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Recent Advances of Ferro‑, Piezo‑, and Pyroelectric Nanomaterials

for Catalytic Applications
Shun Li, Zhicheng Zhao, Jinzhu Zhao, Zuotai Zhang,* Xu Li,* and Jianming Zhang*

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ABSTRACT: Ferro-, piezo-, and pyroelectric materials are emerging as potential candidates
for converting various forms of primary energy from the ambient environment (e.g., sunlight,
mechanical, and thermal energy) into secondary energy (e.g., chemical energy). Despite the
relatively short investigation time, much progress has been made related to this field. This
review covers the fundamental principles of coupling ferro-, piezo-, and pyroelectric effects with
different catalytic reactions; the crucial role of a polarization-induced internal electric field in
charge separation and transport in these materials is discussed. We particularly focus on recent
notable examples of using these three types of nanostructured materials for a variety of catalytic
applications in the fields of renewable energy production (e.g., water splitting and CO2
reduction), environmental remediation (e.g., organic pollutant decontamination), and
materials synthesis (e.g., selective growth/deposition and organic synthesis). Finally, we
conclude this review by proposing critical challenges and future perspectives for developing
ferro-, piezo-, and pyroelectric nanomaterial-based catalysts for efficient energy harvesting.
KEYWORDS: energy conversion, environmental remediation, internal electric field, polarization, piezocatalysis, pyrocatalysis

1. INTRODUCTION semiconducting properties in a controllable manner make

The steady increase in fossil-fuel consumption and severe
environmental contamination have promoted extensive
research activities in developing alternative clean energy
resources. Harvesting and converting natural and primary
energy from the environment such as solar light and thermal
(e.g., geothermal and industrial heat) and mechanical (e.g.,
wind, water flow, vibration, and noise) energy as potential
candidates to replace fossil fuels have attracted considerable
research interest. In recent years, ferro-, piezo-, and pyro-
electric nanomaterials that can directly couple energy harvest-
ing with diverse catalytic reaction processes have provided a
revolutionary paradigm to solve environmental problems and
produce renewable energy. The catalytic properties of these
materials can be effectively modulated or promoted by
polarization-induced internal electric fields,1−4 namely, the
ferro-, piezo-, and pyroelectric potentials, which are caused by
spontaneous electric polarization, applied external mechanical
forces, and temperature fluctuations, respectively.
Although the mechanisms for these conversions had been
discovered very early (back to the 1950s), research on energy
harvesting based on these concepts has only been initiated
recently, which has brought new hope and a vital force for
depollution and clean energy production. Significant progress
in the synthesis and application of low-dimensional ferro-,
piezo-, and pyroelectric materials has been made during the
past few decades.5−8 The unique coupling effects between their
inherent ferro-, piezo-, and pyroelectric characteristics and
these materials not only intriguing for exploring novel physical
phenomena at the nanoscale9−12 but also promising for
developing new applications by directly harvesting weak and
dispersive energy resources from the surrounding ambient
environment such as light, vibration, motion, and a temper-
ature gradient.13−16
In the past few years, several excellent reviews or book
chapters focusing on energy-harvesting materials and devices
for electrochemical applications,17 polarization-modulated
photocatalysis,2,18,19 piezoelectric materials for the catalytic/
photocatalytic removal of organic pollutants,20 and piezo/
ferroelectric-regulated (photo)electrochemical/catalytic reac-
tions21−24 have been published. In this review, we focus on
recent advances in ferro-, piezo-, and pyroelectric nanomateri-
als for a wide variety of catalytic applications including
renewable energy generation (e.g., water splitting and CO2
reduction), environmental remediation (e.g., organic pollutant
degradation), and materials synthesis (e.g., selective growth/
deposition and organic synthesis). First, we start by
introducing the fundamentals and basic concepts of ferro-,
piezo-, and pyroelectric effects. Next, three coupling effects are
Special Issue: Young Investigator Forum
Received: January 6, 2020
Accepted: January 7, 2020

© XXXX American Chemical Society https://dx.doi.org/10.1021/acsanm.0c00039

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Figure 1. Schematic illustration of the mechanisms of ferro-, piezo-, and pyrocatalytic effects.

presented in detail: (1) the ferrocatalytic effect, which uses

the ferroelectric potential to drive or control different catalytic
reactions; (2) the piezocatalytic effect, which can directly
convert mechanical into chemical energy or promote the
photocatalytic activity of piezoelectric material-based catalysts
by an external mechanical-force-induced piezopotential; (3)
the pyrocatalytic effect, which converts heat into chemical
energy via temperature-fluctuation-induced polarization varia-
tions using pyroelectric materials. The mechanisms of these
three effects are schematically summarized in Figure 1, which
will be explained in detail in the following sections. Meanwhile,
the most important developments contributing to the progress
in energy harvesting for catalytic application of these
nanostructured materials are highlighted. Finally, the critical
challenges and a future outlook to further promote the
polarization-modulated catalytic activity are discussed.

2. FERRO-, PIEZO-, AND PYROELECTRIC EFFECTS

The piezoelectric effect is associated with noncentrosymmetric
crystals. As illustrated in Figure 2b, when subjected to an
applied mechanical stress, electric dipoles can be modulated,
with positive charges accumulating on one side of the
piezoelectric crystal and negative charges on the opposite
side.25 A crystal that possesses spontaneous polarization (Ps)
even under unstrained conditions is defined as a pyroelectric
material, whose electric polarization varies as a function of the
temperature (Figure 2c).26,27 As a special subclass of
pyroelectrics, ferroelectrics exhibit a spontaneous polarization
that can be reversed by applying an electric field, giving rise to
a ferroelectric hysteresis loop (Figure 2d).28,29 However, if
heated above the Curie temperature (Tc), a phase transition
from the ferro- to paraelectric state would occur in ferro-
electrics. For a ferroelectric material with a single domain,
localized charges are present on the two end surfaces due to
alignment of the polarization. In polycrystalline ferroelectrics,
randomly oriented domains will be aligned by exerting a
sufficiently large external electric field (i.e., poling treatment).
The relationships among piezo-, pyro-, and ferroelectric
materials are displayed in Figure 2a. Obviously, pyroelectrics
are a subgroup of piezoelectrics, and ferroelectrics belong to
both pyroelectrics and piezoelectrics.
3. FERROCATALYTIC EFFECT
As early as the 1950s, ferroelectric materials were employed to
modulate adsorption and redox reactions on their charged
B https://dx.doi.org/10.1021/acsanm.0c00039
Figure 2. (a) Interrelationship among piezo-, ferro-, and pyroelectric
materials. (b) Illustration of the piezoelectric effects due to
compression and tension. Plots depicting polarization (P) changes
versus (c) temperature (T) for pyroelectrics and (d) electric field (E)
for ferroelectrics.
polar surfaces arising from spontaneous polarization.30,31 The
mechanism of ferroelectric polarization-modulated catalytic
reactions is illustrated in Figure 1. In ferroelectrics, a built-in
electric field is created as a result of spontaneous polarization,
which can drive the separation of free carriers in different
directions. In particular, both the direction and magnitude of
the polarization can be controlled by applying an external
electric field. These unique properties endow these materials
with more degrees of freedom for tuning the local band
bending at the interface of ferroelectric/reactive species,
leading to dynamical control of the surface character as well
as catalytic redox reactions.18,32 In this part, we concentrate on
the use of ferroelectric polarization to control various catalytic
redox reactions that include controllable materials synthesis
(selective deposition and epitaxial growth), tunable photo-
electrochemical (PEC) water splitting, and enhanced photo-
catalytic activity (e.g., water splitting, organic pollutant
degradation, and CO2 adsorption/reduction).
3.1. Ferroelectric Regulation of Material Growth and
Deposition. For a ferroelectric crystal, different locations of
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Figure 3. Ferroelectric polarization-modulated selective deposition/growth. (a) Band bending diagram of BaTiO3 in an aqueous solution for
positive and negative domains and (b) atomic force microscopy image of BaTiO3 after reaction in a silver nitrate solution.36 Copyright 2010
American Chemical Society. (c) Cross-sectional high-angle annular dark-field scanning transmission electron microscopy image and (d) schematic
of the proposed growth mechanism for SrTiO3/PbTiO3 heterostructures.41 Copyright 2018 Wiley. (e) Schematic epitaxial growth model of TO2
islands on a single-crystal PbTiO3 nanoplate with two oppositely charged square {001} facets. SEM images of the (f) pristine PbTiO3 and (g and h)
PbTiO3 plates with anatase TiO2 islands selectively grown on their (001̅) facets.42 Copyright 2018 Cell Press.

the surface possess varying degrees of band bending depending
on the polarization states (Figure 3a), which can greatly
influence the migration of interfacial carriers to specific
locations.24 This effect offers a new route for controllable
molecular/ionic binding and surface catalytic reactions at the
interface of ferroelectrics/solution,33−37 which, in turn, results
in selective adsorption, deposition, and growth of certain
species and materials, driven by polarization-induced surface
charges.
The surface photochemistry of ferroelectrics was initially
investigated by Rohrer’s group with a series of works on the
classical BaTiO3 ferroelectric crystals.33−36 As an example,
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when BaTiO3 was irradiated by UV light in an aqueous
solution containing cations (Pb2+ or Ag+), Ag ions were
preferentially reduced to Ag clusters and deposited on the
surface of positively charged polarization domains (Figure 3b),
while Pb2+ oxidation occurred on the domains with negative
polarization charges. These findings prove that internal electric
fields, formed by polarization, can cause the separation of
photogenerated charge carriers and drive them toward
different locations. As a result, the corresponding reduction
and oxidation half-reactions occur on different regions of the
surface. These pioneering works have motivated a flurry of
studies on the fabrication of several metal/semiconductor−
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Figure 4. Tunable PEC performance by ferroelectric polarization. (a) J−V curves of photoelectrodes and (b) EQE profile of BiFeO3 electrodes
before and after poling.48 Copyright 2014 Wiley. (c) J−V curves of an epitaxial Bi2FeCrO6 thin-film photocathode and (d) schematic illustrations
under different poling treatments.59 Copyright 2015 Wiley. (e) Piezoresponse curve of a single KNbO3 nanowire obtained by PFM. (f) Transient
photocurrent responses for a KNbO3 nanowire array photoelectrode after being poled under different conditions at 0 V vs Ag/AgCl. (g) SEM
image of a KNbO3 nanowire array epitaxially grown on a Nb-SrTiO3(100) substrate.55 Copyright 2017 Elsevier.

ferroelectric heterojunction structures.38,39 As an example,
noble metals (e.g., Pt and Au) and metal oxides were
selectively deposited on the positively and negatively charged
(001) facets of single domain PbTiO3 nanoplates, respec-
tively.38,40 As a consequence, the photocatalytic H2 evolution
rate for PbTiO3 with selectively deposited Pt particles was
more than 10 times higher than that with Pt particles deposited
randomly.
Epitaxial heterostructures have received tremendous re-
search attention because of their intriguing properties, which
are crucial in fundamental materials science.43 The interaction
of the charged surface and corresponding ion adsorption offers
a great opportunity for the epitaxial growth of heterojunctions.
Ren and co-workers proposed the use of the ferroelectric polar
surface-induced electrostatic force to drive the growth of
epitaxial heterojunctions via a facile solution route at low
temperature.41,44 Guided by this strategy, TiO2/PbTiO3,
SrTiO3/PbTiO3, and BiFeO3/PbTiO3 epitaxial heterostruc-
tures with atomically sharp and coherent interfaces were
successfully obtained (Figure 3c). Ferroelectric polarization
screening plays a decisive role in the growth at the interface,
where charge transfer and accumulation occurred for electrical
compensation (Figure 3d). More recently, Liu et al. reported
that anatase TiO2 nanoislands can grow epitaxially on
positively charged single-domain ferroelectric PbTiO3 nano-
plates (Figure 3e−h). The greatly improved photocatalytic
activity shows the advantage of overcoming the limitation of
the large Schottky barrier encountered when using a metal
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cocatalyst such as Pt particles.42 Compared with commonly
used physical deposition methods, such as pulsed-laser
deposition and molecular beam epitaxy, these synthetic
approaches show a superior experimental manipulation
convenience for the epitaxial growth of heterostructures with
desirable interface functionalities.
3.2. PEC Systems Tunable by Ferroelectric Polar-
ization. Semiconductive material-based PEC cells have shown
great potential for solar-driven water splitting in recent years.45
However, the photogenerated charge carriers can be easily
recombined because of their short lifetime, which severely
hinders the PEC efficiency. A permanent and controllable
internal electric field is highly beneficial to facilitating the
separation and transportation of photoexcited electron/hole
pairs.2,46 In ferroelectric materials, the internal electric field
originating from spontaneous polarization can effectively drive
the migration of carriers in opposite directions, thus improving
the performance of the photoelectrode.47
The performance of a PEC electrode is very sensitive to the
electronic band structure at the semiconductor−electrolyte
interface. Unique band-structure engineering via ferroelectric
polarization could change the interfacial energetic state of
electrode/electrolyte junctions and further allow controllable
catalytic reactions. As of now, several commonly used
ferroelectric materials such as BiFeO3,48−50 Pb(Zr,Ti)O3,51−53
KNbO3,54,55 and NaNbO356 have been reported as tunable
PEC devices through manipulation of their polarization
directions. Additionally, an enhanced PEC performance in a
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ferroelectric material-based photoelectrode can be achieved via
a simple prepoling treatment, without any difference from a
conventional PEC cell. This simple working principle holds
great promise for realizing a ferroelectric-enhanced PEC
performance. Representative examples are discussed as follows.
BiFeO3 has been widely investigated as a photoelectrode
because of its suitable band gap (∼2.2 eV). Cao et al. first
demonstrated a considerable polarization-modulated PEC
response in BiFeO3 thin films (∼300 nm) grown on
indium−tin oxide (ITO) substrates by a simple sol−gel
method.48 The photocurrent density can be manipulated to a
large extent between 0 and 10 mA·cm−2; the open-circuit
potential was varied from 33 to 440 mV (0 V vs Ag/AgCl) by
tuning the poling voltage from −8 to +8 V (Figure 4a).
Moreover, the external quantum efficiency (EQE) greatly
changed after poling treatment (Figure 4b). These results
undoubtedly validate the direct correlation of the photoexcited
charge-transfer behavior with the polarization conditions of the
films. Besides in polycrystalline films, ferroelectric-controlled
PEC properties were also observed in epitaxial BiFeO3 thin
films.49,57
The development of perovskite ferroelectric oxides with
narrow band gaps is crucial to extending the absorption
spectrum toward the visible-light region. Remarkable band-gap
engineering (1.4−2.8 eV) has been realized in Bi2FeCrO6
double perovskites by tailoring the Fe/Cr cationic ordering.58
On the basis of these findings, Li et al. first reported a
Bi2FeCrO6 epitaxial thin-film (∼100 nm) photocathode grown
on different CaRuO3(100)-coated substrates (Figure 4c,d).59
PEC measurements demonstrated that the optimal photo-
current density in the Bi2FeCrO6 photocathode was up to
∼−1.0 mA·cm−2, exceeding the highest value reported for
ferroelectric material-based photoelectrodes. Most importantly,
the photocurrent density was twice after negative poling
pretreatment due to the band structure-engineering, facilitating
the move of electrons to the electrolyte and holes to the
bottom electrode.
Compared to the regular film photoelectrode, vertically
aligned nanowire arrays exhibit prominent advantages for PEC
applications owing to their largely exposed surface areas, good
conductivity, and short diffusion length for carriers. Epitaxial
nanowires are an ideal material form to study the effect of
ferroelectric polarization on the PEC characteristics. To this
end, Li and co-workers reported for the first time the growth of
an epitaxial KNbO3 nanowire array on a Nb-doped SrTiO3
substrate as an electrode for solar water splitting (Figure 4e−
g).55 A well-defined hysteresis loop, obtained by piezoresponse
force microscopy (PFM), confirmed the existence of
spontaneous ferroelectric polarization along the nanowires.
By tuning the poling voltage between +15 and −15 V, the
photocurrent could be effectively tuned by more than 15 times
(0.7−11.5 μA·cm−2 at 0 V vs Ag/AgCl) under irradiation of
simulated sunlight. Meanwhile, the onset potential switched
from −0.32 to −0.46 V, which is favorable for the PEC
reactions. Obviously, the nanowire arrays possess a higher
tunability of the PEC property via ferroelectric polarization
regulation compared to the planar films, showing great
potential for use in highly efficient PEC devices.
Additionally, heterostructure photoelectrodes have been
developed to further promote the PEC performance by
combining the ferroelectric effect and semiconductor charac-
teristics, as presented in the following notable works. (1)
Metal−ferroelectric heterojunctions. For example, Wang et
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al. observed efficient charge-carrier transfer between a
plasmonic Au nanoarray and a ferroelectric Pb(Zr,Ti)O3
film.51 A remarkable photocurrent enhancement (by an order
of magnitude) was obtained by controlling the ferroelectric
polarization of the Pb(Zr,Ti)O3 film. (2) Semiconductor−
ferroelectric heterojunctions. Using epitaxial TiO2/BaTiO3
core/shell nanowires as photoanodes, Yang et al. showed that
the electric polarization of the ferroelectric BaTiO3 shell layer
(5 nm) could fortify the band bending of TiO2 nanowires and
thus promote charge-carrier separation, giving rise to an
enhanced photocurrent density for splitting water.60 In
addition, a systematic study was conducted on hybrid
photoelectrodes combining ferroelectric materials with n-type
(TiO2 and ZnO) or p-type (g-C3N4 and Bi2Mo2O9) semi-
conductors,61 which displayed enhanced water-splitting
properties. This work suggests the universal utilization of
ferroelectric materials in improving the PEC activity. (3)
Multiple semiconductor−ferroelectric heterojunctions.
More recently, multiple-junction architectures have been
designed. A full-spectrum photoelectrode with a multilayered
coaxial n-type TiO2/BaTiO3/p-type Ag2O vertical nanorod
array as a photoanode was reported,62 achieving a high
photocurrent density of 1.8 mA·cm−2 (0.8 V vs Ag/AgCl) after
poling pretreatment. Additionally, a tandem architecture of a
Si/ITO/Au/BiFeO3 hybrid photocathode was designed by
combining the advantages of the surface plasmonic resonance
effect of Au, the built-in electric field of BiFeO3 due to
ferroelectric polarization, and the catalytic active sites of the
MoS2/Pt catalyst.63 In addition, the ferroelectric single-domain
Pb(Mg1/3Nb2/3)0.7Ti0.3O3 (PMN-PT) was employed in a CdS/
Au/Ti/PMN-PT hybrid to facilitate charge separation, with a
photocurrent density of 1.70 mA·cm−2 for the positively
polarized sample, which was approximately 20 times higher
than that of the nonpolarized sample.64
3.3. Ferroelectric Modulation of the Photocatalytic
Activity. As previously mentioned, the activity of a photo-
catalyst is mainly hindered by the rapid recombination of
photogenerated charge carriers.45 Similar to that in ferro-
electric PEC cells, manipulation of the internal electric field
through the ferroelectric effect can also be applied to promote
the separation of photoexcited electron/hole pairs in photo-
catalysts.19 In the 1980s and 1990s, pioneering work on solar
water splitting using ferroelectrics was performed by Inoue and
co-workers. They found out that the photocatalytic activity of
potassium-doped lead niobates (Pb1−xK2xNb2O6) was rela-
tively higher for the positively charged surface than for the
negatively charged surface.68 In addition, the ferroelectric
polarization field in single crystals of LiNbO3 or LiTaO3 can
remarkably improve the photocatalytic H2 evolution rate of the
combined semiconducting TiO2 films.69
Inspired by these works, photocatalytic organic dye
degradation and water splitting for H2 production using
ferroelectric nanomaterial powders (e.g., BaTiO 3 ,
K x Na 1 − x NbO 3 , and Sr 0 . 7 Ba 0 . 3 Nb 2 O 6 ) were investi-
gated.65−67,70,71 In addition, the relationship between the
ferroelectricity and photocatalytic activity at the nanoscale was
revealed. The accumulation of electrons on the positively
charged surface gives rise to downward band bending and
holes on the negatively charged surface results in upward band
bending. As a result, the photogenerated electron/hole pairs
can be separated toward opposite directions driven by the
built-in electric field resulting from the polarization, leading to
oxidation and reduction reactions occurring on opposite
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Figure 5. Ferroelectric polarization-modulated photocatalysis. (a) Schematic of the effect of free charge reorganization on the band structure and
photogenerated electron/hole pairs. (b) Photocatalytic degradation curves of RhB for different catalysts under solar light.65 Copyright 2013
American Chemical Society. (c) High-resolution transmission microscopy image of BaTiO3 nanoparticles and (d) photocatalytic degradation rate
for RhB over BaTiO3 nanoparticles (30 and 80 °C for 40 min) and proposed schematic mechanisms (inset).66 Copyright 2015 Wiley. (e)
Schematic of the corona-poling system and (f) amount of H2 evolution for polarized and nonpolarized Na0.5K0.5NbO3 powder under UV light.67
Copyright 2014 Royal Society of Chemistry.

surfaces (Figure 5a). Cui et al. first explored the photocatalytic
decomposition of rhodamine B (RhB) using BaTiO3,65 which
displayed a significantly enhanced (∼3 times) removal rate in
the tetragonal phase (ferroelectric) compared to that in the
cubic phase (nonferroelectric), especially when loaded with Ag
nanoparticles (Figure 5b). Later, BaTiO3 nanoparticles (sizes
of ∼7.5 nm; Figure 5c) with a diffuse ferroelectric transition
(∼80 °C) were selected to explore the effect of ferroelectric
polarization on photocatalysis at different temperatures.66 The
degradation rate of RhB upon UV-light irradiation decreased
by ∼11.9% under a temperature change between 30 and 80 °C
(Figure 5d), indicating that ferroelectric polarization plays a
significant role in determining the charge-transfer behavior.
Similarly, investigation of Sr0.7Ba0.3Nb2O6 possessing a low
transition temperature (65 °C) from the ferro- to paraelectric
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phase also confirmed that H2 can only be generated from water
by the ferroelectric phase.71
Despite these achievements, enhancement of the photo-
catalytic efficiency by modulating the ferroelectric potential of
powder samples remains a great challenge. Because of the
difficulty of depositing an electrode on the nanopowders, it is
hard to pole ferroelectric nanomaterials using a conventional
method. To achieve this goal, Park et al. proposed an effective
way to pole KxNa1−xNbO3 powder photocatalysts through a
corona-poling method (Figure 5e), by which a strong built-in
electric field was established in the particles owing to the
alignment of the ferroelectric domain.67 As shown in Figure 5f,
the H2 generation rate of the K0.5Na0.5NbO3 powder after
poling treatment reached ∼2.4 mmol·g−1, which is much
higher than that of the pristine sample without poling (∼0.3
mmol·g−1). These results prove that spontaneous polarization
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Table 1. Comparison of the Photocatalytic/PEC Performance of Representative Ferroelectric Photocatalysts

catalyst catalytic conditions catalytic applications catalytic activity ref
BaTiO3 nanoparticles solar simulator (AM 1.5 filter) degradation of RhB (10 k = 0.0012 min−1 (cubic phase) 65
mg·L−1)
k = 0.0036 min−1 (tetragonal phase)
BaTiO3 nanoparticles UV lamp (500 W) degradation of RhB (10 k = 0.012 min (30 °C) 66
mg·L−1)
k = 0.008 min−1 (80 °C)
Fe3O4/TiO2/BaTiO3 xenon lamp (500 W) degradation of RhB (10 k = 0.022 min−1 70
mg·L−1)
K0.5Na0.5NbO3 particles mercury lamp (300 W) H2 evolution 2.4 mmol·g−1 (polarized) 67
0.3 mmol·g−1 (nonpolarized)
TiO2/PbTiO3 nanoplates xenon lamp (300 W) H2 evolution 436.5 μmol·g−1·h−1 42
KNbO3 nanowire array xenon lamp (300 W, AM 1.5G) PEC 0.7−11.5 μA·cm−2 (0 V vs Ag/AgCl) 55
Au/Pb(Zr0.20Ti0.80)O3 films xenon lamp (300 W, cutoff filter ⩾ PEC 2.4−16.7 μA·cm−2 (poling from −10 to 51
455 nm) +10 V)
TiO2/BaTiO3 nanowire array xenon lamp (150 W) PEC 0.65−0.96 mA·cm−2 (1.23 V vs RHE) 60
TiO2/BaTiO3/Ag2O nanowire xenon lamp (150 W, AM 1.5G) PEC 1.8 mA·cm−2 (0.8 V vs Ag/AgCl) 62
array
Si/ITO/Au/BiFeO3 film xenon lamp (100 mW·cm−2) PEC H2 evolution 62.5 μmol·h−1 63
CdS/Au/Ti/PMN-PT simulated sunlight (AM 1.5 G) PEC H2 evolution 0.4 μmol·cm−2·h−1 64
SrBi4Ti4O15 nanosheets xenon lamp (300 W) CO2 reduction to CH4 19.8 μmol·h−1·g−1 74

Figure 6. Theoretical studies of polarization-dependent adsorption and catalytic reactions. (a) Calculated OER free energy profile on unsupported
TiO2, and on the positively and negatively polarized TiO2/SrTiO3.75 Copyright 2014 American Physical Society. (b) Supercell of ZnO(112̅0)/
PbTiO3 (positively and negatively polarized) used for DFT calculations. (c) CO2 dissociation reaction pathway using bare ZnO and ferroelectric
PbTiO3/ZnO with different polarization directions.76 Copyright 2016 American Chemical Society.

in the ferroelectric phase can directly affect the separation of
electron/hole pairs and the photocatalytic water-splitting
property.
In addition to photocatalytic organic pollutant degradation
in wastewater and water splitting, investigations on ferro-
electric-modulated gas−solid adsorption and reaction pro-
cesses are emerging, followed by a pioneering work on
photocatalytic H2 and CO oxidation using ferroelectrics
reported by Van Damme et al.72 Later, the differences in the
physical adsorption behavior on the surface of ferroelectric
BaTiO3 and Pb(Zr,Ti)O3 for CH3OH and CO2 were
studied.73 More recently, ferroelectric SrBi4Ti4O15 nanosheets
were used for the photocatalytic reduction of CO2 to CH4,
reaching a high conversion rate (19.8 μmol·h−1) and an
apparent quantum yield of 1.33% (λ = 365 nm), far exceeding
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most of the reported values.74 The ferroelectric hysteresis loop
and time-resolved fluorescence spectra suggest that the
superior CO2 reduction activity under light may be attributed
to the strong spontaneous ferroelectric polarization, which
enables efficient charge separation in single-crystal SrBi4Ti4O15
nanosheets along the [100] direction.
A detailed comparison of the photocatalytic/PEC perform-
ance of representative ferroelectric photocatalysts is listed in
Table 1.
3.4. Theoretical Studies. In addition to the experimental
works mentioned above, a great deal of theoretical and
computational efforts have been carried out for deepening the
understanding of ferroelectric polarization-modulated adsorp-
tion and surface catalytic reactions at the atomic level. In the
following subsection, we will present selected examples
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Table 2. Comparison of Piezocatalytic/Piezophotocatalytic Performance of Representative Piezoelectric Material Systems

catalyst catalytic conditions catalytic applications catalytic activity ref
KNbO3 nanosheets xenon lamp (300 W) + ultrasound (40 kHz, 110 W) degradation of RhB (10 mg·L−1) k = 0.022 min−1 54
BiFeO3 nanowires xenon lamp (300 W) + ultrasound (132 kHz, 80 W) degradation of RhB (4 mg·L−1) k = 0.058 min−1 99
ZnO nanowires mercury lamp (50 W) + swing degradation of MB (5 mg·L−1) k = 0.038 min−1 85
NaNbO3 nanorods UV light + ultrasound (40 kHz, 100 W) degradation of MB (0.01 mM) k = 0.024 min−1 94
BaTiO3 nanowires ultrasound (40 kHz, 80 W) degradation of MO (6 mg·L−1) k = 0.015 min−1 89
ZnO nanorods UV irradiation (24 W) + ultrasound (40 kHz, 150 W) degradation of AO7 (10 mg·L−1) k = 0.044 min−1 84
MoS2/KNbO3 xenon lamp (300 W) + ultrasound (40 kHz, 100 W) degradation of RhB (10 mg·L−1) k = 0.037 min−1 129
Ag2O/BaTiO3 mercury lamp/xenon lamp + ultrasound (40 kHz, 50 W) degradation of RhB (15 mg·L−1) k = 0.051 min−1 140
Pb(Zr,Ti)O3/TiO2 LED (15 mW·cm−2) + stirring degradation of RhB (10 mg·L−1) k = 0.058 min−1 138
ZnSnO3 nanowires xenon lamp (150 W) + ultrasound (40 kHz, 250 W) H2 evolution 857 μmol·g−1·h−1 103
multiphase BaTiO3 nanoparticles ultrasonic (40 kHz) H2 evolution 655 μmol·g−1·h−1 90
BiFeO3 nanosheets ultrasonic (45 kHz, 100 W) H2 evolution 124 μmol·g−1·h−1 98
MAPbI3 tungsten−halogen lamp (500 W) + ultrasound H2 evolution 23.3 μmol·h−1 117
Bi4NbO8X (X = Cl, Br) xenon lamp (300 W, λ > 420 nm) + ultrasound (240 W) H2 evolution 204 μmol·g−1·h−1 108
Au/MoS2 ultrasound (280 W) H2 evolution 1250 μmol·g−1·h−1 114

employing first-principles calculations in the frame of density
functional theory (DFT).32,75−80
Kolpak et al. predicted that switching the polarization
direction of the PbTiO3(100) substrate can significantly
modify the adsorption energies of several molecules and
atoms (e.g., CO, O, C, and N) on the surface of a Pt film,
indicating potential utilizations in controllable catalysis.32 In
addition, Sanna and co-workers found that the adsorption
configuration/energy of H2O molecules on LiNbO3(0001) are
highly dependent on the polarization state. The distinct affinity
of H2O to the positive and negative surfaces can be attributed
to the electrostatic interactions between the ferroelectric
substrate and polar H2O molecules.78
On the basis of DFT and thermodynamic calculations, the
effects of ferroelectric polarization on the overpotentials and
thermodynamic barriers that are the determining factors for
oxygen evolution reaction (OER) and hydrogen evolution
reaction (HER) were investigated. Lee et al. examined the
influence of the electric dipoles on the OER reactivity in
epitaxial anatase TiO2/strained polar SrTiO3 films. The results
showed that the thermodynamic barriers for the OER reaction
can be drastically reduced by the epitaxial strain compared to
using bare TiO2 (Figure 6a), which may greatly enhance the
reaction efficiency.75 Another work by Dues et al. predicted a
lower overpotential on the polar surface of LiNbO3(0001)
compared to commonly used catalysts, with the lowest
overpotential of 0.4 V for HER at the positive surface and
1.2 V for OER at the negative surface.80
The conversion of CO2 into high-value-added chemicals and
fuels has become an important research topic in the past few
decades. DFT investigation of ZnO(112̅0)/PbTiO3 showed
that their interface properties are highly dependent on the
polarization direction of the ferroelectric substrate (Figure
6b,c). The lowering of the CO2 adsorption energy by switching
the polarization provides useful guidance for the effective
dynamical control of the reactive pathway and energetics for
CO2 dissociation reaction in other ferroelectric heterogeneous
systems.76
4. PIEZOCATALYTIC EFFECT
The interaction of piezoelectric, optical, and semiconducting
properties has resulted in two new effects, termed piezotronics
and piezophototronics,81−83 which can effectively control the
carrier transport through the built-in electric potential caused
H https://dx.doi.org/10.1021/acsanm.0c00039
by piezoelectric polarization. Analogously, two new coupling
effects (i.e., piezocatalysis and piezophotocatalysis) for catalytic
applications have been proposed. The mechanism of these
effects are schematically illustrated in Figure 1. Piezocatalysis
can directly convert mechanical energy into chemical energy
under dark conditions using abundant low-frequency vibration
energy sources, endowing it with enormous advantages over
other existing techniques. In this case, the polarized charges
and intrinsic free carriers can participate in the redox reactions.
For piezophotocatalysis, the photogenerated free electron/hole
pairs can be effectively separated by the piezopotential arising
from exerting a mechanical stress. Consequently, the photo-
catalytic performance of piezoelectric materials can be greatly
enhanced.
Over the past few years, great accomplishments have been
accumulated in this research area, and a number of
piezoelectric material-based catalysts have been reported.
Notable examples include the following: oxides such as
ZnO,84−87 BaTiO3,88−93 NaNbO3,94,95 Pb(Zr,Ti)O3,96,97
KNbO3,54 BiFeO3,98−100 ZnSnO3,101−103 K0.5Na0.5NbO3,104
(Ba,Sr)TiO3,105,106 Bi0.5Na0.5TiO3,107 Bi4NbO8X (X = Cl,
Br),108 Pb(Mg1/3Nb2/3)O3-xPbTiO3,109 and (Ba0.875Ca0.125)-
(Ti0.95Sn0.05)O3;110 nonoxide materials such as C3N4,111
CdS,92,112 MoS2,113−115 MoSe2,116 and CH3NH3PbI3;117
metal−semiconductor heterojunctions such as Au/ZnO,118
Au/MoS2,119 Ag/BaTiO3,120,121 Al/BaTiO3,122 Au/BaTiO3,123
and Au/BiVO4;124 semiconductor−semiconductor heterojunc-
tions such as CuS/ZnO,125 TiO2/ZnO,126−128 KNbO3/
MoS 2 , 129 TiO 2 /MoS 2 , 130 BiFeO 3 /TiO 2 , 131,132 TiO 2 /
PbTiO3,133 and BaTiO3/Ag3PO4;134 other composite systems
such as BaTiO3/poly(dimethylsiloxane),135 RuO2/BaTiO3/
Pt,136 and FeTCPP/MoS2.137 In these works, ultrasonic
variation, stirring, or fluidization was employed as a mechanical
energy resource to cause deformation of the materials.138,139
The piezocatalytic and piezophotocatalytic properties of typical
piezoelectric material systems are presented in Table 2.
4.1. Piezoelectric Materials for Energy Generation
and Pollutant Degradation. Piezopotential-driven water
splitting to produce H2 was first reported by Hong et al. using
ZnO and BaTiO3 micro/nanofibers through the harvesting of
ultrasonic vibrations.88 Deformation of the piezoelectric ZnO
fiber changed its polarization to create free surface charges,
which can drive redox reactions on the surfaces of the fiber.
Subsequently, the piezocatalytic and piezophotocatalytic effects
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in plenty of piezoelectric materials were systematically

investigated. For example, Xue et al. reported strong
frequency-dependent photocatalytic dye degradation activity
in ZnO nanowires by applying strain on the wires.85 Taking
ferroelectric KNbO3 as a representative material, Yu et al.
showed that two-dimensional (2D) nanosheets exhibit largely
improved piezocatalytic removal efficiency for a RhB solution
compared to that of the nanocube sample, which should be
ascribed to the higher piezoepotential generated in the sheets
under a mechanical force.54 Moreover, a new mechanism
different from solar-driven water splitting was revealed for
piezopotential-induced water splitting. As reported previously,
BiFeO3 cannot split water to produce H2 under light
illumination because of the inapposite conduction band
position that is lower than that of the potential of H2/
H2O.142,143 However, a high H2 production rate of 124.1 μmol·
g−1 was achieved using BiFeO3 nanosheets under ultrasonic
vibration (100 W), by which the band can be tilted under the
induced piezoelectric field.98 Very recently, well-defined
BaTiO3 nanoparticles (10 nm), which have high electro-
mechanical coefficients owing to the coexistence of multiple
phases, have been used as a highly efficient piezocatalysts.90
This was the first demonstration of the overall water splitting
via piezocatalytic processes, with the highest H2 production
rate of 655 μmol·g−1·h−1.
Figure 7. Piezocatalytic-effect-induced organic dye degradation and
To overcome the issue of easy saturation by the free carriers
water splitting. (a) Absorption spectral changes of the RhB solution
that arise from electrostatic screening during the piezophoto- and (b) cycling degradation curves using a Ag2O/BaTiO3 composite
catalytic process, Li et al. developed a new Ag2O−ferroelectric under both UV and ultrasonic waves. (c) Schematic of the mechanism
BaTiO3 hybrid catalyst,140 which can drastically improve both of band tuning and charge transfer.140 Copyright 2015 American
of the activity and cycling performance of piezophotocatalysis Chemical Society. (d) Degradation ratio of RhB dye using MoS2
(Figure 7a,b). When mechanically excited by ultrasonic waves, nanoflowers, commercial MoS2, and P25 under ultrasonic irradiation.
a switching polar charge-induced electric field can be (e) Generation of reactive species to drive decomposition reactions of
established in BaTiO3, leading to the band bending and a dye molecule.113 Copyright 2016 Wiley. (f) H2 evolution rate and
separation of charge carriers to the two opposite sides of the calculated e11 values of MoS2, WS2, and WSe2. (g) Schematic of the
BaTiO3 nanocubes (Figure 7c). mechanism of piezopotential-induced catalytic reactions in 2D TMD
nanosheets.141 Copyright 2019 Elsevier.
In addition to traditional perovskite oxides, new piezo-
electric materials are emerging as efficient catalysts. Recently,
few-layer 2D transition-metal dichalcogenides (TMDs) with few representative works for piezopotential-induced organic
strong piezoelectric responses have been utilized as piezoca- synthesis (polymer and small molecule) published recently.
talysts. MoS2 nanoflowers were first discovered to exhibit Mechanical initiation of polymerization using piezoelectric
ultrahigh degradation activity with the assistance of ultrasonic materials offers great opportunities to generate polymers using
waves under dark conditions.113 The decomposition ratio of waste mechanical energy sources from the environment. In
RhB dye was approximately 93% in only 60 s (Figure 7d). 2017, Zhao et al. proposed for the first time a micro-
Upon ultrasonic vibration, active species were generated on the pseudoelectrochemical route for the polymerization of polyani-
surface of MoS2, which can decompose dye molecules (Figure line on BaTiO3 nanocubes’ surfaces (Figure 8a−d).144 Periodic
7e). Later, a systematic study on a series of few-layer TMD mechanical forces provided by ultrasonic irradiation were
materials (Figure 7f,g) showed that the piezocatalytic H2 introduced to generate charges to initiate the polymerization
production rates followed the order of MoS2 > WS2 > reaction. Another example is to use ZnO nanoparticles for
WSe2.141 The calculated piezoelectric stress coefficients (e11) of generating free-radical species based on the piezoelectric effect,
these compounds were in good agreement with the enabling the formation of a polymer or gel (Figure 8e,f).145
piezocatalytic results, indicating the high correlation of the These works shed light on harnessing mechanical energy for
piezoelectricity and catalytic performance. More recently, the controllable chain-growth polymerization for large-scale
noncentrosymmetric organolead halide perovskite reactions via piezocatalytic effects. Very recently, Kubota et
CH3NH3PbI3 (MAPbI3) was reported.117 MAPbI3 exhibited al. developed a very simple mechanical ball-milling route for
a H2 generation rate of 23.3 μmol·h−1 in a HI solution under the activation of arylation and borylation reactions employing
both light and ultrasonic waves, which is much higher than that BaTiO3 via the piezoelectric effect, which sheds light on the
of solely piezocatalytic (2.21 μmol·h−1) and photocatalytic potential for the gram-scale synthesis of small organic
(3.42 μmol·h−1) reactions. This work opens a new avenue for molecules by applying mechanical energy.146
developing an organic−inorganic hybrid material family for
piezocatalytic applications. 5. PYROCATALYTIC EFFECT
4.2. Piezocatalytic-Effect-Induced Organic Synthesis. As mentioned above, pyroelectric materials exhibit a change-
Lately, applications based on the piezocatalytic effect have able spontaneous polarization under a temporal temperature
been extended to other fields. In this section, we will present a gradient. The mechanism of the pyrocatalytic effect can be
I https://dx.doi.org/10.1021/acsanm.0c00039
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ACS Applied Nano Materials www.acsanm.org Review

Figure 8. Piezocatalytic-effect-induced polymerization. Simulated electric properties of BaTiO3 nanocubes by COMSOL: (a) electric field; (b) flux;
(c) potential. (d) Schematic of the proposed micropseudoelectrochemical polymerization synthetic process.144 Copyright 2017 Elsevier. (e)
Mechanoradical polymerization process of n-butyl acrylate. (f) Gel permeation chromatography traces of the product.145 Copyright 2017 Wiley.

Table 3. Comparison of the Pyrocatalytic Performances of Different Pyroelectric Materials

catalyst catalytic conditions catalytic applications catalytic activity ref
black phosphorene nanosheets thermal cycling between 15 and 65 °C degradation of RhB (5 mg·L−1) 100% degradation efficiency within 5 cycles 154
thermal cycling between 15 and 65 °C H2 evolution 0.54 mmol·g−1 within 24 cycles
BiFeO3 nanoparticles thermal cycling between 27 and 38 °C degradation of RhB (5 mg·L−1) 100% degradation efficiency within 85 cycles 146
NaNbO3 nanoparticles thermal cycling between 23 and 50 °C degradation of RhB (5 mg L−1) 100% degradation efficiency within 24 cycles 158
Ba0.7Sr0.3TiO3/Ag nanoparticles thermal cycling between 25 and 50 °C degradation of RhB (5 mg L−1) 100% degradation efficiency within 50 cycles 159
LiNbO3 and LiTaO3 particles thermal cycling between 20 and 45 °C antibacterial activity 95% inactivation rate within 60 min 149
Ba0.7Sr0.3TiO3 nanoparticles thermal cycling between 25 and 50 °C H2 evolution 47 μmol·g−1 within 36 cycles 153

explained as follows (Figure 1).147 For pyroelectric catalysts, as
the temperature varies, the thermodynamic equilibrium can be
broken and reestablished because of the change of the
polarization states. As a result, adsorption and desorption of
chemical species from the electrolyte occur on the catalysts.
Consequently, more free carriers can participate in the redox
reactions and thus enhance the catalytic performance. This
ecofriendly pyrocatalytic effect utilizing transient low-grade
waste heat and natural temperature fluctuations (e.g., geo-
thermal energy and solar and industrial waste heat) offers a
new and exciting research direction for H2 generation and
pollution removal. However, at this moment, investigations on
pyrocatalysis are still lacking, only focusing on a few examples
such as ZnO,148 LiNb(Ta)O3,149 BiFeO3,147 BaTiO3,150,151
PZT,152 Ba0.7Sr0.3TiO3,153 black phosphorene,154 and Au/
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BaTiO3.155 Notable materials used for pyroelectric catalysis are
summarized in Table 3.
The pyrocatalytic performance of BaTiO3 materials has been
studied. For example, BaTiO3 nanowires grown along a polar
axis showed higher pyrocatalytic activity compared to nano-
particles.150 Finite-element simulations indicated that the
enhanced catalytic efficiency should be ascribed to larger
pyropotential induced in the BaTiO3 nanowires. The
intermediate oxygen reactive species of OH• and O2•−
detected by trapping experiments were responsible for the
pyroelectrocatalytic degradation of organic dye. In addition, a
pyrocatalytic approach was proposed for the synthesis of Au-
BaTiO3 hybrids, which demonstrated drastically improved
catalytic performances for decomposing dye molecules.155
During the synthetic process, electrons were induced by a fast
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ACS Applied Nano Materials www.acsanm.org Review

Figure 9. Pyroelectric-effect-enabled water splitting. (a) Simulation of the pyropotential by COMSOL in 2D black phosphorene. (b) Band diagram
for H2 generation from water by the pyroelectric effect. (c) Temperature fluctuation curve between 15 and 65 °C. (d) Pyrocatalytic H2 production
rate with different thermal cycles.154 Copyright 2018 Nature. (e) Schematic of the use of the pyroelectric effect for water splitting. (f) H2 and O2
amounts and production rates after 6 h.156 Copyright 2019 Elsevier.

temperature change on pyroelectric BaTiO3, resulting in a
reduction of the metal ions on BaTiO3 with no need for using
any reducing reagent. This work opens an entirely new and
convenient avenue not only for the fabrication of hetero-
structured materials but also for the promotion of pyrocatalysis
processes.
To further promote the heat-driven chemical energy
conversion efficiency of pyrocatalytic processes, accelerating
the temperature variation rate of the test system is crucial. To
this end, a highly efficient carbon black/poly(vinylidene
fluoride)/BaTiO3 nanoparticle porous membrane was devel-
oped.151 This unique design allows the composite membrane
to float on the surface of the liquid, resulting in a very high
temperature variation rate. As a consequence, the composite
membrane demonstrated 4-fold pyrocatalytic activity of a
BaTiO3 nanoparticle dispersed in solution. This study offers a
rationally designed prototype for pyrocatalysis device systems
for efficient thermal-to-chemical energy conversion from solar
light.
In addition to the degradation of organic pollutants,
pyroelectric materials have very recently been used for H2
production from water through cold−hot alternation. First, on
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the basis of ab initio DFT calculations, Kakekhani et al.
predicted a catalytic cycle to split water into H2 and O2 that
employs the pyroelectric effect in typical ferroelectric
PbTiO3.157 Later, pyropotential-driven splitting of water via
modulation of the temperature was realized in several
pyroelectric materials experimentally. For example, Xu et al.
reported an evolution rate of H2 reaching 46.89 μmol·g−1 over
Ba0.7Sr0.3TiO3 nanoparticles after 36 thermal cycles fluctuating
between 25 and 50 °C.153 Another work on 2D black
phosphorene nanosheets showed a high H2 production rate in
splitting water of approximately 540 μmol·g−1 after 24 cycles
under cold−hot alternation in the range of 15−65 °C (Figure
9a−d).154 More recently, a sufficiently large potential differ-
ence for water electrolysis of 2.34 V was obtained using
Pb(Zr,Ti)O3 sheets as a pyroelectric harvester to provide an
external charge source (Figure 9e,f).156 When the frequency of
the heating−cooling cycle was reduced, an optimized H2
production rate of 0.654 μmol·h−1 was achieved in the absence
of sacrificial reagents.
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ACS Applied Nano Materials
6. CONCLUSIONS AND PERSPECTIVES
With increasing worldwide concern regarding clean energy
production and severe environmental pollution, ferro-, piezo-,
and pyroelectric materials have drawn renewed attention in
these aspects because of their ability to harvest multifarious
natural energy resources (e.g., solar light, wave/water flow,
vibration, motion, and temperature gradients) from the
surrounding environment. In this article, we reviewed the
recent progress in exploiting these three different types of
nanomaterials for energy conversion based on ferro-, piezo-,
and pyrocatalytic effects for versatile applications such as solar
water splitting, pollutant degradation, selective growth/
deposition, and organic synthesis. We presented notable
examples of a polarization-induced internal electric field to
manipulate the catalytic performance. Although intensive
research efforts and impressive advantages have recently
already been made, in general, polarization-modulated energy
harvesting for catalytic applications still remains at an initial
stage, with many unsolved issues and exciting opportunities.
To make further advances in this promising research area,
more efforts need to be devoted to further improving the
conversion efficiencies and expanding the applications of these
three types of polar materials.
First, new material systems, advanced fabrication methods,
and rational synthetic strategies are highly desired. Emerging
materials such as single-layer 2D materials, organic−inorganic
hybrid perovskites, and molecular piezo/ferroelectrics may
provide new opportunities to further enhance the catalytic
performance. Additionally, the development of ferro-, piezo-,
and pyroelectric nanomaterials or heterostructures with well-
engineered composition, phase, exposed crystal facets,
geometry, and interface is essential. In addition, because
electric polarization plays a crucial role in their catalytic
performance, the key issue lies in precise control of the domain
structures at the nanoscale in these materials. Engineering the
anisotropic domain structure or domain walls with higher
electrostatic potential would offer new strategies to promoting
the charge-transfer properties in ferro-, piezo-, and pyrocata-
lysts.
Second, the performance of ferroelectric material-based
photoelectrodes is far from sufficient compared to that of
commonly studied oxide materials and thus needs to be further
optimized. To more fully utilize solar energy, the development
of novel ferroelectric materials with narrow band gaps but
without deterioration of their ferroelectric properties is crucial.
Additionally, the fabrication of a single crystal with single
domain structure and superlattices of related heterostructures
is promising to separate charge carriers by making as much use
of the ferropotential as possible. Future theoretical work is
highly necessary toward understanding the electronic structure
and charge dynamics of the interface of ferroelectrics/
electrolytes, metal/ferroelectrics, and ferroelectric superlattices.
A deep understanding and novel design along these lines can
be anticipated to eventually lead to optimization of the
polarization-modulated photo/electrochemical catalytic activ-
ity.
Third, sophisticated experimental design and theoretical
investigation will help to elucidate the piezocatalytic
mechanism and further develop efficient piezocatalysts.
Currently, ultrasonic variation, magnetic stirring, or fluidization
was employed as a mechanical energy resource to trigger the
piezocatalytic reactions. In these cases, the magnitude of the
L https://dx.doi.org/10.1021/acsanm.0c00039
www.acsanm.org Review
compressive force cannot be measured precisely, making the
present studies lack quantitative analysis. Therefore, a new
experimental setup that can provide measurable and control-
lable mechanical forces is highly desirable. In addition, the
contribution of key factors determining the piezocatalysis
efficiency such as the piezoelectric coefficient, charge-carrier
density, charge mobility, and band gap is not fully understood
yet. Also, the role of polarized and free charge carriers in the
catalytic redox reactions is not clear so far. Systematic studies
on different piezoelectric material systems are highly
demanded to establish the relationship between their physical
characteristics and catalytic behavior. Moreover, several
fundamental issues need to be clarified. For example, how
will a piezoelectric field impact the electronic states of the
surface of piezoelectrics? What is the quantitative relationship
between the applied force and band gap/piezocatalytic
activity? To answer these questions, finite-element-method
and DFT calculations are recommended for gaining more
physical insight into the local fields at the interfaces, especially
for heterojunction structures at the atomic level.
Fourth, the combination of different harvesting processes is
expected to be favorable for overcoming the limitation
intermittent nature of various energy sources. In general, a
single material can concurrently possess more than one
character among the ferro-, piezo-, and pyroelectric properties.
As a consequence, these materials show an intriguing prospect
for simultaneously harvesting diversiform energy sources such
as solar light, mechanical vibrations, and fluctuating waste heat.
For instance, piezo/pyropotential-driven organic pollutant
degradation using NaNbO3 nanofibers was demonstrated for
synergistically scavenging mechanovibration and cold−hot
fluctuating thermal energy.160 A very recent work reported
by Ji et al. showed significant enhancement of the charge
quantity in ferroelectric BaTiO3 by coupling piezo-, pyro-, and
photoelectric effects.161 Therefore, much room remains for
further enhancing diverse catalytic reactions in these material
systems by simultaneously combining different energy-harvest-
ing mechanisms.
Last but not least, new applications using these polar
materials are highly expected. Energy harvesting based on
ferro-, piezo-, and pyroelectric materials is a rather new field,
mainly focusing on polarization-modulated water splitting and
organic pollutant decomposition at this moment. These
exciting results are anticipated to further stimulate the research
and development of other catalytic redox applications. To date,
only a few works have shown applications of selective
deposition/growth, CO2 reduction, and synthesis of small
molecules and high-molecular-weight polymers initiated by
polarization-modulated catalytic effects. Hence, more efforts
should be made in these directions in the future.
■ AUTHOR INFORMATION
Corresponding Authors
Zuotai Zhang − Southern University of Science and
Technology, Shenzhen, China; orcid.org/0000-0002-
3580-6018; Email: zhangzt@sustech.edu.cn
Xu Li − Agency for Science Technology and Research
(A*STAR), Singapore, Singapore; orcid.org/0000-
0001-5589-2905; Email: x-li@imre.a-star.edu.sg
Jianming Zhang − Jiangsu University, Zhenjiang, China;
orcid.org/0000-0002-7752-1192; Email: zhangjm@
ujs.edu.cn
ACS Appl. Nano Mater. XXXX, XXX, XXX−XXX
ACS Applied Nano Materials
Other Authors
Shun Li − Southern University of Science and Technology,
Shenzhen, China; orcid.org/0000-0002-9488-8279
Zhicheng Zhao − Southern University of Science and
Technology, Shenzhen, China
Jinzhu Zhao − South China Normal University,
Guangzhou, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsanm.0c00039
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Science Foundation
of China (Grants 51802143 and 51872128), Shenzhen Science
and Technology Innovation Committee (Grants
JCYJ20170817111443306 and JCYJ20180504165648211),
and Shenzhen Peacock Plan (Grant
KQTD2016022619584022). Additional support was provided
by the Shenzhen Clean Energy Research Institute (Grant
CERI-KY-2019-003) and Guangdong Province Universities
and Colleges Pearl River Scholar Funded Scheme 2018.
■
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