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Accepted Article

Title: The role of polarization in photocatalysis

Authors: Fang Chen, Hongwei Huang, Lin Guo, Yihe Zhang, and Tianyi
Ma

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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201901361

Angew. Chem. 10.1002/ange.201901361

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http://dx.doi.org/10.1002/ange.201901361
Angewandte Chemie International Edition
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The role of polarization in photocatalysis
Fang Chen, Hongwei Huang*, Lin Guo, Yihe Zhang, and Tianyi Ma*
Abstract: Semiconductor photocatalysis as a desirable
technology shows huge potential in environmental remediation
and renewable energy generation, but its efficiency is severely
restricted by the rapid recombination of charge carriers in bulk
phase and on the surface of photocatalysts. Polarization has
emerged as one of the most effective strategies for conquering
the above-mentioned issues, tremendously promoting
photocatalysis. Herein, this review summarizes the recent
advances on improvement of photocatalytic activity by
polarization promoted bulk and surface charge separation. We
highlighted the recent progresses in charge separation
advanced by different types of polarization, such as macroscopic
polarization, piezoelectric polarization, ferroelectric polarization
and surface polarization, and the related mechanisms. Finally,
the strategies and challenges for polarization enhancement to
further boost the charge separation and photocatalysis are
discussed.
1. Introduction
With the environmental pollution and reckless consumption of
fossil fuels, the ecological unbalance and energy shortage
seriously threaten the sustainable development of society. [1]
Since the TiO2 single crystal has been reported as a
photoelectrode for water splitting by Fujishima and Honda,
photocatalytic applications of semiconductors are considered as
a highly desirable and green strategy to solve the
aforementioned problems. Hence, numerous efforts are
concentrated on developing excellent semiconductor
photocatalysts.[2] However, the performance of photocatalysts
that substantially relies on the photogenerated charge
separation and transfer kinetics is far from fulfilling the actual
application requirements. The quick recombination of
photoinduced electrons (e-) and holes (h+) in bulk phase and on
the surface of photocatalysts (ranging from several ps to dozens
[*] F. Chen, Prof. H. W. Huang, Prof. Y. H. Zhang
Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals
and Solid Wastes, School of Materials Science and Technology,
China University of Geosciences, Beijing 100083, China.
Email: hhw@cugb.edu.cn
Prof. L. Guo
School of Chemistry, Beijing Advanced Innovation Center for
Biomedical Engineering, Beihang University, Beijing 100191, China.
Dr. T. Y. Ma
Discipline of Chemistry, The University of Newcastle, Callaghan,
NSW 2308 Australia.
E-mail: Tianyi.Ma@newcastle.edu.au
1
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10.1002/anie.201901361
of ns) leads to the low charge separation efficiency, and thus low
photocatalytic activity.[3] The most commonly used strategies,
including heterojunction fabrication, decoration with metal or
metal oxide, and surface defect engineering are effective in
promoting charge separation on the surface, but advances on
bulk charge separation gained little success. Recently,
Accepted Manuscript
polarization field engineering has been demonstrated to be an
efficient tactic for improving photogenerated charge separation
both in bulk and on surface of photocatalysts. [4]
Polarity is widespread in the interior of non-centrosymmetric
(NCS) materials, such as piezoelectrics, pyroelectrics,
ferroelectrics and nonlinear optical materials. In the crystal
structure of NCS materials, the non-centrosymmetric
arrangement of ions or ionic groups (non-overlap of positive and
negative charge centers) induces positive charge on one side of
the surface (C+ region) and negative charge in the other side (C -
region), giving rising to a polarization electric field pointing from
C- to C+ region.[5] Recently, polarization electric field with the
ability to promote separation of photoexcited charges is
recognized by photocatalysis.[4] For a NCS photocatalyst, the
polarization electric field as a direct driving force can propel the
photoinduced e- and h+ to migrate to the C+ and C- regions,
respectively, due to the shielding effect. It largely benefits the
fast migration of charge carriers from the bulk to surface during
the photocatalytic process, thus promoting the following redox
reactions in the respective locations. [6] On the other hand, the
polar materials can also serve as effective co-catalysts of
semiconductor photocatalysts, of which the polarization electric
field was applied to accelerate the surface charge transfer of
photocatalysts. Besides, the photocatalysts can be polarized by
different surface terminals, which allows the charge re-
distribution and fast transfer on the surface (Figure 1). [7]
Figure 1. Polarization promoted bulk charge separation and surface
charge separation.
In this minireview, we highlight the recent advances on
polarization promoted bulk or surface charge separation that
 Angewandte Chemie International Edition 10.1002/anie.201901361

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promoted photocatalysis, and summarize the different
polarization types, such as macroscopic polarization,
piezoelectric polarization, ferroelectric polarization, and surface
polarization, the polarization-promoted catalytic mechanism, and
various catalytic applications to provide a well-organized
overview and to better understand the role of polarization in
photocatalysis. Finally, the outlook for the future development of
polarization enhancement strategies and applications are
presented.
2. Polarization promoted bulk charge separation
pm/V[9a]. Wang et al demonstrated that BiOIO3 can be used as
an efficient photocatalyst for decomposition of methyl orange
(MO). The high photodegradation activity is attributed to that the
local dipole moments of the IO3 pyramids lead to strong
macroscopic polarization along the c axis direction that drives
the electrons and holes to opposite directions.[9b] Our group
proposed an ionic substitution strategy for macroscopic
polarization enhancement by replacing I5+ with V5+ to increase
the dipole moment of IO3 polyhedron (Figure 3a), which was
confirmed by the strengthened SHG signals and theoretical
calculations (Figure 3b). The polyhedral distortion index D can
be calculated by equation:[9d,e]
1 n li  lav
D  (2)

Accepted Manuscript
n i 1 lav

where li is the distance from the central atom to the ith ligands
and lav is the average bond length. The polyhedral distortion of
IO3 is determined to be 0.065 in BiOI0.926V0.074O3, which is bigger
than that in BiOIO3 (0.063). The macroscopic polarization
enhancement largely facilitates the bulk charge separation of
BiOIO3 both in the photocatalytic and piezoelectric-catalytic
processes, which results in substantially boosted oxygen
activation ability for producing superoxide radicals (•O2-) and
hydroxyl radicals (•OH) under light and ultrasonic irradiation
(Figure 3c). Fan et al demonstrated that the NLO material
Na3VO2B6O11 can be used for efficient photocatalytic
Figure 2. The scheme of polarization promoted bulk charge separation. dechlorination under UV-vis light, and the dechlorination
efficiency is ~90 times higher that of TiO2 (P25).[12] The excellent
During the photocatalytic process, the first step is the
photocatalytic performance is mainly attributed to that the
generation of e-h pairs through photoexcitation. Then, these
orderly arrangement of the B6O11 and VO4 units along the [010]
charge carriers would travel from bulk to the catalytically active
direction causes a large macroscopic polarization (Figure 3d), as
sites on the surface to participate in redox reactions. The charge
evidenced by Kelvin probe force microscopy (KPFM), which
migration process requires hundreds of ps. However, the charge
promotes the bulk charge separation of Na3VO2B6O11 (Figure
recombination in the bulk only takes several ps, much faster
3e). Lou et al reported the introduction of transition-metal cations
than charge transportation.[8] Therefore, polarization electric field
leads to distortion of SiO4 tetrahedra, which generates a
as an effective strategy is urgently needed to promote the bulk
polarization field via accumulation of SiO4 tetrahedra in Ag6Si2O7
charge separation, which would be greatly beneficial to
(Figure 3f).[15] Theoretical calculations demonstrated that the
enhancing the photocatalytic performance (Figure 2.)
photoinduced electrons transfer from Ag(c)O4 to Ag(b)O3, and
then to Ag(a)O2, in good accordance with the direction of internal
2.1 Macroscopic polarization promoted bulk charge
polar electric field produced by the arrangement of polar SiO4
separation
tetrahedra (Figure 3g). The promoted separation and transfer of
charge carries result in efficient photocatalytic methylene blue
Due to the absence of symmetric center in crystal structure,
(MB) degradation. More examples for macroscopic polarization
the accumulation of microcosmic polarization from polar units of
promoted photocatalysis are listed in Table 1.
NCS materials can result in a large macroscopic polarization as
a driving force for charge transfer and separation, tremendously
benefitting photocatalytic activity. The nonlinear optical (NLO)
materials with NCS crystal structure produces a polarization
electric field caused by the intrinsic dipole moment, which were
recently reported as efficient photocatalysts, such as BiOIO 3[9b],
BiOI0.926V0.074O3[9c,d], Bi2O2(OH)(NO3),[10] K3B6O10X (X=Cl and
Br),[11] Na3VO2B6O11,[12] M2B5O9Cl (M=Ca, Sr, Ba, Pb),[13]
Bi2O2[BO2(OH)],[14] Ag6Si2O7,[15] and Ag9(SiO4)2NO3.[16] The local
dipole moment generated by this particular type of structure can
be calculated from the Debye equation:[9b]
  ne  r (1)
where  is the local dipole moment, n is the total number of
electrons, e is the charge of an electron, and r is the difference
between the “centroids” of the positive and negative charge.
In 2011, Nguyen et al reported that BiOIO3 is a new NLO
crystal with a strong second-harmonic generation (SHG) effect
(~12.5 KDP) and a high piezoelectric coefficient d33 of ∼26

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conditions. (d-e) Adapted with permission from Ref. [12] Copyright 2015
Figure 3. (a) Crystal structure of V-BiOIO3 (BiOI0.926V0.074O3) along b-c
Royal Society of Chemistry. (f) Crystal structure of Ag6Si2O7. Atoms of a
planes (black arrows indicate polarization direction of I1-xVxO3). (b) SHG
unit cell. Red circle = O, gray circle = Si, green cylinder = Ag−O bond,
response for BiOIO3 and BiOI0.926V0.074O3. (c) O2- and ·OH evolution
gray cylinder = Si−O bond, pink circle = Ag atom of AgO2, yellow circle =
curves over BiOIO3 and BiOI0.926V0.074O3 under ultrasonic irradiation (40
Ag of AgO3, and green circle = Ag of AgO4 and the arrangements of the
kHz, 300 W). (a-c) Adapted with permission from Ref. [9d] Copyright
Si2O7 units. (g) Directions for photoinduced electron transfer between
2017 Wiley. (d) Ball-and-stick diagram of the NVB structure (orange
different non-equivalent Ag atoms. (f-g) Adapted with permission from
arrows indicate the direction of the dipole moments for NVB units). (e)
Ref. [15] Copyright 2014 American Chemical Society.
The enhanced photodechlorination efficiency of 2,4-DCP by NVB
materials upon irradiation of UV-visible light (λ> 320 nm) under anoxic

Table 1. Comparison of photocatalytic performance over photocatalysts with macroscopic polarization.

Photocatalysts Catalytic conditions Catalytic applications Catalytic activity Ref.
BiOIO3 nanoplates UV light (300 W Degradation of MO (c = 20 92% degradation efficiency within [9b]

Accepted Manuscript
-1
mercury lamp) mg L ) 12 min
BiOIO3 nanoplates UV-vis light (500 W H2 evolution 133 μmol g-1 L-1 [9c]
(150 nm Xe-lamp)
BiOI0.926V0.074O3 UV/Vis light (300 W Reactive oxygen species 11.1μmol g-1 L-1 for •O2-; 3.9 μmol [9d]
-1 -1
nanostrips mercury lamp /500 W evolution g L for •OH
Xe-lamp)
Bi2O2(OH)(NO3) UV light (300 W Degradation of RhB (c = 98% degradation efficiency within [10a]
nanosheets mercury lamp) 0.01 mM) 15 min
Bi2O2(OH)(NO3) UV light (300 W Degradation of MO (c = 90% degradation efficiency within [10b]
nanosheets with {001} mercury lamp) 0.03 mM) 25 min
exposed facet
K3B6O10Br UV light (500 W Dechlorination of 99.8% dichlorination efficiency [11a]
nanoparticles mercury lamp) chlorophenols (2,4-DCP, c = within 3 min
-1
50 mg L )
Na3VO2B6O11 UV-vis light (500 W Dechlorination of 99.9% dichlorination efficiency [12]
mercury lamp) chlorophenols (2,4-DCP, c = within 3 min
-1
50 mg L )
M2B5O9Cl (M=Ca, UV light (500 W Dechlorination of Conversion rate of chloride to Cl- [13]
Sr, Ba, Pb) mercury lamp) chlorophenols (2,4-DCP, c = of 66.8% for CBC, 69.1% for SBC,
-1
50 mg L ) 86.9% for BBC, and 41.9% for PBC
Bi2O2[BO2(OH)] Simulated solar light Degradation of MB (c = 10- 99.9% dichlorination efficiency [14]
5 -1
nanoparticles (1000 W Xe-lamp) mol L ) within 80 min
Ag6Si2O7 Visible light (300 W Degradation of MB (c = 20 99% degradation efficiency within [15]
Xe-lamp) mg L-1) 9 min
Ag9(SiO4)2NO3 Visible light (300 W Degradation of RhB (c = 97% degradation efficiency within [16]
-1
Xe-lamp) 20 mg L ) 12 min
Bi2MoO6 nanosheets Visible light (300 W Degradation of 1.65×10-2 ppm/J degradation of [17]
Xe-lamp) sulfamethoxazole (SMX, c = SMX; 40% degradation efficiency of
2 ppm) and phenol (c = 10 phenol within 120 min
ppm)
2.2 Piezoelectric polarization promoted bulk charge separated and impelled to migrate towards the opposite
separation directions, which benefits the migration of bulk charges to
surface active sites for participating in various photocatalytic
reactions.[19] Xue et al reported a piezo-photocatalytic system
Piezo-phototronics that combines piezoelectricity and fabricated by braiding ZnO nanowires vertically on carbon fibers
photoactivity is proposed for piezoelectric semiconductor (CFs, Figure 4a). [20] The electron-hole pairs were generated
materials.[18] Piezoelectrics can produce polarized positive from ZnO nanowires under UV illumination and rapidly migrated
charges on one end and negative charges on the other end to the opposite surfaces due to periodic pressure-induced
under stress or strain. Driven by the piezoelectric polarization polarization fields, which efficiently degrade MB. With increasing
field, the photoinduced electrons and holes can be efficiently

3
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 Angewandte Chemie International Edition
Minireview
the frequencies of the applied force, a larger polarization field
was obtained, which enhances the MB decomposition
performance (Figure 4b). The piezoelectric assisted
photocatalytic activity of ZnO nanowires was further improved by
silver deposition. Chang et al demonstrated that the
photonexcitation and strain derived from mechanical bending
largely increase the local conductance and effectively reduce the
barrier height by producing a positive piezopotential, rendering
enhanced charge carries transfer.[21] ZnSnO3 is a piezoelectric
material with a higher piezoelectric coefficient than ZnO.[22] Lo et
al prepared vertically aligned ZnSnO3 nanowires on FTO glass,
and demonstrated the higher UV photocatalytic activity for MB
degradation under stress than that without applied stress (Figure
4c).[23] The enhancement was ascribed to the lessened
recombination of photoinduced electrons and holes and
reinforced mobility of these charge carries resulted from the
energy band distortion caused by stress-induced piezoelectric
polarization. They further surveyed the synergistic mechanism
for piezo-photocatalysis by piezo-assisted photocatalytic
degradation of MB over the single-crystal Zn1-xSnO3 nanowires,
and quantitatively verified the corresponding Schottky-barrier
modulation under various applied stresses. Under ultrasonic
vibration, the photodegradation rate of Zn1-xSnO3 (0.015 min-1) is
~4 times higher than that of Zn1-xSnO3 nanowires in the absence
of stress, which is mainly attributed to the band bending and
polarization field created by alternating ultrasonic vibration
(Figure 4d).[24] More examples of piezoelectric polarization
promoted bulk charge separation and photocatalysis are
provided in Table 2.
Figure 4. (a) The degradation of MB solution by the piezo-photocatalytic
activity of ZnO nanowires/CFs under UV irradiation and periodically
applied force. The inset is the piezo-photocatalytic process in ZnO
nanowires/CFs. The inset shows that the e- reacts with dissolved oxygen
molecules to yield ·O2-, and h+ are ultimately trapped by hydroxyl groups
(or H2O) at the surface to yield ·OH. The ·OH can oxidize MB in aqueous
solution, generating non-toxic CO2 and H2O. The photocatalytic efficiency
of ZnO nanowires is enhanced by the piezo-assistance due to the
reduced recombination of photo-generated carriers. (b) Photodegradation
kinetic curves of MB solution catalyzed by ZnO nanowires/CFs. (a-b)
Adapted with permission from Ref. [20] Copyright 2015 Elsevier. (c)
Photocatalytic activity for the samples with and without applied stresses
under UV irradiation. The inset shows a schematic illustrates of the
bended R-ZTO nanowires to generate piezoelectric voltages. (c) Adapted
with permission from Ref. [23] Copyright 2015 American Chemical
Society. (d) The photodegradation rate constant k for each set of
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10.1002/anie.201901361
samples and piezopotential distribution model under compressive (up)
and lateral (down) stress along a single Zn1-xSnO3 nanowire. (d) Adapted
with permission from Ref. [24] Copyright 2016 Wiley.
2.3 Ferroelectric polarization promoted bulk charge
separation
Different from piezoelectrics discussed above, ferroelectric
materials have spontaneous dipole moment without applying
stress, which generate spontaneous polarization electric field to
drive the separation and transfer of charge carries from bulk to
surface, facilitating photocatalytic process. Recently, some
ferroelectric materials are demonstrated to be directly used as
Accepted Manuscript
photocatalysts.
BaTiO3 is one of the most typical ferroelectric perovskite
oxides according with the universal formula ABO3 (A, B =
cationic elements) with the curie temperature at 120℃.[26] Cui et
al reported that tetragonal-phase ferroelectric BaTiO3 can be
obtained by annealing the cubic-phase paraelectric one at 1200
o
C for 10 h. The existence of the spontaneous polarization field
with polarization vector P drives the photogenerated electrons
and holes to the opposite directions, which facilitates the spatial
separation and transfer of photogenerated charges (Figure 5a).
The ferroelectric BaTiO3 with a high tetragonal content shows a
3-fold increase in the Rhodamine B (RhB) decolorization under
simulated light compared to paraelectric BaTiO3 (Figure 5b).[27]
Besides, silver particles were photochemically deposited on the
surface of the tetragonal BaTiO3 to further promote spatial
separation and transfer of photogenerated charges. The similar
strategy was also applied to obtain the ferroelectric one-
dimensional KNbO3 single crystal by controlling the phase
transition.[28] Zhang et al revealed that the orthorhombic KNbO 3
with a larger polarity shows a higher RhB photodegradation
activity compared to the monoclinic KNbO3.[29]
Our group first reported the soft-chemical preparation and
photocatalytic CO2 reduction of the ferroelectric layered
perovskite SrBi4Ti4O15 nanosheets.[30] The ferroelectric
hysteresis loop and KPFM revealed that the annealed
SrBi4Ti4O15 nanosheets at 350 ℃ has the strongest ferroelectric
polarization (Figure 5c), which gives rise to the highest charge
separation efficiency, thus showing the most prominent CO2
photoreduction performance. The CH4 evolution rate reaches
19.8 μmol h-1 g-1 (AQY = 1.33% at 365 nm), superior to most
reported photocatalysts in gas-solid reaction system (Figure 5d).
In the photocatalytic process, the photoinduced electron and
holes are efficiently separated along [100] of SrBi4Ti4O15 (the
direction of ferroelectric polarization field), as evidenced by the
calculations on carrier effective mass, confirming the crucial role
of ferroelectric polarization in promoting bulk charge separation
and photocatalysis (Figure 5e). Park et al synthesized
K0.5Na0.5NbO3 photocatalyst with a permanent polarization field.
The photocatalytic H2 production activity increased by 7.4 times
after applying corona electric field polarization method (Figure
5f).[31] The lifetime determined from time-resolved
photoluminescence (PL) spectra increases from 1.64 ns to 3.31
ns after external polarization (Figure 5g), verifying that
ferroelectric polarization largely promotes the separation of
photogenerated electron and holes in bulk (Figure 5h).
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Figure 5. (a) Schematic of a ferroelectric material showing internal
polarization and screening mechanisms. (b) Photodecolorization profiles
of RhB with different catalysts under solar simulator. The catalysts
consisting of higher T-BaTiO3 after annealing show higher activity,
especially when modified by Ag nanoparticles. (a-d) Adapted with
permission from Ref. [27] Copyright 2013 American Chemical Society. (c)
2D phase maps and corresponding curve of the SrBi4Ti4O15 piezoelectric
response. (d) CO and CH4 yield rates over SrBi4Ti4O15, Bi4Ti3O12, P25
and BiOBr. (e) Schematic diagram of polarization-feld enhanced
separation of photogenerated charge carriers. (c-e) Adapted with
permission from Ref. [30] Copyright 2017 Elsevier (f) Amount of
hydrogen evolution for polarized and non-polarized Na0.5K0.5NbO3
powder under UV-light irradiation. The experiment of aqueous methanol

Accepted Manuscript
solution without any photocatalysts was also carried out. (g) Decay
profile of photoluminescence from K0.5Na0.5NbO3 powders before and
after corona poling (h) Scheme of polarization behavior for Na1-xKxNbO3
semiconducting powder. (f-h) Adapted with permission from Ref. [31]
Copyright 2014 Royal Society of Chemistry.

Table 2. Comparison of photocatalytic performance over piezoelectric and ferroelectric photocatalysts

Photocatalysts Catalytic conditions Catalytic applications Catalytic activity Ref.

-1 -1
ZnO nanowires UV light + swing Degradation of MB (c = 5 mg L ) Kobs = 0.025 min [20]
- -1
Ag-ZnO UV light + bending Degradation of RhB (c = 50 μmol L Kobs = 0.052 min [21]
1
nanowires )
ZnSnO3-FTO UV light + stress Degradation of MB (c = 4 ppm) Kobs = ~0.007 min-1 [23]
-1
Zn1-xSnO3-FTO UV light + ultrasonic Degradation of MB (c = 10 ppm) Kobs = 0.015 min [24]
NaNbO3 UV light + ultrasonic Degradation of MB (c = 0.01 mM) - [25]
nanorods
BaTiO3 Simulated solar light Degradation of RhB (c = 10 ppm) Kobs = 0.087 min-1 [27]
(AM 1.5 filter)
KNbO3 Full sunlight at 100 PEC hydrogen production 0.7-11.5 μA·cm−2 (0 V vs. [28]
2
nanowire arrays mW/cm Ag/AgCl)
KNbO3 UV light Degradation of RhB Kobs = 4.21×10-3 min-1 [29]
nanowires
SrBi4Ti4O15 Simulated solar light CO2 reduction (the gas-solid 19.8 μmol g-1 L-1 for CH4 [30]
(300 W Xe-lamp) reaction)
K0.5Na0.5NbO3 UV light (300 W mercury H2 evolution 40 μmol g-1 L-1 [31]
lamp)
BaTiO3 UV light (500 W mercury Degradation of RhB (c = 10 ppm) 98% degradation [32]
nanoparticles lamp) efficiency within 40 min
KNbO3 particles UV light Degradation of RhB (c = 10 mg L-1) Kobs = 0.317 min-1 [33]
-2
Sr0.7Ba0.3Nb2O6 Visible light (300 W Xe- Degradation of sulfamethoxazole 1.65×10 ppm/J [34]
lamp) (SMX, c = 2 ppm) degradation of SMX

5
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 Angewandte Chemie International Edition 10.1002/anie.201901361

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3. Polarization promoted surface charge separation
As discussed above, polarization occured in the interior of
photocatalysts allows the efficient separation of photogenerated
charge carriers in bulk, impelling the fast migration of from the
bulk to the surface, while the recombination of electrons and
holes on the surface of photocatalysts is still severe, which can
also be conquered by polarization. By coupling a polar
component or creating a locally polarized region on the surface
of a photocatalyst, a polarization field can be established, which
facilitates the migration of electrons and holes along different
directions to reactive sites to participate in the redox reactions
applied in Ag/Ag2S-ZnO/ZnS branched heterostructure[38] and
TiO2/ZnO nanowires,[39] which all depend on ZnO to provide
piezoelectric polarization field for promoting interface charge
separation.
Piezoelectric film is highly anticipated in the environmental
and energy fields because of their high sensitivity to capture
moderately intermittent pressure, such as the gentle stirring.[40]
Recently, our group designed a series of composite films by
hybridizing various photocatalysts (TiO2, BiOI, or CdS) with a
flexible porous piezoelectric polymeric film rGO-F/PVDF-HFP (4-
azidotetrafluorobenzoic acid-modified graphene/polyvinylidene
fluoride-co-hexafluoropropylene), which can harvest gentle
mechanical disturbances (magnetic stirring) as the self-powered

Accepted Manuscript
(Figure 6). energy for piezoelectric-catalysis and promoting photocatalytic
activity (Figure 7d).[41] The MO decomposition rate of
TiO2@rGO-F/PVDF-HFP shows a 3-fold increase over
TiO2@Cotton (inert substrate), and 99% degradation efficiency
is achieved within 60 min UV light irradiation. For the CdS
catalyst system, the H2 production rate reaches 10.4 mmol h-1 g-
1
, increases by 400% (Figure 7e). The significantly enhanced
interfacial charge separation driven by the piezoelectric
polarization confirmed the important role of polarization in the
catalytic process. In addition, the broadening of external
excitation sources widespread in nature make piezo-
photocatalysis closer to future realistic applications.

Figure 6. The scheme for polarization promoted surface charge

separation.

3.1 Piezoelectric polarization promoted surface charge

separation

In a heterostructured piezo-photocatalyst, the piezo-potential

induced polarization electric field can be generated from the
piezoelectric component under the stress or strain. Due to the
intimate interfacial interaction and Fermi energy equilibration,
the band bending drives the surviving photoexcited charge
carriers on the surface of the photocatalytic component to
opposite directions, achieving efficient interfacial charge
separation between different components.[35]
As a typical piezoelectric material, ZnO is employed to capture
mechanical energy and provides a piezoelectric polarization field
in heterojunction. In 2016, Wang et al revealed the potential of
Figure 7. (a) Schematic illustration for the piezo-photocatalytic process
piezotronics in photocatalysis on account of the research of
of CuS/ZnO nanowires on stainless steel mesh and the energy band
polarization-induced interface band bending by assembling TiO2
diagram of CuS/ZnO heterostructure under both solar and ultrasonic
nanoparticles on ZnO nanoplatelets.[36] Meanwhile, Hong et al
irradiation. (b) SEM images of CuS/ZnO nanowire arrays on stainless
reported the preparation of CuS/ZnO heterostructured nanowire
steel mesh (400 mesh) with different magnifications. (c) Photocatalytic
arrays by vertically aligning them on stainless steel mesh using
degradation kinetic curves of MB solution catalyzed by bare ZnO and
a simple two-step wet-chemical method (Figure 7a,b)[37] The
CuS/ZnO nanowires on stainless steel mesh under different experimental
CuS/ZnO nanocomposite displayed excellent piezo-
conditions. (a-c) Adapted with permission from Ref. [37] Copyright 2016
photocatalytic performance for degrading MB (degradation ratio
American Chemical Society. (d) Schematic illustration of the design
of ~100% within 20 min) under light and ultrasonic irradiation
concept of the hybrid piezophotocatalyst. The process includes the
(Figure 7c), which is ascribed to the interfacial polarization field
mounting of semiconductor catalysts onto a selfpowered energy cushion,
caused by ZnO nanowires. Driven by this polarization field, the
which is a composite film of rGO-F/PVDF-HFP. (e) Schematic illustration
photoinduced electrons in the conduction band (CB) of CuS
of the catalytic experiments of the semiconductor@rGO-F/PVDF-HFP.
moved to that of ZnO, while the holes migrated into the opposite
The photocatalytic degradation of MO catalyzed by TiO2@rGO-F/PVDF-
side from the valence band (VB) of ZnO to that of CuS. In
HFP under UV light, the absorbance of MO catalyzed by BiOI@rGO-
consequence, the photogenerated electron-hole pairs are
F/PVDF-HFP after 24 h under ambient light, and the photocatalytic H2
separated at the interface of CuS/ZnO nanowires, greatly
evolution rate of CdS@rGO-F/PVDF-HFP under visible light. (d-e)
benefitting the photocatalysis. The similar strategy is also
Adapted with permission from Ref. [41] Copyright 2013 Elsevier. (f)

6
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 Angewandte Chemie International Edition
Minireview
Schematic diagrams for charge separation and transfer process of C-
BaTiO3/BiOI and T-BaTiO3/BiOI heterostructures. (g) Photocatalytic
degradation curves of MO over C-BaTiO3, T-BaTiO3, C-BaTiO3/BiOI, T-
BaTiO3/BiOI and BiOI under visible light irradiation (λ > 420 nm). (f-g)
Adapted with permission from Ref. [43] Copyright 2018 Elsevier.
3.2 Ferroelectric polarization promoted surface charge
separation
The surface chemistry of ferroelectrics with a fixed polarization
state has been explored experimentally.[42] The ferroelectric
spontaneous polarization can not only improve the charge
separation and transfer in the bulk, but also promote the surface
charge separation of photocatalysts by forming a heterojunction
between a photocatalyst and a ferroelectric. Our group disclosed
the influence of ferroelectric spontaneous polarization on surface
charge migration behavior and photocatalytic properties through
comparing the paraelectric C-BaTiO3 (cubic-phase)/BiOI and
ferroelectric T-BaTiO3 (tetragonal-phase)/BiOI
heterostructures.[43] Owing to the spontaneous-polarization
induced electric field of T-BaTiO3, the recombination of
photogenerated electrons and holes on the surface of BiOI is
greatly depressed. Therefore, T-BaTiO3/BiOI shows much higher
visible-light photocatalytic activity for MO degradation and
superoxide radicals (·O2-) production than BiOI and C-
BaTiO3/BiOI (Figure 7g,f). It demonstrated that the ferroelectric
spontaneous polarization plays an important role in enhancing
surface charge separation of semiconductor photocatalysts.
In order to further promote the charge separation, the
ferroelectrics are always poled to enable an enlarged
polarization intensity. Wu et al reported the fabrication of TiO2-
SrTiO3 core-shell nanowires (NWs) for photoelectrochemical
(PEC) water-splitting. The ferroelectric SrTiO3 thin shell induced
the upward band bending of the TiO2 core, which effectively
drives the separation and transport of photogenerated charge
carriers. This ferroelectric PEC system with 10 nm-thickness
positively poled SrTiO3 shows the highest photocatalytic activity,
where the charge-separation efficiency (ηseparation) and
photocurrent density (Jph) reach 87.7% and 1.43 mA cm−2 at
1.23 V vs RHE, respectively.[44] This work disclosed the large
potential of ferroelectric polarization in photoelectrocatalytic
applications. Li et al demonstrated that introduction of
ferroelectric BiFeO3 poled layer between BiVO4 and CuInS2 can
results in the fabrication a Z-scheme photocatalytic system with
enhanced photodegradation.[46] The ferroelectric BiFeO3 layer
induces the band bending of BiVO4 and CuInS2, improving the
Z-schematic charge transfer and photocatalytic redox ability.
The positively poled BiVO4-BiFeO3-CuInS2 shows the most
improved photocatalytic activity for degradation of 4-nitrophenol
and 2,4-dichlorophenol (2,4 DCP). A recent work delivers the
new application of ferroelectrics for polarization-dependent
epitaxial growth of TiO2 on the single-crystal and single-domain
ferroelectric PbTiO3 nanoplates. It is demonstrated that the
ferroelectric polar surface can effectively tailor the growth of
secondary crystal from selective facets, growth mode to
morphology, and the tunable epitaxial growth of oxide
heterostructures for enhancing the photocatalytic degradation
and water splitting.[47]
3.3 Surface polarization promoted surface charge
separation
7
This article is protected by copyright. All rights reserved.
10.1002/anie.201901361
Semiconductor photocatalysis as a kind of surface catalysis
depends greatly on the surface states of catalysts.[48] The
surface decoration with enthetic species can induce the re-
distribution of surface charges, benefiting their separation and
transfer. In 2014, Bai et al proposed the concept of surface
polarization in a Pt-Pd-rGO electrocatalytic system, the
enhanced HER performance is attributed to the difference in
work function between Pt and Pd.[49] The similar interfacial
charge polarization mechanism is also proposed in the TiO2-
Pd@Pt photocatalysts.[50] Hence, surface polarization is
considered as an efficient strategy for improving the
photocatalytic activities.[51] Herein, we mainly summarize the
metal/semiconductor-free surface modification strategies for
Accepted Manuscript
promoted surface charge separation.
Yu et al reported that the surface modification on polymeric
carbon nitride (g-C3N4) with graphited carbon rings established a
built-in electric fields, which impelled the photoinduced electrons
and holes to diverse directions, leading to a 21-fold improvement
in the photocatalytic H2 evolution rate (Figure 8a).[52] The
surface modification with halogens was demonstrated by Li et al
to induce polarization to greatly enhance the charge separation
of g-C3N4, which results in increased photocatalytic activities for
degrading 2,4-DCP and converting CO2 to CH4.[53] Our group
disclosed the surface hydroxylation as a new way for surface
polarization drastically promotes the local charge separation and
H2 production of g-C3N4.[54] The surface hydroxylated g-C3N4
(OH-CN) achieved by a plain hydrothermal process shows an
increased H2 production rate by ~5 times, and the pH-regulated
deep hydroxylation process enhances the H2 evolution rate by
~11 times (AQY = 9.1% at 420 nm ± 15 nm, Figure 8b).
Experimental results and DFT calculations demonstrated that
the electrons are inclined to migrate from the g-C3N4 lattice to
the surface -OH due to the formation of stable H-O-C=N
covalent bond (Figure 8c), leading to local spatial charge
separation (Figure 8d). Besides, the N atoms were polarized by
surface hydroxyls, accelerating the adsorption of protons. Both
of which contribute to the high photocatalytic H2 production.
More examples of the catalysts based on polarization promoted
surface charge separation are summarized in Table 3.
Figure 8. (a) The band structure layouts in GD-C3N4 before (top) and
after (down) accommodation of Fermi levels. (a) Adapted with permission
from Ref. [52] Copyright 2018 wiley. (b) H2 production curves and
production rates of different samples and OH-CN3 with addition of
different ammonium salts. (c) Electronic localization function and (d)
charge difference at top view and side view. (a-c) Adapted with
permission from Ref. [54] Copyright 2018 Elsevier.
 Angewandte Chemie International Edition 10.1002/anie.201901361

Minireview
Table 3. Comparison of photocatalytic performance over catalysts based on polarization promoted surface charge

separation.

Photocatalysts Catalytic conditions Catalytic applications Catalytic activity Ref.

-1
Ag2O-BaTiO3 UV light + ultrasonic Degradation of RhB (c = Kobs = 0.031 min [35a]
-1
15 mg L )
PZT/TiO2 UV light + stirring Degradation of RhB (c = 100% degradation efficiency [35b]
10 mg L-1) within 80 min at 800 rpm
ZnO-TiO2 UV light Degradation of MO (c = 20 Kobs = ~0.038 min-1 [36]
-1
mg L )
CuS/ZnO UV-vis light + ultrasonic Degradation of MB (c = 5 Kobs = 0.82 min-1 [37]

Accepted Manuscript
-1
mg L )
Vulcanized ZnO- UV light + ultrasonic Degradation of MB (c = 10 Kobs = 0.015 min-1 [38]
Ag/Cu ppm)
TiO2/ZnO UV-vis light + ultrasonic H2 evolution 3.052 μmol g-1 L-1 [39]
nanowires
(TiO2, BiOI, UV/Vis light + shaking Degradation of MO (c = - [41]
-5 -1 -1 -1
CdS)@rGO-F/PVDF- 2.5×10 mol L )/H2 evolution 10.4 mmol h g for H2
HFP film
BiOI-BaTiO3 Visible light (300 W Xe- Degradation of MO (c = 95.4% degradation rate [43]
lamp) 0.02 mM) within 90 min
•O2- evolution 11.02×10-7 mol L-1 h-1
TiO2-SrTiO3 Core– Simulated solar light PEC water splitting 1.43 mA cm−2 (1.23 V vs. [44]
Shell RHE)
BiVO4/BiFeO3 Simulated solar light PEC water splitting 0.63 mA cm−2 (0.6 V vs. [45]
Ag/AgCl)
BiVO4-BiFeO3- Visible light (500 W Xe- Degradation of 4-NP (c = 5 Kobs = 1.19 h-1 [46]
-1 -1
CuInS2 lamp) mg L )/ Kobs = 1.11 h
-1
2,4-DCP (c = 5 mg L )
TiO2-PbTiO3 Visible light (300 W Xe- Degradation of MB (c = Kobs = 0.057 min-1 [47]
-5 -1 -1 -1
lamp) 1×10 mol L )/ 132.58 μmol h g
H2 evolution
GD-C3N4 Visible light (300 W Xe- H2 evolution 23.06 mmol h−1 g−1 [52]
lamp)
Cl-g-C3N4 Visible light (150 W Xe- 2,4-DCP (c = 10 mg L-1) - [53]
-1 -1
lamp) CH4 evolution 14 μmol h g
Visible light (350 W Xe-
lamp)
OH-CN3 Visible light (300 W Xe- H2 evolution 0.73 mmol h−1 g−1 [54]
lamp)
Phosphate- UV-vis light (150 W Xe- PEC degradation of MO (c - [55]
-1
GO/BiOCl lamp) = 20 mg L )

4. Summary and Outlook photocatalysts. Under the spontaneous polarization, external

In summary, polarization, including macroscopic polarization,
piezoelectric polarization, ferroelectric polarization, and surface
polarization, have emerged as promising strategies for
accelerating the separation of photogenerated charge carriers in
the bulk phase or on the surface of semiconductor
stress or electric field, the dipole moment induces appearance of
the positively and negatively polarized charges on the two sides
of the catalysts, establishing a polarization electric field across
the polar materials, which drives the photogenerated electrons
and holes to opposite directions in photocatalysts, thus greatly
improving the photocatalytic activities for degradation of organic

8
This article is protected by copyright. All rights reserved.
 Angewandte Chemie International Edition
Minireview
contaminants, water splitting, CO2 production and generation of
reactive oxygen radicals, etc.
The photocatalysts ranging from NLO materials with polar
units, photo-active piezoelectrics/ferroelectrics to heterojunction
materials consisting of photocatalysts and
piezoelectrics/ferroelectrics as the polarization donor, etc, were
summarized from near-term reports published by our team and
others. The polarization level of the photocatalyst can be
evaluated and analyzed by KPFM, SHG measurement and
theoretical calculations (i.g. diploe moment, polyhedral distortion
index).[9d,31]. With the recognition of pivotal role of polarization in
charge separation and photocatalysis, the creation and
strengthening of polarization become a key issue.
Firstly, elemental doping is an effective strategy to enhance
the polarization.[9d] The introduction of foreign atoms may
increase the polyhedral distortion degree and local asymmetry
in the matrix crystal structure, which increases the dipole
moment or piezoelectric/ferroelectric coefficients to increase the
bulk or surface charge separation. But it should be noted that
the selection of suitable elements is very important. The size
and valence of elements needs to be carefully considered
regardless of ion substitution or gap doping.
Secondly, precise control on microstructure of polar
photocatalysts is also a fundamental method to enhance
polarization. For instance, preparation of single crystals with
growth orientation along the polarization direction will
accumulate the microscopic polarization of every polar unit, of
which the superposition leads to a large macroscopic polarity. [17，
28]
In addition, it is also an efficient strategy to creat or increase
the polarization by controlling the phase-transformation degree
from non-ferroelectrics to ferroelectrics via thermal treatment.[27]
Thirdly, more effective external polarization methods need to
be developed. The electric polarization is well applied for
enhancing the polarization of ferroelectric photoelectrodes
(films),[31] but external polarization for powdery ferroelectric
photocatalysts are rarely realized, which requires suitable
polarization equipment with high voltage. For stress-induced
piezoelectric polarization, more clean energy should be
exploited as excitation source, such as wind, tide, movement,
etc., which can also advance the practical applications of
photocatalysis.[20,23]
Fourthly, development of new types of polarization are highly
anticipated, such as pyroelectric polarization, magnetoelectric
polarization, etc. Similar to stress-induced piezoelectric
polarization, temperature fluctuation of pyroelectrics give rises to
formation of polarization electric field[56], which may promote the
separation of photoexcited electrons and holes.
Moreover, surface polarization as a promising tactic may
attract considerable attention in future due to its high feasibility
and effectiveness. Surface decoration with different species,
such as -OH,[54] halogen ions, have gained successes in
improving charge separation and enriching surface reactive sites
for high-performance photocatalysis.[7b] In future, more kinds of
surface polarization with various alien species are highly
desirable.[57]
As detailed above, we focused on the utilization of polarization
as a promising route for inhibiting the recombination of
photogenerated electrons and holes in bulk phase and on the
surface of photocatalyst, which enables them to rapidly
participate in reductive and oxidative reactions, respectively. We
hope this minireview will provide a new reference for developing
high-performance photocatalytic materials in future and better
9
This article is protected by copyright. All rights reserved.
10.1002/anie.201901361
understanding the mechanisms on charge movement behavior,
and may inspire the work involving charge regulation in other
related fields, such as electrocatalysis, supercapacitors, lithium-
ion batteries, etc.
Acknowledgements
This work was jointly supported by the National Natural Science
Foundations of China (No. 51672258), and Australian Research
Council (ARC) through Discovery Early Career Researcher
Award (DE150101306) and Linkage Project (LP160100927).
Conflict of interest
Accepted Manuscript
The authors declare no conflict of interest.
Keywords: polarization, bulk charge separation, surface charge
separation, photocatalysis
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 Angewandte Chemie International Edition 10.1002/anie.201901361

COMMUNICATION
COMMUNICATION
Polarization, including Fang Chen, Hongwei Huang*, Lin Guo,
macroscopic polarization, Yihe Zhang, Tianyi Ma*

piezoelectric polarization,
ferroelectric polarization, and
Page No. – Page No.
surface polarization, have The role of polarization in
emerged as promising strategies photocatalysis
for accelerating the separation of
photogenerated charge carriers in
the bulk phase or on the surface
of semiconductor photocatalysts.
Entry for the Table of Contents

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