Macroscopic Polarization Enhancement Promoting Photo- and Piezoelectric-Induced Charge Separation and Molecular Oxygen Activation

Article abstract of DOI:10.1002/anie.201706549

Efficient photo- and piezoelectric-induced molecular oxygen activation are both achieved by macroscopic polarization enhancement on a noncentrosymmetric piezoelectric semiconductor BiOIO₃. The replacement of V⁵⁺ ions for I⁵⁺

Full text of DOI:10.1002/anie.201706549

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: Macroscopic Polarization Enhancement Promoting Photo- and
Piezoelectric-Induced Charge Separation and Molecular Oxygen
Activation
Authors: Hongwei Huang, Shuchen Tu, Chao Zeng, Tierui Zhang, A. H.
Reshak, and Yihe Zhang
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201706549
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10.1002/anie.201706549
Angewandte Chemie International Edition
COMMUNICATION
Macroscopic Polarization Enhancement Promoting Photo- and
Piezoelectric-Induced Charge Separation and Molecular Oxygen
Activation
Hongwei Huang,* Shuchen Tu, Chao Zeng, Tierui Zhang, A. H. Reshak, Yihe Zhang*
Abstract: We report that both efficient photo- and piezoelectric-
induced molecular oxygen activation are achieved via
nanoparticles, but its efficiency is still low.[5] Thus, promoting
photocatalytic ROS evolution as well as exploration of new
channels to production of ROS, particularly realized by a single
material, are of significance and challenge. Piezoelectrics
reversibly converting stress into electricity, are widely applied in
optoelectronics. The stress-induced polarization potential can
act as alternating built-in electric field to separate photoinduced
carriers.[6] BiOIO3 as a noncentrosymmetric (NCS) polar material
presents strong second-harmonic generation (SHG, ~12.5 KDP)
and piezoelectricity (d33 ∼26 pm/V).[7] The large macroscopic
polarity is mainly attributed to the alignment of the lone-pair
containing IO3 polyhedra. Recently, BiOIO3 was investigated for
diverse photocatalytic applications.[8] Fan et al and our group
demonstrated that large macroscopic polarity can induce
efficient charge separation, contributing to high photocatalytic
activity.[9] Considering the large polarity of BiOIO3 from IO3
polyhedra, decoration on IO3 may adjust the polarity, and thus
improve photocatalytic molecular oxygen activation. Importantly,
BiOIO3 is piezoelectric. It is worth surveying its performance for
piezoelectric-catalytic ROS generation.
macroscopic
polarization
enhancement
on
a
noncentrosymmetric piezoelectric semiconductor BiOIO3. The
replacement of V5+ ions for I5+ in IO3 polyhedra gives rise to
strengthened macroscopic polarization of BiOIO3, which
facilitates the charge separation in the photocatalytic and
piezoelectric-catalytic process, and renders largely promoted
photo- and piezoelectric induced reactive oxygen species (ROS)
−
evolution, such as superoxide radicals (•O2 ) and hydroxyl
radicals (•OH). The present work advances piezoelectricity as a
new route to efficient ROS generation, and also discloses
macroscopic polarization engineering on improvement of multi-
responsive catalysis.
−
Reactive oxygen species (ROS), such as superoxide (•O2 ),
hydroxyl (•OH), singlet oxygen (1O2), peroxyl (RO2•), and alkoxyl
(RO-) as well as hypochlorous acid (HOCl), as highly-active and
green oxidants, are of great significance for environmental
chemistry and biochemistry.[1] Currently, the ROS are basically
produced in photocatalytic process. E.g., the photogenerated
Herein, we describe the synthesis and photo- and
piezoelectric-induced molecular oxygen activation of vanadium
doped BiOIO3. V is selected for replacing I in BiOIO3 for the
following two reasons: The similar bond length of V-O and I-O
(~1.6-1.9 Å) allows the replacement of V for I. Besides, the
equivalent substitution of I5+ with V5+ can keep the charge
conservation in BiOIO3. The results revealed that V replacement
could give rise to a large macroscopic polarization enhancement
of BiOIO3. It significantly promotes the charge separation in both
the photocatalytic and piezoelectric catalysis process, which
renders strengthened photo- and piezoelectric induced
molecular oxygen activation for producing •O2− and •OH.
−
electron can reduce O2 to •O2 , and •OH are created via a hole
oxidative process on H2O and/or -OH.[2] Particularly, •OH is the
most powerful and nonselective oxidant, which can damage all
types of organic/biomolecules.[3] As the fast carrier
recombination (~several ps) occurred in photocatalytic process,
ROS evolution efficiency through photocatalysis is limited.[4]
Recently, pyroelectrically driven •OH generation was achieved
by synergism of ferroelectric BaTiO3 and superficial Pd
[*]
Dr. H. W. Huang*, S. C. Tu, C. Zeng, Prof. Y. H. Zhang*
Beijing Key Laboratory of Materials Utilization of Nonmetallic
Minerals and Solid Wastes
XRD demonstrates that V-BiOIO3 keeps both the phase and
crystallization orientation unchanged (Fig. S1). XPS was
conducted to reveal the V doping. It is evident that a new peak
at 529.9 eV appears for V-BiOIO3, which is attributed to V 2p
(Fig. 1a). The peaks at 530.4, 164.4, 159.1, 635.4 and 623.8 eV
observed for BiOIO3 correspond well to O 1s, Bi 4f5/2, Bi 4f7/2, I
3d3/2, and I 3d5/2, respectively (Fig. S2). In contrast, the above-
peaks of V-BiOIO3 all show distinct shift, which means the
chemical environment change of related atoms. From Raman
spectra (Fig. 1b), one can see an obvious band around 850 cm-1
appeared for V-BiOIO3, which can be ascribed to V-O
vibration.[10]
School of Materials Science and Technology
China University of Geosciences, Beijing 100083, PR China
E-mail: hhw@cugb.edu.cn; zyh@cugb.edu.cn
Prof. T. R. Zhang
Key Laboratory of Photochemical Conversion and
Optoelectronic Materials, Technical Institute of Physics and
Chemistry
Chinese Academy of Sciences, Beijing 100190, PR China
Prof. A. H. Reshak
New Technologies - Research Centre, University of West
Bohemia, Univerzitni 8, 306 14 Pilsen, Czech Republic
1
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10.1002/anie.201706549
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SEM and TEM revealed that the morphology of BiOIO3
undergoes great change after V replacement. The original 2D
square nanoplates transform into 1D nanostrips (Fig. 1e,f and
Fig. S3a-d). HRTEM showed that the interplanar spacing of
lattice fringe for BiOIO3 and BiOI0.926V0.074O3 is ~0.287 nm,
corresponding to (002) and (200) planes. Their FFT patterns are
also well assigned to the [010] zone-axis diffraction spots of
orthorhombic BiOIO3 or BiOI0.926V0.074O3 (Fig. S3e and f).
Namely, the exposing facet for both samples is the {010} facet
(Fig. 3g and i). It is perpendicular to the [Bi2O2]2+ layer stacking
direction (Fig. 3h), where the internal electric field favors charge
separation. Besides, the specific surface area of BiOIO3 and
BiOI0.926V0.074O3 is determined to be 3.1 and 8.7 m2/g,
respectively, fitting the nonporous characteristic (Fig. S4).
Namely, the V replacement in BiOIO3 causes a 2.5-fold increase
in surface area.
Diffuse reflectance spectra reveal that BiOI0.926V0.074O3
shows visible light absorption with a long absorption tail
extending to 550nm compared with BiOIO3 (Fig. S5),
corresponding to the color change from white to yellow. This
would allow BiOIO3 visible-light active photo-reactivity. The band
gap was determined as 3.07 and 2.95 eV for BiOIO3 and
BiOI0.926V0.074O3, respectively (Fig. S7a). DFT calculation[11]
demonstrated that the narrowed band gap and visible-light
absorption of BiOI0.926V0.074O3 are mainly resulted by the
downshift of conduction band (Fig. S6a and Fig. S7b), which is
contributed by the V 3d orbital (Fig. S6c-e).
Photo-induced molecular oxygen activation was studied
under visible light (λ > 420 nm) and UV light. DMPO-assisted
ESR inspects the spin-trapped paramagnetic oxygen species
−
•O2 and •OH.[2c] BiOIO3 shows no signal under visible light,
confirming no visible-light activity of BiOIO3 (Fig. 2a and b).
Whereas, evident six identical peaks are observed for
BiOI0.926V0.074O3, which is assigned to DMPO-•O2 adduct
Fig. 1. (a) XPS of O 1s and V 2p and (b) Raman spectra of BiOIO3
and V-BiOIO3 (BiOI0.926V0.074O3). (c) XRD Rietveld refinement of V-
BiOIO3. (d) Fourier transform (FT) curves of XAFS data of BiOIO3
and V-BiOIO3. TEM images of (e,g) BiOIO3 and (f,i) V-BiOIO3. (h)
Unit cell illustration of BiOIO3.
−
derived from O2 reduction by electrons.[12] Meanwhile, four peaks
with intensities of 1:2:2:1 attributing to DMPO-•OH also
appear.[2c] •OH should originate from the OH-/H2O oxidation in
water by holes. It demonstrates that V replacement endows
BiOIO3 with the visible-light molecular oxygen activation ability
with generation of the above two powerful oxidative species.
This is understandable because BiOI0.926V0.074O3 exhibit
photoabsorption in visible region. However, it is significant to find
that this property is also greatly enhanced with irradiation of UV
light. BiOI0.926V0.074O3 shows a stronger six-line spectrum than
To deeply understand the crystal structural evolution and the
V action in BiOIO3 structure, Rietveld refinement was carried out
via the computer software General Structure Analysis System
(GSAS). The result show that V-BiOIO3 also crystallizes in
orthorhombic-Pca21 space group, and I5+ and V5+ ions with ratio
of 0.925(3)/0.074(7) co-occupy in the same site (Fig. 1c).
Namely, the final V-BiOIO3 is BiI1-xVxO4: x = 0.074(7). The
corresponding crystallographic data are summarized in Table
S1-3. The unit cell parameters undergo slight changes resulting
from the substitution of I5+ with V5+ according to Vegard's rule.
For confirmation, XAFS data on the I K-edge (33.179 keV) of
pristine BiOIO3 and BiOI0.926V0.074O3 were collected at room
temperature. The Bi L-edge oscillation curves of BiOIO3 and
BiOI0.926V0.074O3 display obvious difference in the energy range
of 33160-33260 eV, which suggests their different local atomic
arrangements (inset of Fig. 1d). Fig. 1d presents the Fourier
transform (FT) curves of XAFS data. The strong peak between 1
and 2 Å is attributed to I-O bond. Remarkably, the I-O radial
distance shows an evident shift (0.08Å) to smaller value, which
is resulted from the replacement of V5+ for I5+. It is in accordance
with the fact that V-O has a slightly shorter bond length than I-O.
The replacement of V5+ would induce a distortion of IO3
polyhedron.
−
BiOIO3 under UV light (Fig. 2c,), meaning a higher •O2
production. Remarkably, a significantly strengthened seven-line
spectrum was generated by BiOI0.926V0.074O3 (Fig. 2d). This type
of peaks with intensity of 1:2:1:2:1:2:1 represents the
appearance of DMPOX, resulting from the oxidation of DMPO by
two •OH radicals.[13] As the amount of free radical is
approximately proportional to the square of the height of
-
signal,[14] the •O2 and •OH amounts for BiOI0.926V0.074O3 is
calculated to be ~ 3.5 and 95.5 times that of BiOIO3. This
observation clearly states that a more powerful UV-light driven
ROS evolution ability was achieved for BiOI0.926V0.074O3 than the
pristine BiOIO3 compared to visible-light-activity enhancement,
and the enormously intensified activity is not associated with
photoabsorption.
2
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possible factor is investigated by transient photocurrent and SPV
spectroscopy.[16] BiOI0.926V0.074O3 produces a markedly increased
current density under UV light (Fig. 3c), beyond 5 times that of
BiOIO3, indicating a higher charge separation in BiOI0.926V0.074O3.
SPV spectroscopy can reveal the surface potential barrier and
charge separation extent of excited states generated by
absorption. It is demonstrated that the SPV signal generated by
BiOI0.926V0.074O3 far exceeds that of BiOIO3 in the range of 310-
390 nm, with enhancement degree of over 10-fold (Fig. 3d).
These results illuminates that the V replacement endues BiOIO3
with significantly promoted charge separation, accounting for the
robust molecular oxygen activation performance. In view of that
BiOI0.926V0.074O3 and BiOIO3 have the same exposing {010} facet,
there must exist some other reasons for the dramatically
strengthened charge separation.
Porlarization engendered in NCS crystal structure can
cause a large intrinsic polarization effect, promoting charge
separation.[9] The polarity of BiOIO3 mainly originates from
alignment of IO3 polyhedra along [001] direction. Along the a and
b axis, the polarity of IO3 polyhedra is offset due to the
completely opposite arrangement of IO3 groups (Fig. 4a). While
along the c-axis, namely [001] direction, the local dipolemoment
of IO3 polyhedra is additive, which results in a large macroscopic
polarization (Fig. 4b).[7] As revealed by TEM, BiOI0.926V0.074O3
crystal grows along the [001] direction. This crystallization
orientation may be induced by the polarization. SHG performed
by irradiation of a 1064 nm Nd:YAG laser confirms the enhanced
macroscopic polarity in BiOI0.926V0.074O3, which produces a
superior SHG response, beyond 2 times that of BiOIO3 (Figure
4c). It verifies that a larger macroscopic polarity is realized in
BiOI0.926V0.074O3, favorable for the separation of photogenerated
electrons and holes.[9b] For in-depth understanding, the
strengthened macroscopic polarization of BiOI0.926V0.074O3 is
analyzed by polyhedral distortion index. The symmetry of
coordination environment in crystal structure can be influenced
by the polyhedral distortion. The polyhedral distortion index D
can be calculated by Eq. (1)[17]
−
Fig. 2. ESR signals for (a,c) DMPO-•O2 and (b,d) DMPO-•OH over
BiOIO3 and V-BiOIO3 (BiOI0.926V0.074O3) under visible light (λ > 420
nm) and UV light illumination for 5 min, respectively.
To further understand the drastically promoted ROS activity,
photodegradation on a dye model RhB is performed (Fig. S8-
S11). The photocatalytic activity of BiOI0.926V0.074O3 is ~10.1 and
21.1 times that of BiOIO3 under visible and UV light, respectively
−
(Fig. 3a). Active species trapping test shows that •O2 and •OH
are the main reactive species and take crucial roles in the photo-
catalytic oxidation reaction regardless of light source (Fig. S12
and 13).[15] These results well confirmed the highly enhanced
molecular oxygen activation of BiOI0.926V0.074O3.
1
∑
(1)
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 BiOI1-xVxO3:x = 0.074(7), which
is bigger than that of BiOIO3 (0.063). Therefore, the
superimposition of microscopic polyhedral distortion contributes
to the large macroscopic polarization of BiOI0.926V0.074O3.
As BiOIO3 is piezoelectric, polarization enhancement
caused by V replacement may also result in an improved
piezoelectric-induce molecular oxygen activation ability. Here,
ultrasonic was employed as a stable irradiation source to
Fig. 3. Reaction rate constant for RhB degradation over BiOIO3 and
V-BiOIO3 (BiOI0.926V0.074O3) under (a) visible light (λ > 420 nm) and (b)
UV light. (c) Transient photocurrent response and (d) surface
photovoltage spectra over BiOIO3 and V-BiOIO3 under UV light.
-
provide press, and NBT was used as a probe to quantify the •O2
concentration.[18] Sharp decrease in the absorbance of NBT
centering at 259 nm is observed, demonstrating that both BiOIO3
and BiOI0.926V0.074O3 show robust pizeoelectric-catalytic activity
for transforming O2 into •O2- (Fig. S14). Based on the reacting
For exploring the origin for the enormously enhanced photo-
reactivity, several factors that predominantly affect the
photochemical reaction, e.g. photoabsorption, surface area and
charge separation efficiency, are considered. As revealed by the
above data, the extended photoabsorption in visible region of
BiOI0.926V0.074O3 is not responsible for the improved UV-light
activity. Their surface area difference (~2.5 times) is also far
small to contribute to huge enhancement on ROS generation
and photodegradation. Therefore, charge separation as the most
-
relation between NBT and •O2 (1:4 in molar ratio),[18] the average
-
•O2 evolution rate of BiOIO3 and BiOI0.926V0.074O3 is determined
to be 6.5 and 11.1 μmol·L-1·h -1, respectively (Fig. 4e). To inspect
if •OH was generated in the piezoelectric-induce process,
terephthalic acid (TA)-photoluminescence (PL) method is
employed, as •OH could react with TA in equal proportion to
produce highly fluorescent 2-hydroxyterephthalic acid at 425
nm.[5] Drastic PL peak intensity increase occurs with increasing
3
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the ultrasonic time (Fig. S15), suggesting the continuous
production of •OH. The plot of •OH concentration vs. ultrasonic
irradiation time is illustrated in Fig. 4f. The •OH concentration
generated by BiOI0.926V0.074O3 far exceeds that by BiOIO3, and
the average production rates are 1.2 and 3.9 μmol·L-1·h -1 for
morphology of BiOI0.926V0.074O3 strengthens the asymmetrical
distribution of positive and negative charges on its surface,
further contributing to the ROS production.
In summary, both photo- and piezoelectric- induced
molecular oxygen activation are achieved on
piezoelectric BiOIO3. More fascinatingly, the replacement of V5+
for I5+ ions in IO3 polyhedra resulted in
macroscopic
a
NCS
BiOIO3
or
BiOI0.926V0.074O3,
respectively.
Therefore,
-
BiOI0.926V0.074O3 shows a much superior pizeoelectric-induce •O2
and •OH evolution, approximately 1.7- and 3.3-times of BiOIO3.
a
polarization enhancement, which largely facilitates the charge
separation, and thus resulting in highly promoted molecular
oxygen activation in both the photocatalytic and ultrasonic-
assisted piezoelectric-catalytic process. Compared to pure
-
Besides, no •O2 and •OH are detected under ultrasonic without
BiOIO3 or BiOI0.926V0.074O3 (Fig. S16), further verifying the
piezoelectric induced ROS evolution process.
-
BiOIO3, the •O2 and •OH evolution rates for BiOI0.926V0.074O3
increase separately ~ 3.5 and 95.5 fold for photocatalysis, and
1.7 and 3.3 times for piezoelectric-catalysis. Besides, the
formation mechanism of reactive oxygen species in
piezoelectric-catalytic process was speculated. This study
exposes the promising prospect of macroscopic polarization
enhancement on promoting photo/piezoelectric-catalysis, and
may have potentials to be extended to other applications, e.g.
supercapacitor, lithium-ion battery, etc.
Experimental Section
The experimental section part is provided in the supporting information.
Acknowledgements
This work was supported by the National Natural Science
Foundations of China (Grant No. 51672258 and 51572246), the
Fundamental Research Funds for the Central Universities
(2652015296), CENTEM project CZ.1.05/2.1.00/03.0088.
Fig. 4. Crystal structure of V-BiOIO3 (BiOI0.926V0.074O3) (a) along a-b
and (b) along b-c planes (Black arrows indicate polarization direction
of I1-xVxO3). (c) SHG generation for BiOIO3 and BiOI0.926V0.074O3. (g)
•O2- and (f) •OH evolution curves over BiOIO3 and BiOI0.926V0.074O3
under ultrasonic irradiation (40 kHz, 300 W).
Conflict of interest
The authors declare no conflict of interest.
Keywords: Macroscopic polarization
•
Photocatalysis
•
On the basis of the above results, the possible piezoelectric-
catalytic molecular oxygen activation and enhancement
mechanism is speculated. As BiOIO3 is pizeoelectric, the
ultrasonic-introduced press could induce the generation and
asymmetrical distribution of positive and negative charges on
two opposite sides of BiOIO3. According to the metal oxide
anode radical production theory, the electro-catalytic effect
would occur which is indued by the as-generated electric
charges:[19]
Piezoelectric-catalysis • BiOIO3 • Molecular oxygen activation
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5
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Entry for the Table of Contents
COMMUNICATION
Macroscopic
enhancement
replacement in piezoelectric
semiconductor BiOIO3 can
greatly facilitate the charge
polarization
by
V5+
Hongwei Huang,* Shuchen Tu,
Chao Zeng, Tierui Zhang, A.
H. Reshak, Yihe Zhang,*
Page No. – Page No.
separation
efficient
piezoelectric-
and
photo-
render
and
induced
Macroscopic
Enhancement
Photo- and Piezoelectric-
Induced Charge Separation
Polarization
Promoting
molecular oxygen activation
for
producing
abundant
powerful
hydroxyl radicals.
superoxide and
and
Molecular
Oxygen
Activation
6
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