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Crystal facet engineering of semiconductor photocatalysts: motivations,

advances and unique properties
Gang Liu,a Jimmy C. Yu,*b Gao Qing (Max) Luc and Hui-Ming Cheng*a
Received 2nd February 2011, Accepted 8th March 2011
DOI: 10.1039/c1cc10665a

Crystal facet engineering of semiconductors has become an important strategy for fine-tuning the
physicochemical properties and thus optimizing the reactivity and selectivity of photocatalysts.
In this review, we present the basic strategies for crystal facet engineering of photocatalysts and
describe the recent advances in synthesizing faceted photocatalysts, in particular TiO2 crystals.
The unique properties of faceted photocatalysts are discussed in relation to anisotropic corrosion,
interaction dependence of adsorbates, photocatalytic selectivity, photo-reduction and oxidation
sites, and photocatalytic reaction order. Ideas for future research on crystal facet engineering
for improving the performance of photocatalysts are also proposed.

1. Introduction This is because many applications such as heterogeneous

catalysis, gas sensing and ion detecting, molecule adsorption,
Engineering the shapes of semiconducting functional materials energy conversion and storage are very sensitive to surface
to desirable morphologies has long been actively pursued. atomic structures, which can be finely tailored by morphology
a control. From the intensive studies on morphology-controlled
Shenyang National Laboratory for Materials Science,
Institute of Metal Research, Chinese Academy of Sciences, materials in the past decades, significant advancements in this
72 Wenhua Road, Shenyang 110016, China. area have been achieved.1–29
E-mail: cheng@imr.ac.cn; Fax: +86 24 23903126; Semiconductor photocatalysts have attracted worldwide
Tel: +86 24 23971611
b attention for their potentials in environmental and energy
Department of Chemistry and Institute of Environment,
Energy and Sustainability, The Chinese University of Hong Kong, applications.30–57 The process of heterogeneous photocatalysis
Shatin, New Territories, Hong Kong, China. with semiconductor photocatalyst involves three mechanistic
E-mail: jimyu@cuhk.edu.hk; Fax: (+852) 2603-5057; steps: the excitation, bulk diffusion and surface transfer of
Tel: (+852) 2609-6268
c
ARC Centre of Excellence for Functional Nanomaterials, photoexcited electrons and holes. Apparently, the reactivity of
The University of Queensland, Qld. 4072, Australia the photocatalyst is definitely affected by surface atomic

Gang Liu received his Bachelor Jimmy C. Yu received his PhD

degree in Materials Physics in
Jilin University in 2003. He
obtained his PhD degree in
Materials Science at Institute
of Metal Research (IMR),
Chinese Academy of Sciences
(CAS) in 2009. During his
PhD study, he worked at Prof.
G. Q. Max Lu’s laboratory for
1.5 years in Australia. Now he
is the recipient of the T. S. Keˆ
Research Fellowship founded
by the Shenyang National
Gang Liu Laboratory for Materials
Science (SYNL), IMR CAS.
His current research interests are to explore semiconductor
photocatalysts to utilize solar energy for clean environment
and renewable energy.
in Chemistry from University
of Idaho in 1985. After teaching
for 10 years in the US, he
returned to Hong Kong to
establish an environmental
science programme at The
Chinese University of Hong
Kong. He is now Professor
and Deputy Director of the
Institute of Environment,
Energy and Sustainability.
With an h-index of 50, Prof.
Yu has published many highly
Jimmy C. Yu cited papers on photocatalytic
nanomaterials. He is also
active in knowledge transfer. Photocatalytic air and water treat-
ment systems based on his patents are commercially available.
Prof. Yu was appointed Chang Jiang Scholar Chair Professor
by the Chinese Ministry of Education in 2009.

This journal is c The Royal Society of Chemistry 2011 Chem. Commun., 2011, 47, 6763–6783 6763

structures because surface atomic arrangement and coordination
intrinsically determines the adsorption of reactant molecules,
surface transfer between photoexcited electrons and reactant
molecules, and desorption of product molecules. Surface atomic
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arrangement and coordination changes with crystal facets in
different orientations. Therefore, the reactivity of a given photo-
catalyst sensitively varies on the enclosed crystal facets.
Although intensive experimental and theoretical studies
have been conducted on the reactivity of different surfaces of
metal oxides such as TiO2,44,58–63 much less attention is paid
on the dependence of photocatalytic reactivity on crystal
facets in different orientations.64,65 Stimulated by the rapid
development of controlling the morphologies of materials in
nanoscience and nanotechnology, interest has emerged in
tuning crystal facets of photocatalysts in order to optimize
the photocatalytic reactivity. For example, the morphology of
anatase TiO2, one of the most important photocatalysts, has
been investigated for sphere, rod, wire, tube, slightly and
heavily truncated octahedron, belt and sheet structures.21,27,66–70
Some of these morphologies are enclosed with recognizable
facets such as {001}, {101} and {010}.21,66,69 By tuning the ratio
of different facets, the photocatalytic reactivity would be corres-
pondingly changed. It is conventionally considered that a facet
with a high percentage of under-coordinated atoms possesses a
superior reactivity to that with a low percentage of under-
coordinated atoms.71–74 A cooperative mechanism involving
both favorable surface atomic structures and surface electronic
structures has been proposed recently to account for the
differences in reactivity.75 Unfortunately, reactive facets usually
have a relatively high surface energy. They are therefore unstable
during the crystal growth as a result of reducing total surface
energy of crystals. Acquiring a high percentage of reactive facets
by crystal facet engineering is highly desirable for improving the
photocatalytic reactivity.
High selectivity in photocatalysis is difficult to achieve.
Many photocatalysts show high reactivity for the degrada-
tion of organic molecules but usually with poor selectivity.76–80
G. Q. Max Lu received his
PhD in Chemical Engineering
from University of Queensland,
Australia. He worked as a
Lecturer in Nanyang Techno-
logical University, Singapore
before returning to Queensland
where he has been Senior
Lecturer, Reader, Professor
and Chair in Nanotechnology.
He has received numerous
prestigious awards including
the Federation Fellowship
(twice). He has been Director
Gao Qing (Max) Lu for the Australian Research
Council Centre for Functional
Nanomaterials since 2003. Professor Lu is co-author of 400
journal publications with an h-index of 48, and total citations of
over 9100. His research interests include carbon, silicate and
oxide nanoparticles and nanoporous materials for energy and
environmental applications.
6764 Chem. Commun., 2011, 47, 6763–6783
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The products from solar-induced photoreduction of CO2 often
consist of mixed hydrocarbons including CH4, CH3OH and
HCOOH.51,81–84 Such poor selectivity may be due to the fact
that most photocatalysts are terminated by too many facets
resulting in excessively dispersed surface atomic and electronic
structures. This causes different adsorption states of reactant
molecules, and generates photoexcited electrons of different
energies on different crystal facets. Although there were
attempts for improving the selectivity,78,85–90 photocatalytic
selectivity control is still in its infancy. It is expected that new
opportunities may be created by lowering the dispersivity of
surface atomic structure and electronic structure of photo-
catalysts via crystal facet engineering. A breakthrough in this
research will intensify further development in selective organic
transformations based on semiconductor photocatalysis.77,79
Several insightful review papers have reported the experimental
and theoretical aspects of crystal shape engineering.26,91–95
However, there has been no comprehensive review specially
dealing with the crystal facet engineering of semiconductor
photocatalysts.94,95 In this reivew, we introduce the motiva-
tions and basic strategies of crystal facet engineering of
photocatalysts. Most attention will focus on the advances
made in synthesizing faceted photocatalysts, in particular
TiO2, and the unique properties of the faceted photo-
catalysts. This paper may shed some light on how crystal facet
engineering can be better applied to design more efficient
photocatalysts.
2. Basic strategies of crystal facet engineering
The evolution of crystal shape during growth is basically
driven by continuously decreasing the total surface energy of
crystal, and finally stops at the minimum surface energy point
in a given growth environment. Such process is apparently
related to the species and concentration of components in the
growth environment, which provides a flexible platform to
play with the shapes of crystals. To tailor the fractions of
Hui-Ming Cheng received his
PhD degree in Materials
Science from Institute of
Metal Research, Chinese
Academy of Sciences (IMR
CAS) in 1992. He worked at
AIST (Kyushu) and Nagasaki
University of Japan, and MIT,
USA. He is Professor and
Head of Advanced Carbon
Research Division in Shenyang
National Laboratory for
Materials Science, IMR CAS.
His current research interests
Hui-Ming Cheng focus on carbon nanomaterials
(carbon nanotubes, graphene
and nanoporous carbon) and new energy materials for high-
performance batteries, supercapacitors, and solar energy conversion.
This journal is c The Royal Society of Chemistry 2011
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Fig. 1 Two-step nucleation of colloidal particles observed at 800 Hz
and 167 V cm 1: (a) Initial dilute liquid phase. (b) Amorphous dense
droplets are first created from the mother phase. (c) Crystalline nuclei
are created from the amorphous phase. Reprinted with permission
from ref. 99. Copyright 2007, American Chemical Society.
terminated facets, both bottom-up and top-down synthesis
routes are available.
The bottom-up route for crystallization from solution involves
the nucleation and growth of crystals. According to the
classical nucleation theory, this is supposed to be a single-step
nucleation process. However, recent studies strongly suggest a
two-step nucleation, with an initially created dense liquid
nucleus and subsequent formation of a crystalline nucleus in
the dense liquid (see Fig. 1).96–99 The significance of the two-
step nucleation is that extended space and time for affecting
the morphology of crystals might provide more chances to
control the whole crystallization process by changing the
reaction conditions.
The density, size distribution and surface chemistry of the
resulting crystalline nucleus is highly dependent on the reaction
environment of the solution. Therefore, the subsequent growth
behaviours (i.e. growing rate and orientation) of surviving
nucleus after coarsening, and thus the final shape can be quite
different. It is well established that solvents, impurities and
additives in solution can substantially influence the ultimate
shape of the crystals.100–104 In summary, the solvent effect on
the crystal shape is generated via the varied solvent–solute
interactions along different orientations of a crystal. This is
because surface atomic arrangement and thus surface affinity
for the solvent to each orientation is different, which can
certainly affect the growth rates to the crystal surfaces and
hence the final shape of the crystal.91 Owing to the possible
strong interaction between adsorbates and faces with some
atomic configurations, introducing impurities or additives in a
given solution environment can further tune the growth rates
to the crystal faces and thus tailor the shape of the crystal by
preferentially adsorbing on some crystal faces. The mechanism
of tailoring the crystal shape by impurity/additive effect is to
change surface relative stability of facets in terms of surface
energy. The effectiveness of this effect depends closely on the
match of impurity and additive with faces in a given solution
environment. The role of solvent and impurity/additive effect
in controlling the shape of the crystal is schematically illuminated
in Fig. 2.
Besides the widely employed bottom-up route, the top-down
route can also be used to control the facets of single crystal
particles. So far, this approach has been adopted in several
systems such as Fe2O3,105 WO3106 and TiO2.107 The nature of
this route is the partial dissolution of mother-crystal particles
and/or subsequent recrystallization on the surfaces of residual
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Fig. 2 Schematic of the effect of solvent and additive/impurity
molecules or ions on the morphological control of crystal facets.
mother-particles in a given solvent environment, which is also
analogical to that of the Karst topography involving two
stages of etch and etch-stop.106 Therefore, the key in this route
is to choose appropriate etching and morphology-controlling
(capping) agents so that the purpose of growing crystals with
desired facets can be reached. The mechanism of etching agent
and capping agent is that the capping agent molecules or ions
preferentially adsorb on some surfaces to prevent them attack
by etching agent while the etching agent molecules or ions will
chelate with cations on exposed surfaces and subsequently
cause the dissolution of the chelated surfaces. Depending on
the property of the mother-crystal, the chosen appropriate
etching agent can vary substantially. For example, hematite
Fe2O3 crystals with major {110} and minor {001} facets can be
selectively etched by oxalic acid along the [001] direction with
phosphate ions as capping agent preferentially adsorbed on
{110}, so that the resultant discs are reversely terminated with
major {001} and minor {110}.105 In contrast, urea acting as
both etching and capping agent is an appropriate candidate
for growing WO3 octahedron crystals from irregular WO3
particles.106
The above part deals with the controllable growth of single
crystal particles with well defined facets. These faceted crystal
units can also be considered as building blocks for constructing
more complex structures so that the facets of crystals can be
selectively exposed outwards in the constructed structures. The
assembly mechanism of forming complex structures usually
involves template methods, Ostwald ripening (‘‘the growth of
larger crystals from those of smaller size which have a higher
solubility than the larger ones’’—IUPAC Compendium of
Chemical Terminology, 2nd edition, 1977), Kirkendall type
diffusion (normally referring to comparative diffusive migrations
among different atomic species in metals and alloys under
heating conditions),28 oriented attachment (a combination
of crystallites through their suitable surface planes),28 space-
predefined growth, and probably their combination, which have
been fully discussed by Zeng.28 In most cases, the constructed
structures are polycrystalline. However, single crystalline nano-
wires have been realized in the case of the assembly of CdTe
nanoparticles driven by strong dipole–dipole interaction.108
Recently, Schliehe et al. reported single crystalline ultrathin
Chem. Commun., 2011, 47, 6763–6783 6765

PbS sheets by two-dimensional oriented attachment of PbS
nanocrystals.109
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3. State of the art of crystal facet engineering
In this section, we first briefly present the definition of surface
energy and Wulff construction, which are the most basic
parameters and method for predicting the equilibrium morpho-
logy of a crystal. Detailed description can be found in the
review paper by Lovette et al.91 Crystalline TiO2, the most
intensively investigated semiconductor photocatalyst, is chosen
as the most representative example to indicate the develop-
ment and resultant unique properties of photocatalysts with
well defined facets. Meanwhile, other photocatalysts are
briefly introduced.
3.1 The surface energy and Wulff construction
The energy of the terminated surface of a solid material is
always higher than that of the bulk and this energy difference
is defined as the surface energy. Based on surface energies of
all facets, one can use the Wulff construction to determine the
equilibrium morphology of a material. In the Wulff construc-
tion, surface energy minimization is the central standard to
optimize the composition of the crystal surface.
3.2 Predicted shapes of TiO2 polymorph crystals
Among various photocatalysts, it is little doubt that crystalline
TiO2 as the most intensive studied photocatalyst plays an
indispensible role in promoting the development of photocatalysis
since the discovery of TiO2 photoanode for photocatalytic
hydrogen evolution in 1972.30 TiO2 polymorphs comprise
anatase, rutile and brookite. It is generally considered that
anatase is the most active, rutile is less active, and brookite
is not active at all for photocatalysis applications, though all
three phases are constructed with TiO6 octahedra. Anatase
and rutile are tetragonal and brookite is rhombohedral. Due
to different arrangements of these TiO6 octahedra in the
polymorphs, the surface terminations in various orientations
and thus the equilibrium morphologies of the crystals are
completely different.
According to the Wulff construction and calculated surface
energy, the shape of anatase under equilibrium conditions is a
slightly truncated tetragonal bipyramid enclosed with the eight
isosceles trapezoidal surfaces of {101} and two top squares of
{001}, as shown in Fig. 3.110 The percentage of {101} is
Fig. 3 The equilibrium shape of a TiO2 crystal in the anatase, rutile
and brookite, according to the Wulff construction and the calculated
surface energies. Reprinted with permission from refs. 110, 112 and
113. Copyright 2001, 1994, 2007, American Physical Society.
6766 Chem. Commun., 2011, 47, 6763–6783
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predicted to be as high as 94%. Although the surface energy
of {010} (0.53 J m 2) was calculated to be between {001}
(0.90 J m 2) and {101} (0.44 J m 2),111 it is surprising that
no {010} will appear in the equilibrium shape of anatase.
Regarding rutile, the predicted equilibrium shape of a macro-
scopic crystal was constructed with (110), (100), (001) and
(011) faces (see Fig. 3).112 It is found that the most stable (110)
face with the lowest surface energy of 15.6 meV au 2 dominates
the shape while (001) with the highest surface energy of
28.9 meV au 2 does not exist in the equilibrium shape at all.
Gong et al. presented the comprehensive results of the struc-
tures and energetics of ten stoichiometric 1  1 low-index
surfaces with different possible terminations of brookite.113
The relative stabilities of different faces determined are found
to be negatively related to the concentration of exposed
coordinatively unsaturated Ti atoms. Fig. 3 shows the equilibrium
shape of brookite crystal, most of which is composed of (111),
(210), (010) and reconstructed (001) facets. It is interesting to
note that brookite (210) as one of the most stable facets has
very similar atomic structure to the most stable facet (101) of
anatase. However, they show differences in electronic states,
which may result in different chemical reactivities.113
All the above equilibrium shapes predicted of TiO2 poly-
morph crystals are conducted in vacuum at absolute zero
temperature, which is clearly different from the actual condi-
tions. Barnard et al. found that the presence of water has
influence on the shapes by changing the size of anatase {001}
and aspect ratio of rutile.114 Therefore, these predicted shapes
are definitely derived from the observed morphologies of
natural or synthetic crystals, to some extent, influenced by
the environmental growth conditions. Despite some differences
between the vacuum conditions used in the calculations and
the real conditions for crystal growth, the most stable facets
predicted usually show the largest fraction in crystal surfaces.
In the practical synthesis procedures, TiO2 crystals are
always subjected to either acidic or alkaline conditions, and
therefore their morphologies varies with the surface chemistry
involved. Based on surface free energies and surface tensions
from first-principles calculations, Barnard et al.115 systemati-
cally studied the effects of surface chemistry in terms of acidic
and alkaline conditions on the morphologies of anatase and
rutile nanoparticles. As shown in Fig. 4a–e, the surface
termination by hydrogen (acidic conditions) results in little
change in the shapes of both polymorphs relative to vacuum.
However, in water terminated surfaces and hydrogen-poor
surfaces, in particular oxygenated surfaces, both polymorphs
are apparently elongated. As a result, it is noteworthy that new
facets {010} as the ‘‘belt’’ appear at the center of anatase
particles. These predictions are very important to experi-
mentally realize the fine tuning of morphology by controlling
surface chemistry.
Retaining a large percentage of facets with high surface
energies (i.e. anatase {001}) in crystals usually result from their
rapid growth rates during crystal growth. Appropriate surface
adsorbates may substantially lower the surface energy and
thus probably obtain a high percentage of high-energy surfaces.
Yang et al.21 started the theoretical investigation the influence
of surface terminated non-mental atoms on the surface energies
of anatase (101) and (001), and found that surface terminated
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Fig. 4 Morphology predicted for anatase (top) with (a) hydrogenated
surfaces, (b) with hydrogen-rich surface adsorbates, (c) hydrated
surfaces, (d) hydrogen-poor adsorbates and (e) oxygenated surfaces,
and rutile (bottom) with (f) hydrogenated surfaces, (g) with hydrogen-
rich surface adsorbates, (h) hydrated surfaces, (i) hydrogen-poor
adsorbates and (j) oxygenated surfaces. Reprinted with permission
from ref. 115. Copyright 2005, American Chemical Society.
fluorine could effectively reverse the stabilities of (101) and
(001). The maximum percentage of {001} was predicted to be
more than 90% (See Fig. 5). Their subsequent experimental
results solidly confirmed the key role of surface fluorine in
stabilizing {001}. This work has triggered the subsequent
intensive research interests in preparing faceted anatase and
also other photocatalysts.
Fig. 5 Slab models and calculated surface energies of anatase TiO2
(001) and (101) surfaces. (a, b) Unrelaxed, clean (001) and (101)
surfaces. Ti and O atoms are represented by grey and red spheres,
with six-fold Ti, five-fold Ti, three-fold O and two-fold O labelled as
6c-Ti, 5c-Ti, 3c-O and 2c-O, respectively. (c, d) Unrelaxed (001) and
(101) surfaces surrounded by adsorbate X atoms. (e) Calculated
energies of the (001) and (101) surfaces surrounded by X atoms.
(f) Plots of the optimized value of B/A and percentage of {001} facets
for anatase single crystals with various adsorbate atoms X.21
This journal is c The Royal Society of Chemistry 2011
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3.3 Anatase TiO2 crystals with well-defined facets
3.3.1 Anatase with a large percentage of {101} facets. As
indicated above, {101} facets will dominate the surface of most
anatase particles prepared conventionally. Well faceted {101}
facets can be achieved by coarsening, in terms of the growth of
large particles at the cost of small particles (namely, Ostwald
ripening). As early as 1999, slightly truncated octahedron
crystals with well defined {101} facets were obtained by
coarsening pristine titania particles from sol–gel route under
various hydrothermal conditions.66 Acidic conditions were
found to accelerate the coarsening relative to deionized water.
The percentage of {101} varies as a result of changed growth
rates along o0014 and o1014 directions during different
growth stages. The driving force for simple particle growth is
the reduction in surface energy. Minimizing the area of
high surface energy faces to further reduce surface energy is
responsible for morphology evolution.
Recently, impressive approaches have been reported to
obtain anatase with a high percentage of {101} with the rapid
development of morphological control. Amano et al.116 reported
a hydrothermal transformation directly from K-titanate nano-
wires (5–15 nm in diameter and several hundreds of nanometres
in length) to octahedral anatase single crystals (particle size is
less than 100 nm) with predominant {101} as shown in Fig. 6.
Dai et al.117 employed very small particles of amorphous TiO2,
prepared by electrospinning, as precursor to prepare truncated
tetragonal bipyramids of anatase in size of less than 50 nm via a
hydrothermal route. The percentage of {101} can be as high
as 90%.
All the above synthesis procedures have a common feature
of using pre-prepared less crystalline TiO2 particles or nano-
structured titanates as precursor. Different from these routes,
Liu et al.118 developed a novel route to prepare TiO2 with
crystalline bulk TiB2 as precursor via an acidic hydrothermal
route. Due to its specific bonds and intrinsic chemical stability
together with its ability for controlled release of titanium
species, TiB2 shows very powerful versatility in tuning both
crystal phases and morphologies of TiO2 by simply controlling
Fig. 6 SEM image of (a) titanate nanowires and (b, c) particles after
hydrothermal reaction of titanate nanowires. (d) TEM image and
electron diffraction pattern of an octahedral bipyramid.116
Chem. Commun., 2011, 47, 6763–6783 6767

the species and amount of mineralizers (Cl , SO42 and
NO3 ). Specifically, anatase bipyramids with a high percen-
tage of {101} can be obtained by tuning the ratio of SO42 to
Cl in solution. This new strategy could also be extendable to
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other metal borides such as ZrB2, TaB, Nb3B4 to synthesize
their corresponding metal oxides.
Although the percentage of {101} in the synthesized
anatase bipyramids can be nearly 100%, it is impossible to
completely eliminate high-energy {001}. This is balanced by
the minimization required for the total surface energy of whole
particle. If {001} grew out of existence, the intersection of
{101} planes would result in an acute angle, which would
presumably show higher energy than the high energy (001)
surface.66
To this end, a large percentage of {101} facets is usually
achieved in bipyramids, which is the equilibrium shape of
anatase. With respect to the bipyramids, anatase nanobelts
with two large (101) faces have been recently realized by Wu
et al.119 The synthesis strategy is to hydrothermally treat
titanium dioxide powder in NaOH solution and the resultant
products after washing with hydrochloric acid were thermally
treated to obtain the final belts (Fig. 7). Experimental
and theoretical studies have revealed that the belt structure
has obvious merits in lowering the recombination of
photoexcited electrons and holes, in contrast to nanospheres,
as a result of greater charge mobility, fewer localized states
near the band edges, and effective trapping of oxygen on the
(101) face.
3.3.2 Anatase TiO2 with a large percentage of {001} facets.
It is no doubt that a large percentage of {001} facets has become
a very popular target in the synthesis of anatase TiO2 crystals
Fig. 7 (a) SEM images of anatase TiO2 nanobelts; (b) bright-field
TEM image of a TiO2 nanobelt; the inset is a selected area electron
diffraction (SAED) pattern taken along the [100] direction of the
nanobelt; (c) HRTEM image of a nanobelt; (d) bright-field TEM
images and corresponding SAED patterns of a TiO2 nanobelt recorded
in different crystallographic orientations while keeping the [010] axis
horizontal, as well as schematic illustrations of the nanobelt and the
relationship between the incident beam and the nanobelt while taking
images and diffraction patterns. Reprinted with permission from
ref. 119. Copyright 2010, American Chemical Society.
6768 Chem. Commun., 2011, 47, 6763–6783
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since Yang et al.21 realized the first case of 47% {001} in
uniform crystals. To this end, improved synthesis procedures
have been developed and exciting advances have been
obtained as summarized in Table 1.117,120–139
The percentage of {001} facets can be well tuned by
controlling the concentrations of precursors and fluorine
species, also the synergistic effects of other capping agents.
For instance, the percentage can increase from 18 to 72% by
simply decreasing the concentration of Ti(SO4)2 from 100 to
10 mM.129 Zhang et al.140 showed that the percentage gradually
improved with increasing amount of 1-butyl-3-methylimidazolium
tetrafluoroborate. The reason for the improved percentage is
the increased surface coverage fractions of fluorine. It is
theoretically predicted that the different surface coverage
fractions can greatly affect the surface energy and thus the
percentage of {001} during the growth of crystals.129 The
calculated surface energies decrease monotonously from
0.96 to 0.64 J m 2 with increasing coverage. On the other
hand, by employing alcohol as synergistic capping agent, the
percentage can be further improved: 2-propanol, ethanol,
tert-butanol and benzyl alcohol are experimentally proved
to be effective in obtaining a higher percentage of {001}
facets.121,141 Yang et al.121 theoretically revealed that the
adsorption energy of fluorine on (001) surface increased by
0.8 eV in contrast to the slightly weakened adsorption energy
by 0.1 eV on (101) when the derived (CH3)2CHO from
2-propanol was bound on surface unsaturated Ti atoms. The
maximum percentage of {001} could reach 89% with the
involvement of only fluorine.120
It is apparent that the substantial role of fluorine in stabilizing
{001} facets has been extensively demonstrated in various
aqueous synthesis routes, though the fluorine may be released
from different sources. So far, the sources of fluorine includes
the most frequently used hydrofluoric acid (HF),21 1-butyl-3-
methylimidazolium tetrafluoroborate,123 ammonium bifluoride
(NH4HF2),142 ammonium fluoride (NH4F),125 and titanium
tetrafluoride (TiF4) precursor itself.134 No evidence suggests
the dependence of the percentage of {001} on the source of
fluorine.
Regarding the precursors for TiO2, the dissolvable TiF4,
Ti(SO4)2 and Ti(OBu)4 have been commonly used to prepare
anatase with {001} facets. It seems that all precursors can be
used for tailoring both the percentage of {001} facets and
particle size. Therefore, the type of dissolvable precursors is
not a decisive factor in growing the desired pure anatase
crystals. However, some undissolvable precursors such as
Ti,130,139 TiN,126 TiS2133 and TiB2128 crystalline powder can
play an important role in securing some of the unique properties
including visible light absorption and oxygen deficiency. In
addition, TiO2 films with oriented anatase {001} facets can be
directly grown on Ti foil substrates by a simple hydrothermal
treatment of Ti foils in HF solution.143
Besides the commonly-employed wet-chemistry routes, two
other methods have also been developed for preparing anatase
crystals with a high percentage of {001} facets of good quality.
One is to directly convert amorphous TiO2 nanotube arrays on
Ti foil to anatase crystals enclosed with well defined {101} and
{001} by calcining at a temperature above 400 1C in air for
2 h.125 Furthermore, both the particle size and the facet
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Table 1 Summary of typical SEM/TEM images, particle size, percentage of 001 facets, photocatalytic activity of anatase TiO2 crystals with
preferential {001} facets from different synthesis procedures. Reprinted with permission from ref. 21, Copyright 2008, Nature Publishing Group;
Reprinted with permission from ref. 120, 121, 124, 125, 126, 128, 131, 135, 140, Copyrights 2009, 2009, 2009, 2009, 2009, 2009, 2010, 2010, 2010,
American Chemical Society. Reprinted with permission from ref. 127, Copyright 2009, Wiley-VCH; Reprinted with permission from ref. 133.
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Copyright 2010, Elsevier

Particle size and

SEM/TEM Image percentage of {001} Photocatalytic activity Typical synthesis parameters Ref.
Size: ca. 1.66 mm No data Precursor: 30 mL 5.33 mM TiF4 21
Percentage: 47% Morphology controlling agent: 0.4 mL
10 wt% HF
Procedure: hydrothermal process, at 180 1C,
414 h

Size: ca. 1.09 mm 5 times higher photoreactivity normalized by Precursor: 14.5 mL 2.76 mM TiF4 121
Percentage: 64% surface area in generating  OH radicals than Morphology controlling agent: 0.5 mL
P25 TiO2. 10 wt% HF, 13.38 mL 2-propanol
Procedure: hydrothermal process,
at 180 1C, 411 h

Size: ca. 2 mm Exhibiting higher reactivity in photodegrada- Precursor: 30 mL 20 mM TiF4 123

Percentage: maximum tion of 4-chlorophenol than selected anatase Morphology controlling agent: 1-butyl-3-
80% TiO2 without dominant {001} facets. methylimidazolium tetrafluoroborate (1 mL)
Procedure: microwave-assisted hydrothermal
process, at 210 1C, 90 min

Size: ca. 2.2 mm Both the NO removal rate and the
Percentage: 27–50% photoactivity in decomposing aqueous
4-chlorophenol increase with increasing
percentage of {001} facets from 0% to 50%.
Precursor: 30 mL 40 mM TiF4 140
Morphology controlling agent: ionic liquid
1-methylimidazolium tetrafluoroborate
(0.5, 1 or 2 mL)
Procedure: microwave-assisted hydrothermal
process, at 210 1C, 90 min

Size: ca. 2 mm Improved photoreactivity in decomposing Precursor: 10 mg Ti powder/30 mL aqueous 130

Percentage: no data methylene blue from 48.1 to 82.5% relative solution containing 3 mL H2O2
to irregular TiO2. Morphology controlling agent: 0.1 mL HF
(40 wt%)
Procedure: hydrothermal process, at 180 1C,
10 h

Size: ca. 50–250 nm H2 evolution: showing a higher rate than P25 Precursor: TiCl4 vapor generated by bubbling
Percentage: TiO2, in particular in the presence of argon (200 mL min 1) into TiCl4 solution at 124
B/A = 0.65–0.75 [Pt(NH3)4]Cl2 under 400 W high-pressure 358 K mixing O2 (1200 mL min 1)
mercury lamp; Procedure: CVD, 1573 K.
Photodecomposition capability: as high as
that of P25 for decomposing acetic acid, much
higher than P25 for decomposing methanol.

Precursor: amorphous TiO2 nanotube arrays

Size: decreasing from 220 No data
with a length 430 mm from the anodization
to 20 nm with the increase 125
process of Ti foil in electrolyte containing
of NH4F from 0.1 to 2%
NH4F
Percentage: Procedure: heat treatment at 4 400 1C for 2 h
B/A = 0.55–0.82 with a ramping rate 416 1C min 1 in air, two
sides of TiO2 tube arrays are covered by two
glass plates.

Size: ca. 30–85 nm Exhibiting photoreactivity both for generating Precursor: 100 mM Ti(SO4)2 129

Percentage: 18% OH radicals and for hydrogen evolution that Morphology controlling agent: 0.2 M 40 mL
is markedly superior—by factors of 5.6 and HF
8.2, respectively—to ca. 3 mm anatase with Procedure: hydrothermal process, at 180 1C,
72% {001} facets. 22 h

Size: ca. 30–130 nm In contrast to the substantially prolonged
Percentage: 68–89% degradation half-rate of methylene orange
with P25 TiO2, the samples obtained exhibit a
gradually shortened half-rate in 7 cycles.
Precursor: tetrabutyl titanate, 5 mL Ti(OBu)4 120
Morphology controlling agent: 0.4–0.8 mL
47 wt% HF
Procedure: hydrothermal process,
at 180/200 1C, 24 h

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Table 1 (continued )
Particle size and
SEM/TEM Image percentage of {001}
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Size: ca. 23–94 nm
Percentage: 50–65%
Size: ca. 1.09 mm
Percentage: 64%
Size: ca. 1.2 mm
Percentage: 41%
Size: ca. 4 mm
Percentage: 56%
Size: ca. 1 mm
Percentage: 22.8%
Size: ca. 130 nm
Percentage: patterned
{001} outwards
Size: 3–6 mm spheres
consisting of sheets with
a side length and thickness
of 40 nm and 4 nm
Percentage: 83%
Size: ca. 1–2 mm spheres
consisting of anatase
polyhedra
Percentage: 20%
Size: ca. 1.2 mm spheres No data
consisting of sheets with a
thickness of 3 nm and size
of 100–300 nm
Percentage: 95–99%
percentage can be tuned by controlling the concentration of
NH4F solution for pre-soaking of TiO2 before calcination.
The critical parameters include the temperature and its
ramping rate, and the presence of NH4F. The other is to use
6770 Chem. Commun., 2011, 47, 6763–6783
View Article Online
Photocatalytic activity Typical synthesis parameters Ref.
Conversion of toluene: highest value of 28% Precursor: 0.16 g TiF4 141
compared to 10% for P25. Morphology controlling agent: 40 mL
Selectivity to benzaldehyde: nearly the same tert-butanol/ benzyl alcohol and tert-butanol
as that of P25 at around 90%. Procedure: hydrothermal process,
Yield of benzaldehyde: highest value of 26% at 160 1C, 72 h
compared to 9% for P25.
Nitrogen heteroatom doping leading to a Precursor: 150 mM TiN 126
capability of generating  OH radicals and Morphology controlling agent: 30 mL 1M HF
photocatalytic hydrogen evolution under Procedure: hydrothermal process, at 180 1C,
visible light. 30 h
Sulfur doping causing the capability of Precursor: 9 mM TiS2 133
generating  OH radicals and decomposing Morphology controlling agent: 20 mL 50 mM
Rhodamine B under visible light. HF
Procedure: hydrothermal process, at 180 1C,
12 h
Oxygen deficiency greatly improving Precursor: 100 mM TiB2 128
photocatalytic hydrogen evolution. Morphology controlling agent: 20 mL 1 M
HF
Procedure: hydrothermal process at 180 1C,
14 h
No data Precursor: 6 mL 0.04 M TiF4 134
Morphology controlling agent: disodium
ethylenediaminetetraacetate (EDTA, 6 mM)
Procedure: hydrothermal process at 200 1C,
4h
Photoelectrochemical water splitting Precursor: Ti foil 143
Morphology controlling agent: HF (10 mM)
Procedure: hydrothermal process at 140 1C,
10 h
Methylene orange (MO) in solution Precursor: 10 mL Ti(OBu)4 in 40 mL absolute
(20 mg L 1) can be fully decomposed by the ethanol
127
sample within 10 min, while only 29% MO is Morphology controlling agent: HF
removed with P25 Procedure: hydrothermal process, at 180 1C,
5.5 h
Depending on the degree of surface fluorine Precursor: 15 mmol Ti(SO4)2
termination, the preferential decomposition of Morphology controlling agent: 15 mmol 135
methylene blue or orange can be tuned. NH4F and ethanol
Procedure: hydrothermal process, at 180 1C,
12-24 h
Precursor: titanium(IV) isopropoxide
Morphology controlling agent: 0.03 mL
131
diethylenetriamine (DETA) in 42 mL
of isopropyl alcohol (IPA)
Procedure: hydrothermal process at 200 1C,
24 h, the subsequent calculation at 400 1C
for 2 h in air
a gas-phase reaction of TiCl4 with O2 at a temperature of
1300 1C.124 The most important feature is that small TiO2
particles of 50–250 nm could be obtained at such high
temperature without using fluorine containing reactants. It is
This journal is c The Royal Society of Chemistry 2011
 View Article Online

claimed that uniform and rapid heating at a high temperature
would enable homogeneous nucleation and subsequent
growth to well faceted crystals with few defects. The low
concentration of TiCl4 and the narrow heating zone would
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shapes.69 The key feature of their approach is the use of water
vapor as hydrolysis agent to accelerate the reaction and the use
of both oleic acid and oleylamine as two distinct capping
surfactants which have different binding strengths to control

prevent formation of large particles and polycrystalline aggre-
gates with grain boundaries.124
Can anatase crystals with a high percentage of {001} grow in
a fluorine-free wet-chemistry route? The answer is yes.
Chen et al. proved that diethylenetriamine (DETA) in
isopropyl alcohol could act as an alternative morphology
controlling agent to fluorine species for stabilizing high energy
(001) faces in the solvothermal system.131 As-prepared TiO2
microspheres consisting of {001} dominant sheets are poor in
crystallinity. Post-calcination at 400 1C in air leads to
increased crystallinity without morphology change. The
percentage of {001} is claimed as nearly 100%. Then, a further
challenge is whether or not anatase crystals with a high
percentage of {001} can be grown without both fluorine and
other capping agents. Self-assembly of nanosized building
blocks with {001} into micron-sized hierarchical structures is
also studied.127 The obvious advantage of this method is the
stabilized ultrathin TiO2 structures and facile separation from
solution.
Zhou et al.144 proposed the interesting oriented transforma-
tion from micron-sized NH4TiOF3 square plates consisting of
mesocrystals to anatase TiO2 without changing the original
architecture due to the well matching lattices of {001} and
{010}/{100} facets in these two materials. Detailed structure
analysis shows that the obtained anatase crystals are enclosed
with {001} and {010}/{100}.
From the energy saving view point, it is very desirable to
shorten the duration of crystal growth as much as possible
before a good percentage of {001} facets can be reached.
Zhang et al. has achieved a good step towards this goal.123
With the assistance of microwave radiation, the period of
hydrothermal process has been substantially reduced from the
usual 410 h to 90 min, while the percentage of {001} can be
kept as high as ca. 80% in the well defined micron-sized
crystals. Further efforts in this direction may lead to new
developments of nanosized anatase with a higher percentage
of {001} facets.
the growth of the TiO2 nanoparticles.69 As a result, different
shapes such as rhombic, truncated rhombic, spherical,
dog-bone, truncated and elongated rhombic and bars could
be formed, as shown in Fig. 8. Although the authors
did not identify crystallographic facets of the exposed
surface, it is easy to conclude that compared to untruncated/
truncated rhombic crystals, the elongated crystals are
enclosed with an additional four {010} facets based on the
symmetries and predicted morphologies of anatase. However,
heavy coating of surface by surfactants makes it impossible
to evaluate the photoreactivity of the crystals with different
shapes.
Very recently, Li et al. used Na-titanate nanotubes as
precursor to prepare uniform anatase tetragonal faceted-
nanorods with a large percentage of {010} facets by a hydro-
thermal process in basic solution (see Fig. 9).146 The proposed
growth mechanism involves the formation of Ti(OH)4 frag-
ments from titanate nanotubes and subsequent anatase crystal
nuclei by dehydration reaction between Ti–OH and HO–Ti. It
is considered that the continuous release of OH during the
hydrothermal process plays a key role in generating {010}
facets. Barnard et al.115 revealed that O-terminated (010) had a
lower surface energy than O-terminated (101) and (001). It was

3.3.3 Anatase with a large percentage of {010} facets.

Compared to the widely investigated {101} and {001}, low-
index {010} facets are experimentally less studied until
recently. Actually, as far as the density of surface unsaturated
Ti atoms is concerned, {010} has the same 100% Ti5c as {001}.
According to the commonly-used criteria to predict the
reactivity of surface, {010} is also favourable for hetero-
geneous reactions. Furthermore, theoretical results have
predicted that, contrary to water being adsorbed molecularly
on (101) face and similar to that water partially dissociates on
Fig. 8 Schematic illustration of the overall formation and shape
the (001) face, water molecules can be adsorbed dissociatively
evolution of TiO2 NCs. TEM images of (A) dog-bone-shaped TiO2
on (010) face. Acquiring a high percentage of {010} facets is
obtained at TB/OA/OM (TB: titanium n-butoxide; OA: oleic acid;
therefore of great significance in optimizing the photocatalytic OM: oleylamine.) = 2 : 6 : 4; (B) truncated and elongated rhombic
activity of anatase. TiO2 obtained at TB/OA/OM = 2 : 5 : 5. Insets are high-magnification
Fabrication of anatase crystals with 43.4% of {010} facets images of the corresponding shapes (left, longitudinal view; right,
was reported by Wu et al. in 2008.145 In 2009, Dinh et al. cross view on panel B). Reprinted with permission from ref. 69.
reported powerful routes to prepare anatase crystals in various Copyright 2009, American Chemical Society.

This journal is c The Royal Society of Chemistry 2011 Chem. Commun., 2011, 47, 6763–6783 6771
 View Article Online

3.4 Rutile TiO2 with defined facets

Rutile is the thermodynamically stable phase of TiO2 poly-
morphs. It can be obtained by either the hydrolysis of Ti
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precursor and subsequent crystallization or the post-

transformation from anatase/brookite phase via thermal treat-
ment (phase transformation temperature required depends on
the particle size of TiO2)148 and mechanical processing.149
Although rutile is considered to be less active in photocatalytic
reactions with respect to anatase, nanostructured rutile has
also been used in photocatalysis applications and some cases
Fig. 9 (a) Low- and (b) high-magnification SEM images of anatase
show higher activity than anatase. One obvious merit is its
TiO2 tetragonal faceted-nanorods (TFNR). The inset of (b) is the top smaller bandgap than anatase by 0.2 eV and thus a wider
view of a single TFNR.146 absorption range.
Various morphologies of rutile have been obtained.27,150–156
The frequently observed morphology of nanostructured rutile
believed that the preferential adsorption of hydroxyl ion on
appears as bundled or self-assembled nanowire/nanorods, as a
(010) face contributed to stabilize the (010) face and hence the
result of the preferential growth along [001] direction, as
high percentage. The above route is similar to that for anatase
shown in Fig. 11.152 Based on the crystallographic symmetries
octahedra with {001}, where nanowires instead of nanotubes
and predicted equilibrium shape of rutile, the exposed lateral
are used as precursor.
surface of these nanowires/nanorods which are parallel to the
By controlling carefully the preparation parameters
[001] direction, must be {110} facets. The ends usually have
(concentrations of precursor and morphological controlling
two types of facets: a square surface perpendicular to [001]
agent and reaction time) to satisfy the surface energy require-
direction and four triangle surfaces at an angle of around 1301
ment for each facet, Pan et al. prepared anatase single crystals
relative to {110}. The square face is {001} and the triangle face
with a respective predominance of {001}, {101} and {010} as
is {111}.
shown in Fig. 10. These products made it possible to compare
The synthesis routes of such rutile nanorods with a
the relative photocatalytic activity of each facet and then
high aspect ratio have been well documented in the
determine the photoreactivity order of facets.
literature.151,155,157–166 Generally speaking, the presence of
An alternative route via topotactic transformation reaction
Cl ions as mineralizer in the synthesis system is favourable
from layered titanate nanosheets has also been developed to
for rutile TiO2, regardless of the source of Cl . This is because
obtain anatase with preferential exposure of {010}.147
that due to different coordination ability and spatial steric
Different from the conventional hydrothermal process
effects of the mineralizers, the crystal phase of TiO2 can be
involving the nucleation and growth of anatase crystals, the
tailored through changing the mineralizers, which affect the
TiO6 octahedra in titanate nanosheets slightly and equably
linkage of six-fold coordinated monomers in different bonding
shift from the positions of the layered lattice to the positions of
modes. According to ligand field theory,156 the nucleation and
the anatase lattice in the topotactic transformation reaction.
crystallization of TiO2 in either anatase, rutile or brookite
This method gives important insight for preparing other metal
phase are strongly affected by the ligands and dehydration
oxides with preferential facets.

Fig. 10 (a) Schematic of anatase TiO2 with different percentages of

{101}, {001} and {010} facets; (b)–(d): scanning electron microscopy
(SEM) images of anatase crystals synthesized with different hydro-
fluoric acid (HF) aqueous solutions (120, 80 and 40 mM) containing
different amounts of TiOSO4 precursor (64, 32 and 32 mg) at 180 1C Fig. 11 XRD pattern (a), SEM (b), TEM (c) and HRTEM (d) image
for different times (12, 12 and 2 h). Reprinted with permission from of self-assembled rutile TiO2 by microwave heating TiCl3 at 200 1C for
ref. 75. Copyright 2011, Wiley-VCH. 1 min.152

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 View Article Online

reactions between possible partially hydrolysed Ti(IV) (3d0)

complexes existing in the solution such as (Ti(OH)n(A1)m(A2)o2
(A: anion, n + m + o = 6). An example demonstrating the
effectiveness of mineralizers (Cl , SO42 , NO3 ) in tailoring
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phases of TiO2 has been given by Liu et al.118

Regarding the specific synthesis routes of controlling
morphology of rutile, two representative examples are given
to illuminate the formation of faceted rutile crystals. One is the
rapid formation of self-assembled microspheres with rutile
nanorods by microwave heating TiCl3 at 200 1C for only
1 min (see Fig. 11).152 The nanorods are exposed with {110}
and {111} facets, though the surface is not smooth probably
due to the extremely rapid growth rate. Interestingly, the
synthetic rutile nanorods have a smaller bandgap of 2.8 eV
than the conventional 3.0 eV, which allows it to work reason-
ably well under visible-light irradiation. The other is the Fig. 13 (a1–d1) Top- and (a2–d2) side-view of samples a–d obtained
reported dependence of degree of perfection of facets on by growing TiO2 on Ta foil at 180 1C at (a1, a2) 3.0, (b1, b2) 10,
(c1, c2) 15, and (d1, d2) 20 h, respectively. (b3) HAADF-STEM and
hydrothermal temperature by Kakiuchi et al.,153 where TiCl3
(b4–b6) elemental mapping images of an individual sample b
was also used as precursor together with NaCl additive. At
(scale bar = 500 nm). Reprinted with permission from ref. 154.
80 1C, only needle-like nanorods without well-recognized Copyright 2009, American Chemical Society.
facets were formed. By elevating the temperature to 200 1C,
well-developed lateral {110} and top {111} facets can be non-recognizable. In contrast, Buonsanti et al.172 developed
observed, as shown in Fig. 12. Apparently, a higher temperature a nonhydrolytic synthesis route to prepare high-quality
is favorable for growing crystals with well-developed facets. anisotropically shaped brookite nanorods with length of
Besides the widely used strategy of employing organic 30–200 nm. These rods are determined to be dominantly
surfactants or inorganic ions as capping agents on crystallo- enclosed with the longitudinal {210}/{100}, and basal {001},
graphic faces, doping into crystal lattices is also an effective which is consistent with the equilibrium shape of brookite
approach to manipulating crystal growth behavior and thus crystals predicted from the Wulff construction.
the final morphology of crystals. The basis of this approach is
both the changed surface energies and resultant crystalline 3.6 Other semiconductor photocatalysts with defined facets
lattice microstrains from the cell distortion.167 Very recently,
As early as 2006, Jang et al.65 have investigated the close
Yang et al. reported that Ta doping can cause the anisotropic
dependence of photocatalytic activity on ZnO facets. Largely
growth along [110] direction and cross-medal shape of rutile
TiO2 with dominant {001} facets (Fig. 13).154 inspired by the rapid development of faceted TiO2, engineering
crystal facets has rapidly moved to other photo-
3.5 Brookite TiO2 with defined facets catalysts including both binary and ternary systems. So far,
ZnO,174,175 Cu2O,176,177 SnO2,25 WO3,106 BiVO4173,178 and
Compared to anatase and rutile, brookite has attracted much
Zn2GeO4179 photocatalysts with well defined facets have been
less interest due to the generally considered lack of photo-
reported. For instance, ZnO nanodisks (see Fig. 14a) with a
catalytic activity. However, increasing examples have shown
large percentage of polar (0001) facets and ZnO nanowires
that brookite is also photocatalytically active and even
has unique photocatalytic properties in some cases.168–171
Among the synthetic brookites, crystal facets are usually

Fig. 12 SEM image of the rutile TiO2 deposits on silica glass Fig. 14 SEM images of ZnO nanodisks (a) and nanowires (b)
substrate. Reprinted with permission from ref. 153. Copyright 2006, (reprinted with permission from ref. 174. Copyright 2009, Elsevier),
Elsevier. WO3 octahedra crystals106 (c) and BiVO4 nanoplates173 (d).

This journal is c The Royal Society of Chemistry 2011 Chem. Commun., 2011, 47, 6763–6783 6773

with dominant {1010} facets (Fig. 14b) can be readily prepared
by simply tuning the synthetic parameters.174 In contrast to
most bottom-up routes, Zhao et al. developed an interesting
top-down strategy to prepare WO3 octahedra enclosed with
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{111} facets from irregular WO3 particles by employing urea
as both etching and capping agent in a simple solvothermal
route.106 The top-down approach was also used to prepare
Fe2O3 nanodisks with exposed {110} and {001} facets from
pristine Fe2O3 particles with oxalic acid as etching agent and
phosphate ions as capping agent.105 Monoclinic BiVO4 nano-
plates with exposed {001} facets (see Fig. 14d) have been
synthesized via a hydrothermal route without the use of any
template or organic surfactant.173 New substantial develop-
ment of various photocatalysts with well defined facets is
greatly anticipated.
3.7 Heterostructures with defined facets
Heterostructuring with different phases or materials is one of
the most important strategies to develop highly efficient
powder photocatalysts and photoanodes. The advantages of
heterostructuring include extended light responsive range
and/or promoted separation of photoexcited electrons and
holes. The most famous heterostructure is Degussa P25 TiO2
with 80% anatase and 20% rutile. This material has been
widely used as a benchmark photocatalyst, though the detailed
structures of anatase and rutile are still not well recognized.
Basically, the ultra-high photoreactivity of P25 is originated
from the synergistic effects of anatase and rutile mixed
phases.180–182 Intensive studies have focused on mimicking
the synergistic effects by combining anatase and rutile in a
variety of ways. For example, Tada and co-workers showed
the electron transfer from the conduction band of anatase to
the CB of rutile in patterned anatase/rutile bilayer-type junc-
tion photocatalysts and a resultant much higher photoactivity
in decomposing CH3CHO than with a pure anatase or rutile
photocatalyst.183 Similarly, Li and co-workers also found that
the junction of anatase nanoparticles on micron-size rutile
particles can be very effective in promoting photocatalytic
hydrogen evolution from methanol solution.184 The key to
realizing the synergistic effects in heterostructures requires the
intimate contact of the two phases.
Currently, most heterostructures employ hetero-units with-
out well-defined facets and thus no clear interfacial atomic
structures can be recognized. One apparent drawback is a less
intimate contact among hetero-units. This would affect the
Fig. 15 SEM images of (A) ZnO nanorods and (B) (ZnO)1–(CdS)0.2
core–shell nanorods. Reprinted with permission from ref. 186.
Copyright 2010, Elsevier.
6774 Chem. Commun., 2011, 47, 6763–6783
View Article Online
long-term stability of the photocatalyst. The potential merits
of employing units with well developed facets for hetero-
structures are not only a more intimate contact facilitated by
the flat facets but also probably generate some new
photocatalytic properties by the unique interface atomic
structures. For instance, Wang et al. reported that ZnO–CdS
nanoparticle heterostructures could work well in a direct
Z-scheme (a type of charge transfer process by recombining
low-energy photoexcited electrons and holes in the inter-
face37), but suffered from a serious decay in photocatalytic
hydrogen evolution rate by more than 50% from Na2S/Na2SO3
solution for 30 h reaction.185 However, by employing ZnO rods
enclosed with well-developed {1100} and {0001} facets to
construct ZnO–CdS heterostructures (see Fig. 15), the hydrogen
evolution rate can retain ca. 96% of the initial rate after 30 h
reaction.186 More interestingly, Liu and co-workers discovered
the first case of quite stable overall water-splitting with CdTe
quantum dots (QDs) sensitized well-faceted ZnO nanowire
array photoanodes in Na2SO4 solution.187
In the above cases, CdS nanoparticles or CdTe QDs were
deposited on ZnO surfaces by post-thermal treating of the Cd
precursor or post-dipping in a QD solution. Heterostructures
with well-developed facets can also been obtained by in situ
crystal growth routes. Through crystallographic-oriented
epitaxial growth of the SnO2 nanorods onto pre-grown
a-Fe2O3 nanospindles and nanocubes, branched SnO2/
a-Fe2O3 heterostructures with (101)SnO2/(110)a Fe2O3 and
(110)SnO2/(110)a Fe2O3 interfaces. respectively, were obtained.188
Due to the different lattice mismatch in the interfaces, SnO2
nanorods grow at an angle of 90 and 651 (see Fig. 16) with
respect to exposed facets of nanospindles and nanocubes,
respectively. The capability of decomposing methylene blue
with the heterostructures under both UV and visible light is
greatly improved in contrast to sole a-Fe2O3 counterparts. In
addition, without any seeds, one-step synthesis of nano-micro
‘chestnut’ TiO2 with rutile nanopins on the anatase micro-
octahedron was reported by Zhou and co-workers.68
3.8 Introducing dopants in well-faceted photocatalysts
It is desirable but challenging to design visible-light responsive
photocatalysts. Doping, in particular nonmetal doping,49,189–194
is an important strategy for modifying electronic band struc-
ture and thus light response range. The current bottleneck in
Fig. 16 HRTEM micrographs of SnO2/a-Fe2O3 (nanocube) semi-
conductor nanoheterostructures (SNHs) at different reaction stages:
(a) having reacted for 90 min; (b) having reacted for 120 min, showing
slanted growth of SnO2 nanorods on surfaces of a-Fe2O3 nanocubes
with a fixed angle of ca. 651. Reprinted with permission from ref. 188.
Copyright 2010, American Chemical Society.
This journal is c The Royal Society of Chemistry 2011

introducing visible light absorption by doping is that
well-faceted anatase TiO2 crystals usually have very high
crystallinity, making it hard or nearly impossible to incorpo-
rate dopants into their structural framework by mild post-
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treatment, while the addition of dopant precursors in the
reaction medium may inevitably influence the nucleation and
growth of anatase TiO2 crystals so that no TiO2 sheets with
desirable properties could be synthesized.126
Recently, a new synthesis route has been developed for the
incorporation of nitrogen dopant into anatase crystals with
ca. 60% {001} facets.126 This visible-light photocatalyst has an
absorption band between 400 and 570 nm. The key strategy in
this route is the use of a crystalline compound, titanium nitride
(TiN), as both a precursor and a source of nitrogen dopant.
The method has been extended to prepare sulfur doped
anatase crystals with preferential {001} facets by employing
a TiS2 precursor.133
Self-doping such as oxygen vacancy and Ti3+ in TiO2 can
not only enhance absorption of visible-light but also promote
the separation of photoexcited electrons and holes. Self-
doping can be usually imparted by post-treatment (i.e. plas-
mon treatment).195 For example, oxygen deficient anatase
crystals with ca. 56% {001}, whose average particle size is 4
mm, can be prepared by one-pot hydrolysis of crystalline
metallic TiB2 in HF solution.128 The central feature for
in situ introducing oxygen deficiency is that gaseous hydrogen
released from the hydrolysis of TiB2 can act as powerful
reductive agent for partially reducing anatase crystals
generated. This strategy may also be used for preparing other
oxygen deficient faceted metal oxides.
Although oxygen vacancies might be reactive sites, the
removal behavior of oxygen atoms from different crystal facets
is quite different due to different atomic arrangement. One
typical instance is that twofold coordinated oxygen atoms is
much easier to be removed from rutile (110) than anatase
(101).196 The reason for this difference is that the oxygen
atoms in the former are bound to fivefold coordinated
titanium atoms while they are connected to sixfold coordi-
nated titanium atoms in the latter.
3.9 Surface steps and reconstructions of crystal facets
Surface steps and reconstructions always exist in crystals. The
presence of steps and reconstructions greatly affects surface
structure and thus the surface chemistry of crystal facets. The
microcosmic structures of various metal oxides in particular
TiO2 have long been investigated in depth.58
Compared to surface point defects, steps and reconstructions
are more complex due to their two-dimensional characteristics.
Edges of monoatomic-height steps at terraces on crystal facets
can be virtually considered as very narrow slices of surfaces.
Furthermore, both the stability and reactivity of a step edge
follows that of the corresponding flat surface as demonstrated
by Gong et al.59 By combining the first-principles calculations
with experiments, it was discovered that (100)-, (112)-, (110)-
and (001)-like step edges may exist on anatase TiO2 (101)
(see Fig. 17), though the later two would be less stable as a
result of higher edge surface energies. Further calculations of
water adsorbed on different step structures suggest that the
This journal is c The Royal Society of Chemistry 2011
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Fig. 17 Structural models of step edges A–E on anatase (101). For
steps A–C, two possible terminations are considered. Some specific Ti
and O atoms at the edges are indicated in the insets. Reprinted with
permission from ref. 59. Copyright 2006, Nature Publishing Group.
reactivity of a step is very similar to that of an extended
surface.59 Therefore, the characteristics of steps on them
substantially affect their surface chemistry besides the intrinsic
atomic structures of crystal facets, which is very indicative for
understanding reactivity of photocatalysts with tailored facets.
It is generally considered that nonpolar and autocompen-
sated metal oxide surfaces should be stable with only limited
relaxations of the ions in the surface region and there
would be no reconstruction.197 However, the stable (1  4)
reconstruction in experimental conditions has been discovered
on the nonpolar and autocompensated anatase (001)
surface.198,199 Subsequent investigation revealed that rows of
TiO3 species periodically replace rows of surface bridging
oxygen of the (1  1) surface (see Fig. 18), namely the
‘ad-molecule’ (ADM) model, to release the large surface
tensile stress present on the surface.197 As a result of the
reconstruction, (001) surface is strongly stabilized by reducing
the surface energy from 0.90 to 0.51 J m 2, but at the same
time the percentage of fivefold coordinated Ti active sites for
water dissociation is decreased by 25%. In addition, (1  2)
and (1  3) reconstructions were studied for the anatase (010)
and (103) surfaces.110,200 Obviously, the reconstruction will be
another inevitable factor in determining the real reactivity of
desired facets.
The above results are related to cases of surface defects on
single crystal surfaces with different orientations. By employing
Raman spectroscopy, surface structures of photocatalysts with
defined facets can be elucidated to some extent. As listed in
Table 1, fluorine species have been widely used to stabilize
Fig. 18 (a) Relaxed (001)-(1  1) surface of TiO2 anatase. (b) Relaxed
structure of the ‘ad-molecule’ (ADM) (1  4) reconstruction. (c)
Projection of the atomic positions of the ADM model on the plane
perpendicular to the ŷ direction. Reprinted with permission from
ref. 197. Copyright 2001, American Physical Society.
Chem. Commun., 2011, 47, 6763–6783 6775

anatase TiO2 {001} facets by forming surface Ti–F bonds.
These surface Ti–F bonds will generate twofold effects:129 (i)
changing fivefold coordinated Ti atoms to sixfold coordinated
Ti atoms; (ii) modifications to the force constants for the
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surface Ti–O–Ti network imposed by the presence of the
surface terminating Ti–F bonds. These can be indicated by
the apparently weakened B1g mode (See Fig. 19a) besides the
shifting of the Eg mode at 144 cm 1 towards higher frequency.
As a consequence, the photoreactivity is greatly impaired in
terms of both photooxidation and photoreduction reactions.
Although fluorine-free surfaces can be obtained by simply
calcining samples in air or washing samples in NaOH solution,
one should keep in mind a possibility that the surface structure
of {001} facets has been modified by the removal of fluorine
from the surface, and whether the photoreactivity evidenced
represents the real level of targeted {001}. As indicated from
the knowledge accumulated from surface science, different
surface defects must also exist in the synthetic photocatalysts
with desired facets. Both the type and amount of surface
defects in microcosmic scale on facets varies with the synthesis
route employed so that faceted photocatalysts, even with a
very similar morphology, may show quite different photo-
reactivity. An extreme example is that serious surface structure
modifications to anatase TiO2 with faceted {001} and {101}
imposed by oxygen deficiency, which is indicated by an
additional Raman mode at 155 cm 1, can lead to an apparently
improved photocatalytic hydrogen evolution.128
3.10 Unique properties of shaped crystals
3.10.1 Anisotropic corrosion of different facets. The high-
energy {001} facets of anatase TiO2 are more prone to
dissolution than {101} facets during hydrothermal reactions
in a corrosive solution containing HF and H2O2.122 This
property can be used to prepare hollow structures with large
surface areas. Liu et al.201 reported the preparation of hollow
rutile TiO2 tubes with rectangular cross-sections from solid
rutile rods by anisotropic corrosion of (001) along the [001]
direction in hydrochloric acid (see Fig. 20). The mechanism
mainly involves a much faster dissolving rate of the high-
energy {001} ends than the low-energy lateral {110} when the
Fig. 19 Raman spectra between 300–800 cm 1 of (a) as-prepared,
(b) calcined micron-sized anatase TiO2 with preferential {001} facets,
and (c) reference anatase TiO2 without preferential {001} facets.129
6776 Chem. Commun., 2011, 47, 6763–6783
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Fig. 20 Schematic diagram of the morphology evolution of rutile
TiO2 nanotubes and their corresponding SEM micrographs.201
parent solid rutile rods with rectangular cross-sections are
exposed to a corrosive solution under hydrothermal conditions.
The property of anisotropic corrosion of facets is expected
to have interesting applications in developing other hollow
materials with faceted surfaces. The stability of photocatalysts
is always important for a long-term retention of photocatalytic
activity. Fortunately, most photocatalysis processes proceed
at room temperature in non-corrosive solutions. The
anisotropic corrosion of facets should not be a major concern
under such mild conditions.
3.10.2 Interaction dependence of adsorbates on crystal
facets. Reactant molecules must be preadsorbed on the surface
of photocatalysts for photocatalytic reactions to occur. Since
the surface atomic structures of facets are different, the
adsorption energy and states of adsorbates vary with different
facets. Water molecules play an important role in photocata-
lytic reactions. Intensive studies on the adsorption behavior of
water molecules on TiO2 surfaces with different orientations
were conducted.72,202–204 Very recently, an overall review on
the theoretical studies of interaction of water and titania has
been given by Sun et al.63 The principal concern is that water
molecules on titania surface are adsorbed molecularly or
dissociatively, which is critically determined by the coordina-
tion numbers and mutual distances of surface atoms. As far as
the adsorptions of water molecules on anatase (101), (001) and
(010) surfaces are concerned, very different trends were
observed: water can only be molecularly adsorbed on Ti5c
atoms on defect free (101),72 while both (001) and (010) with
100% Ti5c atoms can dissociatively adsorb water molecules at
low coverages.72,204 However, the adsorption behavior of
water can be effectively changed by surface defects. For instance,
the bridging oxygen vacancy on anatase (101) can cause the
dissociation of an isolated water molecule at the Ti4c centre near
the vacancy.205 The dependence of other adsorbates such as
maleic anhydride on facets has also been investigated.206
Taking advantage of the different adsorption behaviors of
molecules and ions on crystal facets, it is possible to selectively
deposit metal nanoparticles on different facets of metal
oxides. Recently, Read et al.207 used this approach to
construct anisotropic metal oxide–metal interfaces. The atomic
This journal is c The Royal Society of Chemistry 2011

facet-selective deposition of gold nanoparticles on {100} of
Cu2O crystals was achieved by preferential pre-adsorption of
sodium dodecyl sulfate (SDS) on {111} as shown in Fig. 21.
Furthermore, it was also shown that when Au(CH3COO)3 was
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used as the precursor, Au particles were formed on both
{0001} and {0110}, while Au particles were only found on
{0110} when AuCl3 was the precursor. The proposed reason
for this difference is the preferential adsorption of Cl on
{0001}, which prevents the subsequent deposition of Au.
3.10.3 Reaction selectivity on different facets. Photocatalytic
processes can degrade organic molecules via the formation of
reactive radicals. However, it is often difficult to selectively
transform organic compounds, for example from –CH2OH to
–CHO.76–79,86 The use of photocatalysis in organic synthesis is
still a challenge. A number of innovative strategies have been
developed to enhance the reaction selectivity of photo-
catalysts.87 These strategies involve either modifying the
surface structure (controlling surface electronic charge of
photocatalysts by adjusting pH;87 anchoring surface with
specific molecules for selective adsorption of reactants;88 and
coating a thin layer of molecularly imprinted polymer with
recognition ability toward the template molecules)89 or intro-
ducing a second phase (encapsulating photocatalysts by
porous silica shell with tunable pores for the diffusion of
reactant molecules;90 and loading photocatalysts on some
substrates).80 All these strategies are, however, driven by extrinsic
exertions instead of intrinsic characters of the photocatalysts.
It is also possible to improve the selectivity of a photo-
catalyst by optimizing its intrinsic properties. For example, the
properties of surface structures inherently determine the
adsorption/desorption behaviors of reactant molecules and
reaction intermediates and thus affect significantly the photo-
catalytic selectivity. Morphological control to form different
crystal facets with different surface atomic structures provides
a means to tune the selectivity of photocatalysts. Xamena et al.78
demonstrated the enhanced activity in the shape-selective
photocatalytic degradation of large aromatic molecules with
ETS-10 titanosilicate by controlled defect production. Very
recently, Liu et al.135 reported that anatase polyhedra
with exposed 20% {001} facets show the preferential decom-
position of methylene blue (MB) with respect to methylene
orange (MO) (see Fig. 22b and c), while P25 titania with below
5% {001} facets favors the decomposition of MO, indicating
the importance of intrinsic surface atomic structure in tuning
photocatalytic selectivity. Such photocatalytic selectivity of
MB (MO) is attributed to the adsorption selectivity towards
MB (MO) molecules. Interestingly, even a partial surface
Fig. 21 Utilization of preferential adsorption of additives for shape
control (left) and for atomic plane-selective metal deposition (right).
Reprinted with permission from ref. 207. Copyright 2009, American
Chemical Society.
This journal is c The Royal Society of Chemistry 2011
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fluorine termination can reverse the selective decomposition
order between MB and MO as shown in Fig. 22a. The reversed
selectivity is obviously related to the changed surface atomic
structure by the Ti–F bond, as indicated by the Raman spectra
in Section 3.9. This would affect the adsorption behaviors of
molecules.
3.10.4 Reduction and oxidation sites on crystal facets. It
may sound strange to propose that certain crystal facets favor
reduction while others prefer oxidation. However, it is true
that the photoexcited electrons and holes can be in principle
trapped by surface cation and anion sites, i.e. surface Ti4+ and
O2 ions for TiO2.
It has been demonstrated that Pt particles from the photo-
reduction of Pt6+ can be deposited only on the {110} facets of
rutile TiO2 while PbO2 particles from the photooxidation of
Pd2+ are found mostly on the {011} facets (see Fig. 23a and c).
This suggests that the {110} and {011} facets act as efficient
reduction and oxidation sites respectively.208 A similar trend
was also observed in anatase facets as shown in Fig. 23b and d,
though not as clearly as that in rutile.208 The proposed reason
for different facets as oxidation and reduction sites is that
surface energy levels (namely, surface electronic structures) of
the conduction bands and valence bands of facets are different
so that photoexcited electrons and holes can be driven to
different facets, leading to the separation of electrons
and holes.
Intrigued by the above results, Zheng et al.177 proposed a
possible hole transfer from {110} and {100} to {111}, together
with an electron transfer reversely from {111} to {110} and
{100} in Cu2O microcrystals (see Fig. 24). Moreover, Yanina
et al.209 found interesting interfacial electron transfer reactions
at one surface coupled with those at another via current flow
through the crystal bulk in a faceted hematite (a-Fe2O3) single
crystal. The crystal was exposed to an aqueous solution
containing Fe2+ and oxalate, as shown in Fig. 25. Specifically,
the edge (hk0) surfaces act directly as an oxidant for Fe2+
species at the basal (001) surfaces by involving electron
transfer through the bulk from (001) to (hk0). The driving
force is provided by the potential difference existing between
(001) and (hk0). As a result of this process, (hk0) is gradually
Fig. 22 A comparison of photocatalytic decomposition of methyl
orange (MO) and methylene blue (MB) by hollow TiO2 microspheres
(HTS) before and after surface modification: (a) as-prepared
fluorinated HTS sample; (b) HTS modified by NaOH washing;
(c) sample modified by calcination at 600 1C. The catalytic selectivity
is defined as the ratio (r) of the apparent rate constants (k). Reprinted
with permission from ref. 135. Copyright 2010, American Chemical
Society.
Chem. Commun., 2011, 47, 6763–6783 6777

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Fig. 23 SEM images of a rutile particle (a) and an anatase particle
(b) on which Pt fine particles were deposited by UV-irradiation in a
solution of 1.0 mM H2PtCl6; SEM images of a rutile particle (c) and an
anatase particle (d) showing PbO2 deposits, which were loaded on the
particles by UV-irradiation of the Pt-deposited TiO2 powder in a
solution of 0.1 M Pb(NO3)2.208
Fig. 24 Schematic diagram showing charge separation among
different crystal faces and regeneration of Cu2O nanosheets. Reprinted
with permission from ref. 177. Copyright 2010, American Chemical
Society.
Fig. 25 Schematic diagram depicting the inferred coupled interfacial
electron transfer process operative under the conditions for the
hematite single crystals. Reprinted with permission from ref. 209.
Copyright 2008, AAAS.
6778 Chem. Commun., 2011, 47, 6763–6783
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dissolved and the (001) surface is simultaneously subjected to
an epitaxial growth. However, such a mechanism of electron
transfer between two faces involving the bulk as diffusion path
is established under unique conditions: no light, no oxygen,
appropriate growth temperature, presence of Fe2+ in solution,
and a facile dissolution of Fe2O3. Furthermore, the initial
electrons on the (001) face, which will diffuse through the
bulk to (hk0), are released from Fe2+ in aqueous solution.
Regarding photocatalysts, the photoexcited charge carriers,
most of which are generated within bulk, will diffuse from the
bulk towards the surface before recombination. Once reaching
the surface, the carriers are trapped by the topmost exposed
atoms on different facets. Then, the concern is whether or not
the trapped charge carriers on different facets will transfer
from one facet to others as a result of different surface
electronic structure.
The proposed direct charge transfer process from one facet
to others is debatable when one considers the following
factors: (1) two adjacent facets ideally share only one atomic
line or chain so the probability for transfer between facets
should be very small; and (2) the electronic states related to the
surface terminated atoms are highly localized so the mobility
of the trapped charge carriers should be quite low. Therefore,
most of the trapped charge carriers on different facets should
stay reasonably intact.
Finally but importantly, the possible influence of probing
agents used to reveal the reduction/oxidation facets is often
overlooked. Ionic species such as Cl from H2PtCl6 and NO3
from Pb(NO3)2 may be preferentially adsorbed on some facets,
which can subsequently result in selective deposition of metal
particles on other facets. This possibility has already been
clearly demonstrated in ZnO crystals.175 Furthermore, the
initial solid cluster products from reduced/oxidized ions
deposited on photocatalyst surfaces would accelerate the
subsequent deposition of reduced/oxidized ions on these
clusters. It is uncertain if respective facets for reduction and
oxidation sites can still exist when molecules such as water,
phenol and azo dyes are employed as probing agents. The
products are either intermediate species desorbed from the
photocatalyst surface, or mineralized compounds such as CO2,
which have negligible effects on subsequent photocatalytic
reactions.
3.11 Photoreactivity order of different facets and its origin
Determining the photocatalytic reactivity order of different
facets is necessary for designing efficient photocatalysts with
well-defined facets. The conventional understanding of the
surface atomic structure of a crystal is that facets with a higher
percentage of under-coordinated atoms are usually more
reactive in heterogeneous reactions. This sounds reasonable
when one considers that the under-coordinated atoms may act
as active reaction sites. However, the substantial role of the
electronic structures in affecting the photocatalytic reactivity
of facets is often neglected. Due to the difference in surface
atomic arrangements, the band gap of crystal facets or crystal
slabs would change. This will correspondingly change the
redox power of the photoexcited electrons and holes. As
demonstrated by Liu et al.,129 the UV-visible absorption
spectrum of anatase TiO2 crystals with 82% {101} shows an
This journal is c The Royal Society of Chemistry 2011
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Fig. 26 UV-visible absorption spectra of nanosized anatase crystals

with 18% {001} facets and micron-sized anatase crystals with 72%
{001} facets.129

obvious blue shift compared to that with 72% {001} (see

Fig. 27 (a) Fluorescence signal intensity of TAOH at 426 nm and
Fig. 26), indicating that {101} has a larger bandgap than
(b) hydrogen evolution rate from water containing 10% methanol in
{001}. Further electronic structure analysis suggests that volume for different samples: surface fluorine-terminated anatase TiO2
{101} has the same valence band (VB) maximum as {001}, crystals T001-F, T101-F and T010-F; clean anatase TiO2 crystals
but has a higher conduction band (CB) minimum than {001}. T001, T101 and T010 (T001, T101 and T010 indicates the sample
This electronic band difference, together with a difference in with a respective predominance of {001}, {101} and {010}). Reprinted
atomic coordination, would certainly affect photocatalytic with permission from ref. 75. Copyright 2011, Wiley-VCH.
reactivity.
Very recently, Pan et al. systematically compared photo-
catalytic reactivity in generating  OH radicals and in H2
evolution of anatase crystals enclosed with dominant {001},
{101} and {010}. It was found that despite of the different
surface atomic structure, all three facets had similar photo-
catalytic reactivity when partially terminated with fluorine.
Contrary to conventional understanding, {001} exhibited a
lower reactivity than {101}, and {010} demonstrated the high-
est photoreactivity (see Fig. 27). For the surface under-
coordinated Ti5c atoms, both {001} and {010} exhibited a
higher photoreactivity than {101}. Apparently, {010} facets
possess both a favorable surface atomic structure and a
surface electronic structure so that the stronger reducing Fig. 28 (A) Structure of anatase TiO2 crystal with preferential (001)
electrons on CB can be transferred via the surface Ti5c atoms facets. Transmission image (B) of a single TiO2 crystal on the
as active reaction sites. Such a cooperative mechanism existing cover glass in Ar-saturated 2.0 mm 3,4-dinitrophenyl-BODIPY
on {010} facets is responsible for its unexpectedly high reactivity. (DN-BODIPY) solution under 488 nm laser and UV irradiation.
The higher photocatalytic reactivity of {101} than {001} has The red and blue dots in image (B) indicate the fluorescence bursts
also been validated by probing single molecule fluorescence located on the (101) and (001) surfaces, respectively, observed during 3
min irradiation. Reprinted with permission from ref. 210. Copyright
burst on a single anatase crystal particle.210,211 As shown in
2010, Wiley-VCH.
Fig. 28 by Tachikawa et al.,210 the red and blue dots represent
the fluorescence bursts on (101) and (001), respectively. The
number of red dots on {101} is about three times higher than As presented in Section 3.9, different defects always occur on
the number of blue dots on (001), although the surface area of different facets. Moreover, the abundance and nature of
(001) is more than two times higher than that of (101).129 defects are related to the synthesis routes employed. It is
Based on the above results and discussion, a high density of therefore difficult to compare the activity of photocatalysts
surface under-coordinated atoms does cause a high surface obtained from different synthesis routes.
energy for the crystal facet, but it does not always make the
crystal facet highly reactive in photocatalytic reactions.
4. Conclusions
A crystal facet with a high density of under-coordinated atoms
can be photocatalytically advantageous only if a favourable Crystal facet engineering has attracted increasing attention in
electronic structure co-exists. photocatalysis since Yang et al. reported an anatase TiO2 with
Finally, the possible influence of surface defects on the a large percentage of high surface-energy {001} facets.21 Most
photocatalytic reactivity of facets should also be considered. of the studies focused on developing various synthesis routes

This journal is c The Royal Society of Chemistry 2011 Chem. Commun., 2011, 47, 6763–6783 6779

to prepare pure anatase crystals with higher percentage of
{001} and smaller particle size. Anion doping in anatase
crystals has also been explored. The wet-chemistry methods
are most popular but many solid-state and chemical vapor
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methods have also been developed. As a result, the percentage
of {001} can now approach 100% and the thickness of anatase
crystals is as thin as 1.6 nm. Meanwhile, the interest has
already spread from TiO2 to other metal oxide photocatalysts.
These faceted photocatalysts have already been used in photo-
degradation of organic pollutants, photocatalytic water
splitting and even dye-sensitized solar cells. Facet related
photocatalytic reactivity and selectivity improvements will
have implications on organic synthesis. Unique properties
including anisotropic facet corrosion and preferential
molecule adsorption have been used to produce hollow
structures and anisotropic heterostructures. Importantly, the
understanding of high reactive facets has been extended from
the conventional view of a surface with a high density of
under-coordinated atoms to the cooperative mechanism of
both favourable surface atomic structure and surface
electronic structure. In addition, new technology such as single
molecule fluorescence probing has facilitated the measurement
of photocatalytic activity for each facet.
Although encouraging advances in synthesizing photo-
catalysts with defined facets has been achieved in recent years,
most effort has focused on binary photocatalysts, particularly
TiO2. Faceted ternary photocatalysts are still challenging yet
desirable to be explored for crystal facet engineering to fully
exert its influence. Continuous efforts are needed to develop
feasible synthesis routes for growing crystals with targeted
reactive facets. Most synthesis strategies involve the use of
morphology controlling agents (MCAs) that must be
eventually removed in order to obtain clean facets. This
process may cause some uncontrollable changes to surface
atomic structures. The development of MCA-free synthesis
routes is therefore highly desirable.
Many stable photocatalysts suffer from weak visible-light
absorption and high recombination rate of photoexcited
Fig. 29 Highlighted key points in growing, doping and hetero-
structuring of faceted semiconductor photocatalysts.
6780 Chem. Commun., 2011, 47, 6763–6783
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electrons and holes. Doping and heterostructuring are strategies
that will definitely contribute to the development of more
efficient faceted photocatalysts. Doping changes the surface
atomic structure of facets and thus alters their reactivity.
Heterostructuring allows effective interfacial charge carrier
transfer by constructing favorable interfaces with various
facets from different crystals. The key points related to
growing, doping and heterostructuring of faceted photo-
catalysts are summarized in Fig. 29.
Acknowledgements
The work described in this paper was partially supported
by the NSFC-RGC Joint Research Scheme (Project
N_CUHK464/10), the Major Basic Research Program,
Ministry of Science and Technology of China (No.
2009CB220001), NSFC (Nos. 50921004, 51002160 and
21090343), Solar Energy Initiative and the Funding
(KJCX2-YW-H21-01) of the Chinese Academy of Sciences
for financial support. GL thanks the IMR SYNL-T.S. Kê
Research Fellowship.
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