Composite Titanium Dioxide Nanomaterials

Review
pubs.acs.org/CR
Composite Titanium Dioxide Nanomaterials

Michael Dahl, Yiding Liu,, and Yadong Yin*,,
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,
including high refractive index and ultraviolet (UV) light
absorption, TiO2 has seen considerable use as a white pigment
in paint, food coloring, and personal care products and as a UV
absorber in sunscreens.17 These applications utilize TiO2
across a wide range of sizes from hundreds of nanometers to
several micrometers. Although these applications account for
the majority of global TiO2 consumption, its utilization in
nanoscale research has primarily focused on its near semiconductor electronic properties. Beginning with the initial
discovery of the production of hydrogen from a TiO2 anode
under UV irradiation,8 much work has been done, which has
expanded use of TiO2 to numerous new applications. These
applications range from photovoltaic cells9 to photocatalysts for
hydrogen production and environmental remediation10 as well
as photoelectrochemical sensors.11 Many other niche uses have
also been studied, particularly in the medical and biological
elds, where TiO2-based nanomaterials have been investigated
for in vivo imaging,12,13 cancer therapy,10,14 and protein
separation/purication1524 and as bactericides.2528 Although
applications as a pigment/UV absorber are typically possible
using pure TiO2, it has become clear that this is less feasible for
applications utilizing photoelectrochemical properties as well as
a number of biological applications. Thus, much research has
been dedicated to the construction of nanoscale TiO 2
composite materials.
Various excellent reviews have looked at TiO2 and its
applications to each of the aforementioned elds of study over
the years and give a signicant amount of background for each
TiO2 material.9,10,26,2941 However, many of these reviews look
at either a multitude of materials (i.e., not limited to TiO2
composites) and/or a specic application of TiO2 materials
with a narrow focus. Thus, the intent of this review will be to
discuss the synthesis of TiO2 composite nanomaterials and
their applications across a wide range of elds. To clarify the
focus of this review, we will dene a composite as a
combination of one or more materials (metal, metal oxide,
metal sulde, etc.) with TiO2. These combinations may appear
in many forms such as layered or coreshell structures and can
be produced by various methods including chemical synthesis,
solution- or gas-phase deposition, and templated fabrication.
CONTENTS
1. Introduction
1.1. Scope
1.2. Advantages of TiO2 Composites
2. Metal and Metal OxideTiO2 Composites
2.1. Group I and II Metals
2.2. Early Transition Metals
2.3. Middle Transition Metals
2.3.1. Vanadium, Niobium, and Tantalum
2.3.2. Chromium, Molybdenum, and Tungsten
2.3.3. Manganese and Rhenium
2.4. Late 3d Transition Metals
2.4.1. Iron and Cobalt
2.4.2. Nickel, Copper, and Zinc
2.5. p-Block Metals
2.6. Lanthanides
3. Noble Metal and Metal OxideTiO2 Composites
3.1. Ruthenium and Rhodium
3.2. Palladium
3.3. Platinum
3.4. Silver
3.5. Gold
4. Nonoxide SemiconductorTiO2 Composites
4.1. Metal Pnictogenides
4.2. Metal Chalcogenides
4.2.1. Cadmium Chalcogenides
4.2.2. Other Single-Metal Chalcogenides
4.2.3. Semiconductor Alloy Chalcogenides
5. CarbonTiO2 Composites
5.1. Carbon Nanotubes
5.2. Graphene and Graphene Oxide
5.3. Other Carbon
6. Templated Composites
6.1. YolkShell and CoreShell
6.2. Ordered Mesoporous Silica and Zeolites
6.3. Anodized Aluminum Oxide (AAO)
7. Summary and Outlook
Author Information
Corresponding Author
Notes
Biographies
Acknowledgments
References
2014 American Chemical Society
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Special Issue: 2014 Titanium Dioxide Nanomaterials

Received: November 3, 2013
Published: July 11, 2014
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dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889
Chemical Reviews
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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.
detailed. It is also necessary to note that a number of

composites consist of multiple materials which span dierent
categories. In these cases the composite will be discussed in the
section relevant to the specic component that is yielding the
greatest benet or is the most novel addition.
We do concede that many of the composite materials discussed

herein have shown little improvement in performance toward
their applications and, as such, have been superseded by
superior materials; however, in the interest of being
comprehensive, they will be covered as well. Further, we
acknowledge that the utilization of TiO2 for the photocatalytic
degradation of dyes is only a model system to test
photocatalytic activity; however, especially with how ubiquitous
it is in the literature, this technique has become a useful tool for
determining and comparing the gross improvements of various
composite materials. It is frequently included within this review
to make such comparisons, although we disregard the
likelihood of its extension to a commercial product.
Since the study of TiO2 has become such a widespread,
multidisciplinary eld, a signicant amount of research has been
dedicated to it over the last several decades. Consequently, a
brief search of the literature in the SciFinder Scholar database
for TiO2 returns over 250 000 results. This can be narrowed
to just over 11 000 results when using TiO2 composite,
although many composite materials that are not specically
labeled as such are left out. Thus, it becomes apparent that in
order to best review the state of TiO2 composite materials,
criteria for separating types of composites must be determined.
Here, we will rst organize composite materials by reviewing
specic metal composites based on their positions in the
Periodic Table. Then, we will switch to categorization using
specic material types. The initial sections of the review will
look at metal and metal oxideTiO2 composites. Metals that
are similar chemically or utilized for similar applications will be
grouped together in order to make simpler comparisons. It is
worth noting that while there are numerous composites with
dierent types of metals and metal oxides there are still some
elements which are seldom used outside of doping, and as such,
a number of metals will not be considered. Following this we
will discuss nonoxide semiconductorTiO2 composites, which
have been the subjects of signicant research in the elds of
photocatalysis and photoelectrochemical cells. CarbonTiO2
composites, which have been heavily researched due to the
recent increase in the production of carbon nanomaterials such
as nanotubes and graphene, will then be discussed. The
subsequent section will discuss templated composites, which
have seen an increase in study recently. The synthesis and
utilization of complex TiO2 nanostructures using templates
such as polystyrene, silica, zeolites, and aluminum oxide will be
1.2. Advantages of TiO2 Composites
The photoactivity of TiO2 has been shown to be dependent on

several key properties: crystal phase, surface area, exposed
crystal facets, uncoordinated surface sites, defects in the lattice,
and degree of crystallinity. Morphology control of TiO2 via
synthesis of composite materials has allowed for the improvement and ne tuning of many of these properties. Additionally,
TiO2 composite structures can create and tune other properties
such as mid-band-gap electronic states which can alter charge
migration or produce a red shift in the absorption spectrum.
Further, formation of heterojunctions between TiO2 and other
materials can yield visible light absorption by the added
material with charge separation facilitated by the TiO2. The two
main polymorphs of TiO2 which show the highest photoactivity
are the anatase and rutile phases, which have typically reported
band-gap values of 3.2 and 3.0 eV, respectively. Although the
band gap of rutile is narrower, the anatase phase is typically
considered more favorable as it has a higher reduction potential
and a slower rate of recombination of electronhole pairs.30,32
Unfortunately, its wide band gap dictates that it will primarily
absorb UV radiation. Here the utility of mixed phase TiO2 must
be discussed. Optimization and control of the phase transition
and its applications have been covered in detail elsewhere;4247
however, commercial Degussa P25, or simply P25 for short, is
one of the most commonly used mixed phase TiO2 composites.
This mixed phase material allows for utilization of visible light
wavelengths through excitation of the rutile phase while also
containing benets of anatase TiO2, such as a decreased
recombination rate of charge carriers. The initial mechanism for
this enhancement was ambiguous; however, utilizing electron
paramagnetic resonance (EPR), Hurum et al. studied the fate of
photogenerated charge carriers in order to shed light on the
mechanism.48,49 They found that electrons which were
photogenerated by the rutile component were transferred to
a previously proposed electron trap site in the anatase lattice
which lies 0.8 eV below the anatase conduction band.50 Further,
this is situated lower than the rutile conduction band. A
decrease in electronhole recombination is achieved since the
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such, most of the metals below will be discussed as their metal

oxides. Further, the most common oxide will be preferentially
discussed as other oxides are likely to be unstable and thus do
not form stable composites.
photogenerated holes remain within the rutile component and

the electrons are spatially separated into the anatase
component. It was later determined that the photogenerated
holes are preferentially trapped on the surfaces, whereas
electrons become trapped within the lattice. As such surface
electron trap sites increase the recombination rates, which
indicates that a composite with a second material which is
either a hole or an electron sink can further increase catalytic
eciency.
Beyond the use of mixed phase TiO2, composites with nonTiO2 materials are a very promising means to extend the
usefulness of anatase into the visible wavelengths. Alternatively,
for composites consisting of the rutile phase, inclusion of higher
work function materials can yield slower charge carrier
recombination. Other methods to decrease charge carrier
recombination include increasing crystallinity, which can be
done by high-temperature calcination, addition of dopants, or
specic synthetic protocols. Additionally, defects, which can
serve as charge carrier traps and reduce the recombination of
photogenerated electronhole pairs, can also be either induced
or stabilized by formation of a composite. Composites which
can help to tune the grain size have also been shown, such as
metal oxide solgel precursors which can form composites with
TiO2 and inhibit crystallinity.
Figure 1a shows a general model for photocatalysis on
anatase TiO2 in which light is absorbed to produce an
electronhole pair, charges migrate to the surface, and redox
reactions occur. This ideal case assumes low charge
recombination and easy charge migration to the surfaces.
Charge separation can be enhanced by creation of features such
as surface defects where electrons and holes can be trapped to
prevent recombination or, as discussed earlier, in P25 where a
natural electron trap exists below the anatase conduction band.
Figure 1b shows an improved case utilizing a TiO2 composite
heterojunction. In this case, a structure with a narrower band
gap can utilize visible light to produce an electronhole pair.
Assuming a favorable band oset, the electron can migrate to
the TiO2, while the hole is trapped in the second material.
Redox reactions are now free to occur at the separate surfaces
since the likelihood of charge recombination has been
diminished. A heterojunction composite structure can then be
rationally designed in order to produce a favorable band oset
and band positions in order to develop a catalyst for the needs
of specic reactions, such as water splitting.
In addition to the improvement of photocatalysis, composite
structures can yield other benets. Such advantages include the
ability to tune the surface properties, i.e., acidity/basicity or
open coordination sites, of the resultant materials, which is of
importance to the adsorption of molecules, a critical factor
relevant to catalysis, separation, and further modication.
Numerous mixed metal oxide/TiO2 composites are benecial
for stabilization of thermal catalysts where reactions such as
high-termperature NOx reduction are improved. Composites
such as coreshell materials are also benecial toward the
stabilization of nanoparticles against phenomena such as
sintering or aggregation. Further, composites can be of great
use to create highly porous materials, hollow shells, or
hierarchical structures by templating methods.
2.1. Group I and II Metals
Due to their high oxidation potentials and instability in aqueous

solutions, composites of the Group I and II elements are mainly
based on their oxides. Additionally, many of these elements are
also frequently used for formation of metaltitanate materials,
which exceeds the scope of this review and will not be
specically discussed. The large majority of the Group I and II
metal oxideTiO2 composites were initially studied as part of
more complex aluminosilicate and aluminotitanate glasses
and ceramics for a variety of applications.5153 These
composites are not strictly TiO2 composites, however, as they
are formed from melts of metal oxide mixtures and typically
result in titanate products. Lithium oxide specically has little
use in composites besides as a component in glasses which,
once melted, typically form lithium titanate materials.54,55
Oxides of sodium, rubidium, and cesium have also seen a
considerable portion of their usage as components in
glasses.56,57
Interestingly, potassium oxide, as K2O, has seen interest as a
component in composites for catalytic processes. In a system
containing a mixed composite of TiO2ZrO2, it was shown that
a mixture of K2O and CO2 can be benecial in increasing both
the reactivity and the selectivity of the dehydrogenation of
ethylbenzene to styrene.58 Conversion of ethylbenzene was
increased from 60.59% to 71.95% with addition of 3 wt % K2O,
and the selectivity was increased from 97.04% to 99.63%. It is
worth noting that one previous study of the addition of only
K2O to the TiO2ZrO2 composite for this reaction reported
decreased activity due to K2O neutralizing the acidic sites on
the TiO2ZrO2 composite,59 although it was shown that this
neutralization did have the added benet of increasing the
selectivity by suppressing the dealkylation products.60 The
basicity of K2O has also been shown to inuence other
reactions as well. In one study, by again neutralizing the acidic
sites in a V2O5(WO3)/TiO2 composite, selective reduction of
NO by NH3 was poisoned to nearly zero conversion with 1 wt
% K2O.61 On the other hand, catalytic applications that can
utilize the basicity of K2O have also been studied with positive
results. Recently, Salinas et al. demonstrated the transesterication of commercial canola oil over a K2O/TiO2
catalyst for production of biodiesel.62 The results show that a
20 wt % K2O/TiO2 catalyst can achieve total conversion to
methyl esters in reuxing methanol after 7 h of reaction time.
This compares favorably to other catalysts which utilize
potassium in the forms of KOH, KNO3, or KI supported on
alumina, which have conversions of approximately 90% over
reaction times ranging from 8 to 10 h for similar commercial
oils.6365 A follow up study on this system showed that upon
calcination above 600 C the composite formed an even more
active titanate catalyst which yielded total conversion in under 3
h.66
In addition to K2O/TiO2 composites, MgO/TiO2 composites have also seen use in biodiesel production with similarly
active catalysts being developed.67,68 After the work by Tanabe
et al. in 1978, which detailed the catalytic activity of composites
of MgO/TiO2 based on acidity/basicity,69 little research had
been conducted until the past decade. Aside from the
production of biodiesel, recent work has been established
2. METAL AND METAL OXIDETIO2 COMPOSITES

Most metals are either too chemically reactive, especially on the
nanoscale, not having properties that can be taken advantage of
readily, or unnecessary with regard to composites with TiO2. As
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to a 0.35 Mg/Ti molar ratio; above this ratio the blockage of

hole escape by MgO on TiO2 is thought to be excessive, and
thus, the performance decreased. This recombination was
previously studied by Bandara et al., whereby they monitored
the degradation of various organic molecules under UV
irradiation with TiO2 loaded with dierent amounts of
MgO.73 These catalysts consisted of clusters of MgO on the
surface of TiO2, and the optimal catalyst was determined to
have a composition of 3 wt %. The MgO clusters act as
coordinately unsaturated defect sites where anion vacancies can
eciently separate and trap electrons with the resulting holes
trapped in the TiO2, thus preventing recombination and
allowing for optimal work to be done by the system. This
charge separation was later conrmed by DFT simulation of
MgO clusters on a rutile TiO2 (110) surface. 74 The
combination of these ndings has inspired new research into
these MgO/TiO2 composite structures as inexpensive materials
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
storage/reduction applications. Initial results out of the Toyota
Motor Corp. laboratories showed the ability of NOx to adsorb
onto the basic barium oxide surface to form Ba(NO3)2, which
stored the NOx as a nitrate for reduction at a later step.83
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
TiO2 binding NOx as well, compared to limited binding by the
more acidic Al2O3.84,85 Andonova et al. additionally found that
Ti-containing domains had a strong anity toward Bacontaining domains, to the point that upon calcination at 600
C barium titanates and bariumtitaniumaluminates were
formed as shown in Figure 3. They further determined that the
strong anity between Ti and Ba domains can be benecial for
inhibiting formation of BaSO4, which poisons the NOx uptake
eciency.8587
utilizing MgO/TiO2 composites for photocatalysis and photoelectrochemical cells. One example of such work done by
Taguchi et al. utilized a thin layer of MgO over TiO2 for
stabilization of solid-state dye-sensitized solar cells (DSSCs).70
Magnesium methoxide was deposited onto a TiO2/F-doped
SnO2 (FTO) cell in an ethanolic solution and then sintered to
form a thin (0.25 nm) MgO layer. The cell was completed
with Ru 535 dye, CuI as a hole scavenger, and an Au-coated
FTO slide. The role of MgO was to stabilize the cell and act as
a physical barrier between TiO2 and CuI to prevent charge
recombination and, most importantly, to prevent back electron
transfer between TiO2 and the dye molecules. Consequently,
both the open-circuit voltage (Voc) and the short-circuit current
density (Jsc) improved from 430 to 510 mV and 8.38 to 8.74
mA/cm2, respectively, and the eciency increased from 2.13%
to 2.90%. Additionally, the stability over time for both
parameters improved markedly with the MgO coating as
shown in Figure 2. The increase in Jsc was unexpected as the
Figure 2. Stability of Voc (open square), Jsc (open triangle), ll factor

(cross), and eciency (lled circle) of solid-state DSSCs (a) without
MgO layer and (b) with MgO layer under continuous illumination.
Adapted from ref 70 with permission from The Royal Society of
Chemistry.
MgO layer may reduce the eciency of electrons from excited

dyes being injected into TiO2; however, an unforeseen benet
of the MgO layer was an increase in dye adsorption of 20% as
compared to the TiO2 surface alone.
Later work by Jung et al. also showed similar increases when
dye-sensitized solar cells (DSSCs) were fabricated from TiO2
particles (Degussa, P25) which were predecorated with MgO.71
They also found an optimal weight percentage to be 0.6 wt %
MgO, which yielded an improvement from 3.1% to 4.5% in
their as-constructed cells. Construction of DSSCs for hydrogen
production was also observed to show a minor increase in H2
production when a MgO/TiO2 composite cell was constructed
utilizing an overcoat of MgO on a TiO2:ITO cell.72 It was
found that under bias voltage the decrease in charge
recombination was benecial for MgO loading amounts of up
2.2. Early Transition Metals
Although oxides of scandium have not been commonly utilized

in composites with TiO2, other early transition metal oxides
have seen considerable use. Here we will focus on the
utilization of yttrium, zirconium, and hafnium oxideTiO2
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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

lanthanides section later. Yttrium oxide has been most notably
utilized in composites with TiO2 for enhancement of
upconversion particles. Lu et al. showed that Y2O3 doped
with Tm3+ and Yb3+ (Y2O3:Tm3+,Yb3+), when coated with a
TiO2 layer, showed an upconversion emission intensity
enhancement of up to 5.4 times that of the uncoated sample.88
These core@shell structures were prepared by a modied
Stober process to coat the cores with TiO2 using tetrabutyl
titanate in place of a silica precursor. The reaction was allowed
to proceed for various times in order to tune the shell thickness.
The TiO2 layer showed an amorphous structure by X-ray
powder diraction, since the structure was not calcined post
synthesis and drying. The enhancement of the emission
intensity was attributed to the TiO2 layer, which provides a
ligand eld for surface lanthanide dopant ions to convert from a
dormant state to an active one. However, it is noted that in
composites where the TiO2 shells were too thick, absorption of
the incident light and reabsorption of the emitted light
increased to the point that the enhancement factor would
begin to decrease. Although optimal samples were denoted by
optimum coating time, statistical analysis for an optimized
thickness coating was not performed.
In addition to the upconversion enhancement, composites of
lanthanide-doped Y2O3 and TiO2 have also been utilized for
photocatalysis and DSSCs. Li et al. prepared a composite of
Y2O3:Tm3+,Yb3+/TiO2 by hydrolyzing TiCl4 in an ethanolic
solution containing the upconversion particles, followed by
calcination at 500 C.89 The optimal upconversion particle was
found to have a Yb3+ concentration of 2 mol % with a xed
Tm3+concentration of 0.5 mol %. They found that when
compared to pure TiO2 prepared using the same methods there
was an increase in the degradation rate of methyl orange (MO)
by solar irradiation. Pure TiO2 degraded approximately 40% of
the MO in 150 min, whereas the composite achieved 100%
degradation. The photocatalytic enhancement was attributed to
infrared radiation in the solar spectrum being upconverted to
UV light, which could then be utilized by the TiO2 portion of
the composite. Recently, Y2O3:Er3+ nanorods were utilized to
improve the eciency of a TiO2:FTO DSSC.90 The cells were
constructed by depositing a 12 m thick layer of a TiO2 colloid
onto FTO, then mixing the Y2O3:Er3+ nanorods with a separate
TiO2 colloid solution and adding a 4 m thick layer of the
mixture on top, followed by sintering at 450 C. On the basis of
several trials, the optimum weight percent of the upconversion
particles was found to be 5 wt % compared to the overall TiO2
amount. At this concentration, the cell eciency was found to

increase from 5.84% in the pure TiO2 cell to 7.00%, with
corresponding increases in Voc, Jsc, and the ll factor (FF).
Although the increase in eciency is modest, the benet of
converting infrared light into more usable wavelengths to
increase DSSC performance is notable.
Zirconium oxide has seen considerable usage in TiO2
composite materials. However, it is most frequently incorporated as part of a mixed oxide ceramic system or as a mixed
oxide catalytic support system, although some more recent
usage has focused on the interaction between ZrO2 and TiO2
for photocatalytic applications. The frequent use as a support
can be attributed to optimal surface acidity of the ZrO2/TiO2
composite, 91 which can be ne tuned based on the
concentration of ZrO2 within the composite as well as the
calcination temperature and the synthetic conditions.92,93 The
acidbase tunability of these supports can be utilized for the
catalytic, or photocatalytic, oxidation of organic molecules;9497
dehydrogenation reactions;59,98 and NOx reduction,99,100
among other reactions, which have been reviewed previously.101,102 Also of interest recently is the utilization of ZrO2/
TiO2 composites for photocatalysis, which is tested by dye
degradation or water splitting.103106 Addition of ZrO2 to TiO2
has been shown to retard or even prevent formation of rutile
phase within TiO2 composites, which corresponds to a decrease
in the growth of TiO2 grains in the microstructure and an
increase in the surface area,106109 although the robust nature
of ZrO2 makes it dicult to remove from the TiO2 composite
unlike the case of SiO2. Chen et al. recently utilized this
increase in surface area to optimize ZrO2/TiO2 composite
microspheres for the adsorption of heavy metal oxides.110 They
were able to reach a maximum surface area of 413 m2/g in a
30:70 Zr:Ti molar ratio composite, which compares favorably
to the pure phase surface areas of 108 and 104 m2/g for TiO2
and ZrO2, respectively.
One recent study for the use of this system in a photocatalyst
was done by Li et al., who synthesized a series of composites
containing ZrO2, CeO2, and TiO2.105 The composites were
prepared via the evaporation-induced self-assembly (EISA)
method utilizing Pluronic P123 as a surfactant, Ce(NO3)3,
ZrOCl28H2O, and titanium n-butoxide in an ethanolic solution
followed by calcination at 500 C. The ZrO2-containing
composite consistently showed increases in surface area, pore
diameter, and pore volume when compared to samples without
ZrO2, indicating the inuence of the ZrO2 on the microstructure of the composite. The resistance to sintering provided
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by the ZrO2 allows for stabilization of long-range, ordered

pores throughout the microstructure. The photocatalytic
activity was further tested via the visible light degradation of
Rhodamine B (RhB). The mesoporous ZrO2CeO2TiO2
composite showed the highest photocatalytic activity when
compared to the other catalysts including P25, as shown in
Figure 4.
materials. One study by Triyoso et al. showed that in an

optimum synthesis by atomic layer deposition the mixed oxide
deposition is favorable when compared to alternating layers of
HfO2 and TiO2.112 The mixed oxides yield values of 38 at a
10:1 HfO2/TiO2 ratio and 28 at a 1:2 ratio, as compared to
values between 21 and 25 with layered structures. Other recent
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
vanadium(IV) oxide, VO2, have been used in composites
with TiO2, although much of this research is limited due to the
inherent instability of the lower oxides. However, because of
the considerable amount of research regarding the thermochromic transition of VO2,130132 composites with TiO2 have
been investigated to enhance both the chemical stability of VO2
and the transmittance, with some good results to date,133136
including a slight decrease in the transition temperature, though
it still remains too high for practical use.
Both niobium and tantalum oxides have not been frequently
researched for use in composites with TiO2. Niobium(V) oxide
Nb2O5 has seen some applications in photocatalysis for dye
degradation,137,138 selective photooxidation of organic molecules,139,140 and DSSCs.141144 Nb2O5/TiO2 composites for
DSSC applications focus mostly on the use of Nb2O5 as a
blocking layer between the conducting electrode and TiO2 to
reduce the recombination rate of the charge carriers, which has
been recently shown to improve eciency in DSSCs.145,146
Incorporation of Nb2O5 has been observed to improve the cell
eciency by between 22% and 35%, depending on the
structure of the composite and the thickness of the Nb2O5
layer on the TiO2, where thicknesses on the order of a few
nanometers are optimal. In addition to its use as a blocking
Figure 4. Photocatalytic adsorption, degradation, and reduction of

total organic carbon percentages (a) and photodegradation kinetic
curves (b) of RhB on P25, TiO2, CeO2TiO2, mesoporous CeO2
TiO2, and mesoporous ZrO2CeO2TiO2. Reprinted from ref 105,
with permission from Elsevier. Copyright 2013.
Hafnium oxide (HfO2 )TiO 2 composites have seen

extensive research recently as potential materials for applications as gate dielectrics due to the high relative permittivity
(dielectric constant, ) of HfO2 and TiO2 compared to the
standard gate dielectric, SiO2. The increase of the permittivity
of the gate dielectric is of considerable importance since it
allows for a higher capacitance with a smaller or equal thickness
as compared to SiO2. TiO2 alone should be an ideal material
based on its permittivity measured in the range of = 80110
as compared to SiO2, in which = 3.9. Unfortunately, due the
presence of stable Ti3+ within a TiO2 structure, oxygen
vacancies at these reduced sites act as carrier traps and highleakage paths.111 Thus, HfO2 ( = 25) is seen as a better
alternative, especially when improved values with reduced
current leakage can be found in HfO2/TiO2 composites.
Additionally, composites of HfO2/TiO2 should also improve
the charge mobility, which is one other drawback to pure HfO2
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a dopant in TiO2 materials. Further, Ta2O5 has also been

studied as a single catalyst system for photocatalytic water
splitting.153155
2.3.2. Chromium, Molybdenum, and Tungsten.
Although chromium has been recognized as one of the optimal
non-noble metal dopants in TiO2 materials for enhanced visible
light photoactivity,156,157 research on composites with TiO2 and
chromium oxides has been demonstrated. Composites utilizing
TiO2 as a support material for active chromium oxides have
been studied for NOx reduction158160 as well as photocatalytic
reactions161163 and magnetic applications.164166 Since the
discovery of large negative magnetoresistance in CrO2, it has
been researched in depth; however, one signicant downside of
CrO2 is its poor thermodynamic stability; as such, composites
with TiO2 have been studied to improve this feature. Research
done to this point has shown that composites maintain much of
the necessary properties of CrO2, although its stability has yet
to be signicantly enhanced.
Oxides of both molybdenum and tungsten have seen use for
applications within TiO2 composite materials. The promise in
photocatalysis has drawn a considerable amount of attention to
these systems, especially in the case of tungsten(VI)
oxide.167171 On the other hand, molybdenum oxides, such
as MoO3, have seen less research, and in comparison to WO3/
TiO2 composites, the photocatalytic activity is commonly
lower.170 As such, the focus here will be on tungsten oxides,
which have been frequently utilized in composites with TiO2
for photocatalytic applications. Early studies by Do et al. and
later Kwon et al. demonstrated an enhanced photocatalytic
activity of WO3/TiO2 composites for oxidation of 1,4dichlorobenzene (DCB).172,173 Both of these studies utilized
P25 as the TiO2 component and used an incipient wetness
technique to impregnate the P25 with the tungsten oxide
precursor, followed by calcinations to produce the oxide phase.
It was found that the optimal WO3 concentration was 3 mol %,
which led to degradation rates up to 2.5 times higher than P25
under UV irradiation. Similar studies using thin transparent
lms showed a similar activity enhancement in other photocatalytic degradation experiments as well.170 The improved
photocatalytic activity has been attributed to both favorable
band gap positions for ecient charge separation and formation
of reduced W5+ species, which assist charge separation and act
as reduction sites.172,174,175 Photocatalytic degradation experiments have also been extended to utilize these composite
structures under visible light irradiation as well.174,176179 The
narrower band gap of WO3 (2.8 eV) allows for absorption of
visible light photons by the composite, and accordingly, the rate
of photocatalytic degradation increases markedly as compared
to pure TiO2.174,176 In one study, Li et al. prepared TiO2
colloids by hydrolysis of titanium n-butoxide, followed by in
situ hydrolysis of ammonium tungstate and at dierent
concentrations.174 Samples were then calcined at 700 C, and
their photocatalytic activity was measured through the
degradation of methylene blue under visible light irradiation.
As shown in Figure 6a, the 3 mol % WOx/TiO2 composite
showed optimal photocatalytic activity. Although the XRD
pattern in Figure 6b shows no discernible tungsten oxide phase,
the XPS spectrum, Figure 6c, shows a majority of tungsten
appearing as W6+, which corresponds to the WO3 phase.
An interesting additional result shown in this study is the
eect of WO3 on retardation of the anatase to rutile phase
transition. As seen in the XRD pattern of the pure TiO2, rutile
phase is clearly present as the main phase, whereas in the WOx/
Figure 5. Cross-section SEM images of ordered nanotube arrays

(ONTs) on dierent substrates: (a) pure Ti, (b) Ti:0.2 V alloy, (c)
Ti:3 V alloy, and (d) Ti:18 V alloy by anodization; (e and f) highmagnication cross-section and top-view SEM images of the Ti:18 V
alloy ONTs. (g) Cyclic voltammograms of Ti and Ti-V oxide
nanotubes, performed over a voltage window between 0 and 0.8 V in
0.1 M HClO4 electrolyte with a scan rate of 50 mV s1. Adapted from
ref 127 with permission from The Royal Society of Chemistry.
layer, Nb has also been incorporated into TiO2 thin lms and
nanotubes. Although this Nb inclusion is typically as a dopant,
incorporation of Nb can yield a noticeable red shift in the
absorption as well as a preference for rutile phase formation
upon calcination.147,148 Unfortunately, this incorporation also
yields an increase in recombination centers which is not ideal
and diminishes the photocatalytic properties.149 Synthesis of
TiNb composite nanotubes from anodization of a TiNb
alloy has been shown to allow for signicant control on the
length and diameter of composite nanotubes. These nanotubes
can be synthesized with lengths between 0.5 and 8 m and
diameters of 30120 nm by changing the potential applied.
Importantly, upon calcination to 650 C, the tubular
morphology is well maintained.150 Tantalum(V) oxide,
Ta2O5, composites with TiO2 have also seen some research
for photocatalysis,151,152 although it is more commonly seen as
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structure, followed by growth of another shell layer on the

outside. After the samples were dried, they were calcined at 600
C, and it was found that the crystallinity of TiO2 in the
composite decreased with increasing WO3 content.
2.3.3. Manganese and Rhenium. TiO2 composites
containing both manganese and rhenium oxides are frequently
used for supported catalytic reactions, such as NOx reduction
for manganese oxide183185 and the watergas shift reaction for
metallic rhenium/rhenium oxide.186189 More recently, however, MnO2/TiO2 composites have been developed for
electrochemical applications, specically for supercapacitors190
and Li+ batteries.191,192 MnO2 is utilized due to its high
theoretical capacity193,194 (1230 mAh/g), and development of
composites with TiO2 allows for improved device construction
on a well-developed support material. Although the breadth of
research to date using MnO2/TiO2 composites for electrochemical applications is limited, these materials show great
promise for future growth as research on advanced energy
storage technology progresses. As a cocatalyst with Pt, Re metal
supported on TiO2 has shown signicant enhancement in the
performance of a low-temperature watergas shift reaction. It
has been demonstrated that the activity of Re is facilitated by
formation of oxides. These sites can be reduced by CO to form
CO2 and then reoxidized by H2O, forming H2.188 Utilization of
rhenium or rhenium oxides on TiO2 has been rather limited
beyond these reactions; however, due to its catalytic enhancement, it is an avenue that can still see some improvement when
utilizing rational catalytic design.
2.4. Late 3d Transition Metals
2.4.1. Iron and Cobalt. Due to the instability of metallic

iron on the nanoscale, it has not been commonly utilized for
composites with titania. Although there have been some niche
applications utilizing iron oxide/TiO2 composites,195198 a
signicant amount of research over the past decade has focused
on utilizing the magnetic properties of iron oxide within a
composite. Composites of iron oxide@TiO2 have been
extensively implemented to enable the magnetic recoverability
of TiO2 from reaction media.199206 Recently, these structures
have seen considerable interest based on the signicant
morphological control that can be employed. Lou et al.
demonstrated a direct coating of TiO2 onto -Fe2O3 by
hydrolysis of TiF4 in an ethanolic solution.201 The core@shell
composites could then be converted to magnetic Fe3O4@TiO2
by reduction under H2 ow at 300 C. The TiO2 shell within
the structure showed good crystallinity, with the morphology
retained after crystallization. Further, if so desired, the TiO2
composite could be made completely hollow by dissolution of
the -Fe2O3 in dilute HCl. Xuan et al. utilized poly(styreneacrylic acid) (PSA) as a template onto which they adsorbed
Fe3+ ions, which were chemically converted to Fe3O4 in a
solution of NH3H2O and Na2SO3.202 The composites were
then coated with TiO2 by hydrolysis of titanium(IV) n-butoxide
in an ethanolic solution, and the original template was removed
by dissolution in THF. The as-prepared Fe 3 O 4 @TiO 2
composites were then used for photocatalytic degradation of
RhB under UV irradiation and showed good photoactivity as
well as recoverability and cyclability.
Later Ye et al. established a hierarchical structure where
superparamagnetic Fe3O4 cores (Figure 7a) were rst coated by
a layer of SiO2 by a modied Stober process (Figure 7b). This
was followed by a coating with TiO2 using titanium(IV) nbutoxide in an ethanolic solution to obtain an Fe3O4@SiO2@
Figure 6. (a) Total organic carbon (TOC) removal during MB

degradation. (b) XRD pattern showing evolution of crystal phase with
increasing tungsten oxide content. (c) XPS tting spectrum of 3%
WOxTiO2 powder showing W 4f: arrows indicate the presence of
WO3, W6+ 4f spectrum, WxOy a mixed spectrum of W5+ and W6+, and
WO2 W4+ 4f. Adapted from ref 174, with permission from Elsevier.
Copyright 2001.
TiO2 composite samples only anatase phase is present. This

phenomenon has been seen in other tungsten oxide/TiO2
composites,180 and moreover, other studies have seen not just
an inhibition of the phase transition but a decrease in
crystallinity with increasing WO3 content.181 This decrease in
crystallinity was also observed in a series of core@shell TiO2@
WO3 microspheres. In this study, Yang et al. synthesized core@
shell structures by coating hydrothermally synthesized yolk@
shell TiO2 particles using an incipient wetness impregnation
method.182 As the concentration of tungsten precursor
increased, WO3 rst lled in the cavity within the yolk@shell
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as opposed to carboxylic acids especially, can selectively bind to

the metal oxide surface and be removed from a mixture. One of
the rst of these studies by Chen et al. produced Fe3O4@TiO2
composites by preparing Fe3O4 particles by precipitation of
Fe2+ and Fe3+ with an ammonia solution, followed by adding a
thin layer of SiO2 and nally TiO2 from deposition of
titanium(IV) n-butoxide in ethanol.15 Similar composites with
good enrichment capabilities have also been synthesized.17,21
Separately, one composite of -Fe2O3/TiO2 synthesized by Lu
et al. was a nanocrystal cluster system comprising TiO2 and Fe2O3 nanocrystals, which were combined in a micelle
solution to form clusters.20 The clusters were then coated by
SiO2, calcined, and nally etched by NaOH to obtain a
dispersible, magnetically recoverable -Fe2O3/TiO2 composite,
which is shown in Figure 8a. The XRD pattern seen in Figure
8b indicates crystal phases of both anatase TiO2 and -Fe2O3,
and the elemental composition is further conrmed by EDX as
shown in Figure 8d. Due to their high surface area, these
particles had good enrichment capability, which can be seen in
the MALDI-TOF mass spectrum of the enriched -casein
sample in Figure 8c.
Contrary to iron oxides, less research has been conducted on
cobalt oxide/TiO2 composites, although recently there has
been interest in cobalt oxide/TiO2 composites for photocatalysis. CoO is a semiconductor with a band gap of 2.4 eV,
and Co3O4 has a band gap of 2.19 eV. Recently, Zhang et al.
synthesized TiO2 nanotubes by anodization of TiO2 foil,
followed by cathodic deposition of Co(NO3)3 and calcination
to 450 C to form a CoO/TiO2 composite.207 Addition of CoO
resulted in considerable improvement for the photocatalytic
degradation of methyl orange (MO) under UV irradiation. The
enhanced photocatalysis was attributed to the reduced
recombination of photogenerated electrons with holes due to
the pn junction of the CoO/TiO2 composite. A similar
method was utilized by Dai et al., although Co(NO3)2 was
deposited by hydrolysis in a NaOH solution to form Co(OH)2
nanoparticles on the TiO2 nanotubes. The composite was then
decomposed at 220 C to form a Co3O4/TiO2 composite.208
Wang et al. also synthesized a Co3O4/TiO2 composite,
although this was obtained via coprecipitation of TiCl4 and
Co(acac)3 in benzyl alcohol, followed by calcination at 400
C.209 Samples were then tested for UV photocatalytic
hydrogen production from water with either methanol or
ethanol as a sacricial reagent. It was found that the ideal
composition was 2.9 atom % Co, which resulted in a H2
production rate of 2.17 mmol/g h with 10% methanol by
volume. This represents a signicant improvement when
compared to P25, which had a H2 production rate of 0.02
mmol/g h.
Recently, more attention has been given to the fabrication of
Co3O4/TiO2 composite structures for Li+-battery applications.209211 In one such study Luo et al. synthesized TiO2
nanobelts by a hydrothermal reaction between Ti foil and
NaOH, followed by ion exchange with HCl and calcination at
450 C.211 The nanobelts were then introduced into another
hydrothermal reaction with Co(NO3)2, urea, and NH4F at 120
C for 5 h, followed by washing and calcination at 400 C. The
TiO2@Co3O4 composites were then coated with graphene
oxide to complete the synthesis and showed capacities of 431,
345, and 204 mA h/g at 100, 200, and 800 mA/g,
respectively.
2.4.2. Nickel, Copper, and Zinc. Both nickel and copper
oxides have been extensively studied in composites with TiO2.
Figure 7. (Top) Scheme of as-synthesized composite structure.

(Bottom) TEM images of (a) Fe3O4, (b) Fe3O4/SiO2, (c) Fe3O4/
SiO2/TiO2, and (d) calcined Fe3O4/SiO2/TiO2 particles. Insets in c
and d are magnied images of portions of the composite particles
showing the morphological change in the TiO2 shell due to
calcination. Adapted with permission from ref 203. Copyright 2010
John Wiley and Sons.
TiO2 composite as shown in Figure 7c.203 Finally, the

composite was calcined at 500 C to crystallize the TiO2
shell. As shown in Figure 7d, the as-calcined structures are
uniform and have well-dened morphologies with anatase
crystalline TiO2 on the surface. The composites also showed
good photocatalytic activity for degradation of RhB under UV
irradiation which exceeded that of P25. Further, the magnetic
recoverability and good cyclability allowed for a catalyst which
showed little drop in eciency over 18 cycles. The synthetic
control shown for these systems indicates that other features
could be added as desired, such as noble metal nanoparticles for
further enhanced photocatalytic activity.
A separate application for magnetic iron oxide/TiO 2
composites that has shown promise in recent years is
magnetically recoverable TiO2 for phosphopeptide enrichment.15,17,1924 The eld of metal oxide anity chromatography (MOAC) has seen an increase in research partially due to
magnetically recoverable composites, which allow for easy
separation of phosphopeptides from a complex mixture.18
MOAC relies on the anity of phosphorylated peptides for
metals in metal oxides. The Lewis base phosphate group can
bind in a bidentate fashion to the Lewis acid metal oxides, and
when the pH and solvent are optimized, the phosphate group,
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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.
for pseudocapacitive properties,232 and Wang et al. utilized

NiO/TiO2 nanowire arrays to fabricate stable (to 600 cycles)
composites with a high areal capacity.233 While these studies
can still benet from additional optimization, they have shown
promise for potential pseudocapacitor applications.
Copper oxides have been heavily researched as composites
with TiO2 recently due to their inherent p-type conguration.
The band gaps of CuO and Cu2O are 1.4 and 2.2 eV,
respectively, which makes both materials promising for research
in the conversion of solar radiation.35,234,235 Most composites
featuring copper oxides have shown a considerable dependence
on the copper oxide loading percent in order to create optimal
catalysts. The photocatalytic degradation of organic molecules
over Cu2O/TiO2 composites has been of particular interest,
especially to extend the activity of TiO2 to visible wavelengths.
In addition to visible light excitation, formation of a type II
heterojunction between the n-type TiO2 and p-type Cu2O leads
to improved charge separation where photoexcited electrons
are passed from Cu2O to TiO2 and holes remain localized in
Cu2O. Initial studies utilizing composites of Cu2O/TiO2
showed that deposition of Cu2O onto P25 enhanced both
the UV and the visible light degradation of dyes as compared to
bare P25.236239 Recently, other architectures have been
considered as well, including Cu2O deposited on TiO2
nanowires, Cu2O on TiO2 nanosheets, and Cu2O@TiO2
core@shell structures, all of which showed improved organic
molecule degradation under visible light when compared to
pure TiO2.240242 Chu et al. prepared Cu2O@TiO2 coreshell
heterojunction composites by precipitation of Cu2O from
CuCl, followed by direct coating with titanium(IV) nbutoxide.241 Samples were subsequently calcined at 400 C
Nickel supported on TiO2 has been of interest for decades for a

wide range of catalytic reactions such as hydrogenation,212214
reforming,215 as well as others.216218 More recently, however,
nickel oxide and hydroxide composites have been utilized in p
n junction nickel oxide or hydroxide/TiO2 catalysts for
photocatalytic organic molecule degradation,219223 hydrogen
production,224226 and DSSCs.227230 In one recent report by
Lin et al., TiO2 nanobelts were produced by hydrothermal
synthesis using P25 and NaOH, followed by treatment with
HCl to form protonated H2Ti3O7 nanobelts.222 The nanobelts
could subsequently be coarsened by hydrothermal treatment in
H2SO4. NiO was deposited on the nanobelts by wet
impregnation with Ni(NO3)2, followed by calcination at 600
C. The products of each step can be seen in the SEM images
in Figure 9ad, which clearly show both the coarsened
nanobelts (Figure 9c) and the NiO deposited on the nanobelts
(Figure 9d). The activity of the NiO/TiO2 composite
nanobelts was then tested by both UV and visible light
degradation of methyl orange (MO), as shown in Figure 9e and
9f. It is apparent that addition NiO, as well as the coarsening of
the nanobelts, greatly improves the photocatalytic activity.
Yu et al. showed impressive results when making a simple
mixture of Ni(OH)2 deposited on P25.224 At an optimized 0.5
wt %, the evolution of H2 under UV irradiation was 3.056
mmol/h g in a 25 vol % aqueous methanol solution. DSSCs
fabricated from deposition of NiO onto TiO2 have been studied
recently, and utilization of NiO produced up to a 16% increase
in cell eciency when compared to cells without NiO.229
Additional studies on nickel/TiO2 composites have been done
with applications in batteries.231233 Kim et al. recently
synthesized NiO/TiO2 nanotube arrays which were measured
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Figure 10. (a and b) TEM images of Cu2O/TiO2 nanosheets, (c)

degradation, and (d) kinetic curves of phenol degradation catalyzed by
pure TiO2 nanosheets and Cu2O/TiO2 nanosheets under visible light.
Chemistry.
production.245249 One study by Lalitha et al. showed

signicant H2 production from Cu2O-decorated P25 using a
5 vol % glycerol:water solution while under simulated solar
irradiation.247 These composite structures have exhibited the
signicant advantage of Cu2O/TiO2 composites, although they
still suer the inherent problem of the thermodynamic
instability of copper(I) oxide.
Copper(II) oxide (CuO), which is the more thermodynamically stable oxide of copper under typical conditions, has also
been utilized in composites with TiO2 as a photocatalyst and
for production of hydrogen.235,250252 A promising recent use
was reported by Mor et al., who developed a pn-junction
diode from TiO2 and CuO/TiO2 nanorod arrays for photoelectrochemical water splitting,235 as shown in the scheme in
Figure 11a. TiO2 and CuO/TiO2 nanotubes were synthesized
from anodization of Ti and TiCu lms on FTO, respectively.
Nanotube arrays are shown in Figure 11b and 11c, which
consisted of 74% Cu26% Ti and showed lengths of 1000
nm, pore diameters of 65 nm, and wall thicknesses of 35
nm. The length could be decreased by increasing the Ti
content, resulting in a sample of 60% Cu40% Ti with similar
pore sizes and wall thicknesses but a length of only 850 nm.
The CuO/TiO2 nanotube arrays could then be calcined to
improve the crystallinity. When the diode was placed under
AM1.5 illumination incident on the TiO2 side, the TiO2
absorbed the UV irradiation and allowed visible light to
penetrate to the CuO/TiO2 side, where it was likewise
absorbed. Since the majority of UV light was absorbed by the
pure phase TiO2, photocorrosion of CuO/TiO2 was minimal
after 5 h of operation in 0.1 M Na2HPO4. The overall
conversion eciency of a water:methanol:diethylamine (5:5:2)
solution was found to be 0.48% and might be improved with
further optimization.
In addition to copper oxides, metallic copper has also seen
some utilization for catalysis.253257 Since metallic copper has
similar properties to silver and gold, it can be photodeposited
onto a substrate and utilized as a cheaper alternative. These
composites to this point have seen use for CO oxidation, H2
production, and dye degradation and as bactericides. However,
as the activity of gold catalysts is typically much higher, use of
metallic copper has not been widespread as of yet.
Figure 9. SEM images of (a) TiO2 nanobelts (NBs), (b) NiONP/

TiO2 NBs, (c) surface-coarsened TiO2 NBs, and (d) NiONP/TiO2
coarsened NBs. Degradation of MO by (e) UV and (f) visible light
where catalysts are (a) pristine TiO2 NBs, (b) NiONP/TiO2 NBs,
(c) surface-coarsened TiO2 NBs, (d) NiONP/TiO2 coarsened NBs,
(e) pure NiO nanoparticles, (f) and P-25. Adapted from ref 222 with
permission from The Royal Society of Chemistry.
under N2 protection to avoid oxidation of the copper(I). The

samples showed a signicant improvement over the as-prepared
pure TiO2 and P25 for photocatalytic degradation of 4nitrophenol under visible light irradiation. It is important to
note that the photocatalytic activity of the composite is much
greater than pure TiO2, despite the fact that adsorbed 4nitrophenol will sensitize TiO2 and improve visible light
photocatalytic activity.243 It is unclear what eect this may have
played on the composite structure; however, it is presumed to
be a minor contributor as compared to the advantages of the
heterojunction created by the composite. A separate report on
the synthesis of core@shell Cu2O@TiO2 composites showed
improved morphological control as well. Su et al. demonstrated
that Cu2O octahedra, which were individually coated with thin
layers of TiO2, could show improved surface voltage, although
photocatalytic experiments were not carried out.244
One study by Liu et al. utilized Cu2O loaded on TiO2
nanosheets with exposed (001) facets.242 Figure 10a and 10b
contains TEM images of 2 nm Cu2O loaded on the TiO2
nanosheets with a 3 atom % Cu loading. Figure 10c and 10d
shows the degradation prole and rate constant plot for visible
light degradation of phenol with the composite structures. It is
evident that Cu2O/TiO2 composites with an optimal Cu
loading show an increase in activity of about 12 times compared
to the undecorated nanosheets and about 3 times greater than
nitrogen-doped nanosheets (NTiO2 NS). In addition to the
degradation of organic compounds, Cu2O/TiO2 composites
have also been demonstrated for photocatalytic hydrogen
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Figure 11. (a) Illustration of photoelectrochemical diode for water

splitting comprised of n-type TiO2 and p-type CuTiO nanotube
array lms, (b) lateral and (c) top view FESEM images of a CuTiO
nanotube array sample. Adapted with permission from ref 235.
Figure 12. TEM images of (a) PS/ZnOTiO2 composite particles

and (b) ZnOTiO2 hollow spheres. Electron energy loss (c) Zn and
(d) Ti element mapping images of ZnOTiO2 hollow spheres.
Reprinted with permission from ref 259. Copyright 2009 American
Chemical Society.
The denition of zinc as a transition metal is arbitrary here,

as it is more accurately described as a post transition metal
based on its available oxidation states having lled d orbitals;
however, it can still be categorized as a 3d-block metal.258
Nonetheless, ZnO/TiO2 composites have been utilized for
photocatalysis,259264 hydrogen production,265,266 and construction of solid state DSSCs.267273 Agrawal et al. developed
a hollow ZnO@TiO2 void@shell@shell structure with good
morphology control and enhanced photocatalytic activity.259
The microspheres, as shown in Figure 12a and 12b, were made
by coating polystyrene beads with ZnO, followed by a
subsequent coating through hydrolysis of titanium(IV)
ethoxide. The microspheres were then rendered hollow by
calcination in air at 550 C. XRD shows a majority anatase
phase with some rutile phase and minor ZnO peaks, indicating
good crystallinity after calcination. The composite structures
showed a signicant improvement for degradation of RhB
under UV irradiation as compared to hollow ZnO or TiO2
alone. Since both oxides have similar band gaps (3.37 for
ZnO and 3.2 for TiO2) and absorb in the UV portion of the
electromagnetic spectrum, the improved photocatalytic activity
of ZnO/TiO2 composites is attributed to more ecient charge
separation due to the favorable band positions of ZnO and
TiO2. When ZnO is irradiated to produce photogenerated
charge carriers, the electrons remain in the ZnO while the holes
transfer to TiO2. This charge separation can improve the
photocatalytic eciency by reducing the recombination rate of
the charge carriers.261
In addition to improved photocatalytic performance, ZnO/
TiO2 composites have been prepared for use as DSSCs. One
early study by Wang et al. showed that additional
coprecipitation of ZnO and TiO2 onto a TiO2-coated FTO
substrate resulted in nearly a 27% improvement in eciency
when the cell was constructed.267 This was attributed to
improved electron transport by ZnO as well as a decrease in
dark current generation. Since ZnO has a greater electron

mobility than TiO2, Park et al. constructed DSSCs from ZnO
particulates and coated them with a TiO2 layer, followed by
calcination at 400 C.269 The TiO2 overlayer led to an increase
in cell eciency from 5.2% to 6.3% or an increase of over 20%,
which was later increased further to 30% upon optimization of
the calcination conditions.270
2.5. p-Block Metals
Many oxides of the p-block metals have been utilized in

composites with TiO2 for a variety of applications. Of these
metal oxides, alumina, or Al2O3, is likely the one most
frequently integrated with TiO2 due to the resultant properties
when both are combined as a catalyst support, e.g., tunable
acidity/basicity. Since there are few other applications which
benet from the combination of TiO2 and Al2O3, these
composite supports will not be further reviewed. Additionally,
those elements which are colloquially referred to as metalloids (Si, Ge, As, Sb, and Te) will also not be specically
discussed here.
Gallium oxide has been scarcely researched for TiO2
composites,74,274278 much of which utilizes TiO2 as a support.
One recent application demonstrated by Chandiran et al. was
the deposition of Ga2O3 atop a TiO2 layer within a DSSC to act
as a tunneling layer; the result was a reduction of the charge
carrier recombination rate by nearly 2 orders of magnitude.278
After four Ga2O3 atomic layer deposition cycles, open circuit
voltages increased from 692 mV to an impressive 1100 mV,
with corresponding increases in Jsc from 3.6 to 5.1 mA/cm2 and
cell eciency from 1.4% to 4.0%. This recent development will
likely pave the way for additional research on Ga2O3/TiO2
composites for DSSC applications.
As with gallium oxide, indium oxideTiO2 composites have
not been considerably researched. Most of the composites that
have been developed have been used for photocatalytic
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degradation of organic molecules.279284 Addition of In2O3,

which has a band gap of 2.5 eV, allows for visible light
absorption of In2O3/TiO2 composites. Further, since the
conduction band of In2O3 (0.63 V versus NHE) is oset
higher than that of TiO2 (0.4 V versus NHE), an ecient
heterostructure can be formed which supports ecient
separation of photogenerated charges.282,283 These benecial
attributes ensure that research on In2O3/TiO2 composites is
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
capacity. The large theoretical specic capacity for SnO2 (790

mAh/g) as compared to TiO2 (170 mAh/g), combined with
the better structural and chemical stability of TiO2, suggests a
promising candidate electrode material.303 Jeun et al.
synthesized hollow SnO2@TiO2 void@shell@shell nanotubes
which show Li+ capacities higher than TiO2, with superior
stability to pure SnO2.302 As shown in the scheme in Figure
14a, the composite was prepared via plasma-enhanced atomic
Figure 14. (a) Schematic diagram of the fabrication procedures and

schematic illustration of Li-ion insertion/extraction in SnO2@TiO2
double-shell nanotubes. (b and c) Cyclability of SnO2 and SnO2@
TiO2 nanotube electrodes at 800 and 1500 mA/g, respectively.
Chemistry.
Figure 13. (a) Rates of RhB degradation mediated by TiO2, SnO2,

nitrogen-doped TiO2, TiO2/SnO2 with dierent Ti/Sn mole ratios,
and nitrogen-doped TiO2/SnO2 with dierent mole ratios under
visible light ( > 400 nm) irradiation. (b) Schematic of the anticipated
charge migration and separation on NTiO2/SnO2 composite
photocatalysts under visible light irradiation. Adapted with permission
from ref 291. Copyright 2012 American Chemical Society.
layer deposition of SnO2 and then TiO2 on polyacrylonitrile

electrospun nanobers. The composites were then calcined at
700 C to burn o the organic core and leave a hollow cavity,
which provided space for expansion of the composite upon Li+
insertion. Figure 14b and 14c shows the stability of the
discharge capacity of the composite structures. After the initial
rst cycle capacity loss and 50 subsequent cycles, the reversible
capacities of the SnO2@TiO2 composites were 300 and 200 mA
h/g at current densities of 800 and 1500 mA/g, respectively.
This compares favorably to the case of pure SnO2 nanotubes,
samples showed better performance under UV irradiation. A

proposed mechanism is shown in Figure 13b. It was asserted
that RhB dye sensitization of the NTiO2 catalyst, followed by
improved charge separation and migration on the composite
structure, was responsible for the improved photocatalytic
activity in comparison to the N-doped TiO2 alone.
SnO2/TiO2 composites have also been used as electrode
materials for a lithium ion battery anode to enhance the
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photoactivity of a Rh/TiO2 composite to enhance the

reduction of CO2 to CO in the reverse watergas shift
reaction (reverse of eq 1).341,342 The reaction conditions,
especially the Rh loading and metallic nature, were controlled
to ensure that the photocatalytic reduction was at its highest
when Rh appeared in a metallic state. Further, the loading
amount of Rh was optimized in order to prevent reduction of
CO to CH4 in a reverse of eq 2, which occurred at high Rh
loading. The Rh/TiO2 composite helps facilitate reduction
through formation of formate ions from the reaction of CO2
and H2 which occurs on the partially reduced Rh surface. It is
worth noting, however, that long irradiation time will decrease
catalytic performance as reduction of Rh to metallic states will
increase dissociation of H2 and thus favor production of CH4
over CO. Ru and Rh/TiO2 composites have also been applied
to the photocatalytic degradation of organic molecules.343347
These composites showed little improvement on their own
when compared to TiO 2 ; however, with addition of
cocatalysts347 or dye sensitization,345 the photocatalytic
eciency increased markedly.
which showed a similar initial capacity but continuously

decreased as the cycling continued.
Bismuth oxide, Bi2O3, composites with TiO2 have seen little
research. However, some recent work has been done for
applications in the photocatalytic degradation of organic
molecules.237,304307 Bi2O3/TiO2 composites have shown
improved photocatalytic degradation rates relative to pure
TiO2, especially when under visible light irradiation.
2.6. Lanthanides
Typically, metals from the lanthanide series are used as dopants

for TiO2 nanomaterials, and as such most research on TiO2
lanthanide composites is limited to a few applications. TiO2
composites with La2O3 have been investigated the most as
supports for catalysis in reactions such as NOx reduction.308310 There are also some reports covering TiO2
composites with Er2O3,311,312 Nd2O3,313 and Eu2O3;314,315
however, the most frequently utilized oxide from the lanthanide
series is cerium oxide, CeO2. Recently, CeO2/TiO2 composites
have attracted signicant attention as a means to improve both
the UV and the visible photocatalytic degradation of organic
molecules.316322 CeO2/TiO2 composites have been shown to
have a higher porosity and surface area compared to pure TiO2
samples, which has proven to be benecial in photocatalytic
degradation.318,322 Further TiO2 has been shown to promote
and stabilize the Ce3+ oxidation state, leading to enhancement
of chemical activity. These Ce3+ centers and corresponding
oxygen vacancies within the lattice of mixed CeOx/TiO2
composites act as hole acceptors which reduce recombination
of charge carriers.316,323,324 Additionally, CeOx/TiO2 composites have shown the ability to enhance the activity of metal
nanoparticles (Cu, Au, Pt) for the watergas shift reaction.325,326 It is believed that the Ce3+ ions with improved
stability in the composites eectively bind and dissociate water
on the oxide surface. In the presence of a metal nanoparticle,
OH bound to the oxide and CO bound to the metal form a
HOCO intermediate to H2 and CO2 gas products. In this case
inclusion of each component is necessary in order to best
improve the reactivity.
CH4(g) + H 2O(g) CO(g) + 3H 2(g)

3.2. Palladium
Much like the later noble metal nanoparticles, palladium

nanoparticle composites with TiO2 have seen an extensive
amount of research in recent years. Utilization of Pd/TiO2
composites has provided improved materials for methanol
reforming,348351 hydrogenation,352,353 photocatalysis,354359
and H2 production.360364 Methanol reforming has shown
considerable potential as a source of hydrogen from hydrocarbons, especially when compared to the energy-intensive
syngas method for hydrogen production. Al-Mazroai et al.
showed that Pd deposited on P25 via an incipient wetness
method showed considerable activity for methanol reformation
under visible light irradiation.350 This room-temperature
synthesis is much less energy intensive than syngas formation,
which occurs at temperatures up to 1000 C.
The enhancement of the photocatalytic activity of TiO2
through addition of Pd nanoparticles is evident by the
numerous reports detailing improved dye degradation capabilities of the composites. One of the simplest methods for
preparing Pd/TiO2 composites is photodeposition of Pd
nanoparticles on P25. Iliev et al. utilized this method to
synthesize a Pd/P25 composite with 0.5 and 1.0 atom % Pd
concentration.354 These composites showed improvement over
the blank P25 samples for degradation of xylenol orange under
UV irradiation. The extension of Pd/TiO2 composites for
degradation under visible light irradiation has been carried out
as well. Mohapatra et al. synthesized TiO2 nanowires from
anodization of Ti foil, followed by functionalization with PdCl2
via an incipient wetness method and subsequent calcination
under H2/Ar atmosphere to crystallize the TiO2 and convert
the Pd salt to metallic Pd.355 The as-synthesized composite
with an optimized 1.25 wt % Pd showed considerable
photocatalytic improvement compared to the bare TiO2
nanotubes.
In addition to dye degradation, photocatalytic H2 production
has also been carried on Pd/TiO2 composites. Early reports
from Fujishima and Honda demonstrated that Pd on P25 can
split water under UV irradiation, with activity near that of
platinum.365 Since this report, considerable eort has been
devoted to improving the activity and extending these
3. NOBLE METAL AND METAL OXIDETIO2

COMPOSITES
3.1. Ruthenium and Rhodium
In early research on TiO2 photocatalysis, ruthenium(IV) oxide

(RuO2) was heavily investigated as a cocatalyst for generation
of O2 during photolysis of water.327332 More recently,
composites consisting of either ruthenium or rhodium with
TiO2 have seen some more classic catalytic uses to date with
little recent research on the topic of photocatalysis. One classic
type of catalytic reaction is the use of TiO2 as a support for Ruor Rh-mediated hydrogenation.333,334 Another such reaction
which has seen research utilizing either Ru or Rh/TiO2
composites is the watergas shift reaction.335,336 In these
composites, TiO2 acts as a support for the active metal in the
conversion of CO to CO2 and H2 as shown in eq 1.
CO(g) + H 2O(g) CO2(g) + H 2(g)
(2)
(1)
TiO2 also acts as a support for Ru and Rh in the catalytic

oxidation of methanol for formation of syngas by the reaction
shown in eq 2.337340 These applications of Ru and Rh/TiO2
composites have been well developed; however, they are also of
less use when compared to other catalysts utilizing either Pt as
the active metal or CeO2 as the support. One study utilized the
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To maximize the eciency of the Pd/TiO2 catalysts,

considerable eort has been made to rationally design and
optimize the morphology of the composite. Recent attention
has been especially given to the synthesis of Pd@TiO2 core@
shell catalysts.366368 In a recent study from Zhang et al., Pd@
TiO2 core@shell particles were synthesized by rst reducing
the palladium precursor salt to form nanoparticles, followed by
addition of a TiF4 solution and hydrothermal treatment at 180
C for 48 h.367 SEM and TEM images of the resulting products
are shown in Figure 16a and 16b, respectively, which clearly
show the core@shell structure. The same procedure was
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
composites to visible light activity. Sayed et al. recently

prepared a nitrogen-doped visible light active Pd/TiO 2
composite.362 This composite showed improved H2 production
by incorporation of N doping as compared to a sample with
only Pd deposition.
Ye et al. prepared TiO2 nanotube arrays by three-step
anodization of Ti foil followed by calcination and hydrothermal
reduction of Pd nanoparticles onto the crystalline TiO2
nanotubes in the presence of polyvinylpyrrolidone (PVP) and
NaI.364 The size of the loading could be tuned via controlling
both the PVP concentration and the hydrothermal reaction
time. Figure 15a and 15b shows the SEM image of the as-
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.
prepared nanotube array, and Figure 15c and 15d shows the
array after hydrothermal Pd deposition. Figure 15e shows a
TEM image of a nanotube with Pd nanoparticles clearly
deposited. Production of H2 was carried out through fabrication
of a three-electrode photoelectrochemical cell (PEC). H2
production is shown in Figure 15f, where the optimal catalyst
utilized a Pd loading of 2.15 wt %, and the optimal PEC was
constructed with the Pd/TiO2 composite as both the
photoanode and the cathode.
Figure 16. SEM (a) and TEM (b) of the as-prepared Pd@TiO2 core@
shell composite. (c) XRD patterns of the as-prepared M@TiO2 (M =
Au, Pd, Pt) coreshell nanocomposites; peaks indicated by dashed
lines, and symbols are ascribed to the anatase phase of TiO2 and the
corresponding noble metal. (d) Performances of M@TiO2 (M = Au,
Pd, Pt) coreshell nanocomposites and commercial TiO2 P25 for
photocatalytic degradation of RhB under irradiation of visible light (
> 400 nm). Adapted with permission from ref 367. Copyright 2011
American Chemical Society.
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reforming and thus hydrogen production.380,381 As the standard

reduction potentials of methanol and ethanol, 0.13 and 0.224 V,
respectively, are lower than the standard reduction potential of
oxygen to water, 1.23 V, use of alcohols is more favorable for
the hydrogen-yielding oxidation as well as prevention of back
reactions. This has resulted in a large number of Pt/TiO2
hydrogen production catalysts utilizing alcohols as the main
reactant (reforming)382387 or as the sacricial reagent in an
aqueous solution.388394 Further, selection of alcohols has been
extended to higher alcohols such as isopropanol and polyols
such as glycerol in order to increase the number of moles of
hydrogen produced in a reaction system. In addition to the
extensive research done on hydrogen production from Pt/TiO2
composites, oxidation/degradation of organic pollutants has
seen a signicant amount of research as well, especially since it
can more easily demonstrate the photoactivity of the
catalyst.395402 The improvement of photocatalytic activity
with Pt incorporation is typically ascribed to formation of a
Schottky barrier at the metalTiO2 interface. This occurs
because the work function of Pt (5.365.63 eV)403 is greater
than that of TiO2 (4.64.7 eV);403,404 so, the electrons
transfer to the Pt and the holes are localized within the TiO2,
thus eectively separating the charge carriers to improve the
photocatalytic eciency.
To enhance the activity of Pt/TiO2 composites, steps have
been taken to optimize the interaction between the Pt and the
TiO2. In one study by Kandiel et al. they were able to eectively
tune the surface area and crystallinity of the TiO2 within their
prepared Pt/TiO2 composite and demonstrate that although a
high surface area is benecial an increase in crystallinity is
preferential.405 The increase in photocatalytic activity is
attributed to the decrease in defect sites, which act as centers
for charge recombination, when the crystallinity increases.
Yu et al. recently showed the improvement of photocatalytic
water splitting when using Pt on TiO2 nanosheets with exposed
(001) facets as the catalysts.406 The nanosheets, as shown in
Figure 17a and 17b, were prepared via a hydrothermal method
with titanium(IV) n-butoxide and hydrouoric acid and had
previously showed improved photocatalytic activity by testing
dye degradation as compared to P25.407 The HRTEM image in
Figure 17b clearly indicates the lattice spacing parallel to the
top and bottom facets is 0.235 nm, corresponding to the
(001) plane of anatase TiO2. Pt nanoparticles were then
photodeposited onto the nanosheets, as shown in Figure 17c
and 17d. When Pt nanoparticles were incorporated, photocatalytic hydrogen production from an aqueous ethanol
solution increased as compared to both the nonplatinized
sheets with exposed (001) facets and the platinized nonfaceted
particles.
Also of note, the uoridated surface increased the activity
compared to the nonuoridated one as well. This was
attributed to the ability of uoride surface ions to trap
electrons, which would slow recombination of the charge
carriers and then transfer them to the Pt surface. It is evident
from these studies that further optimization of TiO2 can greatly
benet the photocatalytic activity of Pt/TiO2 composites in the
future.
One further phenomenon that has been found in Pt/TiO2
composites is a red shift of the absorption spectra. Although
not frequently reported, it has nonetheless been apparent in a
number of studies.397,408410 This red shift has been attributed
to unreduced Pt species, as Pt(OH)2 or PtO2, on the surface of
the TiO2 producing lower energy levels on the surface and
both the utility of Pd/TiO2 composites and the potential as

core@shell catalysts.
3.3. Platinum
Since the initial reports of hydrogen evolution from water by

Honda and Fujishima, platinum has been intertwined with
TiO2, even as a just a simple electrode. Kiwi and Gratzel rst
demonstrated the promotion of hydrogen evolution from water
utilizing poly(vinyl alcohol)-stabilized Pt colloids.369 Later Kiwi
et al. demonstrated the visible light photolysis of water to
produce H2 and O2 on a composite consisting of Pt/RuO2/
TiO2,327 which was followed by subsequent studies from the
same group.328331 From these studies as well as others at the
time, photocatalytic production of H2 by Pt/TiO2 composites
has consistently shown an increasing amount of research.365,370,371 Additionally, other researchers were utilizing
Pt/TiO2 composites as well for other photocatalytic reactions.
Kraeutler and Bard showed that a Pt/TiO2 composite can
catalyze the decomposition of acetic acid selectively to methane
under UV illumination.372 Further work from Bard showed
signicant development of Pt/TiO2 for a number of reactions
such as decarboxylation, radical-induced synthesis of amino
acids, and decomposition of organic molecules.373375 These
studies, among others, cemented the role of Pt in TiO2
composites. Recently, with the advances in nanoscale synthesis
and controllable/tunable properties of nanomaterials, interest
in Pt/TiO2 composites has only increased. Synthetic controls
have allowed for optimization of parameters such as
morphology, crystal phase, crystallinity, porosity, and surface
area, each of which can alter the photoactivity of a composite.
Other optimization of the photocatalytic system, such as use
and type of sacricial agents, has seen a considerable amount of
research as well.
Although Pt/TiO2 composites have been frequently utilized
for production of hydrogen from water, there is a signicant
drawback that must be considered. As reported by Sato et al., a
Pt/TiO2 composite (as well as Pd/TiO2 and Rh/TiO2) not
only catalyzes production of H2 and O2 from water but also
catalyzes the back reaction as well.376 As such, eective water
splitting was not possible. Sayama and Arakawa later showed
that addition of an aqueous solution of sodium carbonate to a
reaction system containing Pt/TiO2 eectively suppresses the
back reaction and therefore promotes formation of both H2 and
O2.377,378 The role of the carbonate was proposed to be both a
preferential adsorbate as compared to O2 and a hole (h+)
scavenger. The carbonate species as hole traps could then form
peroxocabonates which could irreversibly decompose to CO2
and O2. This production of O2 does not need to be on the
catalyst surface, and as such, it is less likely to quickly react with
H2 to form water. Iodide anions have also been found to be
advantageous for production of hydrogen and oxygen.379 It was
found that addition of iodide can bind to the Pt surface and
form an iodine layer which can also suppress recombination of
H2 and O2 at the Pt surface. It must be noted though that
addition of too much of either anion will reduce the benecial
aspects as too much will bind to the Pt surface and leave too
few reactive sites for hydrogen reduction. More recently,
however, the focus of reaction systems has been on hydrogen
production rather than oxygen production, and thus,
production of hydrogen has been supplemented by addition
of alcohols such as methanol or as a sacricial hole acceptor.
Early work by Kawai and Sakata showed the ecacy of a Pt/
TiO2 composite for photocatalytic methanol and ethanol
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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

some visible light photocatalysis; however, it implies that the
stability of these catalysts is likely limited since further
photoexcitation of the TiO2 will complete the reduction of
the Pt species to metallic platinum and thus likely eliminate the
red shift produced. It is further possible that a small amount of
doping may occur, as this can lead to a red shift in the
absorption as well by producing sub energy levels between the
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
structures.
Figure 18. IPCEs and overall cell trends. (a) IPCEs for cells with 125
cycles of amorphous TiO2. (b) IPCEs for cells with silver NPs and dye.
Arrow indicates increasing TiO2 thickness. Top four spectra and
bottom four spectra correspond to amorphous and anatase TiO2,
respectively. (c) Eciencies of the cells. Dark blue, orange, and green
symbols correspond to anatase samples. Light blue, red, and yellow
symbols correspond to amorphous samples. (d) Calculated plasmonenhancement factor as a function of TiO2 thickness. Reprinted with
permission from ref 417. Copyright 2009 American Chemical Society.
yielded the greatest enhancements in the incident photon

conversion eciencies (IPCEs) due to the larger electromagnetic eld imparted on the dye by the LSPR of the silver
nanoparticles. This in turn led to greater cell eciencies as
shown in Figure 18c.
In order to better examine the eects of the metalTiO2
interaction in a Ag/TiO2 composite, core@shell Ag@TiO2
structures have been synthesized. Initial core@shell composites
were produced for drug delivery systems by Liz-Marzan et
al.,440,441 followed by others;420,442445 however, core@shell
Ag@TiO2 composites made specically for studying the
interaction were rst synthesized and studied by Hirakawa
and Kamat.446,447 Hirakawa and Kamat showed a reversible
charging and discharging of the Ag core by photogenerated
electrons from the TiO2 shell. When the composite was
irradiated, electrons moved to the Ag core where they were
trapped as the holes generated in the TiO2 were scavenged by
ethanol. As electrons were captured by the Ag core, the surface
plasmon resonance band would subsequently blue shift up to
30 nm, as shown in Figure 19a. Irradiation of the system would
then be discontinued, and once an electron acceptor was added
to the system, the electrons would be discharged by the Ag core
and the SPR band would red shift nearly back to its initial
position. This serves to indicate the propensity of a metal,
based on the work function in relation to TiO2, to capture
photogenerated electrons from TiO2 rather than to inject them
via LSPR.
3.4. Silver
Due to its low cost, as compared to other noble metals, intense

localized surface plasmon resonance (LSPR), and easy shape
control, silver nanomaterials have been utilized in composites
with TiO2 to a signicant extent. Silver has been utilized widely
with TiO2 in order to make composites for photocatalytic
organic molecule degradation,199,412415 DSSCs,416423 photoactive bactericides,424430 photochromic materials,431437 and
other applications. Although silver cannot recombine H+ atoms
for hydrogen production, based on its slightly larger work
function, 4.7 and 4.6 eV for Ag and TiO2, respectively,413,438
it still has the capability of attracting photogenerated electrons
from TiO2 and thus improving charge separation. As such,
many initial reports showed the improved UV photocatalytic
degradation of organic pollutants by Ag/TiO2 composites as
compared to bare TiO2.
Although the exact nature of the LSPR eect on enhanced
photocatalytic activity is not entirely understood, it is clear that
it improves the photocatalytic activity of TiO2 and generation
of photoelectrochemical current. In one study, Awazu et al.
demonstrated that direct contact between Ag and TiO2 is not
necessary for photocatalytic enhancement, suggesting that the
increase in the electromagnetic eld by the Ag LSPR was the
cause.439 In their study the silver nanoparticles were embedded
in SiO2 layers with dierent thicknesses, followed by a TiO2
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are comparable to or better than Pt/TiO2 composites for

hydrogen production when under visible light irradiation
because of the LSPR eect of gold in visible wavelengths.
In addition to applications for organic molecule degradation
and hydrogen production, Au/TiO2 composites have been
heavily used for CO oxidation, which is of environmental
importance due to its release from fossil fuel burning in internal
combustion engines. Au/TiO2 composites have been shown to
eectively convert CO to CO2, even at temperatures below 0
C.449,450 Additionally, a variety of factors can aect the activity
of Au/TiO2 composites for CO oxidation, most notably the size
of the Au particles, but also crystallinity of TiO2 and
preparation method of the composite.451454 Deactivation of
the composite due to sintering of Au particles is particularly
important because for practical applications such as catalytic
converters the composite would be subject to high temperatures (>750 C). To prevent this deactivation, one recent
study by Lee et al. used a yolk@shell Au@TiO2 catalyst which
can eectively prevent sintering of Au nanoparticles by placing
a physical TiO2 barrier.455 In this report, they synthesized a
Au@TiO2 composite consisting of a gold nanoparticle (15
nm) within an otherwise hollow TiO2 shell. The composite was
made by coating Au nanoparticles rst with a SiO2 layer and
then coating the composite with a TiO2 layer. SiO2 could then
be removed from the composite by dissolution with NaOH as
shown in Figure 20a. The composite could then be calcined
and crystallize the TiO2 with no change to the Au nanoparticle
as shown in Figure 20b. This result was compared to
calcination of an Au/TiO2P25 composite where it is clearly
evidenced that the Au nanoparticles sinter substantially (Figure
20d). By comparison to the as-prepared Au/TiO2P25
composite, the yolk@shell composites had similar CO
oxidation activity, as shown in Figure 20e. Although the
catalyst was not signicantly improved, there is still room for
improvement by both decreasing the size of the Au
nanoparticle and improving the crystallinity of the TiO2 shell.
Production of hydrogen from Au/TiO2 composites has seen
a considerable amount of research, although for most reactions
the activity is commonly lower than that of both Pd/TiO2 and
Pt/TiO2.350,438,456,457 Regardless, Au/TiO2 composites have
been applied to reactions for hydrogen production from water
splitting with a sacricial agent,360,388,393,458460 steam and
alcohol reforming,461466 and the watergas shift reaction.253,363,467469 Sastre et al. recently detailed a systematic
study in which they compared various noble metal catalysts of
the same loading on P25 for their photoactivity in hydrogen
production from the watergas shift reaction under simulated
solar light.363 As shown in Table 1, the Au/TiO2 catalyst
showed the highest CO conversion percent as well as the
highest H2 production when compared to other noble metal
catalysts and Au supported on CeO2. Additionally, the catalyst
showed little syngas reactivity as evidenced by the relatively
minor formation of CH4.
Au/TiO2 composites have also been shown to be highly
ecient for photooxidation of organic molecules.255,399,470477
More importantly, many of these catalysts have utilized visible
light irradiation to induce the photoactivity. In one recent study
by Zhang et al. a coreshell hierarchical SiO2@Au@TiO2
composite was developed that had high photocatalytic activity
for degradation of RhB.474 The composite was synthesized
starting with a SiO2 core, to which Au nanoparticles were
chemically attached via interactions with an amine-modied
SiO2 surface. The composite was then coated with TiO2 and
Figure 19. (A) Absorption spectra of Ag@TiO2 colloids in ethanol.

(a) Before UV irradiation, (b, c, and d) after exposure to UV light ( >
300 nm) for 10, 30, and 60 s, and (e) after exposure of the UVirradiated suspension to air. Transmission electron micrograph is
shown in the inset. (B) Shift in the plasmon absorption peak during
UV excitation followed by its exposure to air. Bottom schematic
illustrates the mechanism of the photoinduced charge separation and
charging of the metal core in Ag@TiO2. Adapted with permission
from ref 446. Copyright 2004 American Chemical Society.
Since the antibacterial eect via the oligodynamic eect of

colloidal silver has been common knowledge scientically for
over a century, nding a method to enhance its activity while
mitigating the leaching of silver is benecial. Due to this, Ag/
TiO2 composites have also seen a signicant amount of
research in the past decade. Ag/TiO2 composites have been
shown to be very eective in eliminating bacteria and
preventing growth of bacteria such as Staphylococcus aureus
(S. aureus) and Escherichia coli (E. coli) in Ag concentrations
less than 10 g/mL. Remaining under this concentration is of
utmost importance as it is the point at which silver becomes
toxic in human cells.448 One report by Zhang et al. showed that
when utilizing small Ag nanoparticles in a 3.9 wt % Ag/TiO2
composite E. coli growth could be suppressed by 99.9% when
the concentration of Ag was as low as 1.6 g/mL. These
composites have shown utility for low-cost, highly active
antibacterial applications.
3.5. Gold
As compared to both platinum and silver, gold has advantageous characteristics of each. Like silver, gold has a tunable
LSPR which can be utilized to improve photocatalytic activity,
but gold also has a more robust chemical stability akin to
platinum that silver does not have. Further, like platinum, gold
has a high work function (5.15.3 eV).403,438 On the basis of
this, Au/TiO2 composites are used for many of the same
applications as Pt and Ag, with some improvements depending
on the specic case. In general, Au/TiO2 composites have
better photoactivity than Ag/TiO2 composites because the
higher work function of gold as compared to silver allows for
better charge separation from TiO2. Au/TiO2 composites also
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Table 1. Photocatalytic Activity for Hydrogen Evolution and

Product Distribution after 22 h Irradiation with
Concentrated Sunlighta
photocatalyst
TiO2
Pd/TiO2
(1%)
Pt/TiO2
(1%)
Au/TiO2
(1%)
Ag/TiO2
(1%)
CeO2
Au/CeO2
(0.2%)
Au/CeO2
(0.5%)
CO
conversion
(%)
H2
production
(mol/g
catalyst)
CO2
production
(mol/g
catalyst)
CH4
production
(mol/g
catalyst)
3
24
264
4178
649
4585
4
1
25
4279
4763
64
71
10 506
13 447
10
1650
1823
4
8
350
1380
607
1526
5
15
28
4880
4762
Chemistry.
composite completely degraded the dye in 40 min, whereas in

the same time commercial P25 had only degraded 38% of the
dye. Further, the optimal catalyst showed a signicant decrease
in the amount of gold necessary compared to many other
catalysts as the optimal loading amount was only 0.10 wt %.
The catalyst also showed improvement by nitrogen doping of
the TiO2 shell, which was supposedly doped by decomposition
of the amine layer when the composite was calcined.
4. NONOXIDE SEMICONDUCTORTIO2 COMPOSITES

Nonoxide semiconductors (e.g., CdS, CdSe, GaP) have seen an
increase in their utilization in composites with TiO2 after
development of quantum dot-sensitized solar cells (QDSSCs).
In addition to QDSSCs, other applications centered on
photocatalysis have led to a signicant interest of these
nonoxide semiconductors in composites with TiO2. Controlling
the size of quantum dots allows for the ability to tune the
energetics of the composite system which allows for easier
fabrication of composites with desired properties.
Figure 20. (a) TEM image of as-prepared Au@TiO2 yolk@shell

structure. (b) TEM of calcined Au@TiO2 yolk@shell structure. (c)
TEM image of Au/P25 sample as prepared. (d) TEM image of Au/
P25 sample after calcination. (e) Time dependence of the carbon
monoxide coverage on gold (CO, circles) and the carbon dioxide
partial pressure (PCO2, squares) during room-temperature oxidation of
CO with O2 on gold/titania catalysts. The two left-hand panels
correspond to our Au@TiO2 yolk@shell catalyst and the two righthand panels to a reference Au/TiO2P25 sample. First and third
panels were obtained by rst introducing 200 Torr of CO into the cell
and then adding 200 Torr of O2; in the second and fourth panels the
sequence was reversed. The coverage of CO on Au and the gas-phase
CO2 pressure were estimated from the integrated intensities of the
DRIFT signals in the 20902145 and 23002400 cm1 regions,
respectively. Turnover frequencies (TOF), in units of molecules of
CO2 produced per surface Au atom per second, are also reported.
Adapted from ref 455 with permission, Copyright 2011 John Wiley
and Sons.
4.1. Metal Pnictogenides
Semiconductors containing pnictogenides (N, P, As, and Sb

anions) have seen limited usage toward composites with TiO2
to this point. Early reports of photoelectrochemical cells for
water splitting showed the ability of composites constructed of
TiO2 anodes and GaP cathodes to form stable self-driven
cells.478480 However, the overall eciencies of these cells
(0.01%) were still too low for practical use. Other metal
pnictogenides have seen some utilization in composites with
TiO2, typically with applications to solar cells. In one study,
Ren et al. coated GaAs nanowires with amorphous TiO2 using
solgel methods and found nearly a 20% increase in their cell
eciency.481 Other pnictogenides using indium as the
precursor have seen usage in composites with TiO2 as
well.482486 In one report by Nedeljkovic et al., InP
nanocrystals were grown directly onto TiO2 nanorods with
the focus on developing composites with good contact for later
applications where charge transfer is important (i.e., solar cells
and photocatalysis). Synthesis consisted of using hydrothermally prepared Na2Ti3O7 nanotubes, which are subsequently treated with acid to obtain H2Ti3O7 and calcined to
calcined at 500 C as shown in the scheme in Figure 21a.

Figure 21c shows the energy-dispersive X-ray (EDX) elemental
mapping conrming the sandwich structure where the Au
nanoparticles are located in between the SiO2 core and the
TiO2 layer. This composite showed impressive photocatalytic
activity of the composite structure for degradation of RhB dye
under direct solar irradiation as shown in Figure 21d. The
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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.
CdSe and vice versa has led to even greater utilization of these
materials. 492494 Additionally, although tellurium is an
increasingly rare element, it has seen a considerable amount
of research in composites with TiO2 as well. The signicant
synthetic controls over size, morphology, and composition of
cadmium chalcogenide nanocrystals495501 has led to a
substantial amount of research and review articles being
published on these composites. In a typical scheme, traditional
dye sensitization is replaced by narrow band-gap semiconductor
nanoparticles such as CdSe, as shown in Figure 22.
This sensitization can be further tuned in terms of excitation
wavelength by controlling the properties of the semiconducting
particles, e.g., shape and composition. Many such composites
have been reported over recent years with varying architectures
and methods, many of which are very promising.502511 One
recent report of interest from the Kamat group was the
development of a solar paint which consisted of CdS, CdSe,
and TiO2 particles dispersed in a mixed tert-butyl alcohol/water
solvent to form a paste.510 This could then be painted onto
conducting electrodes followed by completion of a cell with the
counter electrode and electrolyte to produce a simple solar cell.
Although the highest cell eciency reported was 1.08% with an
open circuit voltage of 585 mV and short circuit current of 3.1
mA/cm2, this technique has the advantage of facile cell
produce TiO2 rods. These nanorods could then be dispersed in

9-octadecene and toluene, where InP nanocrystals could be
grown by oxidation of indium nanoparticles with P(SiMe3)3.
Other composites containing metal pnictogenides such as InAs
and InN have been applied toward fabrication of solar cells with
TiO2 as well, but overall research on these composites has been
limited by the more common usage of metal chalcogenides.
4.2. Metal Chalcogenides
As opposed to metal pnictogenides, metal chalcogenides (S, Se,

and Te anions) have seen a considerable amount of research in
regard to composites with TiO2. Since the most common
composition of quantum dots is of metal chalcogenides (CdS,
CdSe, etc.), quantum dot-sensitized solar cells most commonly
utilize one of these in their composites with TiO2. Additionally,
metal chalcogenides have been further utilized in composites
with TiO2 for improving the photocatalytic activity of TiO2.
Here we will look at some of the key recent developments
regarding metal chalcogenides and TiO2 composite materials.
4.2.1. Cadmium Chalcogenides. The discovery that
cadmium chalcogenides (Cds, CdSe, CdTe) can act as
sensitizers for TiO2 has led to these materials becoming the
prototypical quantum dotTiO2 composites over the past few
decades.487491 Additionally, fabrication of core@shell CdS@
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construction and easy to scale methods. Improvement of this

technique in the future may allow for a much larger commercial
application of QDSSCs for next-generation energy production.
In addition to the development of solar cells, cadmium
chalcogenides have also been utilized in composites with TiO2
for photocatalysis. These composites typically are applied to
either photocatalytic hydrogen production from water512516 or
photocatalytic oxidation of organic molecules517519 since they
can extend the usable wavelengths of light into the visible
region. Although these materials have seen some success,
signicant drawbacks occur such as leaching of the cadmium
ions or in the case of hydrogen production needing sacricial
agents such as Na2S or Na2SO3. Due to this, noble metal and
metal oxide TiO2 composites still show greater promise for
cleaner systems for photocatalysis.
4.2.2. Other Single-Metal Chalcogenides. Although the
most common metal chalcogenide semiconductor materials for
research with TiO2 have been cadmium compounds, other
materials have seen some utilization as well in order to mitigate
the utilization of cadmium which is highly toxic. In recent years,
lead sulde (PbS) has been utilized as a potential composite
with TiO2.520525 PbS is benecial since it has a narrow band
gap (0.41 eV) and a large Bohr exciton radius. PbS can also
improve the photoactivity of TiO2 due to its multiple exciton
generation.521 As such these composites have seen some use for
both photocatalytic and photovoltaic applications and will likely
see more in the future due to the low toxicity of the compound
stemming from its low solubility. Another metal chalcogenide
that has seen some recent research in composites with TiO2 is
tin(II) sulde, SnS.526529 This material is promising as both
tin and sulfur are abundant and have low toxicities compared to
other metal chalcogenides. Fabrication of devices to this point
has been minimal; however, there is signicant room to expand
this in the future.
4.2.3. Semiconductor Alloy Chalcogenides. Alloys of
metals within semiconductor nanoparticles have become an
area of research with an increasing amount of interest. Much of
this is due to the decrease in the necessary amount of either
rare or toxic metals and replacement of them with metals such
as zinc or copper. Alloys such as copper indium gallium
diselenide (CIGS) and copper zinc tin sulde (CZTS) have
begun to be utilized as composite materials with TiO2.530535
Another alloy, copper indium sulde (CuInS2), has seen more
signicant research in composites with TiO2 to date for
applications in both photovoltaics536541 and photocatalysis.542544 Much like other semiconductors, they have shown
great promise to date; however, as they have not been studied
to the extent of systems such as CdS or CdSe, optimization is
still needed to yield results which are to the same eciency as
the better known systems. Recently, both Santra et al. and
Chang et al. established systems where a CuInS2/TiO2
composite for photovoltaic applications has been further
sensitized using CdS.540,541 Addition of CdS into these
composites has been able to increase cell eciencies
signicantly; however, they still fall under the eciencies of
many pure semiconductor/TiO2 composites and will need
further optimization in the future to become feasible.
been some early reports of the observation of CNTs,545 their

isolation by Iijima546 accelerated their utilization over the past
two decades. On the basis of the work function of CNTs, 5
eV,547 it is apparent that they can act as electron acceptors to
more eectively separate photogenerated charges on TiO2.
Initial reports for the synthesis of CNT/TiO2 composites were
made by Vincent et al., who demonstrated the embedding of
multiwall carbon nanotubes (MWCNTs) in an amorphous
TiO2 matrix.548 Hernadi et al. later showed a homogeneous
direct coating of an amorphous TiO2 layer on MWCNTs via
direct, solvent-free impregnation of the nanotubes in liquid
titanium(IV) ethoxide.549 Jitianu et al. then demonstrated a
homogeneous coating via both hydrothermal and solgel
coatings, followed by crystallization by annealing to 300
C.550,551 These solgel coatings deposit a thin homogeneous
TiO2 layer onto the MWCNTs. These coatings could also be
mediated with cetyltrimethylammonium bromide (CTAB);
however, the crystallinity was decreased upon calcination as
compared to those prepared without surfactant. These coating
methods provided the foundation for later utilization of these
composites, and although some CNT/TiO2 composites have
been utilized for photocatalytic hydrogen production,552555
they are more frequently utilized in composites for organic
molecule degradation.556561 Proposed mechanisms for the
CNT-mediated enhancement of photocatalysis on TiO2
composite structures have been investigated and typically fall
under one of three categories:562 (1) CNTs as electron sinks, as
mentioned above;563 (2) excitation of the CNT itself followed
by charge injection into TiO2;564 (3) introduction of carbon
impurities in TiO2 forming TiOC bonds leading to creation
of energy states within the band gap of TiO2 to facilitate visible
light absorption.565 Any of these proposed mechanisms can be
correct depending on the method of preparation of the CNT/
TiO2 composite structure. In addition to improved photocatalytic activity, the composites have the additional benet of
enhanced adsorption of dye molecules onto the CNT surface,
which can enhance the rate of degradation as well. Further,
these composites can be improved by addition of other
cocatalysts such as noble metals, which can further improve
charge separation.359,566,567 In addition to applications for
photocatalysis, CNT/TiO2 composites have been utilized for
applications with DSSCs.568572 Typical CNT/TiO2 composites for DSSC applications indicate that 0.10 wt % CNT is
optimal, with cell eciencies that increase between 19% and
50%. The increase in cell eciencies has been attributed to the
improved electron transport mediated by the CNTs.
Further utilization of CNT/TiO2 composites has been done
for applications to Li+ battery materials.573577 One report by
Cao et al. utilized well-controlled TiO2 coatings on MWCNTs
from hydrolysis of titanium(IV) butoxide to form well-dened
coaxial nanocables, shown in the TEM images in Figure 23a
and 23b.574 These composites could achieve a specic capacity
of 244 mA h g1 at a current density of 3000 mA g1, as shown
in Figure 23c. This capacity was retained when cycled over 100
times under a current density of 1000 mA g1 and within a
potential window of 0.013 V (Figure 23d).
5. CARBONTIO2 COMPOSITES
Graphene, which has many extraordinary properties such as

high electron mobility and surface area, has been investigated
heavily with respect to composites with TiO2 over the past
decade. Similar to the case of carbon nanotubes, the higher
work function of graphene (4.95.2 eV)578,579 with respect to
5.2. Graphene and Graphene Oxide
5.1. Carbon Nanotubes
The emerging prominence of carbon nanotubes (CNTs) has

led to their use across many applications. Although there had
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on the surface of amine-functionalized amorphous TiO2

microspheres.598
Figure 23. (a) TEM images of TiO2-precursor-coated CNTs. (b)

HRTEM images of CNT@TiO2 nanocables. (c) Comparison of the
rate performance of CNT@TiO2, TiO2-free CNT, and CNT-free TiO2
sample between voltage limits of 0.013 V. Specic storage capacities
in CNT core and TiO2 sheath are also shown. Shaded areas represent
the capacity contribution from TiO2 or CNT in the CNT@TiO2
nanocables. (d) Cycling performance of CNT@TiO2 nanocables
under a current density of 1000 mA g1 between voltage limits of
0.013 V. (Inset) Corresponding Coulombic eciency proles.
Adapted with permission from ref 574. Copyright 2010 American
Chemical Society.
TiO2 allows for an increase in charge separation by electron

injection into the graphene sheets. Chemical utilization of
graphene has been established through reduction of graphene
oxide (graphitic oxide, GO) sheets, which are commonly
synthesized by the Hummers method580 or a modication
thereof.581 Reduction is done by a number of means such as by
hydrothermal/solvothermal treatment582 or, more frequently,
in situ with TiO2 deposition. One recent study by Zhu et al.
simultaneously formed the graphene/TiO2 composite and
reduced the GO sheets by utilizing TiCl3 as the reductant for
GO and precursor for TiO2.583 Concurrent reduction of GO
and crystallization of TiO2 is one of the optimal methods as it
provides good contact between the two materials with wellcrystallized morphology. It must be noted that reduction is not
always carried out in prior reports, and many claimed
graphene/TiO2 composites are in reality graphene oxide/
TiO2. These graphene/TiO2 composites have seen applications
in the construction of DSSCs,584586 Li+ battery applications,587592 and, most prominently, enhanced photocatalysis.593602
One simple composite reported by Zhang et al. consisted of
graphene oxide mixed with P25. The components were mixed
and held at 120 C for 3 h in waterethanol mixture within a
Teon-sealed autoclave to achieve both reduction of the GO
and deposition on P25.593 This P25graphene (P25GR)
composite showed improved photoactivity for degradation of
methylene blue under both UV and visible light irradiation, as
compared to bare P25, and a slight improvement when
compared to a P25carbon nanotube composite as shown in
Figure 24. In a study by Lee et al., graphene oxide was wrapped
Figure 24. Photodegradation of methylene blue under (a) UV light

and (b) visible light ( > 400 nm) over (1) P25, (2) P25CNTs, and
(3) P25GR photocatalysts. Reprinted with permission from ref 593.
These composites were then hydrothermally treated to

reduce the GO, followed by calcination under argon at 400 C.
Figure 25ad shows the synthetic scheme with corresponding
SEM images of the composite. Figure 25b shows the positively
charged, amine-functionalized TiO2 microspheres, and Figure
25c shows the composite structure after the negatively charged
graphene oxide is wrapped on the positively charged TiO2.
Figure 25d then shows the composite after hydrothermal
treatment. At this stage the graphene oxide has been reduced to
graphene and the TiO2 has crystallized to anatase phase.
Samples showed improved photocatalytic activity compared to
a two-step method where GO was coated on precalcined
anatase microspheres and then subsequently reduced, indicating that the order of preparation was critical. Degradation of
MB by visible light is shown in Figure 25e, showing the
improved photocatalytic activity of the composite as compared
to P25, bare anatase particles, and the two-step method.
An extension of this method was later shown by Zhang et
al.,602 where they wrapped GO on a core@shell SiO2@amine
TiO2 composite, followed by reduction and etching of the SiO2
core to form a hollow TiO2/GO composite structure. With the
simplied synthesis of graphene only recently established it is
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carbon coating on P25 from hydrothermal deposition by

glucose, followed by graphitization of the carbon by calcination
at 800 C under nitrogen.612 The study showed that there was
an optimal thickness of the carbon layer for enhancement of the
photocatalytic degradation of formaldehyde. It was proposed
then that a thin carbon coating of only a few nanometers can be
benecial for charge separation. However, when the coating is
too thick, absorbance and scattering of photons by the carbon
layer led to less light reaching the TiO2 surface, resulting in a
decrease of the photocatalytic activity.
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.
One template material that has been utilized readily over the
past decade is polystyrene (PS) beads.618629 Zhong et al.
utilized commercially purchased PS beads which were rst
assembled into a crystalline array, followed by inltration with
the solgel precursor, titanium(IV) isopropoxide.619 The
composite could then be immersed in toluene to dissolve the
polystyrene template, followed by sonication to free the hollow
amorphous TiO2 spheres from the substrate. Shiho and
Kawahashi synthesized similar core@shell particles and
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
hollow TiO2 shell to anatase phase. Calcination to 900 C
would crystallize the TiO2 to rutile; however, the shell
morphology would be completely degraded. Using similar
templated composites, Syouan et al. later showed that an
optimal amount of TiO2 precursor allowed for the highest
anatase crystallinity, which in turn yielded the best photocatalytic activity for degradation of MB.625 In addition to PS
beads, TiO2 has also been deposited on other carbonaceous
templates which can easily be burned away to reveal a hollow
TiO2 structure. Most prominently, glucose can be hydrothermally treated to form colloidal carbon spheres.630 Ao et al.
showed that these carbon spheres could then be coated by
TiO2 via a solgel process, followed by calcination to remove
the carbon core.631 Doping of the TiO2 shell for improved
photocatalytic activity was also demonstrated by addition of
Figure 25. (A) Schematic illustration of the synthesis steps for

graphene-wrapped anatase TiO2 NPs. (B) SEM images of bare,
amorphous TiO2 NPs prepared by solgel method. (C) SEM images
of GO-wrapped amorphous TiO2 NPs. (D) SEM images of graphenewrapped anatase TiO2 NPs. All scale bars are 200 nm. (B)
Photodegradation of methylene blue (MB) under visible light ( >
420 nm) by (a) P25, (b) bare anatase TiO2 NPs, (c) grapheneTiO2
NPs (two-step hydrothermal), and (d) grapheneTiO2 NPs. The
weight ratio of graphene to TiO2 in the grapheneTiO2 hybrid
materials was 0.02:1. Adapted from ref 598 with permission, Copyright
2012 John Wiley and Sons.
expected that further research on composites of graphene and

TiO2 is only to increase in the coming years.
5.3. Other Carbon
In addition to the above forms of carbon, other types have seen

usage in combination with TiO2 as well. One such material is
activated carbon (AC), which has been used extensively to
promote the photocatalytic degradation of organic molecules.603608 The high surface area allows for a greater
adsorption of the molecules which can then be more readily
degraded by the TiO2 component. Other carbonized materials
such as polymers, glucose, and sucrose have seen use as either a
template for TiO2 coating or as a coating material on top of
TiO2. Many of these composites are then utilized for
applications in photocatalysis609613 or Li+ battery applications.614617 One report by Zhang et al. demonstrated a thin
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dopant sources during the solgel coating.632634 Although

good control of the coating of TiO2 onto PS beads and glucose
has been demonstrated, it has fallen out of favor as compared to
other templates such as silica.
Coating of TiO2 onto silica templates has been widely
demonstrated over the past two decades with varying degrees of
control.635639 One signicant drawback for many of these
early composites is that after crystallization at high temperature
and removal of the SiO2 the TiO2 shell would collapse. This is
likely due to the large degree of structural reorganization that
occurs upon high-temperature crystallization of the amorphous
shell. Once the SiO2 core is removed, the support for these
crystals is gone and the shell falls apart. Interestingly, if a spacer
of dierent composition, such as PS or SnO2, is placed between
the SiO2 core and the TiO2 layer the shell morphology can be
retained after calcination and removal of either the spacer or
the SiO2 core.640,641 More recently, however, research on these
SiO2@TiO2 core@shell composites has led to synthetic
strategies which yield stable, hollow TiO2 shells.
In a recent report by Joo et al., hollow crystalline TiO2 with
well-dened crystallinity and morphology was synthesized by a
SiO2@TiO2@SiO2 core@shell@shell composite.642 The composite was synthesized by sequential solgel coatings of TiO2
and SiO2 on a colloidal SiO2 core. The composite was then
crystallized by high-temperature calcination, and the SiO2 core
and outer shell materials were removed by dissolution with
NaOH. The as-obtained hollow TiO2 consisted of small anatase
grains (5 nm) and displayed a high surface area (300 m2/g)
and porosity. Although a signicant improvement in morphology was shown, the photocatalytic activity was still minimal due
to the small grains yielding more sites for recombination of
photogenerated charge carriers. It was determined that the
silicate oligomers could penetrate into the amorphous TiO2
matrix and inhibit signicant crystallization, thus resulting in
small anatase grains.643 As such, a subsequent report detailed a
partial etching method where the SiO2 at the SiO2TiO2
interface was selectively dissolved followed by recalcination and
then complete removal of the SiO2.644 It was determined that
the TiOSi bonds are less organized and weaker than the
TiOTi and SiOSi bonds such that they are preferentially
etched.
The scheme and corresponding TEM images in Figure 26
show the evolution of the structure by the reported procedure.
This method could signicantly increase the crystallinity as
shown in Figure 27ad, where the grain size increased from 4
nm (Figure 27a) in the original sample to >14 nm (Figure
27d), as determined by the Scherrer equation from the XRD
pattern (Figure 27e). The hollow shells still showed a highly
porous nature with a high specic surface area (300 m2/g).
The increase in crystallinity yielded hollow TiO2 anatase shells
that had comparable photocatalytic activity to P25 for UV
degradation of RhB. Other methods to both increase the
crystallinity and simplify synthetic procedures have also been
reported utilizing SiO2@TiO2 composites.
Shen et al. recently reported highly crystalline hollow TiO2
shells starting from a SiO2@TiO2 composite.645 After synthesis,
the composite was calcined at a desired temperature and the
silica was removed by etching with NaOH in a Teon-lined
autoclave at 80 C for 4 h. The resulting TiO2 maintained its
well-dened hollow shell morphology with large crystal grains.
These hollow structures have shown well-controlled
crystallinity and porosity that have good photocatalytic activity
and allow for facile transport of reactants into the core of the
Figure 26. (Left) Schematic illustration of the partial etching and

recalcination procedure for fabrication of mesoporous TiO2 shell
nanostructures. (Right) Corresponding TEM images of the SiO2@
TiO2@SiO2 particles after sequential treatments: (a) original
calcination, (b) partial etching, (c) recalcination, and (d) nal etching.
After removing all silica, the products are mesoporous TiO2 shells.
Chemistry.
structure.646,647 Further, they can be functionalized even further

with other shell coatings besides SiO2. One such structure was
previously mentioned where SiO2@TiO2 was coated with
graphene oxide followed by reduction to graphene and
dissolution of the SiO2 core to form a hollow TiO2@graphene
composite.602 In a separate report by Zhang et al., a similar
structure was synthesized but a nal layer of SiO2 was coated
on top of the entire composite. However, the nal morphology
was not as well maintained as other published methods.
6.2. Ordered Mesoporous Silica and Zeolites
Ordered templates based on silica such as MCM-41 and SBA15 and zeolites have seen some usage as hard templates for
synthesis of mesoporous TiO2 materials. These templates allow
for synthesis of highly porous TiO2 networks which can be used
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Figure 28. Four main types of guest assembling inside ordered

mesoporous silica (OMS) nanotubular mesopores: (I) ensemble of
nanoparticles with diameter less than that of OMS mesopores; (II)
isolated nanoparticles of dimension comparable with OMS mesopores
diameter; (III) guest phase layer; (IV) combination of guest
nanoparticles inside the OMS mesopores with large guest particles
at the outer surface of OMS crystals. Reprinted from ref 663 with
permission from Elsevier. Copyright 2005.
synthesis and proliferation of ordered mesoporous silica

structures like MCM-41 and SBA-15 the use of zeolites
decreased.
In one recent study Yue et al. showed that by changing the
type of TiO2 precursor added to a SBA-15 template they could
control the phase and structure of the resulting mesoporous
TiO2.661 Titanium(IV) isopropoxide was hydrolyzed and then
dissolved by dierent acids to yield Ti(NO3)4 or TiCl4. The
precursors were then loaded into SBA-15, followed by
calcination and template removal via etching with NaOH. It
was found that the nitrate precursor would form a
interconnected rutile network upon calcination (Figure 29a,
29c, and 29e), whereas the chloride precursor would form a
particulate network consisting of anatase grains (Figure 29b,
29d, and 29f). These interesting properties allow for the
tailored synthesis of TiO2 from mesoporous silica templates
which are hard to form otherwise.
6.3. Anodized Aluminum Oxide (AAO)
Since the discovery of porous alumina templates made by

anodization of aluminum lms, composites with these
templates have been widely researched. The ease of deposition
of precursors into the alumina pores allows for controlled
height and composition of the deposited nanowires. The
general scheme for synthesis of these nanowires is shown in
Figure 30, where an aluminum lm is anodized to form a
porous network. This anodization can be repeated to control
the pore width and height to better enhance the tuning of the
later deposited material. The pores are then lled by deposition
of the precursor material, e.g., titanium alkoxides, and the
alumina/aluminum can be selectively dissolved to yield free
nanorods/nanowires. Alternatively, commercial alumina templates with larger pore widths (200250 nm in diameter) are
available as lters. These templates can then be utilized in the
same fashion for deposition and subsequent template removal.
These templating methods have made the controllable
synthesis of highly crystalline TiO2 nanowires simple and
reproducible.670679 Single-crystal TiO2 nanowires have been
reported by Zhang et al.673 and Miao et al.674 utilizing
electrochemical oxidative hydrolysis and solgel deposition of
TiO2 precursors, respectively. This templating method has
shown great utility for creation of uniform nanowire arrays
which can be used for DSSCs or photocatalysis.676679
Figure 27. (a) TEM image of mesoporous TiO2 shells after calcining
SiO2@TiO2@SiO2 particles and NaOH etching (sample corresponds
to etched in XRD). (bd) TEM images of hollow mesoporous TiO2
shells prepared by calcination followed by partial etching and
recalcination at (b) 700 C for 4 h (PE-700), (c) 800 C for 4 h
(PE-800), and (d) 800 C for 16 h (PE-80016h). (e) XRD patterns
of ad; PE-600 is not pictured. Adapted from ref 644 with permission
from The Royal Society of Chemistry.
for applications in photocatalytic degradation of organic

molecules,648657 H2 production,658660 and Li+ battery
applications.661,662 Further, easy removal of the template can
be done by chemical etching with NaOH or HF.
Figure 28 shows the typical hostguest interactions between
the template and the TiO2 precursor, with cases IIII being
most common depending on the concentration of precursor
and type of template and case IV not typically seen when using
impregnation methods.663 Composites with zeolites were
initially utilized more frequently due to their abundance and
ease of purchase.664669 These composite structures were
shown to enhance photocatalytic activity of reactions such as
photooxidation of alcohols and water splitting. Later, with the
7. SUMMARY AND OUTLOOK

Synthesis of TiO2 composites materials is a eld that has seen
signicant growth over the past few decades and will likely
increase in the coming years. Enhancements to the photocatalytic activity of TiO2 through the use of composite materials
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Figure 29. (a and c) TEM images of mesoporous TiO2 from nitrate

precursor calcined at (a) 200 and (c) 300 C. (b and d) TEM images
of mesoporous TiO2 from chloride precursor calcined at (b) 200 and
(d) 300 C. (e and f) HRTEM images of mesoporous TiO2 from (e)
nitrate and (f) chloride precursors calcined at 300 C. Reprinted from
ref 661 with permission, Copyright 2009 John Wiley and Sons.
Figure 30. General scheme for formation of nanowire-type materials

from an anodized aluminum template.
addition to these metals, carbon materials may allow for cheap

composites with enhanced activity as well. With the decreasing
cost in the synthesis of carbon materials such as graphene or
with synthetic techniques such as carbonization of glucose,
composites of carbonaceous materials with TiO2 have become
much cheaper and easier to produce. As such they are likely to
see a considerable amount of research in the coming years as an
alternative composite material with signicant advantages such
as good photocatalytic activity and high adsorption capacities.
Templated composites show a signicant number of
advantages that are not always seen with the less ordered
composite materials. Although many template syntheses are
labor and energy intensive, much recent progress has been
made in this eld in order to mitigate this. Yolk@shell
composites hold great promise for high-temperature catalytic
applications where sintering of nanoparticles degrades catalyst
performance. Additionally, some of these structures have
possible applications as nanoreactors or bifunctional catalysts
where the inner core and outer shell are functionalized
dierently. AAO templated synthesis of nanowires has
interesting benets such as making composite nanowires of
altering compositions, which may be useful for future
applications.
Overall, composite TiO2 materials can be synthesized in such
a way that they can take advantage of many properties of
dierent materials and be applied to a signicant number of
has great potential for developing commercial catalysts for

hydrogen production, environmental remediation, production
of ne chemicals, as well as other applications. Further
composites with TiO2 show promise in applications for
improved solar cells and lithium ion batteries. With the
increasing need for clean and sustainable energy sources, TiO2
composite materials may hold the key to developing solutions
to many of these problems.
Composites with materials such as noble metals have been
heavily investigated and hold much promise, though market
prices for these metals may slow progress in their
commercialization. However, optimization of the physicochemical properties of these composites has shown a signicant
reduction in the necessary quantity of noble metals, which will
be of importance to reactions where noble metals remain
necessary. These noble metal/TiO2 composites have shown a
substantial potential for applications in hydrogen production
and environmental remediation, two signicant challenges
society faces going forward. More interestingly, however,
composites with cheaper metals and metal oxides as well as
carbon materials hold signicant promise as they become
further developed in the coming years. These composites with
metals such as copper or nickel and the oxides of each have the
potential to be developed to the point that they may be utilized
in place of noble metals for future applications in order to
reduce costs without a signicant decrease in activity. In
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energy- and environment-related applications. Synthetic strategies such as the design of core@shell Cu2O@TiO2 particles by
controlled hydrolysis and condensation of TiO2 precursor onto
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.
Riverside, under the supervision of Yadong Yin. His research interests

include the synthesis and self-assembly of complex colloidal
nanostructures for energy applications.
AUTHOR INFORMATION
Yadong Yin received his Ph.D. degree in Materials Science and
Engineering from the University of Washington in 2002, then worked
as a postdoctoral fellow at the University of California, Berkeley, and
the Lawrence Berkeley National Laboratory, and became a sta
scientist at LBNL in 2005. In 2006 he joined the faculty at the
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.
Corresponding Author
*E-mail: yadong.yin@ucr.edu.
Notes
The authors declare no competing nancial interest.

Biographies
ACKNOWLEDGMENTS
We are thankful for the nancial support provided by the U.S.
Department of Energy (DE-FG02-09ER16096).
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Composite Titanium Dioxide Nanomaterials

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Composite Titanium Dioxide Nanomaterials

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Review

Composite Titanium Dioxide Nanomaterials

Titanium dioxide (titania, TiO2) has been fervently researched

2014 American Chemical Society

Special Issue: 2014 Titanium Dioxide Nanomaterials

dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889

detailed. It is also necessary to note that a number of

We do concede that many of the composite materials discussed

1.2. Advantages of TiO2 Composites

The photoactivity of TiO2 has been shown to be dependent on

dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889

such, most of the metals below will be discussed as their metal

photogenerated holes remain within the rutile component and

2.1. Group I and II Metals

Due to their high oxidation potentials and instability in aqueous

2. METAL AND METAL OXIDETIO2 COMPOSITES

dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889

to a 0.35 Mg/Ti molar ratio; above this ratio the blockage of

Figure 2. Stability of Voc (open square), Jsc (open triangle), ll factor

MgO layer may reduce the eciency of electrons from excited

2.2. Early Transition Metals

Although oxides of scandium have not been commonly utilized

dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889

composites, where lanthanum will be reserved for the

amount. At this concentration, the cell eciency was found to

dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889

by the ZrO2 allows for stabilization of long-range, ordered

materials. One study by Triyoso et al. showed that in an

2.3.1. Vanadium, Niobium, and Tantalum. Much like

Figure 4. Photocatalytic adsorption, degradation, and reduction of

Hafnium oxide (HfO2 )TiO 2 composites have seen

dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889

a dopant in TiO2 materials. Further, Ta2O5 has also been

Figure 5. Cross-section SEM images of ordered nanotube arrays

dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889

structure, followed by growth of another shell layer on the

2.4.1. Iron and Cobalt. Due to the instability of metallic

Figure 6. (a) Total organic carbon (TOC) removal during MB

TiO2 composite samples only anatase phase is present. This

dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889

as opposed to carboxylic acids especially, can selectively bind to

Figure 7. (Top) Scheme of as-synthesized composite structure.

TiO2 composite as shown in Figure 7c.203 Finally, the

dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889

for pseudocapacitive properties,232 and Wang et al. utilized

Nickel supported on TiO2 has been of interest for decades for a

dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889

Figure 10. (a and b) TEM images of Cu2O/TiO2 nanosheets, (c)

production.245249 One study by Lalitha et al. showed

Figure 9. SEM images of (a) TiO2 nanobelts (NBs), (b) NiONP/

under N2 protection to avoid oxidation of the copper(I). The

dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889

Figure 11. (a) Illustration of photoelectrochemical diode for water

Figure 12. TEM images of (a) PS/ZnOTiO2 composite particles

The denition of zinc as a transition metal is arbitrary here,

dark current generation. Since ZnO has a greater electron

Many oxides of the p-block metals have been utilized in

dx.doi.org/10.1021/cr400634p | Chem. Rev. 2014, 114, 98539889

degradation of organic molecules.279284 Addition of In2O3,

capacity. The large theoretical specic capacity for SnO2 (790

Figure 14. (a) Schematic diagram of the fabrication procedures and

Figure 13. (a) Rates of RhB degradation mediated by TiO2, SnO2,

layer deposition of SnO2 and then TiO2 on polyacrylonitrile

samples showed better performance under UV irradiation. A