite was prepared via plasma-enhanced atomic
likely to increase in the future.
Tin(IV) oxide, SnO2, has seen considerable usage in
composites with TiO 2 for photocatalysis, 2 8 5 2 9 2
DSSCs,293296 and battery applications.297302 In one recent
study by Xu et al., N-doped TiO2 was synthesized, followed by
addition of SnO2 of dierent compositions and calcination at
400 C.291 The SnO2/NTiO2 composites showed superior
performance for degradation of RhB under visible light
irradiation as shown in Figure 13a. Interestingly, the NTiO2
which showed a similar initial capacity but continuously photoactivity of a Rh/TiO2 composite to enhance the
decreased as the cycling continued. reduction of CO2 to CO in the reverse watergas shift
Bismuth oxide, Bi2O3, composites with TiO2 have seen little reaction (reverse of eq 1).341,342 The reaction conditions,
research. However, some recent work has been done for especially the Rh loading and metallic nature, were controlled
applications in the photocatalytic degradation of organic to ensure that the photocatalytic reduction was at its highest
molecules.237,304307 Bi2O3/TiO2 composites have shown when Rh appeared in a metallic state. Further, the loading
improved photocatalytic degradation rates relative to pure amount of Rh was optimized in order to prevent reduction of
TiO2, especially when under visible light irradiation. CO to CH4 in a reverse of eq 2, which occurred at high Rh
2.6. Lanthanides loading. The Rh/TiO2 composite helps facilitate reduction
through formation of formate ions from the reaction of CO2
Typically, metals from the lanthanide series are used as dopants
and H2 which occurs on the partially reduced Rh surface. It is
for TiO2 nanomaterials, and as such most research on TiO2
worth noting, however, that long irradiation time will decrease
lanthanide composites is limited to a few applications. TiO2
catalytic performance as reduction of Rh to metallic states will
composites with La2O3 have been investigated the most as
increase dissociation of H2 and thus favor production of CH4
supports for catalysis in reactions such as NOx reduc-
over CO. Ru and Rh/TiO2 composites have also been applied
tion.308310 There are also some reports covering TiO2
to the photocatalytic degradation of organic molecules.343347
composites with Er2O3,311,312 Nd2O3,313 and Eu2O3;314,315
These composites showed little improvement on their own
however, the most frequently utilized oxide from the lanthanide
when compared to TiO 2 ; however, with addition of
series is cerium oxide, CeO2. Recently, CeO2/TiO2 composites
cocatalysts347 or dye sensitization,345 the photocatalytic
have attracted signicant attention as a means to improve both
eciency increased markedly.
the UV and the visible photocatalytic degradation of organic
molecules.316322 CeO2/TiO2 composites have been shown to CH4(g) + H 2O(g) CO(g) + 3H 2(g) (2)
have a higher porosity and surface area compared to pure TiO2
samples, which has proven to be benecial in photocatalytic 3.2. Palladium
degradation.318,322 Further TiO2 has been shown to promote
and stabilize the Ce3+ oxidation state, leading to enhancement Much like the later noble metal nanoparticles, palladium
of chemical activity. These Ce3+ centers and corresponding nanoparticle composites with TiO2 have seen an extensive
oxygen vacancies within the lattice of mixed CeOx/TiO2 amount of research in recent years. Utilization of Pd/TiO2
composites act as hole acceptors which reduce recombination composites has provided improved materials for methanol
of charge carriers.316,323,324 Additionally, CeOx/TiO2 compo- reforming,348351 hydrogenation,352,353 photocatalysis,354359
sites have shown the ability to enhance the activity of metal and H2 production.360364 Methanol reforming has shown
nanoparticles (Cu, Au, Pt) for the watergas shift reac- considerable potential as a source of hydrogen from hydro-
tion.325,326 It is believed that the Ce3+ ions with improved carbons, especially when compared to the energy-intensive
stability in the composites eectively bind and dissociate water syngas method for hydrogen production. Al-Mazroai et al.
on the oxide surface. In the presence of a metal nanoparticle, showed that Pd deposited on P25 via an incipient wetness
OH bound to the oxide and CO bound to the metal form a method showed considerable activity for methanol reformation
HOCO intermediate to H2 and CO2 gas products. In this case under visible light irradiation.350 This room-temperature
inclusion of each component is necessary in order to best synthesis is much less energy intensive than syngas formation,
improve the reactivity. which occurs at temperatures up to 1000 C.
The enhancement of the photocatalytic activity of TiO2
3. NOBLE METAL AND METAL OXIDETIO2 through addition of Pd nanoparticles is evident by the
COMPOSITES numerous reports detailing improved dye degradation capa-
bilities of the composites. One of the simplest methods for
3.1. Ruthenium and Rhodium preparing Pd/TiO2 composites is photodeposition of Pd
In early research on TiO2 photocatalysis, ruthenium(IV) oxide nanoparticles on P25. Iliev et al. utilized this method to
(RuO2) was heavily investigated as a cocatalyst for generation synthesize a Pd/P25 composite with 0.5 and 1.0 atom % Pd
of O2 during photolysis of water.327332 More recently, concentration.354 These composites showed improvement over
composites consisting of either ruthenium or rhodium with the blank P25 samples for degradation of xylenol orange under
TiO2 have seen some more classic catalytic uses to date with UV irradiation. The extension of Pd/TiO2 composites for
little recent research on the topic of photocatalysis. One classic degradation under visible light irradiation has been carried out
type of catalytic reaction is the use of TiO2 as a support for Ru- as well. Mohapatra et al. synthesized TiO2 nanowires from
or Rh-mediated hydrogenation.333,334 Another such reaction anodization of Ti foil, followed by functionalization with PdCl2
which has seen research utilizing either Ru or Rh/TiO2 via an incipient wetness method and subsequent calcination
composites is the watergas shift reaction.335,336 In these under H2/Ar atmosphere to crystallize the TiO2 and convert
composites, TiO2 acts as a support for the active metal in the the Pd salt to metallic Pd.355 The as-synthesized composite
conversion of CO to CO2 and H2 as shown in eq 1. with an optimized 1.25 wt % Pd showed considerable
CO(g) + H 2O(g) CO2(g) + H 2(g) photocatalytic improvement compared to the bare TiO2
(1)
nanotubes.
TiO2 also acts as a support for Ru and Rh in the catalytic In addition to dye degradation, photocatalytic H2 production
oxidation of methanol for formation of syngas by the reaction has also been carried on Pd/TiO2 composites. Early reports
shown in eq 2.337340 These applications of Ru and Rh/TiO2 from Fujishima and Honda demonstrated that Pd on P25 can
composites have been well developed; however, they are also of split water under UV irradiation, with activity near that of
less use when compared to other catalysts utilizing either Pt as platinum.365 Since this report, considerable eort has been
the active metal or CeO2 as the support. One study utilized the devoted to improving the activity and extending these
9866 dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889
Chemical Reviews Review
composites to visible light activity. Sayed et al. recently To maximize the eciency of the Pd/TiO2 catalysts,
prepared a nitrogen-doped visible light active Pd/TiO 2 considerable eort has been made to rationally design and
composite.362 This composite showed improved H2 production optimize the morphology of the composite. Recent attention
by incorporation of N doping as compared to a sample with has been especially given to the synthesis of Pd@TiO2 core@
only Pd deposition. shell catalysts.366368 In a recent study from Zhang et al., Pd@
Ye et al. prepared TiO2 nanotube arrays by three-step TiO2 core@shell particles were synthesized by rst reducing
anodization of Ti foil followed by calcination and hydrothermal the palladium precursor salt to form nanoparticles, followed by
reduction of Pd nanoparticles onto the crystalline TiO2 addition of a TiF4 solution and hydrothermal treatment at 180
nanotubes in the presence of polyvinylpyrrolidone (PVP) and C for 48 h.367 SEM and TEM images of the resulting products
NaI.364 The size of the loading could be tuned via controlling are shown in Figure 16a and 16b, respectively, which clearly
both the PVP concentration and the hydrothermal reaction show the core@shell structure. The same procedure was
time. Figure 15a and 15b shows the SEM image of the as- utilized for synthesis of Au@TiO2 and Pt@TiO2. The resulting
core@shell particles showed a high degree of crystallinity, as
evidence by the XRD pattern in Figure 16c. Further, the Pd@
TiO2 composites showed the highest activity for visible light
degradation of RhB as shown in Figure 16d. This result shows
Figure 15. (a) Top and (b) cross-sectional SEM images of TiO2
nanotube arrays (TNTAs) obtained from electrochemical anodization.
SEM images of Pd QDs deposited on TNTAs: (c) top view at low and
high (inset) magnications, and (d) cross-sectional view (high
magnication of a broken tube is shown in the inset). (e) TEM
image of TiO2 nanotubes with Pd QDs deposited showing that they
were uniformly dispersed on the nanotube. (f) Amount of hydrogen
generated by TiO2 nanotubes and Pd@TNTAs nanocomposites as
photoanodes and Pt foil and Pd@TNTA nanocomposites as cathodes.
Pd% = 2.15 wt%. PE and CE indicate photoanode electrode and
cathode electrode, respectively. Adapted with permission from ref 364.
Copyright 2012 American Chemical Society.
prepared nanotube array, and Figure 15c and 15d shows the
array after hydrothermal Pd deposition. Figure 15e shows a Figure 16. SEM (a) and TEM (b) of the as-prepared Pd@TiO2 core@
TEM image of a nanotube with Pd nanoparticles clearly shell composite. (c) XRD patterns of the as-prepared M@TiO2 (M =
Au, Pd, Pt) coreshell nanocomposites; peaks indicated by dashed
deposited. Production of H2 was carried out through fabrication lines, and symbols are ascribed to the anatase phase of TiO2 and the
of a three-electrode photoelectrochemical cell (PEC). H2 corresponding noble metal. (d) Performances of M@TiO2 (M = Au,
production is shown in Figure 15f, where the optimal catalyst Pd, Pt) coreshell nanocomposites and commercial TiO2 P25 for
utilized a Pd loading of 2.15 wt %, and the optimal PEC was photocatalytic degradation of RhB under irradiation of visible light (
constructed with the Pd/TiO2 composite as both the > 400 nm). Adapted with permission from ref 367. Copyright 2011
photoanode and the cathode. American Chemical Society.
both the utility of Pd/TiO2 composites and the potential as reforming and thus hydrogen production.380,381 As the standard
core@shell catalysts. reduction potentials of methanol and ethanol, 0.13 and 0.224 V,
3.3. Platinum respectively, are lower than the standard reduction potential of
oxygen to water, 1.23 V, use of alcohols is more favorable for
Since the initial reports of hydrogen evolution from water by the hydrogen-yielding oxidation as well as prevention of back
Honda and Fujishima, platinum has been intertwined with reactions. This has resulted in a large number of Pt/TiO2
TiO2, even as a just a simple electrode. Kiwi and Gratzel rst hydrogen production catalysts utilizing alcohols as the main
demonstrated the promotion of hydrogen evolution from water reactant (reforming)382387 or as the sacricial reagent in an
utilizing poly(vinyl alcohol)-stabilized Pt colloids.369 Later Kiwi aqueous solution.388394 Further, selection of alcohols has been
et al. demonstrated the visible light photolysis of water to extended to higher alcohols such as isopropanol and polyols
produce H2 and O2 on a composite consisting of Pt/RuO2/ such as glycerol in order to increase the number of moles of
TiO2,327 which was followed by subsequent studies from the hydrogen produced in a reaction system. In addition to the
same group.328331 From these studies as well as others at the extensive research done on hydrogen production from Pt/TiO2
time, photocatalytic production of H2 by Pt/TiO2 composites composites, oxidation/degradation of organic pollutants has
has consistently shown an increasing amount of re- seen a signicant amount of research as well, especially since it
search.365,370,371 Additionally, other researchers were utilizing can more easily demonstrate the photoactivity of the
Pt/TiO2 composites as well for other photocatalytic reactions. catalyst.395402 The improvement of photocatalytic activity
Kraeutler and Bard showed that a Pt/TiO2 composite can with Pt incorporation is typically ascribed to formation of a
catalyze the decomposition of acetic acid selectively to methane Schottky barrier at the metalTiO2 interface. This occurs
under UV illumination.372 Further work from Bard showed because the work function of Pt (5.365.63 eV)403 is greater
signicant development of Pt/TiO2 for a number of reactions than that of TiO2 (4.64.7 eV);403,404 so, the electrons
such as decarboxylation, radical-induced synthesis of amino transfer to the Pt and the holes are localized within the TiO2,
acids, and decomposition of organic molecules.373375 These thus eectively separating the charge carriers to improve the
studies, among others, cemented the role of Pt in TiO2 photocatalytic eciency.
composites. Recently, with the advances in nanoscale synthesis To enhance the activity of Pt/TiO2 composites, steps have
and controllable/tunable properties of nanomaterials, interest been taken to optimize the interaction between the Pt and the
in Pt/TiO2 composites has only increased. Synthetic controls TiO2. In one study by Kandiel et al. they were able to eectively
have allowed for optimization of parameters such as tune the surface area and crystallinity of the TiO2 within their
morphology, crystal phase, crystallinity, porosity, and surface prepared Pt/TiO2 composite and demonstrate that although a
area, each of which can alter the photoactivity of a composite. high surface area is benecial an increase in crystallinity is
Other optimization of the photocatalytic system, such as use preferential.405 The increase in photocatalytic activity is
and type of sacricial agents, has seen a considerable amount of attributed to the decrease in defect sites, which act as centers
research as well. for charge recombination, when the crystallinity increases.
Although Pt/TiO2 composites have been frequently utilized Yu et al. recently showed the improvement of photocatalytic
for production of hydrogen from water, there is a signicant water splitting when using Pt on TiO2 nanosheets with exposed
drawback that must be considered. As reported by Sato et al., a (001) facets as the catalysts.406 The nanosheets, as shown in
Pt/TiO2 composite (as well as Pd/TiO2 and Rh/TiO2) not Figure 17a and 17b, were prepared via a hydrothermal method
only catalyzes production of H2 and O2 from water but also with titanium(IV) n-butoxide and hydrouoric acid and had
catalyzes the back reaction as well.376 As such, eective water previously showed improved photocatalytic activity by testing
splitting was not possible. Sayama and Arakawa later showed dye degradation as compared to P25.407 The HRTEM image in
that addition of an aqueous solution of sodium carbonate to a Figure 17b clearly indicates the lattice spacing parallel to the
reaction system containing Pt/TiO2 eectively suppresses the top and bottom facets is 0.235 nm, corresponding to the
back reaction and therefore promotes formation of both H2 and (001) plane of anatase TiO2. Pt nanoparticles were then
O2.377,378 The role of the carbonate was proposed to be both a photodeposited onto the nanosheets, as shown in Figure 17c
preferential adsorbate as compared to O2 and a hole (h+) and 17d. When Pt nanoparticles were incorporated, photo-
scavenger. The carbonate species as hole traps could then form catalytic hydrogen production from an aqueous ethanol
peroxocabonates which could irreversibly decompose to CO2 solution increased as compared to both the nonplatinized
and O2. This production of O2 does not need to be on the sheets with exposed (001) facets and the platinized nonfaceted
catalyst surface, and as such, it is less likely to quickly react with particles.
H2 to form water. Iodide anions have also been found to be Also of note, the uoridated surface increased the activity
advantageous for production of hydrogen and oxygen.379 It was compared to the nonuoridated one as well. This was
found that addition of iodide can bind to the Pt surface and attributed to the ability of uoride surface ions to trap
form an iodine layer which can also suppress recombination of electrons, which would slow recombination of the charge
H2 and O2 at the Pt surface. It must be noted though that carriers and then transfer them to the Pt surface. It is evident
addition of too much of either anion will reduce the benecial from these studies that further optimization of TiO2 can greatly
aspects as too much will bind to the Pt surface and leave too benet the photocatalytic activity of Pt/TiO2 composites in the
few reactive sites for hydrogen reduction. More recently, future.
however, the focus of reaction systems has been on hydrogen One further phenomenon that has been found in Pt/TiO2
production rather than oxygen production, and thus, composites is a red shift of the absorption spectra. Although
production of hydrogen has been supplemented by addition not frequently reported, it has nonetheless been apparent in a
of alcohols such as methanol or as a sacricial hole acceptor. number of studies.397,408410 This red shift has been attributed
Early work by Kawai and Sakata showed the ecacy of a Pt/ to unreduced Pt species, as Pt(OH)2 or PtO2, on the surface of
TiO2 composite for photocatalytic methanol and ethanol the TiO2 producing lower energy levels on the surface and
9868 dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889
Chemical Reviews Review
layer. It was shown that when the SiO2 layer was thinner the
photocatalytic degradation of methylene blue increased, even
without any TiO2 contact. In another study, Standridge et al.
demonstrated the eect of the distance between silver
nanoparticles and a dye on the photocurrent of a DSSC.417
The system was composed of Ag nanoparticles coated with
varying thicknesses of TiO2 separating the particles from the
dye layer. As shown in Figure 18b, the thinnest TiO2 coatings
Figure 17. (a) TEM and (b) HRTEM of prepared TiO2 nanosheets.
(c) TEM and (d) HRTEM of nanosheets clearly showing Pt deposits.
Reprinted with permission from ref 406. Copyright 2010 American
Chemical Society.
resulting in visible light absorption. This may be useful for Figure 18. IPCEs and overall cell trends. (a) IPCEs for cells with 125
some visible light photocatalysis; however, it implies that the cycles of amorphous TiO2. (b) IPCEs for cells with silver NPs and dye.
stability of these catalysts is likely limited since further Arrow indicates increasing TiO2 thickness. Top four spectra and
photoexcitation of the TiO2 will complete the reduction of bottom four spectra correspond to amorphous and anatase TiO2,
the Pt species to metallic platinum and thus likely eliminate the respectively. (c) Eciencies of the cells. Dark blue, orange, and green
red shift produced. It is further possible that a small amount of symbols correspond to anatase samples. Light blue, red, and yellow
doping may occur, as this can lead to a red shift in the symbols correspond to amorphous samples. (d) Calculated plasmon-
enhancement factor as a function of TiO2 thickness. Reprinted with
absorption as well by producing sub energy levels between the
permission from ref 417. Copyright 2009 American Chemical Society.
valence band and the conduction band of TiO2.411 Production
of a red shift via this mechanism will be much more stable and
allow for improved visible light activity in Pt/TiO2 composite
yielded the greatest enhancements in the incident photon
structures.
conversion eciencies (IPCEs) due to the larger electro-
3.4. Silver magnetic eld imparted on the dye by the LSPR of the silver
Due to its low cost, as compared to other noble metals, intense nanoparticles. This in turn led to greater cell eciencies as
localized surface plasmon resonance (LSPR), and easy shape shown in Figure 18c.
control, silver nanomaterials have been utilized in composites In order to better examine the eects of the metalTiO2
with TiO2 to a signicant extent. Silver has been utilized widely interaction in a Ag/TiO2 composite, core@shell Ag@TiO2
with TiO2 in order to make composites for photocatalytic structures have been synthesized. Initial core@shell composites
organic molecule degradation,199,412415 DSSCs,416423 photo- were produced for drug delivery systems by Liz-Marzan et
active bactericides,424430 photochromic materials,431437 and al.,440,441 followed by others;420,442445 however, core@shell
other applications. Although silver cannot recombine H+ atoms Ag@TiO2 composites made specically for studying the
for hydrogen production, based on its slightly larger work interaction were rst synthesized and studied by Hirakawa
function, 4.7 and 4.6 eV for Ag and TiO2, respectively,413,438 and Kamat.446,447 Hirakawa and Kamat showed a reversible
it still has the capability of attracting photogenerated electrons charging and discharging of the Ag core by photogenerated
from TiO2 and thus improving charge separation. As such, electrons from the TiO2 shell. When the composite was
many initial reports showed the improved UV photocatalytic irradiated, electrons moved to the Ag core where they were
degradation of organic pollutants by Ag/TiO2 composites as trapped as the holes generated in the TiO2 were scavenged by
compared to bare TiO2. ethanol. As electrons were captured by the Ag core, the surface
Although the exact nature of the LSPR eect on enhanced plasmon resonance band would subsequently blue shift up to
photocatalytic activity is not entirely understood, it is clear that 30 nm, as shown in Figure 19a. Irradiation of the system would
it improves the photocatalytic activity of TiO2 and generation then be discontinued, and once an electron acceptor was added
of photoelectrochemical current. In one study, Awazu et al. to the system, the electrons would be discharged by the Ag core
demonstrated that direct contact between Ag and TiO2 is not and the SPR band would red shift nearly back to its initial
necessary for photocatalytic enhancement, suggesting that the position. This serves to indicate the propensity of a metal,
increase in the electromagnetic eld by the Ag LSPR was the based on the work function in relation to TiO2, to capture
cause.439 In their study the silver nanoparticles were embedded photogenerated electrons from TiO2 rather than to inject them
in SiO2 layers with dierent thicknesses, followed by a TiO2 via LSPR.
9869 dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889
Chemical Reviews Review
Figure 21. (a) Schematic illustration of the fabrication process of the sandwich-structured SiO2/Au/TiO2 photocatalyst. (b) Typical SEM image of
the composite photocatalyst. (c) Elemental mapping of a single particle with the distribution of individual elements shown in the bottom row. (d)
Photodegradation of RhB under direct sunlight illumination. Adapted from ref 474 with permission, Copyright 2012 John Wiley and Sons.
Figure 22. Charge injection of excited CdSe quantum dot into TiO2 nanoparticle. The scheme on the right shows the tuning of energy levels (and
hence the charge injection) by size control. Reprinted with permission from ref 504. Copyright 2008 American Chemical Society.
produce TiO2 rods. These nanorods could then be dispersed in CdSe and vice versa has led to even greater utilization of these
9-octadecene and toluene, where InP nanocrystals could be materials. 492494 Additionally, although tellurium is an
grown by oxidation of indium nanoparticles with P(SiMe3)3. increasingly rare element, it has seen a considerable amount
Other composites containing metal pnictogenides such as InAs of research in composites with TiO2 as well. The signicant
and InN have been applied toward fabrication of solar cells with synthetic controls over size, morphology, and composition of
TiO2 as well, but overall research on these composites has been cadmium chalcogenide nanocrystals495501 has led to a
limited by the more common usage of metal chalcogenides. substantial amount of research and review articles being
4.2. Metal Chalcogenides published on these composites. In a typical scheme, traditional
dye sensitization is replaced by narrow band-gap semiconductor
As opposed to metal pnictogenides, metal chalcogenides (S, Se, nanoparticles such as CdSe, as shown in Figure 22.
and Te anions) have seen a considerable amount of research in This sensitization can be further tuned in terms of excitation
regard to composites with TiO2. Since the most common wavelength by controlling the properties of the semiconducting
composition of quantum dots is of metal chalcogenides (CdS, particles, e.g., shape and composition. Many such composites
CdSe, etc.), quantum dot-sensitized solar cells most commonly have been reported over recent years with varying architectures
utilize one of these in their composites with TiO2. Additionally, and methods, many of which are very promising.502511 One
metal chalcogenides have been further utilized in composites recent report of interest from the Kamat group was the
with TiO2 for improving the photocatalytic activity of TiO2. development of a solar paint which consisted of CdS, CdSe,
Here we will look at some of the key recent developments and TiO2 particles dispersed in a mixed tert-butyl alcohol/water
regarding metal chalcogenides and TiO2 composite materials. solvent to form a paste.510 This could then be painted onto
4.2.1. Cadmium Chalcogenides. The discovery that conducting electrodes followed by completion of a cell with the
cadmium chalcogenides (Cds, CdSe, CdTe) can act as counter electrode and electrolyte to produce a simple solar cell.
sensitizers for TiO2 has led to these materials becoming the Although the highest cell eciency reported was 1.08% with an
prototypical quantum dotTiO2 composites over the past few open circuit voltage of 585 mV and short circuit current of 3.1
decades.487491 Additionally, fabrication of core@shell CdS@ mA/cm2, this technique has the advantage of facile cell
9872 dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889
Chemical Reviews Review
construction and easy to scale methods. Improvement of this been some early reports of the observation of CNTs,545 their
technique in the future may allow for a much larger commercial isolation by Iijima546 accelerated their utilization over the past
application of QDSSCs for next-generation energy production. two decades. On the basis of the work function of CNTs, 5
In addition to the development of solar cells, cadmium eV,547 it is apparent that they can act as electron acceptors to
chalcogenides have also been utilized in composites with TiO2 more eectively separate photogenerated charges on TiO2.
for photocatalysis. These composites typically are applied to Initial reports for the synthesis of CNT/TiO2 composites were
either photocatalytic hydrogen production from water512516 or made by Vincent et al., who demonstrated the embedding of
photocatalytic oxidation of organic molecules517519 since they multiwall carbon nanotubes (MWCNTs) in an amorphous
can extend the usable wavelengths of light into the visible TiO2 matrix.548 Hernadi et al. later showed a homogeneous
region. Although these materials have seen some success, direct coating of an amorphous TiO2 layer on MWCNTs via
signicant drawbacks occur such as leaching of the cadmium direct, solvent-free impregnation of the nanotubes in liquid
ions or in the case of hydrogen production needing sacricial titanium(IV) ethoxide.549 Jitianu et al. then demonstrated a
agents such as Na2S or Na2SO3. Due to this, noble metal and homogeneous coating via both hydrothermal and solgel
metal oxide TiO2 composites still show greater promise for coatings, followed by crystallization by annealing to 300
cleaner systems for photocatalysis. C.550,551 These solgel coatings deposit a thin homogeneous
4.2.2. Other Single-Metal Chalcogenides. Although the TiO2 layer onto the MWCNTs. These coatings could also be
most common metal chalcogenide semiconductor materials for mediated with cetyltrimethylammonium bromide (CTAB);
research with TiO2 have been cadmium compounds, other however, the crystallinity was decreased upon calcination as
materials have seen some utilization as well in order to mitigate compared to those prepared without surfactant. These coating
the utilization of cadmium which is highly toxic. In recent years, methods provided the foundation for later utilization of these
lead sulde (PbS) has been utilized as a potential composite composites, and although some CNT/TiO2 composites have
with TiO2.520525 PbS is benecial since it has a narrow band been utilized for photocatalytic hydrogen production,552555
gap (0.41 eV) and a large Bohr exciton radius. PbS can also they are more frequently utilized in composites for organic
improve the photoactivity of TiO2 due to its multiple exciton molecule degradation.556561 Proposed mechanisms for the
generation.521 As such these composites have seen some use for CNT-mediated enhancement of photocatalysis on TiO2
both photocatalytic and photovoltaic applications and will likely composite structures have been investigated and typically fall
see more in the future due to the low toxicity of the compound under one of three categories:562 (1) CNTs as electron sinks, as
stemming from its low solubility. Another metal chalcogenide mentioned above;563 (2) excitation of the CNT itself followed
that has seen some recent research in composites with TiO2 is by charge injection into TiO2;564 (3) introduction of carbon
tin(II) sulde, SnS.526529 This material is promising as both impurities in TiO2 forming TiOC bonds leading to creation
tin and sulfur are abundant and have low toxicities compared to of energy states within the band gap of TiO2 to facilitate visible
other metal chalcogenides. Fabrication of devices to this point light absorption.565 Any of these proposed mechanisms can be
has been minimal; however, there is signicant room to expand correct depending on the method of preparation of the CNT/
this in the future. TiO2 composite structure. In addition to improved photo-
4.2.3. Semiconductor Alloy Chalcogenides. Alloys of catalytic activity, the composites have the additional benet of
metals within semiconductor nanoparticles have become an enhanced adsorption of dye molecules onto the CNT surface,
area of research with an increasing amount of interest. Much of which can enhance the rate of degradation as well. Further,
this is due to the decrease in the necessary amount of either these composites can be improved by addition of other
rare or toxic metals and replacement of them with metals such cocatalysts such as noble metals, which can further improve
as zinc or copper. Alloys such as copper indium gallium charge separation.359,566,567 In addition to applications for
diselenide (CIGS) and copper zinc tin sulde (CZTS) have photocatalysis, CNT/TiO2 composites have been utilized for
begun to be utilized as composite materials with TiO2.530535 applications with DSSCs.568572 Typical CNT/TiO2 compo-
Another alloy, copper indium sulde (CuInS2), has seen more sites for DSSC applications indicate that 0.10 wt % CNT is
signicant research in composites with TiO2 to date for optimal, with cell eciencies that increase between 19% and
applications in both photovoltaics536541 and photocataly- 50%. The increase in cell eciencies has been attributed to the
sis.542544 Much like other semiconductors, they have shown improved electron transport mediated by the CNTs.
great promise to date; however, as they have not been studied Further utilization of CNT/TiO2 composites has been done
to the extent of systems such as CdS or CdSe, optimization is for applications to Li+ battery materials.573577 One report by
still needed to yield results which are to the same eciency as Cao et al. utilized well-controlled TiO2 coatings on MWCNTs
the better known systems. Recently, both Santra et al. and from hydrolysis of titanium(IV) butoxide to form well-dened
Chang et al. established systems where a CuInS2/TiO2 coaxial nanocables, shown in the TEM images in Figure 23a
composite for photovoltaic applications has been further and 23b.574 These composites could achieve a specic capacity
sensitized using CdS.540,541 Addition of CdS into these
of 244 mA h g1 at a current density of 3000 mA g1, as shown
composites has been able to increase cell eciencies
in Figure 23c. This capacity was retained when cycled over 100
signicantly; however, they still fall under the eciencies of
times under a current density of 1000 mA g1 and within a
many pure semiconductor/TiO2 composites and will need
potential window of 0.013 V (Figure 23d).
further optimization in the future to become feasible.
5.2. Graphene and Graphene Oxide
5. CARBONTIO2 COMPOSITES Graphene, which has many extraordinary properties such as
high electron mobility and surface area, has been investigated
5.1. Carbon Nanotubes heavily with respect to composites with TiO2 over the past
The emerging prominence of carbon nanotubes (CNTs) has decade. Similar to the case of carbon nanotubes, the higher
led to their use across many applications. Although there had work function of graphene (4.95.2 eV)578,579 with respect to
9873 dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889
Chemical Reviews Review
6. TEMPLATED COMPOSITES
In order to have a well-dened and easy to control morphology,
templates such as SiO2 and polystyrene have been utilized with
techniques such as incipient wetness impregnation and solgel
coatings. These composite structures can yield TiO2 with
tailored properties such as morphology, high surface area, and
well-controlled crystallinity. In this section, we will focus on
templated composite structures which yield pure TiO2 upon
removal of the template, regardless of if the template was
removed or not.
6.1. YolkShell and CoreShell
Template-mediated syntheses have been utilized quite regularly
in recent years to create hollow TiO2 shells with well-controlled
properties. Synthesis of these materials typically follows several
sequential steps: (i) preparation of the core material template;
(ii) deposition of the shell materials on the surface of the
templates, usually via a solgel process; (iii) removal of the
core materials. A number of core@shell and yolk@shell
materials have been mentioned to this point utilizing a variety
of core materials such as Ag, Au, SiO2, iron oxides, and glucose;
however, they were synthesized with a focus on the synergistic
eects of the composite. Here we will focus on methods that
yield pure TiO2 as the nal product or can yield this with a
simple removal of the template.
Figure 25. (A) Schematic illustration of the synthesis steps for One template material that has been utilized readily over the
graphene-wrapped anatase TiO2 NPs. (B) SEM images of bare, past decade is polystyrene (PS) beads.618629 Zhong et al.
amorphous TiO2 NPs prepared by solgel method. (C) SEM images utilized commercially purchased PS beads which were rst
of GO-wrapped amorphous TiO2 NPs. (D) SEM images of graphene- assembled into a crystalline array, followed by inltration with
wrapped anatase TiO2 NPs. All scale bars are 200 nm. (B) the solgel precursor, titanium(IV) isopropoxide.619 The
Photodegradation of methylene blue (MB) under visible light ( > composite could then be immersed in toluene to dissolve the
420 nm) by (a) P25, (b) bare anatase TiO2 NPs, (c) grapheneTiO2 polystyrene template, followed by sonication to free the hollow
NPs (two-step hydrothermal), and (d) grapheneTiO2 NPs. The amorphous TiO2 spheres from the substrate. Shiho and
weight ratio of graphene to TiO2 in the grapheneTiO2 hybrid
Kawahashi synthesized similar core@shell particles and
materials was 0.02:1. Adapted from ref 598 with permission, Copyright
2012 John Wiley and Sons. subsequently removed the core PS bead by calcination under
air.618 It was found that calcination to 600 C for 3 h could
completely remove the PS core and crystallize the remaining
expected that further research on composites of graphene and
hollow TiO2 shell to anatase phase. Calcination to 900 C
TiO2 is only to increase in the coming years.
would crystallize the TiO2 to rutile; however, the shell
5.3. Other Carbon morphology would be completely degraded. Using similar
In addition to the above forms of carbon, other types have seen templated composites, Syouan et al. later showed that an
usage in combination with TiO2 as well. One such material is optimal amount of TiO2 precursor allowed for the highest
activated carbon (AC), which has been used extensively to anatase crystallinity, which in turn yielded the best photo-
promote the photocatalytic degradation of organic mole- catalytic activity for degradation of MB.625 In addition to PS
cules.603608 The high surface area allows for a greater beads, TiO2 has also been deposited on other carbonaceous
adsorption of the molecules which can then be more readily templates which can easily be burned away to reveal a hollow
degraded by the TiO2 component. Other carbonized materials TiO2 structure. Most prominently, glucose can be hydro-
such as polymers, glucose, and sucrose have seen use as either a thermally treated to form colloidal carbon spheres.630 Ao et al.
template for TiO2 coating or as a coating material on top of showed that these carbon spheres could then be coated by
TiO2. Many of these composites are then utilized for TiO2 via a solgel process, followed by calcination to remove
applications in photocatalysis609613 or Li+ battery applica- the carbon core.631 Doping of the TiO2 shell for improved
tions.614617 One report by Zhang et al. demonstrated a thin photocatalytic activity was also demonstrated by addition of
9875 dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889
Chemical Reviews Review
has great potential for developing commercial catalysts for addition to these metals, carbon materials may allow for cheap
hydrogen production, environmental remediation, production composites with enhanced activity as well. With the decreasing
of ne chemicals, as well as other applications. Further cost in the synthesis of carbon materials such as graphene or
composites with TiO2 show promise in applications for with synthetic techniques such as carbonization of glucose,
improved solar cells and lithium ion batteries. With the composites of carbonaceous materials with TiO2 have become
increasing need for clean and sustainable energy sources, TiO2 much cheaper and easier to produce. As such they are likely to
composite materials may hold the key to developing solutions see a considerable amount of research in the coming years as an
to many of these problems. alternative composite material with signicant advantages such
Composites with materials such as noble metals have been as good photocatalytic activity and high adsorption capacities.
heavily investigated and hold much promise, though market Templated composites show a signicant number of
prices for these metals may slow progress in their advantages that are not always seen with the less ordered
commercialization. However, optimization of the physicochem- composite materials. Although many template syntheses are
ical properties of these composites has shown a signicant labor and energy intensive, much recent progress has been
reduction in the necessary quantity of noble metals, which will made in this eld in order to mitigate this. Yolk@shell
be of importance to reactions where noble metals remain composites hold great promise for high-temperature catalytic
necessary. These noble metal/TiO2 composites have shown a applications where sintering of nanoparticles degrades catalyst
substantial potential for applications in hydrogen production performance. Additionally, some of these structures have
and environmental remediation, two signicant challenges possible applications as nanoreactors or bifunctional catalysts
society faces going forward. More interestingly, however, where the inner core and outer shell are functionalized
composites with cheaper metals and metal oxides as well as dierently. AAO templated synthesis of nanowires has
carbon materials hold signicant promise as they become interesting benets such as making composite nanowires of
further developed in the coming years. These composites with altering compositions, which may be useful for future
metals such as copper or nickel and the oxides of each have the applications.
potential to be developed to the point that they may be utilized Overall, composite TiO2 materials can be synthesized in such
in place of noble metals for future applications in order to a way that they can take advantage of many properties of
reduce costs without a signicant decrease in activity. In dierent materials and be applied to a signicant number of
9878 dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889
Chemical Reviews Review
energy- and environment-related applications. Synthetic strat- Riverside, under the supervision of Yadong Yin. His research interests
egies such as the design of core@shell Cu2O@TiO2 particles by include the synthesis and self-assembly of complex colloidal
controlled hydrolysis and condensation of TiO2 precursor onto nanostructures for energy applications.
the Cu2O core can yield heterojunctions which can more
eectively separate photogenerated charge carriers as well as
increase the visible light response. Many of these structures can
be tuned by controlling the composition in order to decrease
the charge carrier recombination rate or adjust the band gap of
the composite. This is the case with materials such as CNT/
TiO2 composites where the CNTs can act as electron sinks or
create energy states between the TiO2 bands, depending on the
synthesis method. Many properties of these composites are
only now being explored and controlled, and as the synthetic
approaches mature even further, it is likely that fabrication of
devices with tailored properties using TiO2 composites will be
made easier, faster, and cheaper.
AUTHOR INFORMATION
Corresponding Author Yadong Yin received his Ph.D. degree in Materials Science and
Engineering from the University of Washington in 2002, then worked
*E-mail: yadong.yin@ucr.edu.
as a postdoctoral fellow at the University of California, Berkeley, and
Notes the Lawrence Berkeley National Laboratory, and became a sta
The authors declare no competing nancial interest. scientist at LBNL in 2005. In 2006 he joined the faculty at the
Biographies Department of Chemistry at the University of California, Riverside.
His research interests include the synthesis and application of
nanostructured materials, self-assembly processes, and colloidal and
interface chemistry.
ACKNOWLEDGMENTS
We are thankful for the nancial support provided by the U.S.
Department of Energy (DE-FG02-09ER16096).
REFERENCES
(1) Weir, A.; Westerhoff, P.; Fabricius, L.; Hristovski, K.; von Goetz,
N. Environ. Sci. Technol. 2012, 46, 2242.
(2) Pfaff, G.; Reynders, P. Chem. Rev. 1999, 99, 1963.
(3) Meacock, G.; Taylor, K. D. A.; Knowles, M. J.; Himonides, A. J.
Sci. Food Agric. 1997, 73, 221.
Michael Dahl received his B.S. in Chemistry at California State (4) Phillips, L. G.; Barbano, D. M. J. Dairy Sci. 1997, 80, 2726.
University, Fullerton, in 2009. He is currently a Ph.D. student in (5) Robichaud, C. O.; Uyar, A. E.; Darby, M. R.; Zucker, L. G.;
Chemistry at the University of California, Riverside, under the Wiesner, M. R. Environ. Sci. Technol. 2009, 43, 4227.
supervision of Yadong Yin. His research interests include synthesis and (6) Jaroenworaluck, A.; Sunsaneeyametha, W.; Kosachan, N.;
utilization of nanostructured materials for applications in catalysis and Stevens, R. Surf. Interface Anal. 2006, 38, 473.
(7) Morison, W. L. N. Engl. J. Med. 2004, 350, 1111.
energy storage.
(8) Fujishima, A.; Honda, K. Nature 1972, 238, 37.
(9) ORegan, B.; Gratzel, M. Nature 1991, 353, 737.
(10) Fujishima, A.; Rao, T. N.; Tryk, D. A. J. Photochem. Photobiol., C
2000, 1, 1.
(11) Yang, L.; Luo, S.; Cai, Q.; Yao, S. Chin. Sci. Bull. 2010, 55, 331.
(12) Endres, P. J.; Paunesku, T.; Vogt, S.; Meade, T. J.; Woloschak,
G. E. J. Am. Chem. Soc. 2007, 129, 15760.
(13) Smith, L.; Kuncic, Z.; Ostrikov, K.; Kumar, S. J. Nanomaterials
2012, 2012, 1.
(14) Yamaguchi, S.; Kobayashi, H.; Narita, T.; Kanehira, K.;
Sonezaki, S.; Kubota, Y.; Terasaka, S.; Iwasaki, Y. Photochem. Photobiol.
2010, 86, 964.
(15) Chen, C.-T.; Chen, Y.-C. Anal. Chem. 2005, 77, 5912.
(16) Jones, B. J.; Vergne, M. J.; Bunk, D. M.; Locascio, L. E.; Hayes,
M. A. Anal. Chem. 2007, 79, 1327.
(17) Li, Y.; Xu, X.; Qi, D.; Deng, C.; Yang, P.; Zhang, X. J. Proteome.
Res. 2008, 7, 2526.
Yiding Liu received his B.S. degree in Materials Physics at the (18) Leitner, A. TrAC, Trends Anal. Chem. 2010, 29, 177.
University of Science and Technology of China in 2010. He is (19) Lu, Z.; Ye, M.; Li, N.; Zhong, W.; Yin, Y. Angew. Chem. 2010,
currently pursuing his Ph.D. degree at the University of California, 122, 1906.
(20) Lu, Z.; Duan, J.; He, L.; Hu, Y.; Yin, Y. Anal. Chem. 2010, 82, (62) Salinas, D.; Guerrero, S.; Araya, P. Catal. Commun. 2010, 11,
7249. 773.
(21) Ma, W.-F.; Zhang, Y.; Li, L.-L.; You, L.-J.; Zhang, P.; Zhang, Y.- (63) Xie, W.; Li, H. J. Mol. Catal. A: Chem. 2006, 255, 1.
T.; Li, J.-M.; Yu, M.; Guo, J.; Lu, H.-J.; Wang, C.-C. ACS Nano 2012, (64) Noiroj, K.; Intarapong, P.; Luengnaruemitchai, A.; Jai-In, S.
6, 3179. Renewable Energy 2009, 34, 1145.
(22) Li, H.; Shi, X.; Qiao, L.; Lu, X.; Xu, G. J. Chromatogr. A 2013, (65) Vyas, A. P.; Subrahmanyam, N.; Patel, P. A. Fuel 2009, 88, 625.
1275, 9. (66) Salinas, D.; Araya, P.; Guerrero, S. Appl. Catal., B 2012, 117
(23) Lu, J.; Deng, C.; Zhang, X.; Yang, P. ACS Appl. Mater. Interfaces 118, 260.
2013, 5, 7330. (67) Wen, Z.; Yu, X.; Tu, S.-T.; Yan, J.; Dahlquist, E. Bioresour.
(24) Lu, J.; Wang, M.; Deng, C.; Zhang, X. Talanta 2013, 105, 20. Technol. 2010, 101, 9570.
(25) Sunada, K.; Kikuchi, Y.; Hashimoto, K.; Fujishima, A. Environ. (68) Mguni, L. L.; Mukenga, M.; Jalama, K.; Meijboom, R. Catal.
Sci. Technol. 1998, 32, 726. Commun. 2013, 34, 52.
(26) McCullagh, C.; Robertson, J. C.; Bahnemann, D.; Robertson, P. (69) Tanabe, K.; Hattori, H.; Sumiyoshi, T.; Tamaru, K.; Kondo, T. J.
J. Res. Chem. Intermed. 2007, 33, 359. Catal. 1978, 53, 1.
(27) Zhang, S.; Liu, C.; Liu, X.; Zhang, H.; Liu, P.; Zhang, S.; Peng, (70) Taguchi, T.; Zhang, X.-t.; Sutanto, I.; Tokuhiro, K.-i.; Rao, T.
F.; Zhao, H. Appl. Microbiol. Biotechnol. 2012, 96, 1201. N.; Watanabe, H.; Nakamori, T.; Uragami, M.; Fujishima, A. Chem.
(28) Skorb, E. V.; Antonouskaya, L. I.; Belyasova, N. A.; Shchukin, D. Commun. 2003, 2480.
G.; Mohwald, H.; Sviridov, D. V. Appl. Catal., B 2008, 84, 94. (71) Jung, H. S.; Lee, J.-K.; Nastasi, M.; Lee, S.-W.; Kim, J.-Y.; Park,
(29) Matsuda, S.; Kato, A. Appl. Catal. 1983, 8, 149. J.-S.; Hong, K. S.; Shin, H. Langmuir 2005, 21, 10332.
(30) Fox, M. A.; Dulay, M. T. Chem. Rev. 1993, 93, 341. (72) Bae, S.-T.; Shin, H.; Kim, J. Y.; Jung, H. S.; Hong, K. S. J. Phys.
(31) Linsebigler, A. L.; Lu, G.; Yates, J. T. Chem. Rev. 1995, 95, 735. Chem. C 2008, 112, 9937.
(32) Sclafani, A.; Herrmann, J. M. J. Phys. Chem. 1996, 100, 13655. (73) Bandara, J.; Hadapangoda, C. C.; Jayasekera, W. G. Appl. Catal.,
(33) Chen, X.; Mao, S. S. Chem. Rev. 2007, 107, 2891. B 2004, 50, 83.
(34) Ni, M.; Leung, M. K. H.; Leung, D. Y. C.; Sumathy, K. (74) Nolan, M. ACS Appl. Mater. Interfaces 2012, 4, 5863.
Renewable Sustainable Energy Rev. 2007, 11, 401. (75) Liu, L.; Zhao, C.; Zhao, H.; Pitts, D.; Li, Y. Chem. Commun.
(35) Shankar, K.; Basham, J. I.; Allam, N. K.; Varghese, O. K.; Mor, 2013, 49, 3664.
(76) Shrestha, K. M.; Sorensen, C. M.; Klabunde, K. J. J. Mater. Res.
G. K.; Feng, X.; Paulose, M.; Seabold, J. A.; Choi, K.-S.; Grimes, C. A.
2013, 28, 431.
J. Phys. Chem. C 2009, 113, 6327.
(77) Reddy, B. M.; Ratnam, K. J.; Saikia, P. J. Mol. Catal. A: Chem.
(36) Chen, X.; Shen, S.; Guo, L.; Mao, S. S. Chem. Rev. 2010, 110,
2006, 252, 238.
6503.
(78) Hulbert, S. F.; Morrison, S. J.; Klawitter, J. J. J. Biomed. Mater.
(37) Leung, D. Y. C.; Fu, X.; Wang, C.; Ni, M.; Leung, M. K. H.;
Res. 1972, 6, 347.
Wang, X.; Fu, X. ChemSusChem 2010, 3, 681. (79) Zawahreh, Y. I.; Popova, N.; Smith, R. W.; Hendry, J.; Smith, T.
(38) Liu, G.; Wang, L.; Yang, H. G.; Cheng, H.-M.; Lu, G. Q. J. J. N.; Ziolo, T. L. J. Mater. Sci: Mater. Med. 2005, 16, 1179.
Mater. Chem. 2010, 20, 831. (80) Mi, G.; Murakami, Y.; Shindo, D.; Saito, F. Powder Technol.
(39) Chen, D.; Caruso, R. A. Adv. Funct. Mater. 2013, 23, 1356. 1999, 104, 75.
(40) Joo, J. B.; Dahl, M.; Li, N.; Zaera, F.; Yin, Y. Energy Environ. Sci. (81) Wang, W.; Yang, J.; Gong, Y.; Hong, H. Mater. Res. Bull. 2013,
2013, 6, 2082. 48, 21.
(41) Joo, J. B.; Zhang, Q.; Dahl, M.; Zaera, F.; Yin, Y. J. Mater. Res. (82) Han, J.-K.; Choi, S.-M.; Lee, G.-H. Mater. Lett. 2007, 61, 3798.
2013, 28, 362. (83) Takahashi, N.; Shinjoh, H.; Iijima, T.; Suzuki, T.; Yamazaki, K.;
(42) Gribb, A. A.; Banfield, J. F. Am. Mineral. 1997, 82, 717. Yokota, K.; Suzuki, H.; Miyoshi, N.; Matsumoto, S.-i.; Tanizawa, T.;
(43) Zhang, Z.; Wang, C.-C.; Zakaria, R.; Ying, J. Y. J. Phys. Chem. B Tanaka, T.; Tateishi, S.-s.; Kasahara, K. Catal. Today 1996, 27, 63.
1998, 102, 10871. (84) Despres, J.; Koebel, M.; Krocher, O.; Elsener, M.; Wokaun, A.
(44) Ding, Z.; Lu, G.; Greenfield, P. J. Phys. Chem. B 2000, 104, 4815. Appl. Catal., B 2003, 43, 389.
(45) Zhang, H.; Banfield, J. F. J. Mater. Res. 2000, 15, 437. (85) Andonova, S. M.; Senturk, G. k. S.; Kayhan, E.; Ozensoy, E. J.
(46) Zhang, H.; Finnegan, M.; Banfield, J. F. Nano Lett. 2000, 1, 81. Phys. Chem. C 2009, 113, 11014.
(47) Hanaor, D.; Sorrell, C. J. Mater. Sci. 2011, 46, 855. (86) Andonova, S. M.; Senturk, G. k. S.; Ozensoy, E. J. Phys. Chem. C
(48) Hurum, D. C.; Agrios, A. G.; Gray, K. A.; Rajh, T.; Thurnauer, 2010, 114, 17003.
M. C. J. Phys. Chem. B 2003, 107, 4545. (87) Senturk, G. S.; Vovk, E. I.; Zaikovskii, V. I.; Say, Z.; Soylu, A. M.;
(49) Hurum, D. C.; Gray, K. A.; Rajh, T.; Thurnauer, M. C. J. Phys. Bukhtiyarov, V. I.; Ozensoy, E. Catal. Today 2012, 184, 54.
Chem. B 2004, 109, 977. (88) Lu, Q.; Zhao, L.-C.; Guo, F.-Y.; Li, M.-C. Chin. Phys. B 2009, 18,
(50) Leytner, S.; Hupp, J. T. Chem. Phys. Lett. 2000, 330, 231. 4030.
(51) Welham, N. J. J. Mater. Res. 1998, 13, 1607. (89) Li, T.; Liu, S.; Zhang, H.; Wang, E.; Song, L.; Wang, P. J. Mater.
(52) Rao, B. V. J. J. Am. Ceram. Soc. 1964, 47, 455. Sci. 2011, 46, 2882.
(53) Rajendran, V.; Gayathri Devi, A. V.; Azooz, M.; El-Batal, F. H. J. (90) Wang, J.; Wu, J.; Lin, J.; Huang, M.; Huang, Y.; Lan, Z.; Xiao, Y.;
Non-Cryst. Solids 2007, 353, 77. Yue, G.; Yin, S.; Sato, T. ChemSusChem 2012, 5, 1307.
(54) Kim, K. H.; Hummel, F. A. J. Am. Ceram. Soc. 1960, 43, 611. (91) Lahousse, C.; Aboulayt, A.; Mauge, F.; Bachelier, J.; Lavalley, J.
(55) Izquierdo, G.; West, A. R. Mater. Res. Bull. 1980, 15, 1655. C. J. Mol. Catal. 1993, 84, 283.
(56) Miyaji, F.; Yoko, T.; Kozuka, H.; Sakka, S. J. Mater. Sci. 1991, 26, (92) Manrquez, M. E.; Lopez, T.; Gomez, R.; Navarrete, J. J. Mol.
248. Catal. A: Chem. 2004, 220, 229.
(57) Eriksson, G.; Pelton, A. Metall. Trans. B 1993, 24, 795. (93) Zou, H.; Lin, Y. S. Appl. Catal., A 2004, 265, 35.
(58) Burri, D. R.; Choi, K.-M.; Han, S.-C.; Burri, A.; Park, S.-E. J. Mol. (94) Zorn, M. E.; Tompkins, D. T.; Zeltner, W. A.; Anderson, M. A.
Catal. A: Chem. 2007, 269, 58. Appl. Catal., B 1999, 23, 1.
(59) Wang, I.; Chang, W.-F.; Shiau, R.-J.; Wu, J.-C.; Chung, C.-S. J. (95) Zorn, M. E.; Tompkins, D. T.; Zeltner, W. A.; Anderson, M. A.
Catal. 1983, 83, 428. Environ. Sci. Technol. 2000, 34, 5206.
(60) Dulamita, N.; Maicaneanu, A.; Sayle, D. C.; Stanca, M.; Craciun, (96) Zhang, Y.; Xiong, G.; Yao, N.; Yang, W.; Fu, X. Catal. Today
R.; Olea, M.; Afloroaei, C.; Fodor, A. Appl. Catal., A 2005, 287, 9. 2001, 68, 89.
(61) Kamata, H.; Takahashi, K.; Odenbrand, C. U. I. J. Mol. Catal. A: (97) Tidahy, H. L.; Siffert, S.; Lamonier, J. F.; Zhilinskaya, E. A.;
Chem. 1999, 139, 189. Aboukas, A.; Yuan, Z. Y.; Vantomme, A.; Su, B. L.; Canet, X.; De
Weireld, G.; Frere, M.; NGuyen, T. B.; Giraudon, J. M.; Leclercq, G. (132) Chen, S.; Ma, H.; Dai, J.; Yi, X. Appl. Phys. Lett. 2007, 90,
Appl. Catal., A 2006, 310, 61. 101117.
(98) Wu, J.-C.; Chung, C.-S.; Ay, C.-L.; Wang, I. J. Catal. 1984, 87, (133) Jin, P.; Xu, G.; Tazawa, M.; Yoshimura, K. Appl. Phys. A: Mater.
98. Sci. Process. 2003, 77, 455.
(99) Machida, M.; Ikeda, S.; Kurogi, D.; Kijima, T. Appl. Catal., B (134) Zhang, Z.; Gao, Y.; Kang, L.; Du, J.; Luo, H. J. Phys. Chem. C
2001, 35, 107. 2010, 114, 22214.
(100) Perez-Hernandez, R.; Mendoza-Anaya, D.; Fernandez, M. E.; (135) Kang, L.; Gao, Y.; Luo, H.; Chen, Z.; Du, J.; Zhang, Z. ACS
Gomez-Cortes, A. J. Mol. Catal. A: Chem. 2008, 281, 200. Appl. Mater. Interfaces 2011, 3, 135.
(101) Reddy, B. M.; Khan, A. Catal. Rev.-Sci. Eng. 2005, 47, 257. (136) Wang, H.; He, W.; Yuan, G.; Wang, X.; Chen, Q. Thin Solid
(102) Li, K.-T.; Wang, I.; Wu, J.-C. Catal. Surv. Asia 2012, 16, 240. Films 2013, 540, 168.
(103) Ou, C.-C.; Yang, C.-S.; Lin, S.-H. Catal. Sci. Technol. 2011, 1, (137) Cui, H.; Dwight, K.; Soled, S.; Wold, A. J. Solid State Chem.
295. 1995, 115, 187.
(104) Sasikala, R.; Shirole, A. R.; Bharadwaj, S. R. J. Colloid Interface (138) Shen, Y.; Xiong, T.; Shang, J.; Yang, K. Res. Chem. Intermed.
Sci. 2013, 409, 135. 2008, 34, 353.
(105) Li, M.; Zhang, S.; Lv, L.; Wang, M.; Zhang, W.; Pan, B. Chem. (139) Ohuchi, T.; Miyatake, T.; Hitomi, Y.; Tanaka, T. Catal. Today
Eng. J. 2013, 229, 118. 2007, 120, 233.
(106) Fan, M.; Hu, S.; Ren, B.; Wang, J.; Jing, X. Powder Technol. (140) Furukawa, S.; Shishido, T.; Teramura, K.; Tanaka, T. ACS
2013, 235, 27. Catal. 2011, 2, 175.
(107) Hirano, M.; Nakahara, C.; Ota, K.; Tanaike, O.; Inagaki, M. J. (141) Eguchi, K.; Koga, H.; Sekizawa, K.; Sasaki, K. J. Ceram. Soc. Jpn.
Solid State Chem. 2003, 170, 39. 2000, 108, 1067.
(108) Neppolian, B.; Wang, Q.; Yamashita, H.; Choi, H. Appl. Catal., (142) Chen, S. G.; Chappel, S.; Diamant, Y.; Zaban, A. Chem. Mater.
A 2007, 333, 264. 2001, 13, 4629.
(109) Chen, X.; Wang, X.; Fu, X. Energy Environ. Sci. 2009, 2, 872. (143) Xia, J.; Masaki, N.; Jiang, K.; Yanagida, S. J. Phys. Chem. C
(110) Chen, D.; Cao, L.; Hanley, T. L.; Caruso, R. A. Adv. Funct. 2007, 111, 8092.
Mater. 2012, 22, 1966. (144) Barea, E.; Xu, X.; Gonzalez-Pedro, V.; Ripolles-Sanchis, T.;
(111) Wilk, G. D.; Wallace, R. M.; Anthony, J. M. J. Appl. Phys. 2001, Fabregat-Santiago, F.; Bisquert, J. Energy Environ. Sci. 2011, 4, 3414.
89, 5243. (145) Palomares, E.; Clifford, J. N.; Haque, S. A.; Lutz, T.; Durrant, J.
(112) Triyoso, D. H.; Hegde, R. I.; Wang, X.-D.; Stoker, M. W.; Rai, R. J. Am. Chem. Soc. 2002, 125, 475.
R.; Ramon, M. E.; White, B. E.; Tobin, P. J. J. Electrochem. Soc. 2006, (146) Kay, A.; Gratzel, M. Chem. Mater. 2002, 14, 2930.
153, G834. (147) Lee, S.; Noh, J. H.; Han, H. S.; Yim, D. K.; Kim, D. H.; Lee, J.-
(113) Kukli, K.; Ritala, M.; Leskela, M.; Sundqvist, J.; Oberbeck, L.; K.; Kim, J. Y.; Jung, H. S.; Hong, K. S. J. Phys. Chem. C 2009, 113,
Heitmann, J.; Schroder, U.; Aarik, J.; Aidla, A. Thin Solid Films 2007, 6878.
515, 6447. (148) Wang, G. Q.; Lan, W.; Han, G. J.; Wang, Y.; Su, Q.; Liu, X. Q.
(114) Seo, M.; Kim, S. K.; Han, J. H.; Hwang, C. S. Chem. Mater. J. Alloys Compd. 2011, 509, 4150.
2010, 22, 4419. (149) Joskowska, D.; Pomoni, K.; Vomvas, A.; Koscielska, B.;
(115) Seo, M.; Ho Rha, S.; Keun Kim, S.; Hwan Han, J.; Lee, W.; Anastassopoulos, D. L. J. Non-Cryst. Solids 2010, 356, 2042.
Han, S.; Seong Hwang, C. J. Appl. Phys. 2011, 110, 024105. (150) Ghicov, A.; Aldabergenova, S.; Tsuchyia, H.; Schmuki, P.
(116) Seo, M.; Kim, S. K.; Min, Y.-S.; Hwang, C. S. J. Mater. Chem. Angew. Chem., Int. Ed. 2006, 45, 6993.
2011, 21, 18497. (151) Wu, J.-M.; Antonietti, M.; Gross, S.; Bauer, M.; Smarsly, B. M.
(117) Topsoe, N. Y.; Topsoe, H.; Dumesic, J. A. J. Catal. 1995, 151, ChemPhysChem 2008, 9, 748.
226. (152) Stodolny, M.; Laniecki, M. Catal. Today 2009, 142, 314.
(118) Amiridis, M. D.; Wachs, I. E.; Deo, G.; Jehng, J.-M.; Kim, D. S. (153) Takahara, Y.; Kondo, J. N.; Takata, T.; Lu, D.; Domen, K.
J. Catal. 1996, 161, 247. Chem. Mater. 2001, 13, 1194.
(119) Cha, W.; Chin, S.; Park, E.; Yun, S.-T.; Jurng, J. Appl. Catal., B (154) Kondo, J. N.; Uchida, M.; Nakajima, K.; Daling, L.; Hara, M.;
2013, 140141, 708. Domen, K. Chem. Mater. 2004, 16, 4304.
(120) Lomnicki, S.; Lichtenberger, J.; Xu, Z.; Waters, M.; Kosman, J.; (155) Noda, Y.; Lee, B.; Domen, K.; Kondo, J. N. Chem. Mater. 2008,
Amiridis, M. D. Appl. Catal., B 2003, 46, 105. 20, 5361.
(121) Lichtenberger, J.; Amiridis, M. D. J. Catal. 2004, 223, 296. (156) Choi, J.; Park, H.; Hoffmann, M. R. J. Phys. Chem. C 2010, 114,
(122) Zhuiykov, S.; Wlodarski, W.; Li, Y. Sens. Actuators, B 2001, 77, 783.
484. (157) Choi, J.; Park, H.; Hoffmann, M. R. J. Mater. Res. 2010, 25,
(123) Izu, N.; Hagen, G.; Schonauer, D.; Roder-Roith, U.; Moos, R. 149.
Sensors 2011, 11, 2982. (158) Koehler, K.; Engweiler, J.; Viebrock, H.; Baiker, A. Langmuir
(124) Song, M. Y.; Park, Y.-K.; Jurng, J. Powder Technol. 2012, 231, 1995, 11, 3423.
135. (159) Mok, Y. S.; Koh, D. J.; Kim, K. T.; Nam, I.-S. Ind. Eng. Chem.
(125) Wang, Y.; Zhang, J.; Liu, L.; Zhu, C.; Liu, X.; Su, Q. Mater. Lett. Res. 2003, 42, 2960.
2012, 75, 95. (160) Pena, D. A.; Uphade, B. S.; Reddy, E. P.; Smirniotis, P. G. J.
(126) Su, Q.; Zhang, J.; Wang, Y.; Yu, M.; Zhu, C.; Lan, W.; Liu, X. J. Phys. Chem. B 2004, 108, 9927.
Phys. Chem. Solids 2013, 74, 1475. (161) Martin, C.; Martin, I.; Rives, V.; Palmisano, L.; Schiavello, M. J.
(127) Yang, Y.; Kim, D.; Yang, M.; Schmuki, P. Chem. Commun. Catal. 1992, 134, 434.
2011, 47, 7746. (162) Miyazaki, H.; Matsui, H.; Nagano, T.; Karuppuchamy, S.; Ito,
(128) Wang, Y.; Takahashi, K.; Lee, K. H.; Cao, G. Z. Adv. Funct. S.; Yoshihara, M. Appl. Surf. Sci. 2008, 254, 7365.
Mater. 2006, 16, 1133. (163) Chen, M.; Cho, K.; Oh, W. J. Mater. Sci. 2010, 45, 6611.
(129) Hahn, R.; Schmidt-Stein, F.; Salonen, J.; Thiemann, S.; Song, (164) G. Egdell, R.; Brand, E.; Kellett, D. J. Mater. Chem. 1999, 9,
Y.; Kunze, J.; Lehto, V.-P.; Schmuki, P. Angew. Chem., Int. Ed. 2009, 48, 2717.
7236. (165) Chen, Y.-J.; Zhang, X.-Y.; Cai, T.-Y.; Li, Z.-Y. Mater. Lett. 2004,
(130) Morin, F. J. Phys. Rev. Lett. 1959, 3, 34. 58, 262.
(131) Manning, T. D.; Parkin, I. P.; Clark, R. J. H.; Sheel, D.; Pemble, (166) Fan, Y.; Zhang, C.; Du, X.; Wen, G.; Ma, H.; Jia, X. J. Magn.
M. E.; Vernadou, D. J. Mater. Chem. 2002, 12, 2936. Magn. Mater. 2013, 335, 105.
(167) Lee, W.; Do, Y. R.; Dwight, K.; Wold, A. Mater. Res. Bull. 1993, (203) Ye, M.; Zhang, Q.; Hu, Y.; Ge, J.; Lu, Z.; He, L.; Chen, Z.; Yin,
28, 1127. Y. Chem.Eur. J. 2010, 16, 6243.
(168) Papp, J.; Soled, S.; Dwight, K.; Wold, A. Chem. Mater. 1994, 6, (204) Joo, J.; Ye, Y.; Kim, D.; Lee, J.; Jeon, S. Mater. Lett. 2013, 93,
496. 141.
(169) Elder, S. H.; Cot, F. M.; Su, Y.; Heald, S. M.; Tyryshkin, A. M.; (205) Linley, S.; Leshuk, T.; Gu, F. X. ACS Appl. Mater. Interfaces
Bowman, M. K.; Gao, Y.; Joly, A. G.; Balmer, M. L.; Kolwaite, A. C.; 2013, 5, 2540.
Magrini, K. A.; Blake, D. M. J. Am. Chem. Soc. 2000, 122, 5138. (206) Li, W.; Yang, J.; Wu, Z.; Wang, J.; Li, B.; Feng, S.; Deng, Y.;
(170) Song, K. Y.; Park, M. K.; Kwon, Y. T.; Lee, H. W.; Chung, W. Zhang, F.; Zhao, D. J. Am. Chem. Soc. 2012, 134, 11864.
J.; Lee, W. I. Chem. Mater. 2001, 13, 2349. (207) Zhang, G.; Huang, H.; Li, W.; Yu, F.; Wu, H.; Zhou, L.
(171) Matsui, H.; Nagano, S.; Karuppuchamy, S.; Yoshihara, M. Curr. Electrochim. Acta 2012, 81, 117.
Appl. Phys. 2009, 9, 561. (208) Dai, G.; Liu, S.; Liang, Y.; Luo, T. Appl. Surf. Sci. 2013, 264,
(172) Do, Y. R.; Lee, W.; Dwight, K.; Wold, A. J. Solid State Chem. 157.
1994, 108, 198. (209) Wang, Y.-F.; Hsieh, M.-C.; Lee, J.-F.; Yang, C.-M. Appl. Catal.,
(173) Tae Kwon, Y.; Yong Song, K.; In Lee, W.; Jin Choi, G.; Rag B 2013, 142143, 626.
Do, Y. J. Catal. 2000, 191, 192. (210) Kyeremateng, N. A.; Lebouin, C.; Knauth, P.; Djenizian, T.
(174) Li, X. Z.; Li, F. B.; Yang, C. L.; Ge, W. K. J. Photochem. Electrochim. Acta 2013, 88, 814.
Photobiol., A 2001, 141, 209. (211) Luo, Y.; Luo, J.; Zhou, W.; Qi, X.; Zhang, H.; Yu, D. Y. W.; Li,
(175) Higashimoto, S.; Sakiyama, M.; Azuma, M. Thin Solid Films C. M.; Fan, H. J.; Yu, T. J. Mater. Chem. A 2013, 1, 273.
2006, 503, 201. (212) Vannice, M. A.; Garten, R. L. J. Catal. 1980, 66, 242.
(176) Chai, S.; Kim, Y.; Lee, W. J. Electroceram. 2006, 17, 909. (213) Yao, N.; Chen, J.; Zhang, J.; Zhang, J. Catal. Commun. 2008, 9,
(177) Bayati, M. R.; Golestani-Fard, F.; Moshfegh, A. Z. Appl. Catal., 1510.
A 2010, 382, 322. (214) Chen, J.; Yao, N.; Wang, R.; Zhang, J. Chem. Eng. J. 2009, 148,
(178) Su, D.; Wang, J.; Tang, Y.; Liu, C.; Liu, L.; Han, X. Chem. 164.
Commun. 2011, 47, 4231. (215) Bradford, M. C. J.; Vannice, M. A. Appl. Catal., A 1996, 142,
(179) Anandan, S.; Miyauchi, M. Chem. Commun. 2012, 48, 4323. 73.
(180) Lai, C. W.; Sreekantan, S. Electrochim. Acta 2013, 87, 294. (216) Vannice, M. A.; Garten, R. L. J. Catal. 1979, 56, 236.
(181) Riboni, F.; Bettini, L. G.; Bahnemann, D. W.; Selli, E. Catal. (217) Burch, R.; Flambard, A. R. J. Catal. 1982, 78, 389.
Today 2013, 209, 28. (218) Sankar, G.; Rao, C. N. R.; Rayment, T. J. Mater. Chem. 1991, 1,
(182) Yang, X.-L.; Dai, W.-L.; Guo, C.; Chen, H.; Cao, Y.; Li, H.; He, 299.
(219) Zhao, W.; Ma, W.; Chen, C.; Zhao, J.; Shuai, Z. J. Am. Chem.
H.; Fan, K. J. Catal. 2005, 234, 438.
(183) Wu, Z.; Jin, R.; Wang, H.; Liu, Y. Catal. Commun. 2009, 10, Soc. 2004, 126, 4782.
(220) Shrestha, N. K.; Yang, M.; Nah, Y.-C.; Paramasivam, I.;
935.
Schmuki, P. Electrochem. Commun. 2010, 12, 254.
(184) Kim, Y. J.; Kwon, H. J.; Nam, I.-S.; Choung, J. W.; Kil, J. K.;
(221) Chen, C.-J.; Liao, C.-H.; Hsu, K.-C.; Wu, Y.-T.; Wu, J. C. S.
Kim, H.-J.; Cha, M.-S.; Yeo, G. K. Catal. Today 2010, 151, 244.
Catal. Commun. 2011, 12, 1307.
(185) Ettireddy, P. R.; Ettireddy, N.; Boningari, T.; Pardemann, R.;
(222) Lin, J.; Shen, J.; Wang, R.; Cui, J.; Zhou, W.; Hu, P.; Liu, D.;
Smirniotis, P. G. J. Catal. 2012, 292, 53.
Liu, H.; Wang, J.; Boughton, R. I.; Yue, Y. J. Mater. Chem. 2011, 21,
(186) Iida, H.; Igarashi, A. Appl. Catal., A 2006, 303, 48.
5106.
(187) Sato, Y.; Soma, Y.; Miyao, T.; Naito, S. Appl. Catal., A 2006,
(223) Pozan, G. S.; Isleyen, M.; Gokcen, S. Appl. Catal., B 2013,
304, 78. 140141, 537.
(188) Azzam, K. G.; Babich, I. V.; Seshan, K.; Lefferts, L. Appl. Catal., (224) Yu, J.; Hai, Y.; Cheng, B. J. Phys. Chem. C 2011, 115, 4953.
B 2008, 80, 129. (225) Xie, S.; Zhai, T.; Li, W.; Yu, M.; Liang, C.; Gan, J.; Lu, X.;
(189) Iida, H.; Yonezawa, K.; Kosaka, M.; Igarashi, A. Catal. Tong, Y. Green Chem. 2013, 15, 2434.
Commun. 2009, 10, 627. (226) Liu, R.; Yoshida, H.; Fujita, S.-i.; Arai, M. Appl. Catal., B 2014,
(190) Lu, X.; Yu, M.; Wang, G.; Zhai, T.; Xie, S.; Ling, Y.; Tong, Y.; 144, 41.
Li, Y. Adv. Mater. 2013, 25, 267. (227) Gibson, E. A.; Smeigh, A. L.; Le Pleux, L.; Fortage, J.;
(191) Liao, J.-Y.; Higgins, D.; Lui, G.; Chabot, V.; Xiao, X.; Chen, Z. Boschloo, G.; Blart, E.; Pellegrin, Y.; Odobel, F.; Hagfeldt, A.;
Nano Lett. 2013, 13 (11), 5467. Hammarstrom, L. Angew. Chem., Int. Ed. 2009, 48, 4402.
(192) Kang, J.-H.; Paek, S.-M.; Hwang, S.-J.; Choy, J.-H. J. Mater. (228) Lee, Y.-M.; Lai, C.-H. Solid-State Electron. 2009, 53, 1116.
Chem. 2010, 20, 2033. (229) Chou, C.-S.; Lin, Y.-J.; Yang, R.-Y.; Liu, K.-H. Adv. Powder
(193) Wu, M.-S.; Chiang, P.-C. J.; Lee, J.-T.; Lin, J.-C. J. Phys. Chem. Technol. 2011, 22, 31.
B 2005, 109, 23279. (230) Lin, Y.-C.; Chen, Y.-T.; Yao, P.-C. J. Power Sources 2013, 240,
(194) Yu, A.; Park, H. W.; Davies, A.; Higgins, D. C.; Chen, Z.; Xiao, 705.
X. J. Phys. Chem. Lett. 2011, 2, 1855. (231) Wang, Y.-g.; Zhang, X.-g. J. Electrochem. Soc. 2005, 152, A671.
(195) Perkas, N.; Wang, Y.; Koltypin, Y.; Gedanken, A.; (232) Kim, J.-H.; Zhu, K.; Yan, Y.; Perkins, C. L.; Frank, A. J. Nano
Chandrasekaran, S. Chem. Commun. 2001, 988. Lett. 2010, 10, 4099.
(196) Buonsanti, R.; Snoeck, E.; Giannini, C.; Gozzo, F.; Garcia- (233) Wang, W.; Tian, M.; Abdulagatov, A.; George, S. M.; Lee, Y.-
Hernandez, M.; Angel Garcia, M.; Cingolani, R.; Davide Cozzoli, P. C.; Yang, R. Nano Lett. 2011, 12, 655.
Phys. Chem. Chem. Phys. 2009, 11, 3680. (234) Ghijsen, J.; Tjeng, L. H.; van Elp, J.; Eskes, H.; Westerink, J.;
(197) Buonsanti, R.; Grillo, V.; Carlino, E.; Giannini, C.; Gozzo, F.; Sawatzky, G. A.; Czyzyk, M. T. Phys. Rev. B 1988, 38, 11322.
Garcia-Hernandez, M.; Garcia, M. A.; Cingolani, R.; Cozzoli, P. D. J. (235) Mor, G. K.; Varghese, O. K.; Wilke, R. H. T.; Sharma, S.;
Am. Chem. Soc. 2010, 132, 2437. Shankar, K.; Latempa, T. J.; Choi, K.-S.; Grimes, C. A. Nano Lett.
(198) Ahmed, M. A.; El-Katori, E. E.; Gharni, Z. H. J. Alloys Compd. 2008, 8, 1906.
2013, 553, 19. (236) Li, J.; Liu, L.; Yu, Y.; Tang, Y.; Li, H.; Du, F. Electrochem.
(199) Xu, M.-W.; Bao, S.-J.; Zhang, X.-G. Mater. Lett. 2005, 59, 2194. Commun. 2004, 6, 940.
(200) Chen, W.-J.; Tsai, P.-J.; Chen, Y.-C. Small 2008, 4, 485. (237) Bessekhouad, Y.; Robert, D.; Weber, J. V. Catal. Today 2005,
(201) Lou, X. W.; Archer, L. A. Adv. Mater. 2008, 20, 1853. 101, 315.
(202) Xuan, S.; Jiang, W.; Gong, X.; Hu, Y.; Chen, Z. J. Phys. Chem. C (238) Xu, Y.-h.; Liang, D.-h.; Liu, M.-l.; Liu, D.-z. Mater. Res. Bull.
2008, 113, 553. 2008, 43, 3474.
(239) Huang, L.; Peng, F.; Wang, H.; Yu, H.; Li, Z. Catal. Commun. (277) Mohammadi, M. R.; Ghorbani, M.; Cordero-Cabrera, M. C.;
2009, 10, 1839. Fray, D. J. J. Mater. Sci. 2007, 42, 4976.
(240) Yang, L.; Luo, S.; Li, Y.; Xiao, Y.; Kang, Q.; Cai, Q. Environ. Sci. (278) Chandiran, A. K.; Tetreault, N.; Humphry-Baker, R.; Kessler,
Technol. 2010, 44, 7641. F.; Baranoff, E.; Yi, C.; Nazeeruddin, M. K.; Gratzel, M. Nano Lett.
(241) Chu, S.; Zheng, X.; Kong, F.; Wu, G.; Luo, L.; Guo, Y.; Liu, H.; 2012, 12, 3941.
Wang, Y.; Yu, H.; Zou, Z. Mater. Chem. Phys. 2011, 129, 1184. (279) Shchukin, D.; Poznyak, S.; Kulak, A.; Pichat, P. J. Photochem.
(242) Liu, L.; Gu, X.; Sun, C.; Li, H.; Deng, Y.; Gao, F.; Dong, L. Photobiol., A 2004, 162, 423.
Nanoscale 2012, 4, 6351. (280) Rodrguez-Gonzalez, V.; Moreno-Rodrguez, A.; May, M.;
(243) Dieckmann, M. S.; Gray, K. A. Water Res. 1996, 30, 1169. Tzompantzi, F.; Gomez, R. J. Photochem. Photobiol., A 2008, 193, 266.
(244) Su, X.; Zhao, J.; Li, Y.; Zhu, Y.; Ma, X.; Sun, F.; Wang, Z. (281) Yang, X.; Wang, Y.; Xu, L.; Yu, X.; Guo, Y. J. Phys. Chem. C
Colloids Surf., A 2009, 349, 151. 2008, 112, 11481.
(245) Senevirathna, M. K. I.; Pitigala, P. K. D. D. P.; Tennakone, K. J. (282) Mu, J.; Chen, B.; Zhang, M.; Guo, Z.; Zhang, P.; Zhang, Z.;
Photochem. Photobiol., A 2005, 171, 257. Sun, Y.; Shao, C.; Liu, Y. ACS Appl. Mater. Interfaces 2011, 4, 424.
(246) Wu, Y.; Lu, G.; Li, S. Catal. Lett. 2009, 133, 97. (283) Chen, Y.-C.; Pu, Y.-C.; Hsu, Y.-J. J. Phys. Chem. C 2012, 116,
(247) Lalitha, K.; Sadanandam, G.; Kumari, V. D.; Subrahmanyam, 2967.
M.; Sreedhar, B.; Hebalkar, N. Y. J. Phys. Chem. C 2010, 114, 22181. (284) Zhong, J.; Li, J.; Zeng, J.; He, X.; Huang, S.; Jiang, W.; Li, M.
(248) Li, Z.; Liu, J.; Wang, D.; Gao, Y.; Shen, J. Int. J. Hydrogen Appl. Phys. A: Mater. Sci. Process. 2013, 1.
Energy 2012, 37, 6431. (285) Vinodgopal, K.; Bedja, I.; Kamat, P. V. Chem. Mater. 1996, 8,
(249) Wang, Z.; Liu, Y.; Martin, D. J.; Wang, W.; Tang, J.; Huang, W. 2180.
Phys. Chem. Chem. Phys. 2013, 15, 14956. (286) Chen, L.-C.; Tsai, F.-R.; Fang, S.-H.; Ho, Y.-C. Electrochim.
(250) Bandara, J.; Udawatta, C. P. K.; Rajapakse, C. S. K. Photochem. Acta 2009, 54, 1304.
Photobiol. Sci. 2005, 4, 857. (287) Wang, C.; Shao, C.; Zhang, X.; Liu, Y. Inorg. Chem. 2009, 48,
(251) Choi, H.-J.; Kang, M. Int. J. Hydrogen Energy 2007, 32, 3841. 7261.
(252) Yu, J.; Hai, Y.; Jaroniec, M. J. Colloid Interface Sci. 2011, 357, (288) Cao, Y.; He, T.; Chen, Y.; Cao, Y. J. Phys. Chem. C 2010, 114,
223.
3627.
(253) Boccuzzi, F.; Chiorino, A.; Manzoli, M.; Andreeva, D.;
(289) Chai, S.; Zhao, G.; Li, P.; Lei, Y.; Zhang, Y.-n.; Li, D. J. Phys.
Tabakova, T.; Ilieva, L.; Iadakiev, V. Catal. Today 2002, 75, 169.
Chem. C 2011, 115, 18261.
(254) Sunada, K.; Watanabe, T.; Hashimoto, K. Environ. Sci. Technol.
(290) Pan, J.; Huhne, S.-M.; Shen, H.; Xiao, L.; Born, P.; Mader, W.;
2003, 37, 4785.
Mathur, S. J. Phys. Chem. C 2011, 115, 17265.
(255) Sangpour, P.; Hashemi, F.; Moshfegh, A. Z. J. Phys. Chem. C
(291) Xu, L.; Steinmiller, E. M. P.; Skrabalak, S. E. J. Phys. Chem. C
2010, 114, 13955.
(256) Montini, T.; Gombac, V.; Sordelli, L.; Delgado, J. J.; Chen, X.; 2011, 116, 871.
(292) Yang, G.; Yan, Z.; Xiao, T. Appl. Surf. Sci. 2012, 258, 8704.
Adami, G.; Fornasiero, P. ChemCatChem. 2011, 3, 574.
(293) Nasr, C.; Kamat, P. V.; Hotchandani, S. J. Phys. Chem. B 1998,
(257) Wu, G.; Guan, N.; Li, L. Catal. Sci. Technol. 2011, 1, 601.
(258) Cotton, F. A.; Wilkinson, G.; Gaus, P. L. Basic Inorganic 102, 10047.
Chemistry; 4th ed.; Wiley: New York, 1995. (294) Ramasamy, E.; Lee, J. J. Phys. Chem. C 2010, 114, 22032.
(259) Agrawal, M.; Gupta, S.; Pich, A.; Zafeiropoulos, N. E.; Stamm, (295) Sun, W.; Sun, X.; Peng, T.; Liu, Y.; Zhu, H.; Guo, S.; Zhao, X.-
M. Chem. Mater. 2009, 21, 5343. z. J. Power Sources 2012, 201, 402.
(260) Zhang, M.; An, T.; Liu, X.; Hu, X.; Sheng, G.; Fu, J. Mater. Lett. (296) Xing, J.; Fang, W. Q.; Li, Z.; Yang, H. G. Ind. Eng. Chem. Res.
2010, 64, 1883. 2012, 51, 4247.
(261) Xiao, F.-X. ACS Appl. Mater. Interfaces 2012, 4, 7055. (297) Peng, Z.; Shi, Z.; Liu, M. Chem. Commun. 2000, 2125.
(262) Yan, X.; Zou, C.; Gao, X.; Gao, W. J. Mater. Chem. 2012, 22, (298) Roginskaya, Y. E.; Chibirova, F. K.; Kulova, T. L.; Skundin, A.
5629. M. Russ. J. Electrochem. 2006, 42, 355.
(263) Lin, L.; Yang, Y.; Men, L.; Wang, X.; He, D.; Chai, Y.; Zhao, B.; (299) Kim, H. S.; Kang, S. H.; Chung, Y. H.; Sung, Y.-E. Electrochem.
Ghoshroy, S.; Tang, Q. Nanoscale 2013, 5, 588. Solid-State Lett. 2010, 13, A15.
(264) Wu, L.; Xing, J.; Hou, Y.; Xiao, F. Y.; Li, Z.; Yang, H. G. (300) Lin, Y.-M.; Nagarale, R. K.; Klavetter, K. C.; Heller, A.;
Chem.Eur. J. 2013, 19, 8393. Mullins, C. B. J. Mater. Chem. 2012, 22, 11134.
(265) Shaheen, B. S.; Salem, H. G.; El-Sayed, M. A.; Allam, N. K. J. (301) Park, S.; Seo, S.-D.; Lee, S.; Seo, S. W.; Park, K.-S.; Lee, C. W.;
Phys. Chem. C 2013, 117, 18502. Kim, D.-W.; Hong, K. S. J. Phys. Chem. C 2012, 116, 21717.
(266) Guo, S.; Han, S.; Mao, H.; Dong, S.; Wu, C.; Jia, L.; Chi, B.; (302) Jeun, J.-H.; Park, K.-Y.; Kim, D.-H.; Kim, W.-S.; Kim, H.-C.;
Pu, J.; Li, J. J. Power Sources 2014, 245, 979. Lee, B.-S.; Kim, H.; Yu, W.-R.; Kang, K.; Hong, S.-H. Nanoscale 2013,
(267) Wang, Z.-S.; Huang, C.-H.; Huang, Y.-Y.; Hou, Y.-J.; Xie, P.- 5, 8480.
H.; Zhang, B.-W.; Cheng, H.-M. Chem. Mater. 2001, 13, 678. (303) Wang, Y.; Su, F.; Lee, J. Y.; Zhao, X. S. Chem. Mater. 2006, 18,
(268) Meili, W.; Changgang, H.; Yongge, C.; Qingjiang, Y.; 1347.
Zhonghua, D.; Yuan, L.; Zhi, H.; Jiquan, H.; Qiufeng, H.; Wang, G.; (304) Bian, Z.; Zhu, J.; Wang, S.; Cao, Y.; Qian, X.; Li, H. J. Phys.
Jingkui, L. J. Phys. D: Appl. Phys. 2009, 42, 155104. Chem. C 2008, 112, 6258.
(269) Park, K.; Zhang, Q.; Garcia, B. B.; Zhou, X.; Jeong, Y.-H.; Cao, (305) Xu, J.; Ao, Y.; Fu, D.; Yuan, C. Appl. Surf. Sci. 2008, 255, 2365.
G. Adv. Mater. 2010, 22, 2329. (306) Shamaila, S.; Sajjad, A. K. L.; Chen, F.; Zhang, J. Appl. Catal., B
(270) Park, K.; Zhang, Q.; Garcia, B. B.; Cao, G. J. Phys. Chem. C 2010, 94, 272.
2011, 115, 4927. (307) Zhao, X.; Liu, H.; Qu, J. Appl. Surf. Sci. 2011, 257, 4621.
(271) Manthina, V.; Correa Baena, J. P.; Liu, G.; Agrios, A. G. J. Phys. (308) Lin, J.; Yu, J. C. J. Photochem. Photobiol., A 1998, 116, 63.
Chem. C 2012, 116, 23864. (309) Reddy, B. M.; Sreekanth, P. M.; Reddy, E. P.; Yamada, Y.; Xu,
(272) Williams, V. O.; Jeong, N. C.; Prasittichai, C.; Farha, O. K.; Q.; Sakurai, H.; Kobayashi, T. J. Phys. Chem. B 2002, 106, 5695.
Pellin, M. J.; Hupp, J. T. ACS Nano 2012, 6, 6185. (310) Clark, P. D.; Sui, R.; Dowling, N. I.; Huang, M.; Lo, J. M. H.
(273) Xu, C.; Wu, J.; Desai, U. V.; Gao, D. Nano Lett. 2012, 12, 2420. Catal. Today 2013, 207, 212.
(274) Kamiya, S.; Tilley, R. J. D. J. Solid State Chem. 1977, 22, 205. (311) Mohammadi, M. R.; Fray, D. J. Sens. Actuators, B 2009, 141, 76.
(275) Reddy, B. M.; Ganesh, I.; Reddy, E. P.; Fernandez, A.; (312) Li, F.; Gu, Y. Mater. Sci. Semicond. Process. 2012, 15, 11.
Smirniotis, P. G. J. Phys. Chem. B 2001, 105, 6227. (313) Li, L.; Zhou, Z.; Lei, J.; He, J.; Liu, P.; Pan, F. Mater. Lett. 2012,
(276) Chang, K. W.; Wu, J. J. Adv. Mater. 2005, 17, 241. 79, 252.
(314) Liu, Z.; Zhang, J.; Han, B.; Du, J.; Mu, T.; Wang, Y.; Sun, Z. (349) Meyer, S.; Saborowski, S.; Schafer, B. ChemPhysChem 2006, 7,
Microporous Mesoporous Mater. 2005, 81, 169. 572.
(315) Kibombo, H. S.; Weber, A. S.; Wu, C.-M.; Raghupathi, K. R.; (350) Al-Mazroai, L. S.; Bowker, M.; Davies, P.; Dickinson, A.;
Koodali, R. T. J. Photochem. Photobiol., A 2013, 269, 49. Greaves, J.; James, D.; Millard, L. Catal. Today 2007, 122, 46.
(316) Yang, H.; Zhang, K.; Shi, R.; Tang, A. J. Am. Ceram. Soc. 2007, (351) Bahruji, H.; Bowker, M.; Davies, P. R.; Pedrono, F. Appl.
90, 1370. Catal., B 2011, 107, 205.
(317) Li, G.; Zhang, D.; Yu, J. C. Phys. Chem. Chem. Phys. 2009, 11, (352) Ortel, E.; Sokolov, S.; Zielke, C.; Lauermann, I.; Selve, S.; Weh,
3775. K.; Paul, B.; Polte, J.; Kraehnert, R. Chem. Mater. 2012, 24, 3828.
(318) Cao, T.; Li, Y.; Wang, C.; Wei, L.; Shao, C.; Liu, Y. Mater. Res. (353) Tapin, B.; Epron, F.; Especel, C.; Ly, B. K.; Pinel, C.; Besson,
Bull. 2010, 45, 1406. M. ACS Catal. 2013, 3, 2327.
(319) Guzman, C.; del A ngel, G.; Gomez, R.; Galindo-Hernandez, F.; (354) Iliev, V.; Tomova, D.; Bilyarska, L.; Petrov, L. Catal. Commun.
A ngeles-Chavez, C. Catal. Today 2011, 166, 146. 2004, 5, 759.
(320) Liu, H.; Wang, M.; Wang, Y.; Liang, Y.; Cao, W.; Su, Y. J. (355) Mohapatra, S. K.; Kondamudi, N.; Banerjee, S.; Misra, M.
Photochem. Photobiol., A 2011, 223, 157. Langmuir 2008, 24, 11276.
(321) Munoz-Batista, M. J.; Kubacka, A.; Gomez-Cerezo, M. N.; (356) Kuvarega, A. T.; Krause, R. W. M.; Mamba, B. B. J. Phys. Chem.
Tudela, D.; Fernandez-Garca, M. Appl. Catal., B 2013, 140141, 626. C 2011, 115, 22110.
(322) Wang, Y.; Li, B.; Zhang, C.; Cui, L.; Kang, S.; Li, X.; Zhou, L. (357) Maicu, M.; Hidalgo, M. C.; Colon, G.; Navo, J. A. J.
Appl. Catal., B 2013, 130131, 277. Photochem. Photobiol., A 2011, 217, 275.
(323) Luo, M.; Chen, J.; Chen, L.; Lu, J.; Feng, Z.; Li, C. Chem. (358) Zhang, Z.; Yu, Y.; Wang, P. ACS Appl. Mater. Interfaces 2012, 4,
Mater. 2000, 13, 197. 990.
(324) Park, J. B.; Graciani, J.; Evans, J.; Stacchiola, D.; Ma, S.; Liu, P.; (359) Zhang, F.; Xie, F.; Xu, H.; Liu, J.; Oh, W. Kinet. Catal. 2013,
Nambu, A.; Sanz, J. F.; Hrbek, J.; Rodriguez, J. A. Proc. Natl. Acad. Sci. 54, 297.
U.S.A. 2009, 106, 4975. (360) Sreethawong, T.; Yoshikawa, S. Catal. Commun. 2005, 6, 661.
(325) Park, J. B.; Graciani, J.; Evans, J.; Stacchiola, D.; Senanayake, S. (361) Liu, Y.; Guo, L.; Yan, W.; Liu, H. J. Power Sources 2006, 159,
D.; Barrio, L.; Liu, P.; Sanz, J. F.; Hrbek, J.; Rodriguez, J. A. J. Am. 1300.
Chem. Soc. 2009, 132, 356. (362) Sayed, F. N.; Jayakumar, O. D.; Sasikala, R.; Kadam, R. M.;
(326) Maciel, C. G.; Silva, T. d. F.; Assaf, E. M.; Assaf, J. M. Appl. Bharadwaj, S. R.; Kienle, L.; Schurmann, U.; Kaps, S.; Adelung, R.;
Mittal, J. P.; Tyagi, A. K. J. Phys. Chem. C 2012, 116, 12462.
Energy 2013, 112, 52.
(363) Sastre, F.; Oteri, M.; Corma, A.; Garcia, H. Energy Environ. Sci.
(327) Kiwi, J.; Borgarello, E.; Pelizzetti, E.; Visca, M.; Gratzel, M.
2013, 6, 2211.
Angew. Chem., Int. Ed. Engl. 1980, 19, 646.
(364) Ye, M.; Gong, J.; Lai, Y.; Lin, C.; Lin, Z. J. Am. Chem. Soc.
(328) Borgarello, E.; Kiwi, J.; Pelizzetti, E.; Visca, M.; Graetzel, M. J.
2012, 134, 15720.
Am. Chem. Soc. 1981, 103, 6324.
(365) Baba, R.; Nakabayashi, S.; Fujishima, A.; Honda, K. J. Phys.
(329) Borgarello, E.; Kiwi, J.; Pelizzetti, E.; Visca, M.; Gratzel, M.
Chem. 1985, 89, 1902.
Nature 1981, 289, 158.
(366) Chen, S.; Li, J.; Qian, K.; Xu, W.; Lu, Y.; Huang, W.; Yu, S.
(330) Duonghong, D.; Borgarello, E.; Graetzel, M. J. Am. Chem. Soc.
Nano Res. 2010, 3, 244.
1981, 103, 4685. (367) Zhang, N.; Liu, S.; Fu, X.; Xu, Y.-J. J. Phys. Chem. C 2011, 115,
(331) Borgarello, E.; Kiwi, J.; Graetzel, M.; Pelizzetti, E.; Visca, M. J. 9136.
Am. Chem. Soc. 1982, 104, 2996. (368) Bakhmutsky, K.; Wieder, N. L.; Cargnello, M.; Galloway, B.;
(332) Kawai, T.; Sakata, T. Chem. Phys. Lett. 1980, 72, 87. Fornasiero, P.; Gorte, R. J. ChemSusChem 2012, 5, 140.
(333) Hubert, C.; Bile, E. G.; Denicourt-Nowicki, A.; Roucoux, A. (369) Kiwi, J.; Gratzel, M. Nature 1979, 281, 657.
Green Chem. 2011, 13, 1766. (370) Sato, S.; White, J. M. Chem. Phys. Lett. 1980, 72, 83.
(334) Primo, A.; Concepcion, P.; Corma, A. Chem. Commun. 2011, (371) Kiwi, J.; Graetzel, M. J. Phys. Chem. 1984, 88, 1302.
47, 3613. (372) Kraeutler, B.; Bard, A. J. J. Am. Chem. Soc. 1978, 100, 2239.
(335) Utaka, T.; Okanishi, T.; Takeguchi, T.; Kikuchi, R.; Eguchi, K. (373) Kraeutler, B.; Bard, A. J. J. Am. Chem. Soc. 1978, 100, 5985.
Appl. Catal., A 2003, 245, 343. (374) Reiche, H.; Bard, A. J. J. Am. Chem. Soc. 1979, 101, 3127.
(336) Panagiotopoulou, P.; Kondarides, D. I. J. Catal. 2004, 225, 327. (375) Dunn, W. W.; Aikawa, Y.; Bard, A. J. J. Am. Chem. Soc. 1981,
(337) Chudek, J. A.; McQuire, M. W.; McQuire, G. W.; Rochester, C. 103, 6893.
H. J. Chem. Soc., Faraday Trans. 1994, 90, 3699. (376) Yamaguti, K.; Sato, S. J. Chem. Soc., Faraday Trans. 1 1985, 81,
(338) Alibrando, M.; Hahm, H. S.; Wolf, E. E. Catal. Lett. 1997, 49, 1. 1237.
(339) Elmasides, C.; Kondarides, D. I.; Neophytides, S. G.; Verykios, (377) Sayama, K.; Arakawa, H. J. Chem. Soc., Chem. Commun. 1992,
X. E. J. Catal. 2001, 198, 195. 150.
(340) Perkas, N.; Zhong, Z.; Chen, L.; Besson, M.; Gedanken, A. (378) Sayama, K.; Arakawa, H. J. Chem. Soc., Faraday Trans. 1997, 93,
Catal. Lett. 2005, 103, 9. 1647.
(341) Kohno, Y.; Hayashi, H.; Takenaka, S.; Tanaka*, T.; Funabiki, (379) Abe, R.; Sayama, K.; Arakawa, H. Chem. Phys. Lett. 2003, 371,
T.; Yoshida, S. J. Photochem. Photobiol., A 1999, 126, 117. 360.
(342) Kohno, Y.; Yamamoto, T.; Tanaka, T.; Funabiki, T. J. Mol. (380) Kawai, T.; Sakata, T. J. Chem. Soc., Chem. Commun. 1980, 694.
Catal. A: Chem. 2001, 175, 173. (381) Sakata, T.; Kawai, T. Chem. Phys. Lett. 1981, 80, 341.
(343) Ibhadon, A. O.; Greenway, G. M.; Yue, Y. Catal. Commun. (382) Yang, Y. Z.; Chang, C. H.; Idriss, H. Appl. Catal., B 2006, 67,
2008, 9, 153. 217.
(344) Ibhadon, A. O.; Greenway, G. M.; Yue, Y.; Falaras, P.; (383) Daskalaki, V. M.; Kondarides, D. I. Catal. Today 2009, 144, 75.
Tsoukleris, D. J. Photochem. Photobiol., A 2008, 197, 321. (384) Gallo, A.; Montini, T.; Marelli, M.; Minguzzi, A.; Gombac, V.;
(345) Nada, A. A.; Hamed, H. A.; Barakat, M. H.; Mohamed, N. R.; Psaro, R.; Fornasiero, P.; Dal Santo, V. ChemSusChem 2012, 5, 1800.
Veziroglu, T. N. Int. J. Hydrogen Energy 2008, 33, 3264. (385) Lobo, R.; Marshall, C. L.; Dietrich, P. J.; Ribeiro, F. H.; Akatay,
(346) Liu, P.; Li, W.; Zhang, J.; Lin, Y. J. Mater. Res. 2011, 26, 1532. C.; Stach, E. A.; Mane, A.; Lei, Y.; Elam, J.; Miller, J. T. ACS Catal.
(347) Lin, F.; Zhang, Y.; Wang, L.; Zhang, Y.; Wang, D.; Yang, M.; 2012, 2, 2316.
Yang, J.; Zhang, B.; Jiang, Z.; Li, C. Appl. Catal., B 2012, 127, 363. (386) Languer, M. P.; Scheffer, F. R.; Feil, A. F.; Baptista, D. L.;
(348) Bowker, M.; James, D.; Stone, P.; Bennett, R.; Perkins, N.; Migowski, P.; Machado, G. J.; de Moraes, D. P.; Dupont, J.; Teixeira,
Millard, L.; Greaves, J.; Dickinson, A. J. Catal. 2003, 217, 427. S. R.; Weibel, D. E. Int. J. Hydrogen Energy 2013, 38, 14440.
(387) Naldoni, A.; DArienzo, M.; Altomare, M.; Marelli, M.; Scotti, (424) Sokmen, M.; Candan, F.; Sumer, Z. J. Photochem. Photobiol., A
R.; Morazzoni, F.; Selli, E.; Dal Santo, V. Appl. Catal., B 2013, 130 2001, 143, 241.
131, 239. (425) Keleher, J.; Bashant, J.; Heldt, N.; Johnson, L.; Li, Y. World J.
(388) Bamwenda, G. R.; Tsubota, S.; Nakamura, T.; Haruta, M. J. Microbiol. Biotechnol. 2002, 18, 133.
Photochem. Photobiol., A 1995, 89, 177. (426) Akhavan, O. J. Colloid Interface Sci. 2009, 336, 117.
(389) Galinska, A.; Walendziewski, J. Energy Fuel. 2005, 19, 1143. (427) Necula, B. S.; Fratila-Apachitei, L. E.; Zaat, S. A. J.; Apachitei,
(390) Ikuma, Y.; Bessho, H. Int. J. Hydrogen Energy 2007, 32, 2689. I.; Duszczyk, J. Acta Biomater. 2009, 5, 3573.
(391) Kitano, M.; Takeuchi, M.; Matsuoka, M.; Thomas, J. M.; Anpo, (428) Wu, T.-S.; Wang, K.-X.; Li, G.-D.; Sun, S.-Y.; Sun, J.; Chen, J.-
M. Catal. Today 2007, 120, 133. S. ACS Appl. Mater. Interfaces 2010, 2, 544.
(392) Patsoura, A.; Kondarides, D. I.; Verykios, X. E. Catal. Today (429) Li, M.; Noriega-Trevino, M. E.; Nino-Martinez, N.; Marambio-
2007, 124, 94. Jones, C.; Wang, J.; Damoiseaux, R.; Ruiz, F.; Hoek, E. M. V. Environ.
(393) Rosseler, O.; Shankar, M. V.; Du, M. K.-L.; Schmidlin, L.; Sci. Technol. 2011, 45, 8989.
Keller, N.; Keller, V. J. Catal. 2010, 269, 179. (430) Roguska, A.; Belcarz, A.; Piersiak, T.; Pisarek, M.; Ginalska, G.;
(394) Yoo, J. B.; Yoo, H. J.; Lim, B. W.; Lee, K. H.; Kim, M. H.; Lewandowska, M. Eur. J. Inorg. Chem. 2012, 2012, 5199.
Kang, D.; Hur, N. H. ChemSusChem 2012, 5, 2334. (431) Ohko, Y.; Tatsuma, T.; Fujii, T.; Naoi, K.; Niwa, C.; Kubota,
(395) Crittenden, J. C.; Liu, J.; Hand, D. W.; Perram, D. L. Water Res. Y.; Fujishima, A. Nat. Mater. 2003, 2, 29.
1997, 31, 429. (432) Naoi, K.; Ohko, Y.; Tatsuma, T. J. Am. Chem. Soc. 2004, 126,
(396) Yang, J. C.; Kim, Y. C.; Shul, Y. G.; Shin, C. H.; Lee, T. K. 3664.
Appl. Surf. Sci. 1997, 121122, 525. (433) Kawahara, K.; Suzuki, K.; Ohko, Y.; Tatsuma, T. Phys. Chem.
(397) Li, F. B.; Li, X. Z. Chemosphere 2002, 48, 1103. Chem. Phys. 2005, 7, 3851.
(398) Sun, B.; Vorontsov, A. V.; Smirniotis, P. G. Langmuir 2003, 19, (434) Naoi, K.; Ohko, Y.; Tatsuma, T. Chem. Commun. 2005, 1288.
3151. (435) Matsubara, K.; Tatsuma, T. Adv. Mater. 2007, 19, 2802.
(399) Sakthivel, S.; Shankar, M. V.; Palanichamy, M.; Arabindoo, B.; (436) Paramasivam, I.; Macak, J. M.; Ghicov, A.; Schmuki, P. Chem.
Bahnemann, D. W.; Murugesan, V. Water Res. 2004, 38, 3001. Phys. Lett. 2007, 445, 233.
(400) Wang, C.; Yin, L.; Zhang, L.; Liu, N.; Lun, N.; Qi, Y. ACS Appl. (437) Crespo-Monteiro, N.; Destouches, N.; Nadar, L.; Reynaud, S.;
Mater. Interfaces 2010, 2, 3373. Vocanson, F.; Michalon, J. Y. Appl. Phys. Lett. 2011, 99, 173106.
(401) Ismail, A. A.; Bahnemann, D. W. J. Phys. Chem. C 2011, 115, (438) Chiarello, G. L.; Aguirre, M. H.; Selli, E. J. Catal. 2010, 273,
5784. 182.
(402) Wu, H.-S.; Sun, L.-D.; Zhou, H.-P.; Yan, C.-H. Nanoscale 2012, (439) Awazu, K.; Fujimaki, M.; Rockstuhl, C.; Tominaga, J.;
4, 3242. Murakami, H.; Ohki, Y.; Yoshida, N.; Watanabe, T. J. Am. Chem.
(403) Lee, S.; Scott, J.; Chiang, K.; Amal, R. J. Nanopart. Res. 2009, Soc. 2008, 130, 1676.
11, 209. (440) Pastoriza-Santos, I.; Koktysh, D. S.; Mamedov, A. A.; Giersig,
(404) Chung, Y. W.; Lo, W. J.; Somorjai, G. A. Surf. Sci. 1977, 64, M.; Kotov, N. A.; Liz-Marzan, L. M. Langmuir 2000, 16, 2731.
588. (441) Koktysh, D. S.; Liang, X.; Yun, B. G.; Pastoriza-Santos, I.;
(405) Kandiel, T. A.; Ismail, A. A.; Bahnemann, D. W. Phys. Chem. Matts, R. L.; Giersig, M.; Serra-Rodrguez, C.; Liz-Marzan, L. M.;
Chem. Phys. 2011, 13, 20155. Kotov, N. A. Adv. Funct. Mater. 2002, 12, 255.
(406) Yu, J.; Qi, L.; Jaroniec, M. J. Phys. Chem. C 2010, 114, 13118. (442) Tom, R. T.; Nair, A. S.; Singh, N.; Aslam, M.; Nagendra, C. L.;
(407) Han, X.; Kuang, Q.; Jin, M.; Xie, Z.; Zheng, L. J. Am. Chem. Philip, R.; Vijayamohanan, K.; Pradeep, T. Langmuir 2003, 19, 3439.
Soc. 2009, 131, 3152. (443) Du, J.; Zhang, J.; Liu, Z.; Han, B.; Jiang, T.; Huang, Y.
(408) Beck, K. M.; Sasaki, T.; Koshizaki, N. Chem. Phys. Lett. 1999, Langmuir 2006, 22, 1307.
301, 336. (444) Sakai, H.; Kanda, T.; Shibata, H.; Ohkubo, T.; Abe, M. J. Am.
(409) Furube, A.; Asahi, T.; Masuhara, H.; Yamashita, H.; Anpo, M. Chem. Soc. 2006, 128, 4944.
Chem. Phys. Lett. 2001, 336, 424. (445) Demirors, A. F.; van Blaaderen, A.; Imhof, A. Langmuir 2010,
(410) Chen, H.-W.; Ku, Y.; Kuo, Y.-L. Water Res. 2007, 41, 2069. 26, 9297.
(411) Vijayan, B. K.; Dimitrijevic, N. M.; Wu, J.; Gray, K. A. J. Phys. (446) Hirakawa, T.; Kamat, P. V. Langmuir 2004, 20, 5645.
Chem. C 2010, 114, 21262. (447) Hirakawa, T.; Kamat, P. V. J. Am. Chem. Soc. 2005, 127, 3928.
(412) Kondo, M. M.; Jardim, W. F. Water Res. 1991, 25, 823. (448) Vik, H.; Andersen, K. J.; Julshamn, K.; Todnem, K. Lancet
(413) Sclafani, A.; Mozzanega, M.-N.; Pichat, P. J. Photochem. 1985, 325, 872.
Photobiol., A 1991, 59, 181. (449) Shastri, A. G.; Datye, A. K.; Schwank, J. J. Catal. 1984, 87, 265.
(414) Lee, W.; Shen, H. S.; Dwight, K.; Wold, A. J. Solid State Chem. (450) Haruta, M.; Tsubota, S.; Kobayashi, T.; Kageyama, H.; Genet,
1993, 106, 288. M. J.; Delmon, B. J. Catal. 1993, 144, 175.
(415) Vamathevan, V.; Amal, R.; Beydoun, D.; Low, G.; McEvoy, S. J. (451) Bamwenda, G. R.; Tsubota, S.; Nakamura, T.; Haruta, M.
Photochem. Photobiol., A 2002, 148, 233. Catal. Lett. 1997, 44, 83.
(416) Sudeep, P. K.; Takechi, K.; Kamat, P. V. J. Phys. Chem. C 2006, (452) Boccuzzi, F.; Chiorino, A.; Manzoli, M.; Lu, P.; Akita, T.;
111, 488. Ichikawa, S.; Haruta, M. J. Catal. 2001, 202, 256.
(417) Standridge, S. D.; Schatz, G. C.; Hupp, J. T. J. Am. Chem. Soc. (453) Wolf, A.; Schuth, F. Appl. Catal., A 2002, 226, 1.
2009, 131, 8407. (454) Overbury, S. H.; Schwartz, V.; Mullins, D. R.; Yan, W.; Dai, S.
(418) Jeong, N. C.; Prasittichai, C.; Hupp, J. T. Langmuir 2011, 27, J. Catal. 2006, 241, 56.
14609. (455) Lee, I.; Joo, J. B.; Yin, Y.; Zaera, F. Angew. Chem., Int. Ed. 2011,
(419) Lin, S.-J.; Lee, K.-C.; Wu, J.-L.; Wu, J.-Y. Appl. Phys. Lett. 2011, 50, 10208.
99, 043306. (456) Greaves, J.; Al-Mazroai, L.; Nuhu, A.; Davies, P.; Bowker, M.
(420) Qi, J.; Dang, X.; Hammond, P. T.; Belcher, A. M. ACS Nano Gold Bull. 2006, 39, 216.
2011, 5, 7108. (457) Bowker, M.; Davies, P.; Al-Mazroai, L. Catal. Lett. 2009, 128,
(421) Sun, M.; Fu, W.; Yang, H.; Sui, Y.; Zhao, B.; Yin, G.; Li, Q.; 253.
Zhao, H.; Zou, G. Electrochem. Commun. 2011, 13, 1324. (458) Iwase, A.; Kato, H.; Kudo, A. Catal. Lett. 2006, 108, 7.
(422) Lin, S.-J.; Lee, K.-C.; Wu, J.-L.; Wu, J.-Y. Sol. Energy 2012, 86, (459) Dillon, R. J.; Joo, J.-B.; Zaera, F.; Yin, Y.; Bardeen, C. J. Phys.
2600. Chem. Chem. Phys. 2013, 15, 1488.
(423) Zhang, X.; Liu, J.; Li, S.; Tan, X.; Yu, M.; Du, J. RSC Adv. 2013, (460) Gomes Silva, C.; Juarez, R.; Marino, T.; Molinari, R.; Garca,
3, 18587. H. J. Am. Chem. Soc. 2010, 133, 595.
(461) Goebl, J.; Joo, J. B.; Dahl, M.; Yin, Y. Catal. Today 2014, 225, (495) Murray, C. B.; Norris, D. J.; Bawendi, M. G. J. Am. Chem. Soc.
90. 1993, 115, 8706.
(462) Bowker, M.; Millard, L.; Greaves, J.; James, D.; Soares, J. Gold (496) Peng, X.; Wickham, J.; Alivisatos, A. P. J. Am. Chem. Soc. 1998,
Bull. 2004, 37, 170. 120, 5343.
(463) Wu, G.; Chen, T.; Su, W.; Zhou, G.; Zong, X.; Lei, Z.; Li, C. (497) Peng, Z. A.; Peng, X. J. Am. Chem. Soc. 2000, 123, 183.
Int. J. Hydrogen Energy 2008, 33, 1243. (498) Al Salman, A.; Tortschanoff, A.; Mohamed, M. B.; Tonti, D.;
(464) Chiarello, G. L.; Ferri, D.; Selli, E. J. Catal. 2011, 280, 168. van Mourik, F.; Chergui, M. Appl. Phys. Lett. 2007, 90, 093104.
(465) Puga, A. V.; Forneli, A.; Garca, H.; Corma, A. Adv. Funct. (499) Milliron, D. J.; Hughes, S. M.; Cui, Y.; Manna, L.; Li, J.; Wang,
Mater. 2013, n/a. L.-W.; Paul Alivisatos, A. Nature 2004, 430, 190.
(466) Murdoch, M.; Waterhouse, G. I. N.; Nadeem, M. A.; Metson, J. (500) Yin, Y.; Alivisatos, A. P. Nature 2005, 437, 664.
B.; Keane, M. A.; Howe, R. F.; Llorca, J.; Idriss, H. Nat. Chem. 2011, 3, (501) Peng, X.; Manna, L.; Yang, W.; Wickham, J.; Scher, E.;
489. Kadavanich, A.; Alivisatos, A. P. Nature 2000, 404, 59.
(467) Boccuzzi, F.; Chiorino, A.; Manzoli, M.; Andreeva, D.; (502) Huynh, W. U.; Dittmer, J. J.; Alivisatos, A. P. Science 2002, 295,
Tabakova, T. J. Catal. 1999, 188, 176. 2425.
(468) Rebrov, E. V.; Berenguer-Murcia, A.; Johnson, B. F. G.; (503) Robel, I.; Subramanian, V.; Kuno, M.; Kamat, P. V. J. Am.
Schouten, J. C. Catal. Today 2008, 138, 210. Chem. Soc. 2006, 128, 2385.
(469) Shekhar, M.; Wang, J.; Lee, W.-S.; Williams, W. D.; Kim, S. M.; (504) Kamat, P. V. J. Phys. Chem. C 2008, 112, 18737.
Stach, E. A.; Miller, J. T.; Delgass, W. N.; Ribeiro, F. H. J. Am. Chem. (505) Kongkanand, A.; Tvrdy, K.; Takechi, K.; Kuno, M.; Kamat, P.
Soc. 2012, 134, 4700. V. J. Am. Chem. Soc. 2008, 130, 4007.
(470) Orlov, A.; Jefferson, D.; Macleod, N.; Lambert, R. Catal. Lett. (506) Lee, Y.-L.; Huang, B.-M.; Chien, H.-T. Chem. Mater. 2008, 20,
2004, 92, 41. 6903.
(471) Bian, Z.; Zhu, J.; Cao, F.; Lu, Y.; Li, H. Chem. Commun. 2009, (507) Sun, W.-T.; Yu, Y.; Pan, H.-Y.; Gao, X.-F.; Chen, Q.; Peng, L.-
3789. M. J. Am. Chem. Soc. 2008, 130, 1124.
(472) Wu, X.-F.; Song, H.-Y.; Yoon, J.-M.; Yu, Y.-T.; Chen, Y.-F. (508) Lee, H.; Wang, M.; Chen, P.; Gamelin, D. R.; Zakeeruddin, S.
Langmuir 2009, 25, 6438. M.; Gratzel, M.; Nazeeruddin, M. K. Nano Lett. 2009, 9, 4221.
(473) Wu, Y.; Liu, H.; Zhang, J.; Chen, F. J. Phys. Chem. C 2009, 113, (509) Bang, J. H.; Kamat, P. V. Adv. Funct. Mater. 2010, 20, 1970.
(510) Genovese, M. P.; Lightcap, I. V.; Kamat, P. V. ACS Nano 2011,
14689.
(474) Zhang, Q.; Lima, D. Q.; Lee, I.; Zaera, F.; Chi, M.; Yin, Y. 6, 865.
(511) Zhu, Z.; Qiu, J.; Yan, K.; Yang, S. ACS Appl. Mater. Interfaces
Angew. Chem. 2011, 123, 7226.
2013, 5, 4000.
(475) Ismail, A. A.; Hakki, A.; Bahnemann, D. W. J. Mol. Catal. A:
(512) Fujii, H.; Ohtaki, M.; Eguchi, K.; Arai, H. J. Mater. Sci. Lett.
Chem. 2012, 358, 145.
1997, 16, 1086.
(476) Su, R.; Tiruvalam, R.; He, Q.; Dimitratos, N.; Kesavan, L.;
(513) Jang, J. S.; Li, W.; Oh, S. H.; Lee, J. S. Chem. Phys. Lett. 2006,
Hammond, C.; Lopez-Sanchez, J. A.; Bechstein, R.; Kiely, C. J.;
425, 278.
Hutchings, G. J.; Besenbacher, F. ACS Nano 2012, 6, 6284. (514) Park, H.; Choi, W.; Hoffmann, M. R. J. Mater. Chem. 2008, 18,
(477) Sellappan, R.; Nielsen, M. G.; Gonzalez-Posada, F.; Vesborg, P. 2379.
C. K.; Chorkendorff, I.; Chakarov, D. J. Catal. 2013, 307, 214. (515) Daskalaki, V. M.; Antoniadou, M.; Li Puma, G.; Kondarides, D.
(478) Nozik, A. J. Appl. Phys. Lett. 1976, 29, 150. I.; Lianos, P. Environ. Sci. Technol. 2010, 44, 7200.
(479) Tamura, H.; Yoneyama, H.; Iwakura, C.; Sakamoto, H.; (516) Li, Q.; Guo, B.; Yu, J.; Ran, J.; Zhang, B.; Yan, H.; Gong, J. R. J.
Murakami, S. J. Electroanal. Chem. Interfacial Electrochem. 1977, 80, Am. Chem. Soc. 2011, 133, 10878.
357. (517) Bessekhouad, Y.; Chaoui, N.; Trzpit, M.; Ghazzal, N.; Robert,
(480) Ohashi, K.; McCann, J.; Bockris, J. O. M. Nature 1977, 266, D.; Weber, J. V. J. Photochem. Photobiol., A 2006, 183, 218.
610. (518) Tristao, J. C.; Magalhaes, F.; Corio, P.; Sansiviero, M. T. C. J.
(481) Ren, S.; Zhao, N.; Crawford, S. C.; Tambe, M.; Bulovic, V.; Photochem. Photobiol., A 2006, 181, 152.
Gradecak, S. Nano Lett. 2010, 11, 408. (519) Meng, H. L.; Cui, C.; Shen, H. L.; Liang, D. Y.; Xue, Y. Z.; Li,
(482) Nedeljkovic, J. M.; Micic, O. I.; Ahrenkiel, S. P.; Miedaner, A.; P. G.; Tang, W. H. J. Alloys Compd. 2012, 527, 30.
Nozik, A. J. J. Am. Chem. Soc. 2004, 126, 2632. (520) Hyun, B.-R.; Zhong, Y.-W.; Bartnik, A. C.; Sun, L.; Abruna, H.
(483) Wang, J.-H.; Lin, M. C. ChemPhysChem 2004, 5, 1615. D.; Wise, F. W.; Goodreau, J. D.; Matthews, J. R.; Leslie, T. M.;
(484) Yu, P.; Zhu, K.; Norman, A. G.; Ferrere, S.; Frank, A. J.; Nozik, Borrelli, N. F. ACS Nano 2008, 2, 2206.
A. J. J. Phys. Chem. B 2006, 110, 25451. (521) Ratanatawanate, C.; Xiong, C.; Balkus, K. J. ACS Nano 2008, 2,
(485) Wang, T.-T.; Raghunath, P.; Lu, Y.-F.; Liu, Y.-C.; Chiou, C.-H.; 1682.
Lin, M. C. Chem. Phys. Lett. 2011, 510, 126. (522) Acharya, K. P.; Hewa-Kasakarage, N. N.; Alabi, T. R.; Nemitz,
(486) Wu, C.-W.; Lu, C.-W.; Lee, Y.-P.; Wu, Y.-J.; Cheng, B.-M.; Lin, I.; Khon, E.; Ullrich, B.; Anzenbacher, P.; Zamkov, M. J. Phys. Chem. C
M. C. J. Mater. Chem. 2011, 21, 8540. 2010, 114, 12496.
(487) Gerischer, H.; Lubke, M. J. Electroanal. Chem. Interfacial (523) Leventis, H. C.; OMahony, F.; Akhtar, J.; Afzaal, M.; OBrien,
Electrochem. 1986, 204, 225. P.; Haque, S. A. J. Am. Chem. Soc. 2010, 132, 2743.
(488) Vogel, R.; Pohl, K.; Weller, H. Chem. Phys. Lett. 1990, 174, (524) Kang, Q.; Liu, S.; Yang, L.; Cai, Q.; Grimes, C. A. ACS Appl.
241. Mater. Interfaces 2011, 3, 746.
(489) Kohtani, S.; Kudo, A.; Sakata, T. Chem. Phys. Lett. 1993, 206, (525) Bubenhofer, S. B.; Schumacher, C. M.; Koehler, F. M.;
166. Luechinger, N. A.; Grass, R. N.; Stark, W. J. J. Phys. Chem. C 2012,
(490) Liu, D.; Kamat, P. V. J. Electroanal. Chem. 1993, 347, 451. 116, 16264.
(491) Hao, E.; Yang, B.; Zhang, J.; Zhang, X.; Sun, J.; Shen, J. J. (526) Yang, C.; Wang, W.; Shan, Z.; Huang, F. J. Solid State Chem.
Mater. Chem. 1998, 8, 1327. 2009, 182, 807.
(492) Peng, X.; Schlamp, M. C.; Kadavanich, A. V.; Alivisatos, A. P. J. (527) Koteeswara Reddy, N.; Devika, M.; Ahsanulhaq, Q.;
Am. Chem. Soc. 1997, 119, 7019. Gunasekhar, K. R. Cryst. Growth Des. 2010, 10, 4769.
(493) Li, J. J.; Wang, Y. A.; Guo, W.; Keay, J. C.; Mishima, T. D.; (528) Wang, Y.; Gong, H.; Fan, B.; Hu, G. J. Phys. Chem. C 2010,
Johnson, M. B.; Peng, X. J. Am. Chem. Soc. 2003, 125, 12567. 114, 3256.
(494) Goebl, J. A.; Black, R. W.; Puthussery, J.; Giblin, J.; Kosel, T. (529) Guo, W.; Shen, Y.; Wu, M.; Ma, T. Chem. Commun. 2012, 48,
H.; Kuno, M. J. Am. Chem. Soc. 2008, 130, 14822. 6133.
(530) Neumann, B.; Bogdanoff, P.; Tributsch, H. J. Phys. Chem. C (565) Pyrgiotakis, G.; Lee, S.-H.; Sigmund, W. MRS Online Proc. Libr.
2009, 113, 20980. 2005, 876, null.
(531) Wenger, S.; Seyrling, S.; Tiwari, A. N.; Gratzel, M. Appl. Phys. (566) Wang, S.; Gong, Q.; Zhu, Y.; Liang, J. Appl. Surf. Sci. 2009, 255,
Lett. 2009, 94, 173508. 8063.
(532) Daisuke, Y.; Tsutomu, M.; Kazuo, J.; Takashi, H.; Guijun, M.; (567) Oh, W.-C.; Zhang, F.-J.; Chen, M.-L. J. Indust. Eng. Chem.
Masao, K.; Jun, K.; Hironori, K.; Kazunari, D. Appl. Phys. Express 2010, 2010, 16, 321.
3, 101202. (568) Lee, T. Y.; Alegaonkar, P. S.; Yoo, J.-B. Thin Solid Films 2007,
(533) Dai, P.; Zhang, G.; Chen, Y.; Jiang, H.; Feng, Z.; Lin, Z.; Zhan, 515, 5131.
J. Chem. Commun. 2012, 48, 3006. (569) Muduli, S.; Lee, W.; Dhas, V.; Mujawar, S.; Dubey, M.;
(534) Rovelli, L.; Tilley, S. D.; Sivula, K. ACS Appl. Mater. Interfaces Vijayamohanan, K.; Han, S.-H.; Ogale, S. ACS Appl. Mater. Interfaces
2013, 5, 8018. 2009, 1, 2030.
(535) Wang, Y.; Li, C.; Yin, X.; Wang, H.; Gong, H. ECS J. Solid State (570) Chen, J.; Li, B.; Zheng, J.; Zhao, J.; Zhu, Z. J. Phys. Chem. C
Sci. Technol. 2013, 2, Q95. 2012, 116, 14848.
(536) Nanu, M.; Schoonman, J.; Goossens, A. Nano Lett. 2005, 5, (571) Dembele, K. T.; Selopal, G. S.; Soldano, C.; Nechache, R.;
1716. Rimada, J. C.; Concina, I.; Sberveglieri, G.; Rosei, F.; Vomiero, A. J.
(537) Nanu, M.; Schoonman, J.; Goossens, A. Adv. Funct. Mater. Phys. Chem. C 2013, 117, 14510.
2005, 15, 95. (572) Zhang, X.; Liu, J.; Li, S.; Tan, X.; Zhang, J.; Yu, M.; Zhao, M. J.
(538) OHayre, R.; Nanu, M.; Schoonman, J.; Goossens, A.; Wang, Mater. Chem. A 2013, 1, 11070.
Q.; Gratzel, M. Adv. Funct. Mater. 2006, 16, 1566. (573) Moriguchi, I.; Hidaka, R.; Yamada, H.; Kudo, T.; Murakami,
(539) Yun, J.-H.; Ng, Y. H.; Huang, S.; Conibeer, G.; Amal, R. Chem. H.; Nakashima, N. Adv. Mater. 2006, 18, 69.
Commun. 2011, 47, 11288. (574) Cao, F.-F.; Guo, Y.-G.; Zheng, S.-F.; Wu, X.-L.; Jiang, L.-Y.; Bi,
(540) Chang, J.-Y.; Lin, J.-M.; Su, L.-F.; Chang, C.-F. ACS Appl. R.-R.; Wan, L.-J.; Maier, J. Chem. Mater. 2010, 22, 1908.
Mater. Interfaces 2013, 5, 8740. (575) Hyder, M. N.; Gallant, B. M.; Shah, N. J.; Shao-Horn, Y.;
(541) Santra, P. K.; Nair, P. V.; George Thomas, K.; Kamat, P. V. J. Hammond, P. T. Nano Lett. 2013, 13, 4610.
Phys. Chem. Lett. 2013, 4, 722. (576) Zhang, P.; Qiu, J.; Zheng, Z.; Liu, G.; Ling, M.; Martens, W.;
(542) Kang, S.-Z.; Yang, Y.-K.; Bu, W.; Mu, J. J. Solid State Chem. Wang, H.; Zhao, H.; Zhang, S. Electrochim. Acta 2013, 104, 41.
2009, 182, 2972. (577) Zhou, H.; Liu, L.; Wang, X.; Liang, F.; Bao, S.; Lv, D.; Tang,
(543) Liu, R.; Liu, Y.; Liu, C.; Luo, S.; Teng, Y.; Yang, L.; Yang, R.; Y.; Jia, D. J. Mater. Chem. A 2013, 1, 8525.
Cai, Q. J. Alloys Compd. 2011, 509, 2434. (578) Huang, J.-H.; Fang, J.-H.; Liu, C.-C.; Chu, C.-W. ACS Nano
(544) Shen, F.; Que, W.; Liao, Y.; Yin, X. Ind. Eng. Chem. Res. 2011, 2011, 5, 6262.
50, 9131. (579) Song, S. M.; Park, J. K.; Sul, O. J.; Cho, B. J. Nano Lett. 2012,
(545) Monthioux, M.; Kuznetsov, V. L. Carbon 2006, 44, 1621. 12, 3887.
(546) Iijima, S. Nature 1991, 354, 56. (580) Hummers, W. S.; Offeman, R. E. J. Am. Chem. Soc. 1958, 80,
(547) Shiraishi, M.; Ata, M. Carbon 2001, 39, 1913. 1339.
(548) Vincent, P.; Brioude, A.; Journet, C.; Rabaste, S.; Purcell, S. T.; (581) Marcano, D. C.; Kosynkin, D. V.; Berlin, J. M.; Sinitskii, A.;
Le Brusq, J.; Plenet, J. C. J. Non-Cryst. Solids 2002, 311, 130. Sun, Z.; Slesarev, A.; Alemany, L. B.; Lu, W.; Tour, J. M. ACS Nano
(549) Hernadi, K.; Ljubovic, E.; Seo, J. W.; Forro, L. Acta Mater. 2010, 4, 4806.
2003, 51, 1447. (582) Nethravathi, C.; Rajamathi, M. Carbon 2008, 46, 1994.
(550) Jitianu, A.; Cacciaguerra, T.; Benoit, R.; Delpeux, S.; Beguin, (583) Zhu, C.; Guo, S.; Wang, P.; Xing, L.; Fang, Y.; Zhai, Y.; Dong,
F.; Bonnamy, S. Carbon 2004, 42, 1147. S. Chem. Commun. 2010, 46, 7148.
(551) Jitianu, A.; Cacciaguerra, T.; Berger, M.-H.; Benoit, R.; Beguin, (584) Kim, S. R.; Parvez, M. K.; Chhowalla, M. Chem. Phys. Lett.
F.; Bonnamy, S. J. Non-Cryst. Solids 2004, 345346, 596. 2009, 483, 124.
(552) Ahmmad, B.; Kusumoto, Y.; Somekawa, S.; Ikeda, M. Catal. (585) He, Z.; Guai, G.; Liu, J.; Guo, C.; Chye Loo, J. S.; Li, C. M.;
Commun. 2008, 9, 1410. Tan, T. T. Y. Nanoscale 2011, 3, 4613.
(553) Cargnello, M.; Grzelczak, M.; Rodrguez-Gonzalez, B.; (586) Chang, J.; Yang, J.; Ma, P.; Wu, D.; Tian, L.; Gao, Z.; Jiang, K.;
Syrgiannis, Z.; Bakhmutsky, K.; La Parola, V.; Liz-Marzan, L. M.; Yang, L. J. Colloid Interface Sci. 2013, 394, 231.
Gorte, R. J.; Prato, M.; Fornasiero, P. J. Am. Chem. Soc. 2012, 134, (587) Chen, J. S.; Wang, Z.; Dong, X. C.; Chen, P.; Lou, X. W.
11760. Nanoscale 2011, 3, 2158.
(554) Khan, G.; Choi, S. K.; Kim, S.; Lim, S. K.; Jang, J. S.; Park, H. (588) Wang, D.; Choi, D.; Li, J.; Yang, Z.; Nie, Z.; Kou, R.; Hu, D.;
Appl. Catal., B 2013, 142143, 647. Wang, C.; Saraf, L. V.; Zhang, J.; Aksay, I. A.; Liu, J. ACS Nano 2009,
(555) Veluru, J. B.; Manippady, K. K.; Rajendiren, M.; Mya Mya, K.; 3, 907.
Rayavarapu, P. R.; Appukuttan, S. N.; Seeram, R. Int. J. Hydrogen (589) Yang, S.; Feng, X.; Mullen, K. Adv. Mater. 2011, 23, 3575.
Energy 2013, 38, 4324. (590) Xin, X.; Zhou, X.; Wu, J.; Yao, X.; Liu, Z. ACS Nano 2012, 6,
(556) Yu, Y.; Yu, J. C.; Chan, C.-Y.; Che, Y.-K.; Zhao, J.-C.; Ding, L.; 11035.
Ge, W.-K.; Wong, P.-K. Appl. Catal., B 2005, 61, 1. (591) Zhang, X.; Suresh Kumar, P.; Aravindan, V.; Liu, H. H.;
(557) Yao, Y.; Li, G.; Ciston, S.; Lueptow, R. M.; Gray, K. A. Environ. Sundaramurthy, J.; Mhaisalkar, S. G.; Duong, H. M.; Ramakrishna, S.;
Sci. Technol. 2008, 42, 4952. Madhavi, S. J. Phys. Chem. C 2012, 116, 14780.
(558) Tettey, K. E.; Yee, M. Q.; Lee, D. ACS Appl. Mater. Interfaces (592) Hu, T.; Sun, X.; Sun, H.; Yu, M.; Lu, F.; Liu, C.; Lian, J. Carbon
2010, 2, 2646. 2013, 51, 322.
(559) Xu, Y.-J.; Zhuang, Y.; Fu, X. J. Phys. Chem. C 2010, 114, 2669. (593) Zhang, H.; Lv, X.; Li, Y.; Wang, Y.; Li, J. ACS Nano 2009, 4,
(560) Li, Z.; Gao, B.; Chen, G. Z.; Mokaya, R.; Sotiropoulos, S.; Li 380.
Puma, G. Appl. Catal., B 2011, 110, 50. (594) Liang, Y.; Wang, H.; Sanchez Casalongue, H.; Chen, Z.; Dai,
(561) Liu, B.; Zeng, H. C. Chem. Mater. 2008, 20, 2711. H. Nano Res. 2010, 3, 701.
(562) Woan, K.; Pyrgiotakis, G.; Sigmund, W. Adv. Mater. 2009, 21, (595) Ng, Y. H.; Lightcap, I. V.; Goodwin, K.; Matsumura, M.;
2233. Kamat, P. V. J. Phys. Chem. Lett. 2010, 1, 2222.
(563) Hoffmann, M. R.; Martin, S. T.; Choi, W.; Bahnemann, D. W. (596) Zhang, Y.; Tang, Z.-R.; Fu, X.; Xu, Y.-J. ACS Nano 2010, 4,
Chem. Rev. 1995, 95, 69. 7303.
(564) Wang, W.; Serp, P.; Kalck, P.; Faria, J. L. J. Mol. Catal. A: Chem. (597) Zhang, Y.; Pan, C. J. Mater. Sci. 2011, 46, 2622.
2005, 235, 194. (598) Lee, J. S.; You, K. H.; Park, C. B. Adv. Mater. 2012, 24, 1084.
(599) Pan, X.; Zhao, Y.; Liu, S.; Korzeniewski, C. L.; Wang, S.; Fan, (637) Hanprasopwattana, A.; Srinivasan, S.; Sault, A. G.; Datye, A. K.
Z. ACS Appl. Mater. Interfaces 2012, 4, 3944. Langmuir 1996, 12, 3173.
(600) Perera, S. D.; Mariano, R. G.; Vu, K.; Nour, N.; Seitz, O.; (638) Guo, X.-C.; Dong, P. Langmuir 1999, 15, 5535.
Chabal, Y.; Balkus, K. J. ACS Catal. 2012, 2, 949. (639) Zhou, J.; Chen, M.; Qiao, X.; Wu, L. Langmuir 2006, 22,
(601) Wang, Z.; Huang, B.; Dai, Y.; Liu, Y.; Zhang, X.; Qin, X.; 10175.
Wang, J.; Zheng, Z.; Cheng, H. CrystEngComm 2012, 14, 1687. (640) Chen, J. S.; Luan, D.; Li, C. M.; Boey, F. Y. C.; Qiao, S.; Lou,
(602) Zhang, J.; Zhu, Z.; Tang, Y.; Feng, X. J. Mater. Chem. A 2013, X. W. Chem. Commun. 2010, 46, 8252.
1, 3752. (641) Zhang, K.; Zhang, X.; Chen, H.; Chen, X.; Zheng, L.; Zhang, J.;
(603) Torimoto, T.; Ito, S.; Kuwabata, S.; Yoneyama, H. Environ. Sci. Yang, B. Langmuir 2004, 20, 11312.
Technol. 1996, 30, 1275. (642) Joo, J. B.; Zhang, Q.; Lee, I.; Dahl, M.; Zaera, F.; Yin, Y. Adv.
(604) Herrmann, J.-M.; Matos, J.; Disdier, J.; Guillard, C.; Laine, J.; Funct. Mater. 2012, 22, 166.
Malato, S.; Blanco, J. Catal. Today 1999, 54, 255. (643) Dahl, M.; Dang, S.; Bong Joo, J.; Zhang, Q.; Yin, Y.
(605) Matos, J.; Laine, J.; Herrmann, J. M. J. Catal. 2001, 200, 10. CrystEngComm 2012, 14, 7680.
(606) Arana, J.; Dona-Rodrguez, J. M.; Tello Rendon, E.; Garriga i (644) Joo, J. B.; Zhang, Q.; Dahl, M.; Lee, I.; Goebl, J.; Zaera, F.; Yin,
Cabo, C.; Gonzalez-Daz, O.; Herrera-Melian, J. A.; Perez-Pena, J.; Y. Energy Environ. Sci. 2012, 5, 6321.
Colon, G.; Navo, J. A. Appl. Catal., B 2003, 44, 153. (645) Shen, H. L.; Hu, H. H.; Liang, D. Y.; Meng, H. L.; Li, P. G.;
(607) da Silva, C. G.; Faria, J. L. s. J. Photochem. Photobiol., A 2003, Tang, W. H.; Cui, C. J. Alloys Compd. 2012, 542, 32.
155, 133. (646) Liang, X.; Li, J.; Joo, J. B.; Gutierrez, A.; Tillekaratne, A.; Lee,
(608) Arana, J.; Dona-Rodrguez, J. M.; Cabo, C. G. i.; Gonzalez- I.; Yin, Y.; Zaera, F. Angew. Chem., Int. Ed. 2012, 51, 8034.
Daz, O.; Herrera-Melian, J. A.; Perez-Pena, J. Appl. Catal., B 2004, 53, (647) Li, J.; Liang, X.; Joo, J. B.; Lee, I.; Yin, Y.; Zaera, F. J. Phys.
221. Chem. C 2013, 117, 20043.
(609) Nagaoka, S.; Hamasaki, Y.; Ishihara, S.-i.; Nagata, M.; Iio, K.; (648) Aronson, B. J.; Blanford, C. F.; Stein, A. Chem. Mater. 1997, 9,
Nagasawa, C.; Ihara, H. J. Mol. Catal. A: Chem. 2002, 177, 255. 2842.
(610) Xu, C.; Killmeyer, R.; Gray, M. L.; Khan, S. U. M. Appl. Catal., (649) Zheng, S.; Gao, L.; Zhang, Q.; Sun, J. J. Solid State Chem. 2001,
B 2006, 64, 312. 162, 138.
(611) Yun, S.-M.; Palanivelu, K.; Kim, Y.-H.; Kang, P.-H.; Lee, Y.-S. J. (650) Bhattacharyya, A.; Kawi, S.; Ray, M. B. Catal. Today 2004, 98,
Indust. Eng. Chem. 2008, 14, 667. 431.
(612) Zhang, L.-W.; Fu, H.-B.; Zhu, Y.-F. Adv. Funct. Mater. 2008, 18, (651) Do, Y.-J.; Kim, J.-H.; Park, J.-H.; Park, S.-S.; Hong, S.-S.; Suh,
2180. C.-S.; Lee, G.-D. Catal. Today 2005, 101, 299.
(613) Zhao, L.; Chen, X.; Wang, X.; Zhang, Y.; Wei, W.; Sun, Y.; (652) Ding, H.; Sun, H.; Shan, Y. J. Photochem. Photobiol., A 2005,
Antonietti, M.; Titirici, M.-M. Adv. Mater. 2010, 22, 3317. 169, 101.
(614) Park, S.-J.; Kim, H.; Kim, Y.-J.; Lee, H. Electrochim. Acta 2011, (653) Lopez-Munoz, M.-J.; Grieken, R. v.; Aguado, J.; Marugan, J.
56, 5355.
Catal. Today 2005, 101, 307.
(615) Ming, J.; Wu, Y.; Nagarajan, S.; Lee, D.-J.; Sun, Y.-K.; Zhao, F.
(654) Busuioc, A. M.; Meynen, V.; Beyers, E.; Mertens, M.; Cool, P.;
J. Mater. Chem. 2012, 22, 22135.
Bilba, N.; Vansant, E. F. Appl. Catal., A 2006, 312, 153.
(616) Wang, W.; Sa, Q.; Chen, J.; Wang, Y.; Jung, H.; Yin, Y. ACS
(655) Wang, W.; Song, M. Microporous Mesoporous Mater. 2006, 96,
Appl. Mater. Interfaces 2013, 5, 6478.
255.
(617) Zheng, R.; Meng, X.; Tang, F. J. Solid State Chem. 2009, 182,
(656) Yang, J.; Zhang, J.; Zhu, L.; Chen, S.; Zhang, Y.; Tang, Y.; Zhu,
1235.
(618) Shiho, H.; Kawahashi, N. Colloid Polym. Sci. 2000, 278, 270. Y.; Li, Y. J. Hazard. Mater. 2006, 137, 952.
(619) Zhong, Z.; Yin, Y.; Gates, B.; Xia, Y. Adv. Mater. 2000, 12, 206. (657) Wang, Z.; Zhang, F.; Yang, Y.; Xue, B.; Cui, J.; Guan, N. Chem.
(620) Caruso, R. A.; Susha, A.; Caruso, F. Chem. Mater. 2001, 13, Mater. 2007, 19, 3286.
400. (658) Zhang, Z.; Zuo, F.; Feng, P. J. Mater. Chem. 2010, 20, 2206.
(621) Imhof, A. Langmuir 2001, 17, 3579. (659) Zhao, D.; Budhi, S.; Rodriguez, A.; Koodali, R. T. Int. J.
(622) Cheng, X.; Chen, M.; Wu, L.; Gu, G. Langmuir 2006, 22, 3858. Hydrogen Energy 2010, 35, 5276.
(623) Wang, P.; Chen, D.; Tang, F.-Q. Langmuir 2006, 22, 4832. (660) Peng, R.; Zhao, D.; Dimitrijevic, N. M.; Rajh, T.; Koodali, R. T.
(624) Syoufian, A.; Inoue, Y.; Yada, M.; Nakashima, K. Mater. Lett. J. Phys. Chem. C 2011, 116, 1605.
2007, 61, 1572. (661) Yue, W.; Randorn, C.; Attidekou, P. S.; Su, Z.; Irvine, J. T. S.;
(625) Syoufian, A.; Satriya, O. H.; Nakashima, K. Catal. Commun. Zhou, W. Adv. Funct. Mater. 2009, 19, 2826.
2007, 8, 755. (662) Yue, W.; Xu, X.; Irvine, J. T. S.; Attidekou, P. S.; Liu, C.; He,
(626) Yang, J.; Lind, J. U.; Trogler, W. C. Chem. Mater. 2008, 20, H.; Zhao, D.; Zhou, W. Chem. Mater. 2009, 21, 2540.
2875. (663) Vradman, L.; Landau, M. V.; Kantorovich, D.; Koltypin, Y.;
(627) Song, X.; Gao, L. Langmuir 2007, 23, 11850. Gedanken, A. Microporous Mesoporous Mater. 2005, 79, 307.
(628) Yang, Z.; Niu, Z.; Lu, Y.; Hu, Z.; Han, C. C. Angew. Chem., Int. (664) Green, K. J.; Rudham, R. J. Chem. Soc., Faraday Trans. 1993,
Ed. 2003, 42, 1943. 89, 1867.
(629) Agrawal, M.; Pich, A.; Zafeiropoulos, N.; Stamm, M. Colloid (665) Liu, X.; Iu, K.-K.; Thomas, J. K. J. Chem. Soc., Faraday Trans.
Polym. Sci. 2008, 286, 593. 1993, 89, 1861.
(630) Sun, X.; Li, Y. Angew. Chem., Int. Ed. 2004, 43, 597. (666) Xu, Y.; Langford, C. H. J. Phys. Chem. 1995, 99, 11501.
(631) Ao, Y.; Xu, J.; Fu, D.; Yuan, C. Catal. Commun. 2008, 9, 2574. (667) Chen, H.; Matsumoto, A.; Nishimiya, N.; Tsutsumi, K. Colloids
(632) Ao, Y.; Xu, J.; Fu, D.; Yuan, C. J. Hazard. Mater. 2009, 167, Surf., A 1999, 157, 295.
413. (668) Fukahori, S.; Ichiura, H.; Kitaoka, T.; Tanaka, H. Environ. Sci.
(633) Ao, Y.; Xu, J.; Zhang, S.; Fu, D. Appl. Surf. Sci. 2010, 256, 2754. Technol. 2003, 37, 1048.
(634) Wang, C.; Ao, Y.; Wang, P.; Hou, J.; Qian, J.; Zhang, S. J. (669) Rayalu, S. S.; Dubey, N.; Labhsetwar, N. K.; Kagne, S.;
Hazard. Mater. 2010, 178, 517. Devotta, S. Int. J. Hydrogen Energy 2007, 32, 2776.
(635) Srinivasan, S.; Datye, A. K.; Hampden-Smith, M.; Wachs, I. E.; (670) Hoyer, P. Langmuir 1996, 12, 1411.
Deo, G.; Jehng, J. M.; Turek, A. M.; Peden, C. H. F. J. Catal. 1991, (671) Lakshmi, B. B.; Dorhout, P. K.; Martin, C. R. Chem. Mater.
131, 260. 1997, 9, 857.
(636) Hsu, W. P.; Yu, R.; Matijevic, E. J. Colloid Interface Sci. 1993, (672) Zhang, M.; Bando, Y.; Wada, K. J. Mater. Sci. Lett. 2001, 20,
156, 56. 167.
(673) Zhang, X. Y.; Zhang, L. D.; Chen, W.; Meng, G. W.; Zheng, M.
J.; Zhao, L. X.; Phillipp, F. Chem. Mater. 2001, 13, 2511.
(674) Miao, Z.; Xu, D.; Ouyang, J.; Guo, G.; Zhao, X.; Tang, Y. Nano
Lett. 2002, 2, 717.
(675) Li, X. H.; Liu, W. M.; Li, H. L. Appl. Phys. A: Mater. Sci. Process.
2005, 80, 317.
(676) Foong, T. R. B.; Shen, Y.; Hu, X.; Sellinger, A. Adv. Funct.
Mater. 2010, 20, 1390.
(677) Lee, J.; Jho, J. Y. Sol. Energy Mater. Sol. Cells 2011, 95, 3152.
(678) Liang, Y.-C.; Wang, C.-C.; Kei, C.-C.; Hsueh, Y.-C.; Cho, W.-
H.; Perng, T.-P. J. Phys. Chem. C 2011, 115, 9498.
(679) Chang, W.-T.; Hsueh, Y.-C.; Huang, S.-H.; Liu, K.-I.; Kei, C.-
C.; Perng, T.-P. J. Mater. Chem. A 2013, 1, 1987.