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org/JPCC Article

Piezo-photocatalytic Activity of Bi0.5Na0.5TiO3@TiO2 Composite

Catalyst with Heterojunction for Degradation of Organic Dye
Molecule
Xingang Xu, Xiujuan Lin,* Fanghui Yang, Shifeng Huang,* and Xin Cheng
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ABSTRACT: The low-yield and high-recombination rate of carriers are the

main factors that limit the efficiency of traditional piezocatalysis and
photocatalysis. In this paper, the Bi0.5Na0.5TiO3@TiO2 composite catalyst
with heterojunction was prepared and applied to obtain superior piezo-
photocatalytic activity. On the one hand, the narrow band gap (2.77 eV) made
it easy for the composite to excite photogenerated carriers under visible light.
On the other hand, the piezoelectric field that originated from the bending
deformation of Bi0.5Na0.5TiO3 effectively promoted the separation and
migration of carriers. Driven by ultrasonic vibration and visible light irradiation,
the poled composite catalyst degraded over 97% of RhB dye solution through
piezo-photocatalytic effect in 90 min. Compared with pure BNT and TiO2, the
enhanced catalytic performance of the BNT@TiO2 composite indicated the
superiority of the heterojunction.

■ INTRODUCTION
In today’s world, environmental and energy issues are getting
al, lead zirconate titanate (Pb(ZrxTi1−x)O3, PZT) has been
used in piezocatalysis.11,12 Li and Bian13 investigated the
piezocatalytic activity of PZT micron particles where the
worse and need to be resolved urgently, especially water
degradation efficiency of RhB dye molecules by PZT-doped Fe
pollution and energy shortage. According to recent studies,
and Bi reached 83% after 150 min. Some lead-free piezoelectric
catalysis has become a promising approach to treat sewage and
materials such as BaTiO3 also have excellent piezoelectric
produce clean energy, which includes photocatalysis, piezoca-
properties and play an important role in piezocatalysis.
talysis and piezo-photocatalysis. In particular, the photo-
Furthermore, many researches have reported that the physical
catalytic degradation of organic pollutants in sewage was the
properties of piezoelectric materials are affected by their
earliest and most widely studied. At present, the most
morphology and size. For example, the BaTiO3 nanowires with
commonly used photocatalysts are semiconductors, such as
a large aspect ratio demonstrated a better piezoelectric catalytic
titanium dioxide, which has the characteristics of high catalytic
performance than grained particles, which was attributed to the
activity, low price, and being nontoxic and harmless. However,
larger deformation induced by ultrasonic vibration.14 Also, the
its catalytic performance is restricted by many factors with the
piezoelectric properties can also be improved by doping the
most important being the high recombination rate of the
material to obtain higher piezocatalytic performance. Bao et
photoinduced charge carriers.
al.15 found that (Ba,Sr)TiO3 nanowires exhibited much higher
In order to overcome this limitation of inhibiting photo- piezocatalytic efficiency than BaTiO3 due to the synergy of
catalytic performance, some researchers turned their attention higher permittivity and higher polarization potential. The
to piezoelectric and ferroelectric materials, which can generate former completely degraded the target organic dye solution 40
piezoelectric potential under external mechanical force to min in advance.
promote the separation and migration of carriers.1−3 Wang et However, even piezoelectric fields can promote carrier
al.4−7 first proposed the theories of the piezotronic and separation and migration, the efficiency of general piezocatal-
piezophototronic effects, and the latter combined semi-
conductor transport, piezoelectricity, and photonic excitation
to promote the charge transmission. The group of Zhang et Received: May 25, 2020
al.8−10 first proposed the concept of piezocatalysis and Revised: October 9, 2020
investigated the roles of piezoelectric field in the separation
of carriers. Inspired by these theories, more and more
researchers are focusing on the fields of piezocatalysis and
piezo-photocatalysis. As the most famous piezoelectric materi-

© XXXX American Chemical Society https://dx.doi.org/10.1021/acs.jpcc.0c04700

A J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
ysis is limited by other factors, such as low carrier density and
limited free radical species. Therefore, piezo-photocatalysis,
which combines the piezoelectricity and photocatalytic activity
to obtain a significant catalytic efficiency, is a better choice.
Above all, there are many pure materials that have both the
photocatalytic activity and piezo/ferroelectric properties.
Zhang et al.16 investigated the multifield coupling effect of
piezo-photocatalytic and ferro-photoelectrochemical effects in
KNbO3 nanostructures. This study compared the catalytic
performance of KNbO3 nanosheets and nanocubes under
different conditions. Among them, the piezo-photocatalytic
degradation rate of RhB dye solution by KNbO3 nanosheets
reached 92.60% in 120 min. Singh and Khare17 demonstrated
an efficient coupling effect of mechanical, optical, and electrical
properties of NaNbO3 nanostructures in water splitting and
piezo-photocatalytic activities, and 80% degradation of MB
dyes was achieved in 180 min.
In recent years, much research has focused on the piezo-
photocatalytic performance of core−shell structured or
heterojunction materials, which combined the traditional
piezoelectric material and semiconductor photocatalyst like
TiO2 and ZnO. Because of the special structures, carrier
separation and migration can be effectively promoted to
improve the piezo-photocatalytic performance.18−20 Liu and
Wu21 prepared the BiFeO3/TiO2 core−shell nanocomposites
to investigate their degradation activities under the ultrasonic
vibration and visible light irradiation. The target organic dye
molecules were completely degraded within 120 min. In
addition, they concluded that the piezophototronic effect was
the coupling effect of photonic excitation, semiconductor
transport, and piezoelectricity. Zhai et al.22 revealed that ZnO/
BaTiO3 with heterojunction exhibited better piezo-photo-
catalytic performance than that of pure BaTiO3 and ZnO due
to the enhanced carrier separation and migration efficiency,
which benefited from the built-in electric field at the
heterojunction interface. In summary, preparation of a
composite catalyst with a core−shell structure or hetero-
junction is an effective method to improve the efficiency of
piezo-photocatalysis, and the key to it is to find a suitable
piezo/ferroelectric and successfully combine it with a photo-
catalyst. Sodium bismuth titanate (Na0.5Bi0.5TiO3, BNT) is a
typical piezo/ferroelectric with a large remnant polarization,
high chemical stability, high Curie temperature, and high
piezoelectric coefficient, which is considered as the most
important lead-free ferro/piezoelectric to replace lead-based
materials.23−25 These characteristics make it possible to obtain
high piezoelectric performance while maintaining stability in a
harsh environment, especially in high-temperature wastewater.
In addition, its high electrical conductivity is beneficial for
facilitating the migration of charge carries.26−28 There have
been some studies about the application of BNT in
piezocatalytic and piezo-photocatalytic field in recent years,
but the performance of a single material is limited after
all.26,29,30 The group of Chauhan31 has combined BNT with
BiOCl to prepare the BNT-BiOCl composite and used it to
degrade the dissolved organic impurities. With the catalyst, the
RhB dye solution was completely degraded within 20 min
under acidic conditions and visible light. In addition, the
formation of BiOCl on the surface of BNT did not influence
intrinsic properties of BNT. However, there has not been a
report about using BNT as a raw material to prepare the
composite with heterojunction or core−shell structure and
study its piezo-photocatalytic performance.
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In this paper, BNT (Na0.5Bi0.5TiO3) nanowires were
synthesized through the hydrothermal method and coated
with anatase TiO2 nanoparticles in sol−gel process to prepare
the BNT@TiO2 composite. After sintering, the composite
obtained a complete and uniform crystal structure. Attributing
to the modified energy band structure, the absorption edge of
the composite fell in the visible region and its band gap was
reduced compared to the pure photocatalyst, allowing it to
show stronger photocatalytic activity. Furthermore, the
ultrasonic vibration induced an internal piezoelectric field to
facilitate the separation and migration of photoinduced carriers
so that their recombination was suppressed effectively.
Furthermore, the applied electric field polarization also had a
certain promotional effect on the piezocatalytic performance of
the composite. The poled BNT@TiO2 composite achieved
high piezo-photocatalytic efficiency, and the degradation rate
of target organic dye reached 97% in 90 min.
■ EXPERIMENTAL SECTION
Materials. Bismuth nitrate pentahydrate (Bi(NO3)3·5H2O,
≥99.99%), sodium nitrate (NaNO3, 99.99%), titanium
butoxide (Ti(OC 4 H 9 ) 4 , ≥99%), acetate (CH 3 COOH,
≥99.9%), and sodium hydroxide (NaOH, 96%) were bought
from Aladdin (China), and ammonium hydroxide solution
(≥28%) and ethanol anhydrous (CH3CH2OH, 99.5%) were
bought from Macklin (Shanghai, China).
Synthesis of Bi0.5Na0.5TiO3 (BNT) Nanowires. The BNT
nanowires were prepared by the hydrothermal process. First,
0.006 mol of (Bi(NO3)3·5H2O, 0.006 mol of NaNO3, and
0.012 mol of Ti(OC4H9)4 were respectively dissolved in 9 mL
of CH3COOH, 3 mL of distilled water, and 12 mL of
CH3CH2OH with the solutions named A, B, and C. Then,
solution A and B were successively instilled slowly into
solution C to form a suspension with the addition of 12 M
NaOH solution and stirred for over 2 h. The mixture was
poured into the Teflon reactor lining, and heated at 180 °C for
48 h with stirring. The products were washed several times
with ethanol anhydrous and deionized water alternately and
freeze-dried under vacuum for 48 h. Finally, the obtained BNT
nanowires were calcined at 800 °C for 3h.
Synthesis of BNT@TiO2 Composite with Heterojunc-
tion. The BNT@TiO2 composite with heterojunction was
prepared by the sol−gel process. At first, 0.5 g of BNT
nanowires were dispersed into 300 mL of alcohol, mixed with
1.1 mL of ammonium hydroxide solution. The mixture was
sonicated for 1 h, as solution A. Subsequently, 2.5 mL of
tetrabutyl titanate was dissolved in 60 mL of anhydrous
ethanol, as solution B. Next, solution B was dropped into
solution A, and the mixture was heated at 45 °C for 24 h. The
products were centrifugal cleaned several times with anhydrous
ethanol and deionized water alternately and freeze-dried under
vacuum for 48 h. In order to prepare the composite with a
well-developed crystal structure, the powders were ultimately
sintered at 500 °C for 2 h.
The pure TiO2 was also prepared by the sol−gel process.
Ammonium hydroxide solution (0.8 mL) was added into 100
mL of anhydrous ethanol, as solution A. One milliliter of
tetrabutyl titanate was dissolved in 20 mL of anhydrous
ethanol to form solution B and dropped into solution A under
ultrasonic vibration for 30 min. The products were centrifugal
cleaned several times with anhydrous ethanol and deionized
water alternately and freeze-dried under vacuum for 48 h. The
final TiO2 products were also sintered at 500 °C for 2 h.
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Figure 1. (a) XRD patterns of TiO2 and BNT@TiO2 composite. (b) SEM image of BNT product. (c) TEM and (d) HRTEM images of BNT@
TiO2 composite.
Characterization. The crystal structure of the products
was analyzed by X-ray diffractometer (XRD, Bruker D8
Advanced, Germany). The morphology and microstructure
of the samples were observed by a field emission scanning
electron microscopy (SEM, JSM-7610F, Japan) and trans-
mission electron microscopy (TEM, JEM-2100F, Japan). UV−
visible diffuse reflectance spectrum was performed on UV−
visible spectrometer (Evolution 220, U.S.A.) with BaSO4 as a
reference. The three-electrode electrochemical workstation
(CHI600E, CH Instruments) was used to measure the
photocurrent with a xenon lamp (PL-X300D, Beijing Princess)
as the light source.
Piezo-photocatalytic Activity Measurements. The
piezo-photocatalytic performance was evaluated by degrada-
tion of RhB dye solution. The degradation experiments were
performed under visible light (λ > 420 nm) irradiation and
ultrasonic vibration, provided by a 300 W xenon lamp (HSF-
F300, Beijing NBET) and ultrasonic cleaner (40 kHz, 100 W),
respectively. In a typical catalytic measurement, 25 mg of
catalyst was dispersed into the RhB aqueous solution (10 mg·
L−1, 50 mL). The solution was first stirred for 60 min in the
darkness to establish an adsorption−desorption equilibrium
between the catalyst and the solution. In the degradation
process, the temperature was kept at room temperature
through water circulation to exclude the effect of temperature
on the experiment. Two milliliters of the solution was collected
at an interval of 15 min and subsequently centrifuged to
remove the catalyst. The absorption intensity of RhB in
supernatant was measured by a Cary 5000 UV−vis
spectrophotometer.
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■ RESULTS AND DISCUSSION
Characterization Results. Figure 1a shows the XRD
diffraction patterns of prepared samples. The results indicated
that the pure perovskite BNT phase was successfully prepared
by the hydrothermal method, because all of the diffraction
peaks indexed to the monoclinic perovskite BNT (JCPDS No.
46-0001) were present and no other hybrid peaks were found.
The pure anatase TiO2 was successfully prepared through the
sol−gel method and sintering process, and all of diffraction
peaks were indexed to the anatase TiO2 (JCPDS No. 21-
1272). In order to verify the influence of the sintering process
on the preparation of the BNT@TiO2 composite, the
diffraction patterns before and after sintering were compared.
It can be seen that there were no characteristic peaks of any
crystalline form of TiO2 in the XRD diffraction pattern of
unsintered BNT@TiO2 composite. After sintering at 500 °C
for 2 h, the diffraction peaks indexed to (101), (004), and
(200) plane proved the existence of anatase TiO2 in the
composite, whereas the characteristic peak of BNT had hardly
changed. The results indicated that the sintering process
played a decisive role in the formation of the designed BNT@
TiO2 composite.
In order to investigate the morphology feature of samples,
SEM and TEM characterizations were performed. As shown in
Figure 1b, there were sufficient BNT nanowires with a large
aspect ratio, uniform diameter, and smooth surface. Mean-
while, a small amount of separate spherical particles was
present in the sample, which was an inevitable phenomenon in
hydrothermal synthesis of BNT nanowires.32−35 Figure 1c
shows the morphology of the sintered BNT@TiO2 composite.
The results indicated that TiO2 nanoparticles were successfully
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Figure 2. (a) The diffuse reflectance UV−vis spectra of BNT@TiO2 composite catalyst. (b) The corresponding plot of (αhυ)1/2 versus photon
energy (hυ).

Figure 3. UV−visible absorption spectrum of RhB dye solution degraded by BNT@TiO2 composite catalyst through (a) piezocatalysis, (b)
photocatalysis, (c) piezo-photocatalysis, and (d) piezo-photocatalysis after external polarization.

coated on the surface of the BNT phase through the sol−gel
and sintering processes. The crystal structure of the BNT@
TiO2 heterojunction was investigated by high-resolution
transmission electron microscopy (HRTEM). As shown in
Figure 1d, TiO2 nanoparticles on the surface of the BNT
nanowire formed a typical anatase structure, where the lattice
fringe spacing of 0.350 nm corresponded to the (101) crystal
plane. The BNT phase of the composite maintained the lattice
fringe spacing of 0.274 nm, corresponding to the (110) crystal
plane of the perovskite phase. The above analysis based on
XRD and HRTEM confirmed that the sintering process was
essential for the formation of the complete crystal structure of
the BNT@TiO2 composite. It can be concluded that the
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BNT@TiO2 composite with heterojunction was successfully
obtained by the above experimental methods.
The Light Absorption Performance of the Composite.
The light absorption performance of the BNT@TiO 2
composite was measured by the UV−visible diffuse reflectance
spectrum. As shown in Figure 2a, it can be seen that the
absorption edge of the BNT@TiO2 composite was located in
the visible light region. It indicated that the composite could
effectively absorb and utilize the visible light. The band gap
(Eg) of the photocatalyst was closely related to the excitation
and recombination of photoinduced carriers. It can be
calculated according to the following formula
ahυ = A(Eg − hυ)2 (1)
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The Journal of Physical Chemistry C
Figure 4. (a) Degradation rates of RhB dye solution and (b) quasi-first-order kinetic linear fittings for degradation processes.
where A was a constant, h was Planck’s constant, and v was the
frequency of the incident light.36 As shown in Figure 2b, the Eg
of the BNT@TiO2 composite was 2.77 eV, which was much
smaller than that of anatase TiO2 (3.20 eV), indicating that the
energy band structure of the composite had been modified.
Therefore, compared with pure anatase TiO2, BNT@TiO2
composite was more likely to produce separated photoinduced
carriers under visible light radiation and their recombination
would be effectively suppressed. On the basis of the above
analysis, it can be concluded that the BNT@TiO2 composite
catalyst could effectively utilize the visible light to induce the
photocatalysis.
Piezo-photocatalytic Performance. The piezocatalytic,
photocatalytic, and piezo-photocatalytic performances of the
BNT@TiO2 composite with heterojunction were studied by
degradation experiments of RhB dye solution under ultrasonic
vibration, visible light radiation, and both visible light radiation
and ultrasonic vibration, respectively. The time-dependent
UV−visible absorption spectrum of the supernatant was used
to analyze the concentration change of RhB dye solution
during degradation. As shown in Figure 3a, after 90 min the
absorption peak of the dye solution decreased slightly during
the piezocatalytic degradation process. It indicated that the
piezocatalytic efficiency of the composite was weak due the low
yield of the carriers without light irradiation. Because of the
great light absorption performance, the BNT@TiO2 composite
was expected to exhibit an ideal photocatalytic performance. As
shown in Figure 3b, the absorption peak of the dye gradually
decreased to a low level after 90 min, corresponding to the
decrease in the concentration of the RhB dye solution. The
position of the absorption peak of the dye gradually shifted to
the low wavelength region, which was called blueshift caused
by the N-deethylation of the RhB dye molecules.37 As shown
in Figure S1, a part of reactive free radical species acted on the
carbon−nitrogen bond sites of the RhB dye molecules to
remove the molecular ethyl group and generate intermediate
products, making the absorption peak of the dye solution shift
to low wavelength region. As the number of ethyl groups in the
dye molecule decreases, the intermediates produced in
sequence were N,N,N′-triethyl rhodamine, N,N′-diethyl rhod-
amine, N-ethyl rhodamine, and rhodamine, and the wave-
lengths corresponding to their absorption peaks were 539, 522,
510, and 497 nm. Meanwhile, another part of the radicals acted
on the conjugated chromophores of these intermediates, which
cracked and finally mineralized into carbon dioxide and water
molecules. This approach reduced the absorption intensity of
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the dye.36−38 Compared with photocatalytic degradation, in
the piezo-photocatalytic degradation process of Figure 3c the
absorption peak of the dye decreased more drastically and its
position shifted faster. It indicated that both the N-
deethylation and cleavage of molecules were significantly
promoted in piezo-photocatalytic degradation of the RhB dye
solution. In addition, the role of external polarization on piezo-
photocatalytic efficiency was studied by applying a constant
electric field (5KV/mm, 30 min) on the composite. As shown
in Figure 3d, after polarization the whole degradation process
was further accelerated on the basis of piezo-photocatalysis.
Figure S2 shows the color change of the sample solution
corresponding to the above degradation processes. Because of
the low degradation rate in piezocatalysis, the color of the
solution had hardly changed. In photocatalytic and piezo-
photocatalytic degradation of the RhB dye solution, a large
number of intermediate products aggregated to change the
color of the dye solution, and the cleavage of the conjugated
chromophore’s cleavage made the color of the dye solution
lighter.38
The degradation rates were obtained from the UV−visible
absorption spectrum. As shown in Figure 4a, through three
kinds of catalytic effects the degradation rate of the unpoled
BNT@TiO2 composite to RhB dyes in 90 min was 10%, 65%,
and 93%. The results revealed that the piezocatalytic
performance of the composite was poor, mainly because it
did not generate sufficient carriers without the light source. It
was reported that ultrasound could induce the sono-chemical
effects due to cavitation effects, which could improve the
piezocatalytic performance. On the one hand, the ultrasound
could lead to the formation of cavitation bubbles, whose
violent collapse could create local high temperature and high
pressure (5000 K, 500 atm). In the high temperature and
pressure, the solvent vapor and gas molecules could generate
various active radicals like •OH. On the other hand, the sono-
chemical effect can also change the polarization of the
piezoelectric particle by applying a compressive load on it.
These effects would induce a significant improvement in
ultrasound-induced piezocatalysis. The generation of sono-
chemical effects required proper frequency, sufficient power of
ultrasonic vibration, and proper temperature, all of which were
indispensable.39,40 Unfortunately, there was no significant
sono-chemical contribution in this work probably due to the
inappropriate frequency and insufficient power of ultrasound,
and the absence of significant dye degradation during piezo-
catalysis on its own can be the evidence of it. For
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The Journal of Physical Chemistry C
Figure 5. (a) The transient photocurrent responses of samples. (b) Four cycle tests of piezo-photocatalytic degradation of RhB by BNT@TiO2
composites.
photocatalysis, the composite could effectively utilize the
visible light to generate sufficient carriers, and their
recombination was significantly suppressed due to the
existence of the BNT-TiO2 heterojunction.20,41−43 For piezo-
photocatalysis, on the basis of the role of heterojunction the
piezoelectric field induced by BNT under ultrasonic vibration
also effectively accelerated separation and migration of
photoinduced carriers.44−47 After polarization, the degradation
rate through piezocatalysis and piezo-photocatalysis was 15%
and 97%, respectively. Especially for piezo-photocatalysis, its
efficiency was obviously improved at the beginning of the
degradation reaction. It indicated that the intensity of
polarization in the composite was increased by the external
electric field to further promote the separation and migration
of carriers. The comparison of piezo-photocatalytic efficiency
between this work and similar studies is shown in Table S1.
The results indicated that the efficiency in this work was
relatively higher than previous studies.
In addition, the reaction kinetics curves more intuitively
show the difference in catalytic efficiency under the above
three catalytic models (Figure 4b). Because the degradation
activity of RhB dye solution met the first-order reaction, the
reaction kinetics curve was derived from the relationship
between ln(C/C0) and time (t):
iC y
lnjjj 0 zzz = kt
kC{
(2)
The reaction constant k of piezocatalysis, piezocatalysis after
polarization, photocatalysis, piezo-photocatalysis, and piezo-
photocatalysis after polarization was 0.0012, 0.0026, 0.0115,
0.0279, and 0.0341, respectively. The results show that under
the synergistic effect of piezoelectric catalysis and photo-
catalysis, the piezo-photocatalytic efficiency generated by the
composite was extremely high, especially when the polarization
intensity of the material was increased.
In order to verify the superiority of the BNT@TiO2
heterojunction in improving catalytic efficiency, the catalytic
degradation activities of RhB dye solution by pure BNT and
anatase TiO2 were simultaneously investigated. According to
the above analysis, it was suggested that the anatase TiO2 in
BNT@TiO2 composite played a decisive role in producing the
photoinduced carrier, meanwhile the perovskite BNT provided
the piezoelectric field. As shown in Figure S3, compared with
pure catalysts the three catalytic efficiencies of the composite
were significantly improved, especially for photocatalysis and
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piezoelectric photocatalysis. On the one hand, it was because
the modified energy band structure of the BNT@TiO2
heterojunction enabled the composite to efficiently utilize
the visible light.47 On the other hand, the heterojunction
provided an effective approach for carrier separation and
migration due to the existence of the difference in energy
potential between the BNT and TiO2.41,42,48 However, the
piezoelectric field generated by BNT played an important role
in piezo-photocatalysis, because it could significantly force the
carriers to separate and migrate. The results indicated that the
heterojunction played a very important role in improving the
catalytic performance.
The transient photocurrent responses of samples were used
to verify the enhancement by heterojunction in the separation
and migration of carriers. As shown in Figure 5a, pure anatase
TiO2 generated a higher transient photocurrent response than
pure BNT, but it quickly dropped to the same level with the
latter. It indicated that although pure TiO2 could generate
more photoinduced electron−hole pairs than pure BNT, the
recombination rate of them was extremely high. Compared to
pure materials, the BNT@TiO2 composite generated ex-
tremely high photocurrent response and maintained a stable
range. The results indicated that the heterojunction structure
has a significant promotion effect on the separation and
migration of carriers. It can be explained from the following
aspects. First, the energy potential difference between the BNT
and TiO2 promoted the electron transport through the
heterojunction interface. The BNT nanowire with a large
aspect ratio provided a natural channel for electron transport
on its surface.44
The recyclability of the BNT@TiO2 composite catalyst was
studied through four cycle tests of piezo-photocatalytic
degradation. The remaining catalyst after the piezo-photo-
catalytic degradation reaction in each cycle was collected,
centrifuged, and washed several times with deionized water
then finally dried at 60 °C for the next cycle of degradation
experiment. As shown in Figure 5b, after four cycle tests the
piezo-photocatalytic degradation rate of RhB dye solution by
the unpoled and poled composite reached 86% and 92%,
respectively. It demonstrated that the BNT@TiO2 composite
catalyst possessed a great recyclability in a certain extent.
The Piezo-photocatalytic Mechanism of BNT@TiO2
Composite. The trapping experiments of active species
were carried out to understand the piezo-photocatalytic
reaction mechanism of BNT@TiO2 composite. Here, silver
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The Journal of Physical Chemistry C
Figure 6. (a) Piezo-photocatalytic degradation efficiencies of RhB after adding radical quenchers. (b) The mechanism of piezo-photocatalytic
degradation of RhB by BNT@TiO2 nanowire with heterojunction.
nitrate (AgNO3), isopropyl alcohol (IPA), benzoquinone
(BQ), and triethanolamine (TEOA) acted as scavengers for
electrons, and •OH, •O2−, and holes (h+) were used to
determine the role of the radical species in the piezo-
photocatalytic degradation activity of RhB. As shown in Figure
6a, the degradation efficiency was slightly influenced upon the
addition of IPA but reduced significantly upon the addition of
TEOA and BQ. The result demonstrated that h+ and •O2−
were the main working free radical species in the piezo-
photocatalytic degradation of RhB dye solution by the BNT@
TiO2 composite catalyst, while h+ was the most important one.
This mechanism can be further studied by electron quenching
experiments. After adding AgNO3, the degradation efficiency
was higher than that adding BQ, but slightly lower than that
adding IPA. It can be explained from two aspects. First, the
decrease of •O2− was attributed to the quenching of electrons,
which should react with the oxygen dissolved in water to
generate it. However, with the decrease of electrons the
separation of electron−hole pairs was promoted, leading to an
increase of holes. According to the above analysis, it can be
inferred that the mechanism followed the equations:
BNT−TiO2 + hυ → BNT−TiO2 (h+ vb)
+ BNT−TiO2 (e−cb) (3)
BNT−TiO2 (e−cb) + O2 → BNT−TiO2 + •O2− (4)
RhB dye + •O2− + h+ → Intermediates → CO2 + H 2O
(5)
Figure 6b depicts the mechanism of piezo-photocatalytic
degradation of RhB by the BNT@TiO2 composite. The
anatase TiO2 particles on the surface of the BNT nanowire in
heterojunction-induced electron−hole pairs under light
radiation and the BNT nanowire bent to generate piezoelectric
field further promoted the carrier migration under ultrasonic
vibration. On the surface of a TiO2 nanoparticle near the
“negative” end of the piezoelectric field, the negatively charged
electrons were repelled to stay at the conduction band, and the
positively charged holes were attracted to move from the
valence band of the TiO2 nanoparticle toward the surface of
the sodium BNT nanowire. The direction of charge migration
near the positive end of the piezoelectric field was opposite. In
this way, carrier recombination was effectively suppressed and
its migration was greatly improved. At the same time, oxygen
dissolved in water reacted with electrons to generate
G https://dx.doi.org/10.1021/acs.jpcc.0c04700
pubs.acs.org/JPCC Article
superoxide radicals, which together with holes participated in
the piezo-photocatalytic degradation of the RhB dye
molecules.
■
CONCLUSIONS
The BNT@TiO2 composite catalyst with heterojunction was
successfully synthesized through the sol−gel method and
combined piezoelectric effect and photocatalytic activity to
exhibit excellent piezo-photocatalytic performance. The
composite catalyst not only can effectively utilize natural
light source but also can apply the piezoelectric field to
effectively promote separation and migration of photoinduced
carriers. On the one hand, given the formation of the
heterojunction the energy band structure of BNT@TiO2 was
modified so that its band gap was decreased compared with the
pure catalyst. On the other hand, perovskite BNT nanowires
with large aspect ratio could deform enough to induce a
piezoelectric field. Furthermore, since the external electric field
increased the polarization intensity, the piezoelectric effect of
the BNT@TiO2 composite could be improved. On the basis of
these characteristics, the BNT@TiO2 composite was used to
effectively degrade RhB dye molecules through piezo-photo-
catalytic effects, and the degradation mechanism was well
studied. Compared with previous studies, the piezo-photo-
catalytic performance of BNT@TiO2 composite was at a
higher level. In summary, it is a promising approach for
obtaining excellent piezo-photocatalytic activity by combining
the traditional piezoelectric and photocatalyst to prepare a
composite with heterojunction.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.0c04700.
Stepwise N-deethylation process of RhB dye molecules
during degradation, corresponding color change in
degradation of RhB under different catalytic models,
comparison of degradation efficiency by pure materials
and composite, comparison of piezo-photocatalytic
performance used to degrade organic dye (PDF)
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
■
AUTHOR INFORMATION
Corresponding Authors
Xiujuan Lin − Shandong Provincial Key Laboratory of
Preparation and Measurement of Building Materials, University
of Jinan, Jinan 250022, P.R. China; orcid.org/0000-0002-
2248-5040; Email: mse_linxj@ujn.edu.cn
Shifeng Huang − Shandong Provincial Key Laboratory of
Preparation and Measurement of Building Materials, University
of Jinan, Jinan 250022, P.R. China; Email: mse_huangsf@
ujn.edu.cn
Authors
Xingang Xu − Shandong Provincial Key Laboratory of
Preparation and Measurement of Building Materials, University
of Jinan, Jinan 250022, P.R. China
Fanghui Yang − Shandong Provincial Key Laboratory of
Preparation and Measurement of Building Materials, University
of Jinan, Jinan 250022, P.R. China
Xin Cheng − Shandong Provincial Key Laboratory of
Preparation and Measurement of Building Materials, University
of Jinan, Jinan 250022, P.R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.0c04700
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was financially supported by the National Natural
Science Foundation of China (Nos. 51702120, U1806221,
51632003), University of Jinan (No. 140200322), Shandong
Provincial Key Research and Development Plan (Grant No.
2016JMRH0103), the Taishan Scholars Program and Case-by-
Case Project for Top Outstanding Talents of Jinan.
■
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I https://dx.doi.org/10.1021/acs.jpcc.0c04700
J. Phys. Chem. C XXXX, XXX, XXX−XXX