2012-Nano-Photocatalytic Materials Possibilities and Challenges

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Nano-photocatalytic Materials: Possibilities and Challenges
Review
Hua Tong, Shuxin Ouyang, Yingpu Bi, Naoto Umezawa, Mitsutake Oshikiri,
and Jinhua Ye*
super-hydrophilicity; (v) photoelectro-

Semiconductor photocatalysis has received much attention as a potential chemicalconversion, etc.
solution to the worldwide energy shortage and for counteracting environ-
mental degradation. This article reviews state-of-the-art research activities in 1.1. Fundamental Principles
the field, focusing on the scientific and technological possibilities offered by of Semiconductor Photocatalysis
photocatalytic materials. We begin with a survey of efforts to explore suitable
materials and to optimize their energy band configurations for specific appli- From the point of view of semiconductor
cations. We then examine the design and fabrication of advanced photocata- photochemistry, the role of photocatalysis
lytic materials in the framework of nanotechnology. Many of the most recent is to initiate or accelerate specific reduc-
tion and oxidation (redox) reactions in
advances in photocatalysis have been realized by selective control of the
the presence of irradiated semiconduc-
morphology of nanomaterials or by utilizing the collective properties of nano- tors. Light absorption and the conse-
assembly systems. Finally, we discuss the current theoretical understanding quent photoexcitation of electron-hole
of key aspects of photocatalytic materials. This review also highlights crucial pairs take place when the energy of the
issues that should be addressed in future research activities. incident photons matches or exceeds the
bandgap.[1–3] In semiconductors, the con-
duction-band (CB) electrons (ecb−) have a
1. Introduction chemical potential of +0.5 to –1.5 V versus
the normal hydrogen electrode (NHE), hence they can act as
Ever since the 1970s, steadily worsening environmental pollu- reductants. The valence-band (VB) holes (hvb+) exhibit a strong
tion and energy shortages have raised awareness of a poten- oxidative potential of +1.0 to +3.5 V versus NHE.[1] Initially, the
tial global crisis. For the sustainable development of human energy of the incident photons is stored in the semiconductor
society, the development of both pollution-free technologies for by photoexcitation; it is then converted into chemical form by a
environmental remediation and alternative clean energy sup- series of electronic processes and surface/interface reactions. In
plies is an urgent task. Among the wide variety of green earth contrast to the thermodynamics of conventional catalysis, not
and renewable energy projects underway, semiconductor pho- only spontaneous reactions (ΔG < 0) but also non-spontaneous
tocatalysis has emerged as one of the most promising technol- reactions (ΔG > 0) can be promoted by photocatalysis. In the
ogies because it represents an easy way to utilize the energy of former case, the input energy is used to overcome the activa-
either natural sunlight or artificial indoor illumination, and is tion barrier so as to facilitate photocatalysis at an increased rate
thus abundantly available everywhere in the world. The poten- or under milder conditions. In the latter case, part of the input
tial applications of photocatalysis are found mainly in the fol- energy is converted into chemical energy that is accumulated in
lowing fields: (i) photolysis of water to yield hydrogen fuel; the reaction products.
(ii) photo-decomposition or photo-oxidization of hazardous In general, a semiconductor photocatalytic cycle com-
substances; (iii) artificial photosynthesis; (iv) photo-induced prises three steps (see Figure 1): first, illumination induces
a transition of electrons from the VB to the CB, leaving an
equal number of vacant sites (holes); second, the excited elec-
Dr. H. Tong, Dr. Y. Bi, Prof. J. Ye trons and holes migrate to the surface; third, they react with
International Center for Materials Nanoarchitectonics (MANA) absorbed electron donors (D) and electron acceptors (A),
National Institute for Materials Science (NIMS) respectively. In the second step, a large proportion of electron-
1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan hole pairs recombine, dissipating the input energy in the
Fax: (+)81-29-859-2301
E-mail: jinhua.ye@nims.go.jp form of heat or emitted light. To prevent the recombination of
Dr. S. Ouyang, Dr. N. Umezawa, Dr. M. Oshikiri, Prof. J. Ye electron-hole pairs, the approach that has generally been
Research Unit for Environmental Remediation Materials applied is to load co-catalysts such as Pt, Pd, NiO, and RuO2
National Institute for Materials Science (NIMS) on the semiconductor surface. The hetero-junctions that are
1-2-1 Sengen, Tsukuba, Ibaraki 305-0047, Japan formed between the host semiconductor and the co-catalyst
Dr. N. Umezawa provide an internal electric field that facilitates separation of
PRESTO, Japan Science and Technology Agency (JST)
4-1-8 Honcho Kawaguchi, Saitama 332-0012, Japan the electron-hole pairs and induces faster carrier migration.
Furthermore, these co-catalysts exhibit better conductivity,
DOI: 10.1002/adma.201102752 lower overpotential and higher catalytic activity than the host
Adv. Mater. 2012, 24, 229–251 © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim wileyonlinelibrary.com 229
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Review
Tua Tong obtained his

B.S degree from Zhejiang
University, China, in 2001, and
he received his PhD degree
from Shanghai Institute of
Ceramics, Chinese Academy
of Science (SICCAS), in 2007.
From 2008 to present, he
works in Prof. Ye’s group
as a postdoctoral fellow at
the National Institute for
Materials Science (NIMS),
Japan. His current research concentrates on the synthesis
and properties of nanostructured photocatalytic materials.
Shuxin OuYang received

his B.Sc. degree from the
Figure 1. Schematic illustration of basic mechanism of a semiconductor Nanjing University in 2004
photocatalytic process. and his Ph.D. degree in
Materials Science from
Nanjing University in 2009
under the supervision of
semiconductor, thus they often act as ideal active sites for Prof. Zhigang Zou and
photocatalytic reactions to proceed. Prof. Jinhua Ye. Since 2009,
he works in Prof. Ye’s group
as a postdoctoral fellow at the
1.2. History of Photocatalytic Materials
National Institute for Materials
Science (NIMS), Japan. He is interested in developing and
The discovery of water photolysis on a TiO2 electrode by
fabricating new photocatalyst, electronic structure of semi-
Fujishima and Honda in 1972[4] has been recognized as the
conductor photocatalyst, and mechanism of Photocatalysis.
landmark event that stimulated the investigation of photonic
energy conversion by photocatalytic methods, although the
history of photocatalysis can be traced back to the 1960s.[5–8] Jinhua Ye received her
Since then, intense research has been carried out on TiO2 PhD from the University of
photocatalysis, which has been focused on understanding the Tokyo in 1990. After that,
fundamental principles,[1,9] enhancing the photocatalytic effi- she joined Osaka University
ciency, and expanding the scope of applications.[10] In addition as a faculty staff, and then
to hydrogen fuel production, many other potential uses of TiO2 moved to National Research
photocatalysis have been identified, such as the detoxification Institute for Metals (former
of effluents, disinfection, superhydrophilic self-cleaning, the name of NIMS) 18 months
elimination of inorganic/organic gaseous pollutants, and the later. She was appointed
synthesis of organic fuels.[10–12] as the managing director
Unfortunately, TiO2 is not ideal for all purposes and per- of Photocatalytic Materials
forms rather poorly in processes associated with solar photo- Center in 2006. She is cur-
catalysis. In principle, TiO2 can utilize no more than 5% of the rently the director of Research Unit for Environmental
total solar energy impinging on the surface of the earth due Remediation Materials, and a Principle Investigator of
to its wide bandgap (3–3.2 eV). During the past decade, much International Center for Materials Nanoarchitectonics
effort has been devoted to modifying TiO2, including energy (MANA), NIMS. She is also an adjunct Professor in
band modulation by doping with elements such as N, C, and Department of Chemistry, Hokkaido University. Her current
S,[13,14] the construction of hetero-junctions by combining TiO2 research interests focus on photo functional materials and
with metals such as Pt or Pd, or other semiconductors such as their applications in the fields of environment remediation
NiO, RuO2, WO3 or CdS,[15–17] and the addition of quantum dots and new energy production.
or dyes on the TiO2 surface for better light sensitization.[18–21]
Simultaneously, the use of conventional semiconductors such
as SrTiO3[22,23] and WO3[24] in photocatalysis has been inves- niobates, tantalates, vandates and germanates, which contained
tigated in the search for possible alternatives to TiO2. During the cations of d0 or d10 electronic configurations such as In3+,
the last decade, great efforts have been made to exploit com- Ga3+, Sb5+, Bi5+, and Ag+.[25–36] These novel semiconductors
plex metal oxides as novel photocatalytic materials, including have proved to be among the most successful photocatalysts.
230 wileyonlinelibrary.com © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2012, 24, 229–251
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For example, NiOx/In1-x NixTaO4 was the first material found
Review
to catalyze overall water photolysis under visible light irradia-
tion.[35] A number of sulfides, nitrides and oxynitrides (CdS,
Ta3N5 and TaON are among the most promising examples)
have been investigated as alternative materials for visible light
or solar photocatalysis.[37] In addition to classic semiconduc-
tors, polymeric C3N4 was recently identified as a new photocata-
lyst for the production of hydrogen from water under visible
light.[38]
After a period of lower activity in the 1980s and 1990s,
interest in photocatalysis research from a scientific and engi-
neering viewpoint has grown exponentially. This is largely due
to the rapid development of nanotechnology and advanced
characterization techniques such as TEM, EELS, and XPS,
which provide great opportunities for photocatalysis to realize
its anticipated potential. Through persistent effort over the past
forty years, remarkable progress has been made in semicon-
ductor photocatalysis. A number of commercial photocatalytic
products, including air purifiers and self-cleaning windows, are
already on the market. However, for other important applica-
tions such as the production of hydrogen and organic fuel or
the fabrication of photoelectrochemical solar cells, much devel-
Figure 2. Band-edge positions of semiconductor photocatalysts relative
opment is still needed before commercialization is possible. to the energy levels of various redox couples in water.
1.3. Main Challenges and Opportunities solid-solution strategies have been extensively investigated and
applied.[51–57] Furthermore, the inter-particle electronic coupling
As we have seen, nanomaterials have emerged as pioneering of semiconductor nanocrystals has recently been found effective
photocatalysts and account for most of the current research for energy band reconstruction and bandgap narrowing.[58,59]
in this area. Nanomaterials can provide large surface areas, The utilization efficiency of incident photons in semiconductor
abundant surface states, diverse morphologies, and easy device photocatalytic materials can be further improved by methods
modeling, all of which are properties beneficial to photocatal- other than energy band engineering, such as the improve-
ysis. Significant progress has been made in the development of ment of light sensitization by the inclusion of quantum dots,[60]
novel nanomaterials in recent years.[39–49] Nevertheless, the effi- plasmon-exciton coupling between anchored noble metal nano-
ciency of nanomaterials, especially in solar photocatalysis, must particle co-catalysts and the host semiconductor,[61] and photon
be improved in order to meet engineering requirements. Fur- coupling in semiconductor photonic crystals.[62]
thermore, the stability and cost of these materials should also Another key issue influencing the photocatalytic capability
be carefully considered. It is thus a challenge of great impor- of a semiconductor is the nature of its surface/interface chem-
tance to identify and design new semiconductor materials that istry. The surface energy and chemisorption properties play
are efficient, stable and abundant. crucial roles in the transfer of electrons and energy between
The first property relevant to the photocatalytic activity of a substances at the interface, in governing the selectivity, rate
semiconductor is its energy band configuration, which deter- and overpotential of redox reactions on the photocatalyst sur-
mines the absorption of incident photons, the photoexcitation face, and in determining the susceptibility of the photocata-
of electron-hole pairs, the migration of carriers, and the redox lyst toward photo-corrosion.[63,64] In general, a higher surface
capabilities of excited-state electrons and holes.[50] Therefore, energy yields higher catalytic activity. Recently, much interest
energy band engineering is a fundamental aspect of the design has been focused on research into semiconductor crystals with
and fabrication of semiconductor photocatalysts. Regarding morphologies that provide large percentages of highly reactive
optical absorption, direct and narrow bandgap semiconductors facets.[65–67] Attempts to deliberately fabricate such materials
are more likely to exhibit high absorbance and hence be suitable are challenged by the thermodynamic growth mechanisms of
for the efficient harvesting of low energy photons. However, the the crystals. The selective absorption of polymers or ions on
recombination probability for photo-excited electron-hole pairs is high-energy facets has been employed to suppress the growth
rather high in these types of semiconductors, and the band-edge rate along their axes. In this way, it is possible to grow specific
positions are frequently incompatible with the electrochemical nanostructured materials with surfaces that are nearly 100%
potential that is necessary to trigger specific redox reactions (see comprised of high-energy facets; examples include ultra-thin
Figure 2). Some renowned photocatalysts such as TiO2 and WO3 sheets and highly symmetric polyhedral particles. The stronger
are in fact indirect bandgap semiconductors, but they exhibit the sorption of reagents and desorption of products on the
an abrupt onset of absorption like direct bandgap semiconduc- photocatalyst surface, the easier and faster the photocatalytic
tors. In order to modulate the bandgap and band-edge positions process. Therefore, appropriate modification of the surface is
in a precise manner, both doping with different elements and frequently necessary to facilitate photocatalysis.
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Despite important insight being gained, the mechanisms

Review
involved in photocatalysis are not yet known in detail. Fulfilling

this goal requires the help of theoretical investigations such as
electronic structure calculations and molecular dynamic simu-
lations. Indeed, the theoretical study of photocatalysis has pro-
gressed rapidly alongside the experimental work. The above
computational methods require a degree of understanding of
photocatalysis. The calculation results obtained then raise the
level of this understanding and provide guidance toward the
practical improvement of photocatalytic materials and their
applications.
In recent years a number of literature reviews have appeared,
dealing with diverse topics in the field of photocatalysis such as
the basic principles,[68,69] surface/interface photochemical proc-
esses,[70] environmental remediation,[71,72] water photolysis,[73,74]
materials development,[75,76] and artificial photosynthesis.[12,77]
Here we go beyond the scope of the above reviews and focus
on the design and fabrication of advanced photocatalytic mate-
rials by energy band engineering (Section 2), nanotechnology Figure 3. Three strategies to narrow the bandgap of semiconductor
photocatalysts to match the solar spectrum. Adapted with permission.[129]
(Sections 3 and 4), and modern theoretical simulations and Copyright 2011, American Chemical Society.
calculations (Section 5). In this review, we provide a survey of
the main recent achievements in both experiment and theory,
and highlight the relevance of the approaches and principles 3d states can mix with the CB or VB, and in some cases can
involved with respect to the development of environmentally insert a new band into the original bandgap.[83,84] If the various
acceptable visible-light and solar applications. chemical valences and spin states are also taken into account,
the electronic structures become considerably more complicated.
Zou and co-workers reported on In1-xNixTaO4 (x = 0–0.2), which
represents a pioneering case of doping a 3d-transition metal
2. Energy Band Engineering into a multi-metal oxide.[35,85] This material has been used as a
The energy band configuration of a semiconductor plays a signif- photocatalyst, when loaded with NiOy or RuO2 co-catalysts, to
icant role in the absorption of light and in determining the redox perform overall water splitting under visible light irradiation. An
potentials. For the purpose of effectively utilizing solar energy, apparent quantum efficiency of 0.66% was achieved for NiOy/
energy band engineering represents an effective approach to In0.9Ni0.1TaO4 at an incident wavelength of λ = 402 nm. How-
the exploration and development of visible-light-sensitive photo ever, doping with 3d-transition elements can have two critical dis-
catalysts with advanced performance. In order to narrow the advantages, restricting its applicability. Firstly, foreign elements
bandgap of semiconductors to extend the absorption of light with different chemical valence introduce considerable bulk
into the visible region, three approaches have been widely used: defects and thus increase the recombination probability of photo
(I) modification of the VB, (II) adjustment of the CB, and (III) generated electron-hole pairs. Secondly, the localized d-states in
continuous modulation of the VB and/or CB (see Figure 3). the electronic structure suppress the migration of carriers.
Because there are a very limited number of ways to modify the
electronic structures of simple metal oxides, multi-metal oxides
2.1. Modulation of Valence Band such as Ag+-, Pb2+-, and Bi3+-based compounds[25,27–29,86–91]
have attracted increasing interest over the past decade. In these
In most oxide semiconductors, the CB minima are slightly oxides, the cations with d10 or d10s2 electronic configurations
negative than reduction potential of H2O (versus NHE), while can introduce occupied d or s-states into the VB. Hybridization
the VB maxima are significantly positive with respect to the of these d/s states with O 2p states contributes to an up-shift of
oxidization of H2O (versus NHE). Therefore, for the consid- the top of the VB and therefore to a narrowing of the bandgap.
eration of stability of materials, raising the top of the VB to A typical example is the Bi-based photocatalyst CaBi2O4, which
narrow the bandgap takes precedence over all other methods can decompose gaseous acetaldehyde and degrade methylene
of energy-band modulation. Over previous decades, extensive blue (MB) in solution under visible light irradiation.[29] The effi-
efforts have been devoted to adjusting the level of the VB. Three cient photoactivity of CaBi2O4 can be attributed to its electronic
approaches have proved to be most effective, involving doping structure, which consists of Bi 6p states at the CB and hybrid-
with 3d-transition elements, cations with d10 or d10s2 configura- ized states derived from O 2p and Bi 6s levels at the VB. Accord-
tions, and non-metal elements. ingly, CaBi2O4 is provided with a raised VB maximum that
In early studies, sensitizing TiO2 to visible light by doping narrows the bandgap sufficiently to become sensitive to visible
with 3d-transition elements attracted considerable attention.[78–82] light. Furthermore, the participation of Bi 6s states significantly
Theoretical studies based on ab initio band structure calcula- disperses the VB, which facilitates the migration of holes.
tions revealed that the localized 3d levels shift to lower energy Similarly, Ag+-based and Pb2+-based oxides such as AgNbO3,
with increasing atomic number of the dopants. Thus, the split AgAlO2, Pb3MgNb2O9, Pb3Nb4O13 and so on,[25,27,28,86–88,91] are
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also photoactive toward visible light due to the occupied Ag 4d exceeds its tolerance; transformation to oxynitrides, oxysulfides,
Review
or Pb 6s states at the top of the VB. Based on the same strategy, or oxyhalides then takes place,[101–105] which can induce a signif-
a number of new visible-light-sensitive photocatalysts con- icant increase in visible light absorption. Hitoki and co-workers
taining Cu+ and Sn2+ have also been developed.[92–95] developed TaON to illustrate this effect. Compared with Ta2O5,
The other strategy used to raise the VB maximum is to intro- TaON exhibits a narrower bandgap of 2.5 eV and an absorption
duce different anions on the O sites. For example, TiO2 has edge that is red-shifted by 170 nm.[101] Under visible light irra-
been doped with N, C, B, and S and the photocatalytic proper- diation, TaON enabled the effective evolution of H2 and O2 from
ties of these materials have been extensively investigated.[13,96–98] methanol and AgNO3 solution, respectively. Oxynitrides such as
However, only a limited enhancement in light absorption has LaTiON, oxysulfides such as Sm2Ti2S2O5, and oxyhalides such
thus far been obtained. For N-doping, the light-absorption edge as BiOX (X = Br, I)[102–105] can also effectively harvest visible
remains almost the same as in the undoped material. Doping light and exhibit higher photocatalytic activity for water splitting
with C, B, and S narrows the bandgap by less than 0.3 eV. and organic contaminant degradation than their oxide precur-
Thus, the significant extension of visible light absorption via sors. Among these non-metal elements, S can often completely
anion doping remains a big challenge. Li et al. reported that replace O to convert an oxide into a sulfide, because both O and
the layered structure and protonic acidity of lamellar solid acids S belong to group VIa. A series of sulfides have been reported,
can provide a diffusion channel and strong absorption site for including CdS, AgInZn7S9, ZnIn2S4 and so on,[106–109] in which
a nitrogen source, allowing an increased level of N-doping, as the visible light absorption is better than their oxide analogues.
shown in Figure 4.[56,99,100] In the typical example shown, a facile These sulfides thus exhibit high photocatalytic activity for the
solid-state reaction using urea as the nitrogen source allowed evolution of H2 from Na2S-Na2SO3 aqueous solution under vis-
HNb3O8 to be N-doped without destroying its layered structure. ible light irradiation.
This process yielded a 0.8 eV reduction in the bandgap and a
red-shift of the absorption edge by ∼80 nm. Under visible light
irradiation, N-doped HNb3O8 showed superior catalytic activity 2.2. Adjustment of Conduction Band
to commercial TiO2 (P25) as well as to N-doped Nb2O5 and TiO2
samples.[56] Although the modulation of the VB is generally of high priority,
For some simple oxides and multi-metal oxides, the crystal the level of the CB is closely related to the capability of reducing
structure is destroyed when the proportion of substituted anions H2O and O2 and should therefore also receive attention. When the
Figure 4. (A) Schematic picture of N-doping in the lamellar solid acid (HNb3O8) using urea as the N-source. (B) Schematic band structures of HNb3O8
and N-doped HNb3O8. (C) UV-visible diffuse reflectance spectra of N-doped and undoped HNb3O8 and Nb2O5 samples; the insets show pictures of
the HNb3O8 and N-doped HNb3O8 samples. (D) Photocatalytic degradation of Rhodamine B (RhB) under visible light irradiation (λ > 400 nm), using
no catalyst (a), N-doped Nb2O5 (b), Degussa P25 (c), N-doped TiO2 (d), and N-doped HNb3O8 (e). Adapted with permission.[56]
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CB is at a suitable level, photogenerated elec-

Review
trons in the CB can reduce H+ to produce H2

or combine with O2 to form the highly oxida-
tive •O2− radical for the respective applications
of water splitting and the elimination of organic
contaminants. It should be noted that the
level of the CB determines both whether
these reactions can proceed and how efficient
these processes are. Therefore, adjustment
of the CB should be performed carefully.
The substitution of alkali metal or alkaline-
earth metal elements by elements lower in the
periodic table is known to be effective in low-
ering the minimum of the CB.[110–117] Sato et al.
have systematically investigated this effect
in indates and antimonates such as AInO2
(A = Li, Na), NaSbO3, MIn2O4 (M = Ca, Sr),
M2Sb2O7 (M = Ca, Sr), and CaSb2O6.[113–116]
These studies have helped to provide insight
into the role of crystal structures and elec-
tronic structures on the photocatalytic per-
formance of overall water splitting.
The p-block cations with a d10 electronic
configuration can also be adopted to mani Figure 5. (A) Electronic structures of α-AgMO2 (M = Al, Ga, In). (B) Photocatalytic degradation of
isopropanol using α-AgGaO2 and α-AgInO2, under visible light irradiation (400 nm < λ < 520 nm).
pulate the level of the CB. For example, Zou (C) Apparent photonic efficiency of acetone evolution using α-AgGaO2 for various wavelength
and co-workers incorporated group IIIa ele- ranges (indicated by horizontal error bars) within the UV-visible absorption spectrum. Adapted
ments in Bi2MNbO7 (M = Al, Ga, In) and with permission.[26] Copyright 2009, American Chemical Society.
investigated the influence of these substi-
tutions on the electronic structure and on the photocatalytic quantum efficiency of up to 80% was achieved in the visible
activity of the compounds in water splitting.[118] These photo- region 400–480 nm.[119]
catalysts are almost UV-active because most s and sp states of Another approach to manipulate the CB minimum is based
alkali metal elements, alkaline earth metal elements and IIIa- on substitution with d-block cations that have a d0 electronic
Group elements are significantly negative with respect to the configuration. For example, InMO4 (M = V, Nb, Ta) and BiMO4
reduction potential of H2O (versus NHE). Thus, combining (M = Nb, Ta) were developed as photocatalysts for water split-
these elements with narrow bandgap oxides such as Ag2O, ting.[34,120,121] It was found that incorporation of the group Vb
Fe2O3 and Cu2O is likely to aid the development of visible-light- elements V, Nb and Ta depressed the CB minimum, and the
sensitive photocatalysts. Ouyang and co-workers fabricated effect decreased with decreasing the periodic number. Simi-
four polycrystalline samples of α- and β-AgMO2 (M = Al, Ga, larly, substitution with Mo and Cr also lowered the level of the
In) and studied their photophysical and photocatalytic proper- CB and thus narrowed the bandgap.[122] As a typical example,
ties. As shown in Figure 5A, taking α-AgMO2 (M = Al, Ga,
[26] AgCrO2 and Ag2CrO4 (AgCr1/2O2) were synthesized by sub-
In) as an example, electronic structure calculations provide a stituting the p-block element Al in AgAlO2 with Cr to obtain
reasonable explanation for the narrowing of the bandgap that absorption over a wide range of visible wavelengths and photo
occurs in this system when M is varied in the order Al, Ga, In. catalytic activity. The bandgap could be controlled in a more
The CBs are mainly constructed from the Ag 5s5p and M sp sophisticated manner by modulating the chemical valence of
states, whereas all the VBs are comprised of the Ag 4d and O Cr.[123] A comparative electronic structure study demonstrated
2p states. This results in VBs with similar levels but CBs that that introducing unoccupied Cr 3d states into the CB narrows
vary with M. It was shown that a lower CB minimum enhanced the original bandgap and simultaneously retains the oxidization
the absorption of visible light but suppressed the reduction potential that is necessary to promote visible light photoactivity.
potential. The overall effect was that α-AgGaO2 exhibited the Ag2CrO4 exhibited superior photoactivity to commercial TiO2
highest activity for the photodegradation of isopropanol (IPA) (P25) and AgAlO2 for the elimination of organic contaminants,
(Figure 5B,C). Moreover, a comparative study of α-AgGaO2 and which was attributed to the wide-range visible light absorption
β-AgGaO2 clarified the effect of crystal field on the electronic and respose (l < 640 nm) of this material.
structure and photocatalytic performance. More recently, Yi
et al. investigated an orthophosphate Ag3PO4 photocatalyst and
showed that the 3s3p states of the non-metal element P can be 2.3. Continuous Tuning of Valence Band and/or
used to tune the relatively low-lying CB of Ag2O. The Ag3PO4 Conduction Band
sample exhibited an extremely high photooxidative capability
for the evolution of O2 from water, as well as for the decomposi- To sensitize photocatalysts in the visible region, their bandgaps
tion of organic dyes under visible light irradiation. An apparent can be narrowed via lowering the level of the CB, raising the
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level of the VB, or both processes simulta-
Review
neously. However, all types of manipula-
tion generally suppress the redox potentials,
inevitably giving rise to an implicit conflict
between wide-range visible light absorption
and adequate redox capability. The strategies
that we have mentioned, based on elemental
substitution, do not allow precise adjustment
of the electronic structure and an optimal
balance between effective visible light absorp-
tion and adequate redox potentials is difficult
to achieve. Thus, the fabrication of solid-
solution photocatalysts with continuous
bandgaps has emerged as a requirement.
Three approaches to continuously manipu-
late these bandgaps have been explored,
namely continuous modulation of the VB,
continuous adjustment of the VB, and both
processes simultaneously.
Maeda and co-workers developed a novel
oxynitride, (ZnO)x(GaN)1-x, for use as a visible-
light-sensitive photocatalyst.[124,125] In this
solid solution, the ratios of O/N and Zn/Ga
can be controlled continuously by changing Figure 6. (A) Schematic electronic structures of AgAlO2, AgGaO2, and AgAl1-xGaxO2 solid solu-
the nitriding process. The bottom of the CB tions. (B) UV-visible absorption spectra of β-AgAl1-xGaxO2 solid solutions. (C) Rate of acetone
is mainly constructed from Ga 4s4p states, evolution, bandgap, and color of β-AgAl1-xGaxO2 as a function of x. (D) Apparent quantum effi-
ciency of IPA photodegradation over β-AgAl Ga0.4O2 in various wavelength ranges within the
whereas the top of the VB is composed of N UV-visible absorption spectrum. Horizontal 0.6 error bars indicate the wavelength ranges; vertical
2p states followed by Zn 3d states. A degree of error bars denote the AQE errors induced by the light-intensity measurement. Adapted with
p-d repulsion in the top of the VB induces nar- permission.[129] Copyright 2011, American Chemical Society.
rowing of the bandgap. When a Rh/Cr2O3 co-
catalyst was grafted, a sample with optimal composition exhibited that the level of the CB determines the competition between
a remarkably high apparent quantum yield of 2.5% for overall visible light absorption and redox potentials (see Section 5.3
water photolysis at incident wavelengths of 420–440 nm.[124] for details). Among these solid solutions, the β-AgAl0.6Ga0.4O2
An example of continuous modulation in the VB was provided sample showed the highest photocatalytic performance, with an
by Li et al., who studied NaNbO3-AgNbO3 solid solutions by activity 35 and 63 times higher than the two end-members of
varying the ratio of the metallic element Ag and the non-metal the series, β-AgAlO2 and β-AgGaO2, respectively. The electronic
element O.[126] These solid solutions were applied to the deg- structure of β-AgAl0.6Ga0.4O2 allowed an optimal balance to be
radation of gaseous isopropanol under visible light irradiation achieved between effective visible light absorption and adequate
and enhanced photoactivity was observed. redox potentials. Moreover, due to the in-situ loading of metallic
Continuous adjustment of the CB has attracted extensive Ag on the photocatalyst that occurred during synthesis, the
attention in the field of water splitting, because the level of the multi-electron reaction process taking place in β-AgAl0.6Ga0.4O2
CB plays a critical role in the reduction of H+ to H2. By contin- resulted in superior activity for the complete decomposition
uous substitution with either d0 cations or alkaline-earth metal of isopropanol in comparison with TiO2-xNx. The apparent
elements, the solid solutions BiTa1-xNbxO4, Sr2NbxTa2-xO7, quantum efficiency of β-AgAl0.6Ga0.4O2 for this reaction was
Sr1-xCaxIn2O4, and Ba1−xSrxSnO3 were synthesized and their 37.3% at an incident wavelength of 425 ± 12 nm.
photocatalytic properties with respect to water splitting were Continuous modulation of both the CB and VB is also an effec-
investigated in detail.[115,121,127,128] However, these oxides are tive approach to precisely optimize the light absorption and redox
only active under UV light. Recently, continuous modulation of potentials. For example, Yao et al. fabricated Ca1-xBixVxMo1-xO4
the CB was also applied to the study of organic contaminant and Wang et al. synthesized (AgNbO3)1-x(SrTiO3)x solid
elimination; the multi-electron reaction process is an attrac- solutions.[53,130] In the former material, continuous adjustment
tive and promising approach to the complete decomposition of both the ratio of V 3d states to Mo 4d states in the CB and
of organic pollutants, but the level of the CB is nevertheless of the ratio of Bi 6s states to O 2p states in the VB allowed optimal
importance for this reaction. A novel series of β-AgAl1-xGaxO2 band structures to be realized, achieving enhanced evolution of
solid-solution photocatalysts were synthesized by Ouyang and O2 from AgNO3 aqueous solution under visible light irradiation.
Ye.[129] As shown in Figure 6, varying the ratio of the group Similarly, Tsuji and co-workers developed binary and ternary
IIIa elements Al and Ga allows the bottom of the CB to be con- sulfide solid solutions using ZnS, CuInS2, and AgInS2.[131–133]
tinuously tuned and thereby allows the bandgap to be varied In this section, we have discussed in detail various strate-
between 2.19 and 2.83 eV. A theoretical study revealed that gies to modulate the band structure, indicating that energy
these oxides are typical electron-conductive semiconductors and band engineering is indeed an efficient approach to explore and
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develop visible-light-sensitive photocatalysts. However, because 3.1. One-dimensional Nanostructures

Review
photocatalytic reactions are typically surface-based processes,

the photocatalytic efficiency is also closely related to the mor- One-dimensional (1D) nanostructures such as wires, belts and
phology and micro-structure of the material. These issues will tubes have attracted considerable attention for photocatalytic
be discussed in the following sections. applications due to their distinct electronic, optical and chem-
ical properties, which differ from their bulk counterparts.[134–137]
These properties are dependent on the size and morphology of
the materials, leading to the development of strategies to opti-
3. Morphology Control
mize the photocatalytic reactivity. For example, increasing the
The emergence of nanostructured semiconductor materials as aspect ratio (the ratio of length to diameter or surface to volume)
photocatalysts has given rise to diverse and flexible ways of pro- generally results in an enhancement of activity. Successful exam-
moting photocatalytic efficiency. It is obvious that reducing the ples include 1D nanostructures of CdS, ZnO and GaN.[138–140]
particle size is generally beneficial for surface-dependent photo- In other cases, well-designed surfaces on 1D nanostructures,
catalysis because it leads to quadratic growth of the specific sur- such as the {101} facet on TiO2 nanobelts or the {010} facet on
face area and hence reactive sites. However, it is not always the Zn2GeO4 nanobelts,[141,142] have also been shown to enhance the
case that the smaller the particle size, the higher the efficiency. photocatalytic activity. Moreover, 1D nanostructures allow the lat-
If the feature size, particularly of a spherical particle, is com- eral confinement of electrons and guide the movement of elec-
parable with the electron mean free path, a strong quantum trons in the axial direction. In this regard, remarkable progress
confinement effect appears to increase the recombination prob- has been made in the ordered alignment of 1D nanostructures
ability of photogenerated electron-hole pairs. Although, small for the construction of functional photocatalytic devices.
particle sizes imply that carriers migrating to the surface have Recently, 1D hetero-nanostructures have received tremendous
favourably short distances to travel, this migration requires a interest because of their synergetic effects on photocatalytic per-
suitable concentration gradient or potential gradient from the formance.[135,143,144] Typically, 1D hetero-nanostructures can be
core of the particle to the surface, which is closely correlated classified into three types based on their junction modes: axial
with the morphology, structure and surface properties of nano hetero-nanostructures, radial hetero-nanostructures, and hierar-
structured materials. In recent years, notable progress has been chical hetero-nanostructures. Among these types, 1D coaxial hetero-
made in the shape-controlled synthesis of photocatalytic mate- nanostructures with modulated compositions and interfaces may
rials and investigations of the relationship between the mor- yield significantly improved photocatalytic performance due to the
phological or structural characteristics and the photocatalytic interactions that occur between different chemical species in the core
properties. Furthermore, particular emphasis has been placed and shell. For example, Bi and Ye recently reported on the construc-
on complex or hierarchical hetero-nanostructures for facili- tion of Ag/AgCl core-shell nanowires by heteroepitaxial growth
tating the separation of photogenerated electron-hole pairs in and their photocatalytic behavior in the decomposition of methyl
order to further improve the photocatalytic activity. orange (MO) dye under visible light irradiation (Figure 7).[135,145]
Figure 7. SEM images of Ag nanowires (A), Ag/AgCl core-shell nanowires (B) and Pt/AgCl hetero-nanotubes (C). (D) Photocatalytic activities of Ag/
AgCl core-shell nanowires in the decomposition of MO dye under visible light irradiation (λ > 400 nm). (E) Schematic illustration of the growth process
for Ag/AgCl core-shell nanowires and Pt/AgCl hetero-nanotubes. Adapted with permission.[135,145] Copyright 2009, 2010, Royal Society of Chemistry.
www.advmat.de
It was found that Ag/AgCl core-shell nanowires
Review
in the ratio 8/92 exhibited the best activity;
the complete decomposition of MO dye was
achieved in 8 min under visible light irradiation.
3.2. Facet-controlled Semiconductor Materials
Considering that photocatalytic reactions

take place on the surfaces of semiconductors,
the exposed crystal facets play a critical role
in determining the photocatalytic reactivity
and efficiency.[146] Accordingly, the synthesis
of single crystals with exposed highly reactive
facets has attracted much interest; this may
represent a promising and efficient method
for the further improvement of photocatalytic
performance. However, highly reactive facets
usually disappear rapidly during the growth
process due to their high surface energy. To
address this issue, both organic polymers
and inorganic ions have been employed
to selectively control the growth rates of
planes of interest. For example, Yang and
co-workers used hydrofluoric acid (HF) as
a capping agent under hydrothermal condi-
tions to prepare anatase TiO2 single crystals
for which 47% of the surface was comprised Figure 8. (A) SEM image and (B) high-magnification HRTEM image of m-BiVO4 nanoplates.
of highly reactive {001} facets.[65] The same (C) Photocatalytic degradation of RhB over various photocatalysts (0.1 g) under visible light
authors also reported a new solvothermal (λ > 400 nm) irradiation. (D) Photocatalytic evolution of O2 from an aqueous AgNO3 solution
method using 2-propanol as a synergistic (0.05 M, 270 mL) over various photocatalysts under visible-light irradiation (λ > 400 nm).
[67]
capping agent and reaction medium together Adapted with permission. Copyright 2010, Royal Society of Chemistry.
with HF to synthesize high-quality anatase
single-crystal nanosheets with surfaces comprised of 64% {001} of Ag3PO4 were synthesized in two forms, firstly with rhombic
facets.[147] Liu et al. presented a feasible strategy for the synthesis dodecahedron shapes and exposed {110} facets, and secondly
of hollow TiO2 microspheres composed of polyhedral anatase cubes bounded by {100} facets. These crystals were grown
crystallites with ∼20% {001} facets, which involved a modified using CH3COOAg and a [Ag(NH3)2]+ complex as the silver
fluoride-mediated self-transformation strategy. The photocata- ion precursors, respectively.[66] The Ag3PO4 dodecahedrons
lytic selectivity of these microspheres toward the decomposition were formed by 12 well-defined {110} planes with cubic crystal
of azo dyes could be tuned by varying the percentage of {001} symmetry (Figure 9A), whereas the Ag3PO4 cubes displayed
facets as well as by varying the concentration of adsorbed spe- sharp corners, edges, and smooth surfaces (Figure 9B). Under
cies on the surfaces of the anatase polyhedra.[148] visible-light irradiation, the dodecahedrons exhibited higher
However, we note that the capping agents adsorbed on the photocatalytic activity for the degradation of methyl orange
surfaces of semiconductor crystals during synthesis must be (MO) and RhB dyes than the cubes (Figures 9C and D). This
removed before they can be used in photocatalytic applications, result reveals that the {110} facet is more reactive than the
often requiring complex treatments. The highly reactive facets {100} facet, which is consistent with the higher surface energy
can then lose many of their active sites as a result of surface of 1.31 J/m2 for the {110} facet compared to 1.12 J/m2 for the
reconstruction. Therefore, experimental exploration of the reac- {100} facet.
tivity of different facets requires the fabrication of photocata- It is interesting to note that sheet-like crystallites of molec-
lysts with highly reactive facets exposed but without capping ular thickness and extremely high two-dimensional anisotropy
agents; this is still a great challenge. Recently, Xi et al. reported can provide ratios of reactive sites on the surface that approach
the synthesis of well-defined m-BiVO4 nanoplates with exposed 100%, and they also exhibit intriguing charge-bearing proper-
{001} facets by a straightforward hydrothermal route in which ties due to large-area nonstoichiometry on the surface. Such
no template or organic surfactant was used (Figure 8A and nanoscale materials are known as nanosheets[149] and a variety
B).[67] Under visible light irradiation, the m-BiVO4 nanoplates of promising photocatalysts belong to this category, such as
showed considerable photocatalytic activity for the degradation KCa2Nb3O10,[150,151] Ba5Ta4O15,[152] HCa2Nb3O10,[153] TaO3−,[154]
of RhB (Figure 8C) and for the evolution of oxygen from an and TiNbO5−.[155] Over the past decade, the chemical exfoliation
aqueous AgNO3 solution (Figure 8D). of layered compounds has become a well explored process and
To investigate the effects of the shapes and facets of particular has allowed the synthesis of various nanosheet materials.[156]
photocatalysts on their photocatalytic properties, single-crystals To further investigate the surfaces of nanosheets, further effort
www.advmat.de
metals and of the electron transfer process at

Review
the semiconductor-metal interface.

In semiconductor-semiconductor com-
posite hierarchical nanostructures, both
types of semiconductors can undertake the
task of harvesting incident photons. Syn-
ergetic effects on both carrier separation
and photocatalytic efficiency in such nano
structures have been extensively studied in
recent years.[158–161] For example, Zn-doped
Lu2O3/Ga2O3 and Cr-doped Ba2In2O5/In2O3
composites can be used to perform stoichio-
metric water splitting under UV light irradia-
tion.[160,161] In most cases, a narrow bandgap
semiconductor such as CdS, CdSe, PbS, or
WO3 serves as a visible light sensitizer to
transfer the excited-state electrons to a large
bandgap semiconductor such as TiO2, SnO2,
or ZnO. Typical examples of such systems
are MoS2/CdS, CdS@CdSe/ZnO, and CdSe/
TiO2-xNx.[162–164]
For practical photocatalytic applications in
aqueous solution such as water photolysis
or water purification, the recycling of nano
structured photocatalysts is an important but
Figure 9. SEM images of Ag3PO4 sub-microcrystals with different morphologies: (A) rhombic extremely difficult task due to their small
dodecahedrons and (B) cubes. The photocatalytic activities of Ag3PO4 rhombic dodeca- size. One feasible solution is to develop mag-
hedrons, cubes, spheres, and N-doped TiO2 are shown for the degradation of (C) MO and netic photocatalytic materials. Recently, Xi
(D) RhB under visible light irradiation (λ > 400 nm). Adapted with permission.[66] Copyright et al. presented a successful example by com-
2011, American Chemical Society. bining WO3 with Fe3O4 (Figure 10).[46] Nano
plates of WO3 were grown on the surfaces of
should be applied to the construction of parent compounds
with suitable layered structures.
3.3. Hierarchical Composite Nanostructures
Photocatalysis may be viewed as a type of system engi-

neering dealing with a series of sub-tasks involving opto-
electronic conversion, surface/interface catalysis and the
post-treatment or recycling of the photocatalyst. Thus, all the
relevant functions should be optimized and integrated into
the photocatalytic system when it is put into practical use. This
viewpoint gives rise to the concept of designing and fabricating
advanced photocatalytic materials based on hierarchical com-
posite nanostructures. Indeed, no single composition or struc-
ture is currently able to fulfill all the above designated tasks
satisfactorily by itself.
Many attempts have been made to organize semiconductor-
metal or semiconductor-semiconductor composite hierarchical
nanostructures in order to facilitate charge rectification and
to improve carrier separation in semiconductor photocata-
lysts.[40,46,157] For example, when noble metal nanoparticles
such as Pt, Pd, Au and Ir are deposited on semiconductor nano
materials, they can act as a reservoir for photogenerated elec- Figure 10. SEM images of (A) Fe3O4 microspheres and (B) Fe3O4/WO3
core–shell microspheres. (C) Photocatalytic degradation of RhB over
trons, promoting the interfacial electron transfer process and Fe3O4/WO3 core–shell microspheres, WO3 hollow microspheres, Fe3O4
facilitating catalytic reactions in which electrons are involved. microspheres, and commercial WO3 powder. (D) Digital photographs
To maximize the efficiency of such a system, it is necessary to showing that the Fe3O4/WO3 core–shell microspheres were being recy-
gain a basic understanding of both the influence of different cled by applying a magnetic field. Adapted with permission.[46]
www.advmat.de
Fe3O4 spheres to form chestnut–like core–
Review
shell structures (Figures 10A and B). This
material was used as a photocatalyst to fully
degrade RhB in 1.5 h under visible light
irradiation (Figure 10C). After the reaction
was complete, the catalyst could be removed
under an applied magnetic field and com-
pletely recycled (Figure 10D).
In addition to enhanced efficiency, the
stability of photocatalysts can also be signifi-
cantly improved by employing composite hier-
archical nanostructures. For example, Ag3PO4 Figure 11. Illustration of an electronic bond formed between (A) two atoms and (B) two
exhibits high photocatalytic activity but rela- nanocrystals.
tively poor stability in aqueous solution due to
its degree of solubility and relatively positive Ag+/Ag reduction discuss the energetic aspects of these attempts to enhance
potential (EθAg/Ag3PO4 = 0.45 eV versus NHE). A general proce- the optoelectronic conversion efficiency of photocatalytic
dure to resolve these problems has recently been demonstrated, materials.
involving the epitaxial growth of AgX (X = Cl, Br, I) nanoshells
on the surfaces of rhombic dodecahedral Ag3PO4 crystals at
room temperature.[157] The much lower solubility of the AgX 4.1. Electronic Coupling Assembly
nanoshells effectively protects the core Ag3PO4 crystals from dis-
solution during the photocatalytic process. Moreover, the CB and An ensemble of nanoparticles may exhibit new collective prop-
VB potentials of AgX semiconductors (except AgCl) are more erties resulting from the inter-particle coupling of surface
negative than that of Ag3PO4, which can promote the transfer electrons (excitons), plasmons or magnetic moments.[169–172]
and separation of photoexcited electron–hole pairs through the Recently, we found that electronic coupling in an assembly of
hetero-junctions. semiconductor nanoparticles can induce a substantial alteration
In addition to the examples above, the synergy of two semi- of the electronic structures of the nanoparticle ensemble.[58,59]
conductors is also appealing for the so-called Z-scheme mode. When two nanoparticles are electronically coupled, bonding
Here the two semiconductors take on different functions, for and anti-bonding levels are formed, yielding a new electronic
example, one for the evolution of H2 and the other for O2. In structure as illustrated in Figure 11.
a Z-scheme system, the carrier transfer between the two semi- In early research, nanoparticles were usually embedded in a
conductors proceeds via a pair of redox electrolyte mediators passivating medium of materials with much larger bandgaps
such as IO3−/I+. However, only a few successful cases of overall (e.g., surfactant ligands, polymers, and dielectric substances)
water photolysis have been reported thus far for Z-scheme sys- to eliminate surface defect states.[173] However, the degree of
tems; examples are TaON/WO3 and SrTiO3/BiVO4. [165–168]
inter-particle electronic coupling rapidly decreases with the
One of the most significant opportunities offered by hierar- increased spacing of nanoparticles imposed by the passivating
chical nanostructures with respect to practical applications in medium. Overlap of the wave functions of a pair of nanopar-
photocatalysis lies in the collective properties provided by nano- ticles, for example CdTe, was observed when the nanopar-
assembly. The following section reviews recent advances in this ticles were separated by less than 2 nm and led to a red-shift
topic. of the absorption and photoluminescence emission bands.[171]
For an inter-particle separation of 2 to 10 nm, long-range
dipole-dipole interactions between CdTe nanoparticles were
found to induce resonance energy transfer.[169]
4. Nano-assembly
Studies were later extended to assemblies of nanoparticles
Nano-assembly represents an important aspect of nanotech- with no passivating medium, in which the nanoparticles may
nology and provides a feasible and low-cost approach for the be closely aggregated with negligible spacing between them.
fabrication of hierarchical nanostructures using nanocrystal- In some instances, short-range interactions between surface
line building blocks. Remarkable progress has been made in defect states have been found to strongly influence the proper-
the construction of photocatalytic functional materials with ties of the nanoparticle assembly. For example, covalent Se-Se
wide-ranging architectures, dimensions, morphologies and bonds were formed between assembled CdSe nanoparticles in
patterns; these characteristics represent key elements that the presence of unpassivated Se2− ions on the surface, which
enable the control of electronic and optical properties. Going occurred due to selective photochemical etching.[174] Figure 12
beyond systems comprised of separate individuals, nano- presents recent findings concerning Ti-Ti electronic bonding in
assembly involves more profound scientific considerations in an assembly of anatase TiO2 nanoparticles with an average size
terms of inter-particle electron and energy transfer. To date, of 5 nm (Figure 12A).[58] In contrast to a white TiO2 nanoparticle
strong emphasis has been placed on exploring extraordinary colloid (Figure 12B), the nanoparticle assemblies were bright
properties by engineering the interactions between nano yellow in color (Figure 12C); the white color returned when
crystalline building blocks or by designing the configuration the assemblies were mechanically crushed to form a powder
of assemblies of such building blocks. In this section, we (Figure 12D). These TiO2 nanoparticle assemblies absorbed
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red-shifted (Figure 13G). The narrower band-

Review
gaps of these CdS nanoparticle assemblies allow

the system to more efficiently take advantage of
longer wavelength light in the solar spectrum
for applications (Figure 13H) such as hydrogen
production from photocatalytic water splitting
and photovoltaic current generation.
4.2. Plasmon-exciton Coupling Assembly
Hybrid assembled structures of plasmonic

metal nanoparticles on a semiconductor
exhibit plasmon-exciton coupling interactions
under light illumination, giving rise to many
interesting effects such as the enhancement,
quenching or wavelength shifting of fluores-
cent emission, and nonlinear resonance.[181–183]
The main characteristics of plasmon-exciton
coupling interactions are as follows: the
Figure 12. (A) HRTEM image of TiO2 nanoparticles, and photographs of TiO2 nanoparticle
plasmon resonance of the metal nanoparticles
colloid (B), assemblies (C), and powder sample formed by mechanically crushing assemblies induces an electromagnetic field in the vicinity
(D). (E) UV-visible absorption spectra of the three samples. (F) XPS spectra. (G) Evolution of the semiconductor, and exciton energy is
of CO2 during the decomposition of 2-proponol (initially ∼650 ppm) over TiO2 photocata- transferred from the semiconductor to the
lysts (0.2 g, irradiated area 8 cm2) in a 500 ml (total volume) glass vessel under simulated metal nanoparticles.[184]
sunlight irradiation (AM 1.5G, 100 mW·cm−2). Adapted with permission.[58] Copyright 2011, In contrast to the semiconductor, plasmonic
Royal Society of Chemistry.
metal nanoparticles possess optical absorp-
tion bands in the visible to infrared region of
visible light of up to 500 nm in wavelength (Figure 12E), indi- the spectrum due to coherent electron oscillation known as
cating that their bandgap is narrower than that of the bulk the localized surface plasmon resonance (LSPR). Accordingly,
phase. Such bandgap narrowing can be attributed to energy plasmonic metal nanoparticles may act as photo-sensitizers
band reconstruction (as proposed in Figure 11) induced by the to enhance optical absorption in metal-semiconductor hybrid
generation of inter-particle Ti-Ti bonds, evidence for which is assemblies.[185] For example, Tian et al. studied the plasmon-
found in an increase of the binding energy of Ti core electrons induced photo-electrochemical performance of TiO2 films
(Figure 12F). This finding opens a new way to narrow the band- loaded with Au nanoparticles under visible light irradiation.[186]
gaps of semiconductors by electronic coupling in assemblies of It was found that electrons in the Au nanoparticles were excited
nanoparticles rather than by incorporating dopant atoms; this due to the LSPR effect and transferred to the TiO2 film. Simulta-
approach is highly beneficial in the promotion of solar photo neously, charge-compensating electrons were transferred from
catalysis (Figure 12G). donors in the electrolyte solution to the Au nanoparticles. These
In principle, electronic coupling in assemblies of nanopar- findings indicate that metal-semiconductor hybrid assemblies
ticles should be found for all inorganic semiconductors with can possess not only enhanced optical absorption characteris-
any structure. A number of strategies have been proposed tics but in addition, the electronic hetero-junction facilitates
for the fabrication of complex hierarchical nanostructures the separation of photo-generated electrons and holes. Thus,
with controllable configurations.[175–180] For example, sacrifi- plasmon-exciton coupling assemblies have great potential to
cial KCdCl3 nanowire templates (Figure 13A1) and Cd(OH)2 improve the optoelectronic conversion efficiency.
nanosheets (Figure 13B1) have recently been used to fabricate The practical performance of plasmon-exciton coupling
CdS nanotubes templates (Figures 13A2, 13A3) and nano- assemblies strongly depends on the mutual arrangement,
cages (Figures 13B2, 13B3), respectively.[59] Electronic coupling sizes and shapes of the metal nanoparticles and semicon-
in these CdS nanoparticle assemblies yielded much narrower ductor,[61,171,184,187] as well as on the ratio of metal nanoparticles
bandgaps and red-shifted optical absorption bands compared to semiconductor and the distance between them.[181] Metal
to individual CdS nanoparticles and bulk CdS (Figure 13C). It nanoparticles with a homogeneous size distribution, highly
was suggested that inter-particle Cd-Cd bonds are formed in the symmetric morphology and specific exposed facets may give
assemblies, evidenced by an increase in the binding energy of rise to favorable performance. Therefore, good control over
the Cd core electrons (Figure 13D) and the observation that at the the nature and arrangement of the metal nanoparticles on the
interface of two adjacent CdS nanoparticles (Figure 13E), the semiconductor is necessary to achieve the desired behavior. For
outer Cd atoms are in contact (Figure 13F). Electronic structure example, a monolayer array of polystyrene spheres (∼670 nm)
calculations (see Section 5.4) showed that inter-particle Cd-Cd (Figure 14A) on a nanocrystalline WO3 film (∼50 nm) was
bonds inevitably lead to bandgap narrowing. Consistent with recently used as a template to fabricate an array of Au nano-
this conclusion, the intrinsic photoluminescence bands were prisms.[61] The nanoprisms were extremely uniform in their
www.advmat.de
Review
Figure 13. (A1) TEM image of KCdCl3 nanowire templates used to form assemblies of CdS nanotubes, SEM and HRTEM images of which are shown
in (A2) and (A3). (B) Cd(OH)2 nanosheet templates (B1) used to form assemblies of CdS nanocages (B2) and (B3). (C) UV-visible absorption spectra.
(D) XPS spectra. (E) HRTEM image of an interface between two adjacent CdS nanotubes. (F) EELS spectra collected from two adjacent nanotubes and
their interface, as shown in (E). (G) Photoluminescence spectra. (H) Wavelength-dependent efficiency of sunlight utilization by CdS nano-assemblies
for the production of hydrogen by photocatalytic water splitting and for photovoltaic current generation. Adapted with permission.[59] Copyright 2011,
Royal Society of Chemistry.
size and shape distribution and formed a periodic hexagonal index contrast are referred to as photonic crystals. The propa-
pattern on the WO3 film (Figure 14B). Compared to the bare gation of electromagnetic waves in photonic crystals is affected
WO3 film, the Au-WO3 hybrid film not only harvested photons in the same way as electron motion is affected by the periodic
in the visible to infrared region of the spectrum (Figure 14C) potential in semiconductor crystals.[188] Analogous to the elec-
but also enhanced the intrinsic absorption of WO3 (Figure 14D) tronic bandgap in a semiconductor crystal, a photonic bandgap
due to the plasmon-exciton coupling interactions. Electrochem- can be defined in a photonic crystal; here electromagnetic
ical impedance spectroscopy (Figure 14E) revealed that the waves with a certain frequency range are forbidden due to
Schottky junctions formed between Au and WO3 can facilitate Bragg scattering from the dielectric interfaces.[188] For inverse
the separation of photo-generated carriers as well as the inter- opal photonic crystals, the photonic bandgap is given by the fol-
facial transfer of carriers. Consequently, substantially enhanced lowing equation:[189]
optoelectronic conversion efficiency was exhibited by this photo
electrode (Figure 14F).  
2
8= 2 D n2S f + nai
2
r (1 − f ) − sin 2
2 (1)
3
4.3. Optical Coupling Assembly where λ is the wavelength of forbidden light, D is the pore
size of the inverse opal structure, ns and nair are the refrac-
In addition to inter-particle interactions, a coherent state exists tive indices of the solid matter and the air voids, respectively,
in regularly assembled architectures when the periodicity of the f is the volume percentage of the solid matter, and θ is the
structure is of a length scale compatible with the wavelength of incident angle of light. Fine control over the characteristics
the electromagnetic waves of interest (i.e., 350 ∼ 700 nm). Mate- of photonic crystals can dramatically modulate light-matter
rials possessing such architectures as well as a high refractive interactions.[190,191]
www.advmat.de
reduction in pore size relative to the polysty-

Review
rene spheres was due to the annealing process

used for removal of the polystyrene template
and formation of the WO3 phase. Under white
light, the inverse opals reflected brilliant mono
chromatic colors (insets to Figures 15A–C),
a phenomenon caused by pore-size-dependent
Bragg diffraction of visible light. An absorption
band characteristic of photonic crystals was
observed in the inverse opal samples, but not
in the disordered porous or non-porous WO3
samples (Figure 15D). The photonic band edges
of the three inverse opal samples, in order of
increasing pore size, were located on the blue
side of the electronic band edge, at the elec-
tronic band edge, and on the red side. Meas-
urement of the photocurrent indicated that the
WO3 inverse opals with coinciding photonic
and electronic band edges exhibited the largest
current output (Figure 15E) and optoelectronic
conversion efficiency (Figure 15F).
Photonic crystals have led to many other
achievements in the field of solar cells.
Mallouk et al. introduced TiO2 inverse opal
photonic crystals into a dye-sensitized solar
cell and obtained a 26% increase in the
short-circuit current.[193] This enhancement
was attributed to optical coupling between
the photonic crystal layer and the disordered
nanoparticle layer, resulting in standing
waves that improved the absorption of light
Figure 14. (A) SEM image of a monolayer array of polystyrene spheres (∼670 nm) on a nano
crystalline WO3 (∼50 nm) film. (B) SEM image of a hexagonal array of Au nanoprisms deposited
by the dye molecules. Progress has also been
on a WO3 film using the template shown in (A). The scale bars represent 1 μm. (C) Optical made in silicon solar cells, where a photonic
absorption spectra of a bare WO3 film (black curve) and a WO3 film loaded with a Au nanoprism crystal was used as a high refractive mirror
array (red curve). (D) Absorbance gain spectrum (red curve) resulting from the loading of a Au instead of a common metallic mirror.[194]
nanoprism array on the WO3 film, and the optical absorption spectrum (blue dashed curve) of To take full advantage of the light-matter
a Au nanoprism array on a glass substrate. (E) Photocurrent response of the WO3 photoelec- interactions that occur in photonic crystals,
trodes under illumination at λ > 400 nm. (F) Electrochemical impedance spectroscopy plots of
it is necessary to precisely control their struc-
WO3 photoelectrodes under illumination at λ > 400 nm. Adapted with permission.[61] Copyright
2011, IOP Science. tures.[195] For a given geometry and composi-
tion, theoretical calculations are already able
The utilization of solar energy via photonic crystals has aroused to predict how the optical properties of photonic crystals can
a great deal of interest in recent years due to the urgent demand for be tuned by minor variations of the lattice parameters, filling
enhancing the solar energy conversion efficiency of materials and fraction, topology and refractive indices.[191] However, the fab-
devices. The light in a photonic crystal undergoes strong coherent rication of photonic crystals in accordance with an established
multiple scattering and travels with a very low group velocity near design is much more challenging.
the photonic band edges.[192] This is known as the slow-light effect
and increases the effective optical path length within the photonic
crystal, leading to the delay and storage of light. For inverse opal
5. Theoretical Studies
photonic crystals where air voids are periodically arranged in a
solid matrix, appropriate selection of the structural parameters of Photocatalysis phenomena have been extensively studied theo-
the crystal as described by Equation 1 may offer an optical coup retically using electronic structure calculations and molecular
ling effect where the harmonic resonance occurs at a particular dynamics simulations. Photocatalysis reactions consist of three
frequency around the electronic bandgap. In this way, it is possible processes: (1) the photoexcitation of electron-hole pairs, (2) the
to tune the spectral range in which the absorption enhancement transfer of carriers to the surface, and (3) chemical reactions on
is expected. A number of new photo-functional materials have the surface. Therefore, the theoretical approach adopted depends
been designed using this principle. For example, Chen et al. made on the property of interest. The first process above is relevant to
use of colloidal templates of polystyrene spheres with diameters bandgap engineering because photoexcited carriers are generated
of 200, 260 and 360 nm to fabricate WO3 inverse opals with pore only when the incident photon energy is higher than the bandgap
sizes of 140, 170 and 230 nm (Figures 15A–C).[62] The ∼30% of the photocatalyst. In addition, alignment between the band
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Review
Figure 15. (A-C) SEM images of WO3 inverse opals fabricated using colloidal crystal templates comprised of polystyrene spheres with diameters of
200, 260, and 360 nm, respectively. The insets show photographs of the structures under white light. (D) Light reflectance spectra of the WO3 inverse
opals. The black arrows indicate the photonic band edges and the open circles show the locations of slow light. (E) Photocurrent-potential curves of
WO3 electrodes under light irradiation at λ > 300 nm. (F) Incident photon-to-electron conversion efficiency. Adapted with permission.[62] Copyright
2011, American Chemical Society.
edges and the redox potentials of the target molecules is of great photocatalytically active for water splitting due to its low
importance because photoexcited carriers can only be transferred to bandgap (1.3 eV),[198] causing the CBM and VBM to be too low
the adsorbed molecules when there is a sufficiently large negative and too high in energy compared to the reduction and oxida-
offset of the conduction band minimum (CBM) and a sufficiently tion potentials of water, respectively. The recent discovery of
large positive offset of the valence band maximum (VBM) with the strong oxidation power of Ag3PO4 was made in the course
respect to the redox potentials. Therefore, a great deal of effort has of efforts to optimize the band structure of silver-based oxides
been spent on finding semiconductors with suitable band struc- by incorporating p-block elements,[119] i. e., atomic species with
tures for the photoexcitation and carrier transfer processes. The partially occupied p-valence states.[28] The quantum yield of the
second process above can usually be improved by minimizing the generation of O2 gas by water splitting using Ag3PO4 is nearly
concentration of defects. Both native defects and impurities in 90% under visible light, which is surprisingly high compared to
the semiconductors give rise to states in the bandgap, which act the ∼20% quantum yield of most photocatalysts. The extremely
as carrier recombination centers. An indirect bandgap is believed high efficiency of Ag3PO4 is encouraging and clarification of its
to be advantageous for the separation of carriers. However, the mechanism was eagerly awaited.
detailed mechanism of the carrier recombination process is still A comparative study of the electronic structures of Ag3PO4,
unclear and elucidation of which factors are most relevant to Ag2O, and AgNbO3 by first principles calculations revealed pos-
this process is a challenging subject of theoretical research. The sible explanations for the high performance of Ag3PO4.[199] The
third process above is also a popular subject of theoretical study main difference between Ag3PO4 and Ag2O can be found at the
because there are established computational methods available CBM; this mainly consists of Ag s states in Ag3PO4 and Ag d
to investigate this issue. One such method is the analysis of sur- states in Ag2O. The difference in electronic structure is due to
face energies for different surface orientations in order to identify the rigid PO4 tetrahedral unit; partial charge density originating
chemically reactive facets. The other method used is molecular from O sp and P sp derived bonding states is evident in the local
dynamics simulation for revealing chemical reaction pathways. density of states (DOS). This increases the ionic character of Ag+
One drawback of these approaches is a difficulty in incorporating and (PO4)3−, making the covalent Ag-O bonds weaker. Thus, the
the effect of photoexcited carriers. Therefore, development of the hybridization of Ag d and O p states is negligible in Ag3PO4, giving
computational methods themselves is required to achieve a thor- fully occupied d-states at the VBM. In contrast, covalent Ag-O
ough understanding of photocatalysis processes. In the following bonds are found in Ag2O, and Ag d - O p derived anti-bonding
subsections, we introduce selected topics in this theoretical work. states appear at the CBM. This explains the dominant character
of the CBM (Ag d) in Ag2O. In AgNbO3, the majority of the CBM
is formed by Nb d states and the nature of the Ag-O bonding does
5.1. Electronic Structure of Ag3PO4 not significantly affect the characteristics of the CBM.
In Figures 16A–C, the band structures of Ag3PO4, Ag2O,
Recently, silver-based oxides were found to be promising visible- and AgNbO3 are shown together with the wave function
light-sensitive photocatalysts.[26–28,86,196,197] Ag2O itself is not corresponding to the CBM. In Ag3PO4, the wave function at
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species.[201] A great deal of theoretical effort

Review
has been spent on clarifying the effect of

doping using density functional theory
(DFT). It is rather straightforward to model
an impurity in this computational method;
by introducing a foreign element into a suf-
ficiently large unit cell (supercell).
Nitrogen-doped TiO2 represents a suc-
cessful example of band-edge control for
the utilization of visible light, although its
mechanism is still under debate. Asahi
et al. have used first principles calculations
to study the effect of doping with various
anions, and it was concluded that nitrogen
is the most promising dopant for TiO2.[13] It
was claimed that the red shift of the photo
absorption edge originates from an upward
shift of the VBM caused by hybridization
of the N-related states with the host VB.
However, the calculations were based on a
model structure with a high concentration of
doped nitrogen (∼6 atomic%), whereas only
Figure 16. Band structures for (A) Ag3PO4, (B) Ag2O, and (C) AgNbO3. The square of the 1 atomic% N is necessary to activate photo-
wave function (yellow surface) corresponding to the CBM is also shown in each case, where catalytic reactions under visible light.[13,202,203]
silver, red, mauve, and green particles represent the positions of Ag, O, P, and Nb atoms. The
isosurfaces are at 0.01 electrons/Å3. Adapted with permission.[199] Copyright 2011, American
This model can hence be considered inap-
Physical Society. propriate to provide a clear explanation of
the effect of N-doping in TiO2. Indeed, subse-
quent studies using larger supercells showed
the CBM is significantly delocalized because it mainly con- that substitutional nitrogen at the oxygen site (NO) gives rise
sists of Ag s states. In contrast, the CBM of Ag2O possesses to a deep impurity state above the VBM rather than to a new
the character of Ag d - O p derived anti-bonding states, which band.[204–206] Although such deep impurity states should pro-
are localized at atomic sites and are hence unfavorable for mote the absorption of visible light, one may expect them to
electron transfer. In Ag3PO4, a large degree of hybridization be disadvantageous for photocatalytic activity because they act
between Ag s states on adjacent atoms occurs, which gives as carrier recombination centers; this is inconsistent with the
rise to a dispersive band structure at the CBM without the rather good oxidation power of N-doped TiO2 observed experi-
‘contamination’ of d-states. This contributes to a decreased mentally. Recent studies have suggested that N-doping in TiO2
effective electron mass. In AgNbO3, the CBM mainly con- is accompanied by the formation of trivalent titanium[207,208] via
sists of dxz and dyz states, giving rise to an anisotropic charge donor-type defects. Although some computational results have
distribution (Figure 16C) and allowing electron transfer only supported this idea,[208–210] they do not give a consistent mecha-
along the z-direction. This anisotropy is also observed in the nism for explaining the puzzling beneficial effect of nitrogen
band structure, where the dispersion of the CBM strongly doping. Based on the DFT + U method,[211] We have recently
depends on the direction; it is very dispersive along X-S-Y and approached this problem and proposed a convincing model
flat along S-Γ. This is undesirable for the purposes of photo mechanism that focuses on the interactions between NO and
catalysis because the limited directionality of the electron native donors.[212] These interactions remove deep-lying NO
pathway increases the probability of carrier recombination. states from the bandgap while maintaining the visible light
In contrast, the CBM of Ag3PO4 has a very isotropic distribu- absorption.
tion and is hence favorable for electron transfer (Figure 16A). Other anion dopants in TiO2 such as carbon,[213,214]
We conclude that the excellent photocatalytic performance of boron,[215,216] sulfur,[217,218] phosphorus,[218] and halogen
Ag3PO4 is partly due to the highly dispersive band structure at atoms[219] have been theoretically studied mainly to inves-
the CBM, which results from Ag s–Ag s hybridization without tigate their effects on the band structure. Metal doping has
localized d-states. Similar calculations for Ag3PO4 were subse- also been revisited with a view to enhancing the visible light
quently reported by another group[200] and are consistent with absorption.[220–222] Recently, the effect of co-doping has also
our conclusion. been extensively studied. Valentin et al. have shown that co-
doping with nitrogen and fluorine is advantageous for the
reduction of defect formation and lowers the energy cost for
5.2. Doping the incorporation of nitrogen owing to the charge compensa-
tion effect between the donor (F) and acceptor (N).[223] Mi et al.
The most popular approach for tailoring the absorption edges claimed that hydrogen doped unintentionally during the syn-
of photocatalysts is to dope the host material with foreign thesis of N-doped TiO2 removes the N 2p impurity level from
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Review
Figure 17. (A) Calculated crystal structures of AgAl1-xGaxO2 solid solutions and (B) their corresponding electronic structures. Adapted with permis-
sion.[129] Copyright 2011, American Chemical Society.
the bandgap by the formation of N-H bonds.[224] Chromium- unit cell, geometric optimization was performed using various
doped TiO2 successfully shifts the photoabsorption edge when models for every chemical composition; the most stable model
co-doped with antimony.[225] The bonding effects of pairs of (with the lowest total energy) was then found (Figure 17A).
dopants such as W-N, Ta-N, and Fe-N have also been investi- The corresponding electronic structures of these models were
gated using DFT calculations.[226–228] Many other works have calculated using the widely used Cambridge Serial Total Energy
explored the effects of co-doping in various promising photo- Package (CASTEP) code.[236] It was revealed that the VBs of
catalysts such as SrTiO3,[229–231] NaTaO3,[232] BiVO4,[233] InMO4 AgAl1-xGaxO2 are always composed of Ag 4d and O 2p states,
(M = V, Nb, Ta),[234] and NiO.[235] whereas the CBs are mainly constructed from Ag 5s5p, Al
Previous studies have mainly focused on the red-shift of 3s3p, and Ga 4s4p states. Thus, the VBM is at a similar energy
the photoabsorption edges toward the visible light region, for all compositions, but the energy of the CBM is determined
but not enough attention has been paid to the important by the ratio of Ga/Al. Because the Ga 4s4p levels are lower in
issue of carrier recombination. One must realize that doping energy than the Al 3s3p levels (that is, the Ga 4s4p levels are
is usually accompanied by the formation of defects, and more positive than the Al 3s3p levels relative to the vacuum
photocatalytic activity cannot be improved when the concen- level), the substitution of Al by Ga induces a negative shift
tration of defects is high, even if visible light absorption is of the CBM and a subsequent narrowing of the bandgap.
enhanced. Both the correlation between doping and defect These calculations are consistent with the experimentally
formation and details of the carrier recombination mecha- determined change in bandgap (as shown in Figure 6) and
nism should be intensely studied in order to obtain a com- help to explain the variation in photoactivity across the solid
prehensive understanding of the effect of doping on photo- solution series. They also lend strong support to investiga-
catalytic processes. tions on other solid solutions such as Ca1-xBixVxMo1-xO4 and
(AgNbO3)1-x(SrTiO3)x.[53,130]
Sensitizing TiO2 into the visible region is still a hot topic.
5.3. Solid Solutions The incorporation of sulfur is one of the best methods of con-
tinuously modulating the bandgap because sulfur is isovalent
The synthesis of solid solutions represents an effective with oxygen and can apparently substitute oxygen without the
approach to the precise manipulation of the CB and VB levels, formation of charged defects. A study by Umezawa and co-
which allows an optimal balance between effective visible-light workers found that the bandgap of TiO2 decreases dramatically
absorption and adequate redox potentials to be achieved. The- upon incorporation of a small concentration of sulfur.[237] The
oretical calculations on the electronic structures of solid solu- lowest examined sulfur concentration of x = 0.015625 already
tions provide insight into the configurations of energy-band gave a significant decrease in the bandgap. This originates from
structures and the contributions of the orbitals of each element. the fact that the S 3p states are located above the O 2p states.
The study of Ouyang and Ye on AgAl1-xGaxO2 is a good example A further increase in S content gradually narrows the bandgap
of electronic structure calculation on multi-metal oxide solid to 1.5 eV at x = 0.25. The absorption of light across the entire vis-
solutions.[129] To determine the positions of Al and Ga in the ible spectrum is therefore attainable with a sulfur concentration
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of x < 0.25. The computational results for

Review
TiO2(1-x)S2x are in good agreement with the

experimental study of Umebayashi et al.[238]
5.4. Surface Contact
As introduced in Section 4, increasing the

degree of surface contact between semi-
conductor nanocrystals in an assembly is a
viable way to modulate the absorption edge.
To understand the mechanism of the self-
narrowing bandgap phenomenon exhibited
by assembled CdS nanocrystals, we have
performed electronic structure calculations
for several surface and interface struc-
tures.[59] The ideal (110) surface (Model I)
of zinc blend CdS gives a slightly narrower
bandgap than that of bulk CdS due to the
formation of surface states. The removal
of half of the sulfur atoms from the sur-
face (Model II) introduces extra intra-
band states. We next created structures
to model the surface contact, as shown in
Figure 18A for a pair of ideal surfaces with
mirror symmetry (Model III). The distance
between the two surfaces is 20% longer
than the layer-to-layer distance in the bulk.
The sulfur vacancies at the interface result
in the formation of Cd-Cd bonds (Model Figure 18. Relaxed model structures used for electronic structure calculations. (A) Two (110)
IV, Figure 18B). By calculating the total and surfaces in contact with mirror symmetry, separated by 120% of the layer-to-layer distance in
the bulk (Model III). (B) Half of the sulfur atoms were removed from the interface (Model IV).
local DOS associated with these structures, (C) and (D) Calculated total and local DOS. The DOS projected on the cadmium atoms at the
it was found that the formation of Cd-Cd surface or interface is also shown in (D). The vertical dashed line denotes the highest occupied
bonds dramatically decreases the bandgap state in each system. Adapted with permission.[59] Copyright 2011, Royal Society of Chemistry.
due to an upward shift of the valence band
maximum (Figures 18C-D). The DOS projected on all of In other words, CdS nanocrystals in surface contact should pro-
the cadmium atoms at the interface shows that the newly mote the formation of sulfur vacancies and thereby Cd-Cd bonds
formed states in the bandgap consist of Cd 5s and 5p states at the interfaces, leading to a narrowing of the bandgap. A similar
from atoms located at the interface region (Figure 18D). The effect has also been observed in assembled TiO2 nanocrystals.[58]
electronic charge density corresponding to one of these gap
states shows that the new band is associated with the forma-
5.5. Surface Energy
tion of Cd-Cd bonding states (Figure 18D). In order to ana-
lyze the relative stability of the reduced interface (Model IV) The surface energy is often computed to identify the most
compared to the reduced surface (Model II), we estimated stable surface orientation.[239] Because photocatalysis reactions
the formation energies (Ef ) of sulfur vacancies (Vs) at the occur on the surface, the stability of the surface significantly
non-reduced surface (Model I) and interface (Model III) as affects the efficiency of such reactions.
follows:[59] A good illustration of this concept is found for Ag3PO4,
 where the photocatalytic activity depends on the surface orien-
E Surface (VS ) = E tot (Model II) − E tot (Model I) + 2: S 2 (2)
f tation. In order to clarify the underlying mechanism by which
rhombic dodecahedrons ({110} facets) display higher photocata-
 lytic activity than cubes ({100} facets), as described in Section 3,
E Contact (V ) = E (Model IV) − E (Model III) + 4: 4
f S tot tot S
(3) we have studied the surface energies of Ag3PO4 {100} and {110}
where Etot is the total energy of each model. The chemical potential planes using DFT calculations.[66] Our surface models were
of sulfur (μS) is given by the equilibrium condition μS = Etot[CdS]- based on slabs comprised of 192 atoms with a vacuum region
μCd where Etot[CdS] is the total energy of a two-atom unit cell of of the same thickness for both {100} and {110} facets. Each sur-
bulk CdS and μCd is computed from the total energy of the hexag- face was constructed such that the correct stoichiometry was
onal phase of bulk cadmium. We found that EfContact(Vs) = 0.86 eV satisfied on both sides of the slab. Geometry relaxations were
is much lower than EfSurface(Vs) = 1.30 eV, indicating that sulfur performed with the mid-layers fixed. The surface energy γ was
vacancies are more stable at the contact region than on the surface. computed using[66]
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( = (E slab −nE bulk )/ 2A (4) as well as the higher surface energy of the {110} plane is a pos-
Review

sible origin of the high reactivity of Ag3PO4 rhombic dodecahe-
where Eslab is the total energy of the slab and Ebulk is the total dral crystals.
energy of the bulk per unit cell. Here, n is the number of bulk
unit cells contained in the slab, and A is the surface area of
each side of the slab. The computational results showed that 5.6. Molecular Dynamics Calculations
the surface energy of the {110} facet (1.31 J/m2) is higher than
that of the {100} facet (1.12 J/m2), indicating that the {110} facet Because photocatalytic reactions take place on the catalyst sur-
is more reactive. face, it is important to investigate how the target molecules
To investigate the stability of each surface under a reduced behave on the surface. It is often difficult to observe the reac-
oxygen atmosphere, we next studied the energies of reduced tion dynamics using in-situ experimental techniques. How-
surfaces. A model structure was created by removing an ever, the ab initio theoretical simulation technique based on
oxygen atom from each side of the {100} and {110} slabs. The density functional theory is a powerful alternative tool that is
geometries of the reduced surfaces were fully relaxed with rapidly being developed, in particular taking advantage of the
the mid-layer fixed, in the same way as the ideal surfaces. The astonishing recent progress in computational power that is
energy γ of the reduced surface was computed using[66] available.[240,241] Here we briefly introduce some results of
investigations into the water molecule adsorption properties of
( = (E surf + : O )/A (5) photo-catalyst surfaces, performed using quantum molecular
dynamics simulation (Car-Parrinello method).[242]
E surf = (E slab −nE bulk )/2 (6) Figure 20 indicates a snapshot of the (010) surface of a YVO4
where Eslab is the total energy of the reduced slab and μO is the catalyst, on which adsorbed water molecules are in thermal
chemical potential of oxygen, which is directly related to the equilibrium at 300 K. Good performance in the evolution of
O2 partial pressure in the atmosphere. The surface energy is both H2 and O2 has been observed in experiments performed
shown in Figure 19 as a function of μO, which was referenced under UV light irradiation.[243] The YVO4 bulk crystal contains
with respect to the total energy of a single oxygen molecule. The two kinds of polyhedra: a VO4 tetrahedron (V four-fold coor-
surface structure with lower energy is more likely to be realized. dinated by oxygen; 4c-V) and a YO8 triangular dodecahedron
The ideal surface was found to be stable at higher μO whereas (Y eight-fold coordinated by oxygen; 8c-Y). However, at the
the reduced surface predominated at lower μO. The intersection upper surface of the model structure, not only the 4c-V and
of the two lines corresponding to the ideal and reduced surfaces 8c-Y sites but also the 3c-V and 7c-Y sites are intentionally
gives the transition value of μO, which is higher for the {110} exposed to two monomolecular water layers. Close to thermal
plane than for {100}. This indicates that oxygen vacancies start equilibrium, some of the water molecules approach the V and
to form on the {110} surface even under a relatively high O2 Y sites and one molecule is then dissociatively adsorbed at the
partial pressure. Therefore, the abundance of oxygen vacancies V site that is three-fold coordinated by oxygen (3c-V). Water
molecules that are attracted to the 7c-Y sites are adsorbed only
in stable undissociative fashion on the picosecond time scale
of our simulation. At both the 4c-V and 8c-Y sites, no stable
Figure 19. Energies of reduced and ideal {110} and {100} surfaces of Figure 20. A snapshot of the YVO4 catalyst (010) surface with adsorbed
Ag3PO4 as a function of oxygen chemical potential. Adapted with permis- water molecules in thermal equilibrium at 300 K. Gray spheres: V. Sky blue
sion.[66] Copyright 2011, American Chemical Society. spheres: Y. Red spheres: O. White spheres: H.
www.advmat.de
Review
Table 1. Water molecule adsorption properties.
Material (Polyhedral Adsorption site Adsorption property Equilibrium adsorption distance Adsorption energy Reference
structure) (Å) H2O⋅⋅⋅M- or HO⋅⋅⋅M- (eV/molecule)
YVO4 (4c-V and 8c-Y) 7c-Y Undissociated 2.5 0.64 [244]
YVO4 (4c-V and 8c-Y) 3c-V Dissociated 1.8 2.0 [244]
BiVO4 (4c-V and 8c-Bi) 5c-Bi Undissociated 2.6 0.58 [245]
TiO2 (Rutile) (6c-Ti) 4c-Ti Dissociated 2.0 1.5 This work
TiO2 (Rutile) (6c-Ti) 4c-Ti Undissociated 2.1 1.1 This work
adsorption was observed.[244] Table 1 summarizes the water The function and engineering of co-catalysts is one of the
molecule adsorption properties of YVO4, BiVO4[244,245] and the most important subjects in photocatalysis. Although a number
rutile form of TiO2. For the anatase form of TiO2, Reference of research groups, particularly that of Domen but also others,
[246] can be referred to. The dissociative adsorption of water have performed a lot of work in this field, no satisfactory under-
molecules is expected to be important for hydrogen generation. standing of the mechanisms involved has yet been arrived at.
From our study thus far, we can conclude that it is necessary For example, the question of how multiple-electron reactions
to dissociate water molecules at the catalyst surface, to create take place through co-catalysts has long been confusing to
stable cation sites at the catalyst surface (Msuf) with unsatu- researchers studying water oxidation or CO2 reduction. More
rated oxygen coordination, and to make the distance between than 100 semiconductor photocatalysts are known for the reduc-
the cation and the oxygen of the approaching water molecule tion of protons (H+) to H2, but much fewer for the oxidation of
(Owater) relatively short. These may be regarded as necessary oxygen anions (O2−) to O2 or for the reduction of CO2 to hydro-
conditions for developing a photocatalyst with higher perform- carbon molecules. In addition to the redox potentials, multiple-
ance. Fortunately, because there is a tendency for the adsorp- electron reactions involving co-catalysts are thought to play a key
tion distance between the Msuf and Owater to be similar to the role. For the reduction of CO2 in particular, semiconductor pho-
atomic distance between M and O inside the bulk crystal, our tocatalysts exhibit significant activity only when combined with
results should prove helpful in the search for better materials appropriate co-catalysts such as Pt, Cu, and RuO2.[142,248,249]
for hydrogen generation or molecular decomposition without It is worth noting that solar photocatalysis to convert CO2
the need for detailed computer simulations. into readily transportable hydrocarbon fuels is of great interest
to reduce the level of atmospheric CO2 and partly to relieve
the imbalance between energy supply and demand within the
present fossil fuel infrastructure. To reach this holy grail as well
6. Conclusion and Perspectives
as other challenges that might be overcome by photocatalysis,
In this review, we have selectively discussed and summarized obtaining a substantial breakthrough in efficiency requires a
the main recent achievements in the field of semiconductor good understanding of the surface/interface processes at the
photocatalysis. Our aim has been to reveal the key issues, chal- atom level. In-situ observations are highly desirable to obtain a
lenges and opportunities facing present and future research true picture of photocatalyst surfaces in action. Moreover, both
on photocatalytic materials. With significant fundamental sci- theoretical materials design and photocatalytic process simula-
entific and technological knowledge already accumulated by tions should take into account the surface/interface reactions
past research, photocatalysis represents an encouraging pros- of photoexcited carriers. We will then see a prosperous market
pect in the realization of a sustainable society. However, from involving photocatalytic materials. Energy band engineering,
the point of view of industrialization and commercialization, nanotechnology, modern materials characterization methods
many challenges remain in the areas of materials science and and advanced theoretical calculations and simulations promise
engineering. to sustain rapid development of this grand project.
For an ideal material, first of all a high quantum yield (QY)
must be achieved. In the case of pure water photocatalytic split-
ting, the highest QY thus far is 56%, reported for La-doped Acknowledgements
NaTaO3 under UV irradiation (λ = 270 nm);[247] for visible light
the best QY is 2.5% (λ = 400 ∼ 420 nm) for (GaN)x(ZnO)1-x solid This work was supported by World Premier International Research Center
Initiative on Materials Nanoarchitectonics (MANA), MEXT, Japan.
solutions.[124,125] These results are not yet sufficient for practical
solar engineering. Although energy band alterations have been Received: July 18, 2011
extensively applied, a high QY cannot be achieved simply by Published online: October 4, 2011
extending the absorption of visible light by tuning the bandgap.
Very recently, an extremely high QY of nearly 90% under visible
light (λ = 420 nm) was found using Ag3PO4 for the evolution
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2012-Nano-Photocatalytic Materials Possibilities and Challenges

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Nano-photocatalytic Materials: Possibilities and Challenges

super-hydrophilicity; (v) photoelectro-

Tua Tong obtained his

Shuxin OuYang received

For example, NiOx/In1-x NixTaO4 was the first material found

Despite important insight being gained, the mechanisms

involved in photocatalysis are not yet known in detail. Fulfilling

CB is at a suitable level, photogenerated elec-

trons in the CB can reduce H+ to produce H2

level of the VB, or both processes simulta-

develop visible-light-sensitive photocatalysts. However, because 3.1. One-dimensional Nanostructures

photocatalytic reactions are typically surface-based processes,

It was found that Ag/AgCl core-shell nanowires

3.2. Facet-controlled Semiconductor Materials

Considering that photocatalytic reactions

metals and of the electron transfer process at

the semiconductor-metal interface.

3.3. Hierarchical Composite Nanostructures

Photocatalysis may be viewed as a type of system engi-

Fe3O4 spheres to form chestnut–like core–

red-shifted (Figure 13G). The narrower band-

gaps of these CdS nanoparticle assemblies allow

4.2. Plasmon-exciton Coupling Assembly

Hybrid assembled structures of plasmonic

reduction in pore size relative to the polysty-

rene spheres was due to the annealing process

species.[201] A great deal of theoretical effort

has been spent on clarifying the effect of

of x < 0.25. The computational results for

TiO2(1-x)S2x are in good agreement with the

5.4. Surface Contact

As introduced in Section 4, increasing the

Table 1. Water molecule adsorption properties.

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