Colloids and Surfaces A: Physicochemical and Engineering Aspects 677 (2023) 132412

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Self-Polarized CNT/PVDF Nanocomposites with ultra-high β phase

achieved via water induction for efficient piezo-catalysis
Yingying Zhang a, Carice Chong b, Wangshu Tong c, Haitao Li a, d, *, Hiang Kwee Lee b, e, **,
Jie Han a, ***
a
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, PR China
b
Division of Chemistry and Biological Chemistry, School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, 21 Nanyang Link,
637371 Singapore
c
Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, School of Materials Science and Technology, China University of Geosciences,
Beijing 100083, PR China
d
Yantai Nanshan University Longkou, Shandong Province 265713, PR China
e
Institute of Materials Research and Engineering, The Agency for Science, Technology and Research (A*STAR), 2 Fusionopolis Way, #08–03, Innovis, 138634,
Singapore

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Self-polarized CNT/PVDF nano­

composites with ultra-high β phase Self-polarized CNT/PVDF nanocomposites with ultra-high β phase have been achieved via water induc­
(~95%) have been achieved via water tion for efficient piezo-catalysis in pollutant degradation and H2O2 production.
induction.
• SCP1.5 as efficient piezo-catalysts for the
degradation of organic pollutants at >
95% efficiency with high recyclability
and adaptability.
• Our piezo-catalytic design also enables
superior H2O2 production at 13.5 mmol
1
g−CNT h− 1.

A R T I C L E I N F O A B S T R A C T

Polyvinylidene fluoride (PVDF) is promising for piezo-catalytic applications owing to its excellent biocompati­
Keywords:
bility, flexibility, and durability. However, it is limited by weak electroactivity originating from its intrinsically
Self polarization
Nanocomposite
low β piezoelectric phase content (<20%) and insulating properties. Here, we achieve efficient piezo-catalysis by
Piezo-catalysis introducing a self-polarized PVDF-based composite containing carbon nanotube (CNT) as conductive fillers.

* Corresponding author at: School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, PR China.
** Corresponding author at: Division of Chemistry and Biological Chemistry, School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Techno­
logical University, 21 Nanyang Link, 637371 Singapore.
*** Corresponding author.
E-mail addresses: htli@yzu.edu.cn (H. Li), hiangkwee@ntu.edu.sg (H.K. Lee), hanjie@yzu.edu.cn (J. Han).

https://doi.org/10.1016/j.colsurfa.2023.132412
Received 29 July 2023; Received in revised form 6 September 2023; Accepted 12 September 2023
Available online 15 September 2023
0927-7757/© 2023 Elsevier B.V. All rights reserved.
Y. Zhang et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 677 (2023) 132412

Degradation Notably, our self-polarized CNT/PVDF (SCP) ensemble exhibits a high β phase content of ~95%, which is up to 6-
H2O2 production fold higher than the original PVDF powder, and superior electrical activity by exploiting the polarity induction
effect of water molecules. As a proof-of-concept demonstration, the SCP realizes efficient degradation of organic-
polluted water by at least 95% within 2 h of ultrasonication (240 W), even at high pollutant concentration (40
mgL− 1). Systematic investigations unveil its excellent recyclability and adaptability to various tropical or sub­
tropical natural waters. More importantly, the SCP also achieves efficient H2O2 production of up to ~13.5 mmol
1
g−CNT h− 1, which is > 6-fold and > 19-fold better than standalone self-polarized PVDF (i.e., without CNT content)
and emerging piezo-catalytic designs, respectively. This study offers a unique approach for designing PVDF-based
piezo-catalyst to expedite mechanically-driven catalysis towards practical applications.

1. Introduction
Piezo-catalysis is an emerging approach that harnesses external
mechanical force as a readily accessible energy source to facilitate the
conversion of mechanical energy into chemical reactions[1,2]. One
notable feature of this approach is the utilization of piezoelectric ma­
terials, which possess the unique ability to create positively and nega­
tively charged regions on opposing surfaces when exposed to
mechanical energy, such as ultrasonication. This phenomenon leads to
the generation of built-in electric fields that play a vital role in efficiently
separating electron-hole pairs immediately upon their formation[3].
Consequently, the efficient charge separation enables the piezo-catalysts
to trigger highly efficient redox reactions, rendering them attractive for
a wide range of applications. These applications include the production
of reactive oxygen species (ROS) for wastewater treatment[4], the
generation of green chemical fuels[5], and the synthesis of valuable fine
chemicals like hydrogen peroxide (H2O2)[6,7].
The performance of the piezo-catalysts is highly influenced by the
choice of materials. Current research primarily focuses on inorganic
piezo-catalysts (BaTiO3[6], PZT[8], NaNbO3[9], and MoS2[10]) due to
their superior piezoelectric properties, cost-effectiveness, and tunable
chemical properties. Additionally, their nanomaterials hold great
promise in piezo-catalysis due to their ability to undergo direct
decomposition of water. However, many inorganic piezoelectric mate­
rials suffer from limited durability. This is mainly attributed to their
poor physical and chemical stability which arise from their low corro­
sion resistance and high brittleness. Moreover, these ceramic materials
also exhibit poor biocompatibility which can lead to secondary pollu­
tion. These drawbacks severely hamper their long-term performance
and limit their practical application, such as in large-scale water treat­
ment[2].
Piezoelectric polymers (e.g., polyvinylidene fluoride, PVDF) have
the potential to overcome the limitations associated with ceramic ma­
terials by offering numerous advantages, such as excellent biocompati­
bility, easy casting processing, high mechanical flexibility, strong
chemical stability, and elastic modulus[11]. Notably, the piezoelectric
properties of PVDF and its co-polymer rely heavily on the content of β
crystal phase for spontaneous material polarization and piezoelectric
conversion[12]. Nevertheless, native PVDF materials typically have low
β phase content of < 20%[13]. As a result, the composition and orien­
tation of the piezoelectric phase in PVDF have to be improved via
energy-intensive processes such as electrospinning[14], mechanical
stretching[15], rotational coating[16], hot pressing[17], and additional
polarization under immense electric fields[18]. Another constraint of
PVDF as a piezo-catalyst is its insulating nature, whereby it lacks suffi­
cient concentration of surface charge carriers needed to drive redox
reactions. These drawbacks pose a formidable challenge for practical
applications of piezoelectric polymers in catalysis[19].
Herein, we achieve efficient piezo-catalysis by creating a self-
polarized composite based on polyvinylidene fluoride (PVDF). We
create the composite by inducing nanoscale polarization through water
and by adding conductive carbon nanotubes (CNT). The water mole­
cules induce polarity in PVDF during the phase separation process,
resulting in nanostructured PVDF with a β phase content of
approximately 91%. The CNT component further increases the β phase
content to around 95% by interacting with PVDF through hydrogen
bonding with its oxidized functional groups. Our self-polarized CNT/
PVDF (SCP) ensemble has a β phase content ~6-fold higher than that of
the original PVDF powder.
As a proof-of-concept demonstration, we employ the self-polarized
CNT/PVDF (SCP) ensemble to (1) treat organic-polluted wastewater
and (2) enable the chemical synthesis of H2O2. Our SCP efficiently de­
grades various dye molecules with a degradation efficiency of over 95%
when ultrasonication (240 W) is used as the mechanical energy source
for 2 h, thereby promising effective pollutant removal even at high
concentration (40 mgL− 1). Moreover, this unique piezo-catalyst ach­
1
ieves a superior H2O2 production rate of 13.5 mmol g−CNT h− 1, which is >
6 times and > 19-fold better than standalone self-polarized PVDF (i.e.,
without CNT addition) and emerging piezo-catalytic designs, respec­
tively. Our SCP demonstrates excellent reusability and adaptability in
diverse (sub)tropical natural water environments, such as sea water.
This work provides a unique approach to enhancing the piezo-catalytic
properties of PVDF-based composites for efficient mechanical-to-
chemical transformations, which are crucial for practical environ­
mental, energy, and (bio)chemical applications.
2. Experimental section
2.1. Materials
Polyvinylidene fluoride (PVDF, MW = 500,000), N,N-
dimethylformamide (DMF, 99.5% purity) and potassium iodide (KI)
were purchased from Shanghai Aladdin Biochemical Technology Co.,
Ltd. Rhodamine B (RhB), tetracycline hydrochloride (TH), crystal violet
(CV), methylene blue trihydrate (MB), methyl orange (MO), ammonium
molybdate tetrahydrate (H32Mo7N6O28) and isopropyl alcohol (IPA)
were obtained from Macklin, China. Ethylenediaminetetraacetic acid
disodium salt dihydrate (EDTA-2Na) was obtained from Sigma–Aldrich,
China. Ethanol, hydrogen peroxide (H2O2), p-benzochinon (BQ) and
silver nitrate (AgNO3) were purchased from Sinopharm Chemical Re­
agent Co., Ltd. Carbon nanotubes were supplied from Zhejiang Taobao
Network Co., Ltd. All reagents were used without further purification.
2.2. Fabrication of self-polarized CNT/PVDF nanocomposite
Briefly, low concentration polyvinylidene fluoride (PVDF) solution
was prepared by adding 0.5 g of PVDF powder to 50 mL of DMF with
stirring at 900 rpm and 25 ℃ for 2 h. Various mass fractions of CNTs (w.
r.t. PVDF, 0 wt%, 0.25 wt%, 0.50 wt%, 1.00 wt%, 1.50 wt% and 2.00 wt
%) were added to the solution mixture with continuous stirring until
evenly dispersed to obtain the precursor solution for self-polarized CNT/
PVDF nanocomposite. Subsequently, the precursor solution was quickly
poured into 2000 mL deionized water to allow self-polarization of CNT/
PVDF under the action of water molecules at nanoscale. The colloidal
solution was then filtered and dried at room temperature to obtain the
self-polarized CNT/PVDF nanocomposites for further use. The self-
polarized CNT/PVDF powders were denoted as SCP0, SCP0.25, SCP0.5,
SCP1.0, SCP1.5, and SCP2.0, respectively.

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Y. Zhang et al.
2.3. Piezo-catalytic activity measurements
2.3.1. Piezo-catalytic degradation of dye pollutants
The piezo-catalytic activities of the samples were evaluated by the
removal of organic pollutant under ultrasonication (ultrasonication
power: 120, 180, 240, 300 and 360 W). Self-polarized CNT/PVDF (SCP,
0.015 g) was added to a 20 mL vial containing pollutant aqueous solu­
tion (15 mL, 5 mg/L) and placed for 30 min in dark to achieve adsorp­
tion/desorption equilibrium. The temperature of the degradation
reaction was controlled at 20 ± 2 ◦ C by frequently changing the water in
the ultrasonic cleaner. A 2.5 mL of the reaction solution was extracted at
pre-defined interval of 30 min for subsequent measurement using
UV–visible absorption spectroscopy. The characteristic absorption
wavelength of the pollutant solution at 553 nm was used to monitor the
change in concentration of the solution. The degradation efficiency (%)
was calculated by Eq. (1):
C0 − Ct
Dye degradation (%) = × 100% (1)
C0
where C0 is the initial concentration of the pollutant solution, and Ct is
the concentration of the pollutant solution at reaction time.
In addition, scavenger experiments were also performed to identify
the active species during the piezoelectric catalysis to elucidate the
piezoelectric catalytic mechanism. The contribution of electron (e-),
hole (h+), hydroxyl radical (•OH) and superoxide radical (O-2) in the
piezoelectric degradation process were examined by using AgNO3,
EDTA-2Na, IPA and BQ (1 mM) as scavengers, respectively[20]. The
SCP was collected after each cycle of piezoelectric catalytic reaction,
washed with copious of ethanol and deionized water to remove residual
contaminants, and dried in vacuum at 60 ◦ C for 24 h for subsequent
recycling experiments.
2.3.2. Piezo-catalytic production of H2O2
The piezo-catalytic activity of samples was also evaluated by H2O2
production under ultrasonication at ambient air condition (40 kHz,
300 W). In a typical experimental set-up, self-polarized CNT/PVDF
(SCP, 0.025 g) was dispersed in ethanol solution (10 mL, v/v:1/4)[21].
In addition, the control experiments were carried out in high purity O2,
Ar and N2 atmosphere. The amount of H2O2 generated was determined
by the chromogenic method[22,23]. Briefly, 500 µL of the reaction so­
lution was added to 2 mL of potassium iodide (KI, 0.1 M) and 50 µL of
ammonium molybdate tetrahydrate (H32Mo7N6O28, 0.01 M) to react for
15 min. The reaction solution was collected for subsequent UV–visible
absorption measurement using the characteristic peak intensity at
350 nm to monitor the change in H2O2 concentration. All the above
reactions were carried out in the dark and controlled temperature
environment around 20 ◦ C.
2.4. Instruments and characterizations
The morphology of the all samples was characterized using a field
emission scanning electron microscope (FESEM, S-4800, Hitachi Co.,
Japan). XRD analysis was performed using a Rigaku D/Max-2500 X-ray
diffractometer (Japan) with Cu Kα radiation (l=1.5406 Å) operating at a
voltage of 40 kV and a current of 200 mA. Fourier transform infrared
spectroscopy (FTIR) analysis of the samples was performed on Antains
II. X-ray photoelectron spectrometer (XPS) analysis of the samples was
performed on ESCALAB 250Xi (Thermo Scientific, America). The reac­
tive species produced by the composites were detected through the
electron paramagnetic resonance (EPR) technique with a Bruker EMX-
10/12 spectrometer. A300–10/12 paramagnetic resonance spectros­
copy (EPR, Bruker, Germany). The decomposition ratios of the dye in the
solutions were measured using a UV-6100 Double Beam Spectropho­
tometer (Mapada, China).
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Colloids and Surfaces A: Physicochemical and Engineering Aspects 677 (2023) 132412
3. Results and discussion
3.1. Preparation and application of materials
Fig. 1 illustrates the preparation process of the self-polarized CNT/
PVDF nanocomposites (SCP) and their application as piezo-catalysts for
organic pollutants degradation and H2O2 generation. Briefly, we first
prepare the precursor solution for CNT/PVDF by dissolving PVDF
powder into dimethylformamide (DMF), followed by adding CNT as
conductive fillers due to its exceptional electrical properties. The SCP is
then fabricated by rapidly pouring the precursor solution into deionized
(DI) water for the PVDF molecules to undergo phase separation and
precipitation. Notably, the difference in the solubilities of PVDF in DMF
and water enables polarity induction by water molecules at the nano­
scale. This process leads to the formation of self-polarized CNT/PVDF
nanocomposite with trans-planar zigzag conformation of β phase
(Fig. 1b). Specifically, PVDF is soluble in DMF solution but not in
aqueous solution, whereas water is soluble in DMF. These differences in
solubility are the underlying principle driving the polarity induction
effect by water molecules. Specifically, when DMF solution containing
low concentration PVDF is introduced into a large amount of water,
PVDF nanoparticles will gradually precipitates at the nanoscale water-
DMF interface as DMF diffuses into the aqueous solution. During the
precipitation process of PVDF nanoparticle, its molecular segments are
polarized through the formation of hydrogen bonds between the F atom
of PVDF and the H atom of polar water molecules (Fig. S1)[24].
Compared to traditional phase separation methods, our unique water
induction approach promotes efficient self-polarization of PVDF by
facilitating extensive interaction between water molecules and a low
concentration of PVDF solution during the phase separation process.
Moreover, the addition of CNT serves to improve the conductivity of the
PVDF composite and enhances chemical interactions with target reac­
tant molecules. The as-fabricated SCP is anticipated to possess strong
piezoelectric properties and facilitates the separation of electron-hole
pairs for subsequent piezo-catalytic applications (Fig. 1c).
3.2. Characterization of CNT/PVDF nanocomposite
During the phase separation stage, the DMF solution diffuses into
water and the water molecules interact with the hydrophobic PVDF
chains to cause their polarization and aggregation into nanoparticles
(Fig. 2a). To elucidate the structural features of self-polarized PVDF
(SCP0) and CNT/PVDF composites, we characterize these platforms
using scanning electron microscope (SEM). Neat self-polarized PVDF
(SCP0; i.e., 0 wt% CNT) exhibits a spherical structure with an average
diameter of (205 ± 40) nm. This morphology arises from the low con­
centration of PVDF used during the phase separation process (Fig. 2b,
Fig. S2). The size of the PVDF particles prepared using various PVDF
concentration is further illustrated in Fig. S2. When the PVDF concen­
tration is > 25 mg/mL, PVDF is in a continuous thin film state. When its
concentration is reduced, nano-sized PVDF particles are formed and
their sizes slightly decrease from 240 ± 70 nm to 231 ± 80 nm when
PVDF concentration decreases from 16.7 mg/mL to 8.3 mg/mL,
respectively.
When conductive tubular CNT is added to the PVDF solution (SCP1.5)
solution, the resulting nanocomposite possesses a similar size to SCP0
(~198 ± 30 nm; Fig. 2c) and is uniformly deposited with the CNT
(diameter, ~17 ± 8 nm) on the PVDF core surfaces (Fig. S3). Notably,
Fig. S3 shows that the CNT/PVDF nanoparticles with various CNT
content (0.5–2.0 wt%) also possess similar PVDF nanomorphology and
consistent size of ~200 nm. Moreover, the FTIR spectra indicate the
effect of CNT content on the β phase content of PVDF is relatively small.
This is because the formation of β phase in PVDF is mainly due to the
action of water molecules during the self polarization process of PVDF.
High-resolution X-ray photoelectron spectroscopy (XPS) characteriza­
tion affirms the presence of surface hydroxyl functional group,
Y. Zhang et al.
Fig. 1. Schematic illustrations of the fabrication process of self-polarized CNT/PVDF nanocomposites (SCP) and their piezo-catalytic applications. (a) Preparation
process of the CNT/PVDF precursor solution. (b) Self-polarization process of PVDF in the presence of water molecules. (c) Application of SCP for piezo-catalysis in the
degradation of organic pollutants and H2O2 production.
indicating the successful modification of PVDF surfaces with CNT
(Fig. 2d). This composite design is important as it harnesses the high
conductivity (238 S m− 1) and surface chemistry of CNT to promote the
formation of piezoelectric β phase (Fig. S4). It is also noteworthy that the
self-polarized CNT/PVDF composites are designated as SCPx, where x
represents the weight percentage of CNT in the SCP composites.
We subsequently characterize the as-prepared SCPs using FTIR to
determine the content of piezoelectric phase (Supporting Information Eq
(S1))[25]. We note that the initial concentrations (8.3 – 50 mg/mL) of
PVDF in the precursor solution strongly influence the resulting β phase
content (Fig. S5). As the concentration decreases from 50 mg/mL to
10 mg/mL, the β phase content increases from ~46% to ~91%. Further
reducing the PVDF concentration to 8.3 mg/mL results in a relatively
consistent β phase composition. Moreover, the β phase content of the
optimal self-polarized PVDF nanoparticles (i.e., 10 mg/mL precursor) is
5.5-fold higher than that of the original PVDF powder. This phenome­
non is attributed to the effective self-polarization achieved through
optimal interactions between PVDF chain segments and water molecules
when a low PVDF concentration is used. In contrast, traditional
self-polarization methods require a high PVDF concentration which,
upon precipitation, hinders PVDF-water interactions and leads to a
relatively low β phase content. Interestingly, the incorporation of CNT
further enhances the β phase content of the SCP1.5 composite to ~95%,
which is ~5.8-fold better than the original PVDF powder. X-ray
diffraction (XRD) patterns of both SCP0 and SCP1.5 confirm their higher
β phase composition compared to the original PVDF powder (Fig. S6).
This observation underscores the importance of additional hydrogen
bonding interaction between the PVDF and oxygen-containing func­
tional groups on the CNT’s surface in facilitating the self-polarization
process.
Moreover, we also assess the crystallinity of PVDF (e.g., degree of
order of the β phase) as it is another important factor influencing the
piezoelectric properties of a material. We use DSC characterization to
determine the crystallinity (Seen in the Eq. (S2) of Supporting Infor­
mation). Figs. 2g and 2h show the DSC heating and cooling curves,
respectively, for the original PVDF powder, SCP0 and SCP1.5. The
heating and cooling curves indicate that the crystallization temperature
of the SCP tends to shift towards higher temperatures. Specifically, the
heating curve shifts from 160.5 ℃ to 160.7 ℃, while the cooling curve
shifts from 130.9 ℃ to 136.5 ℃. Notably, the SCP1.5 demonstrates the
highest crystallization temperature, suggesting the formation of a higher
degree of β phase crystallinity. The calculated result reveals that the
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Colloids and Surfaces A: Physicochemical and Engineering Aspects 677 (2023) 132412
crystallinity of SCP1.5 is ~35%, which is ~75% higher than the original
PVDF powder (Supporting Information Eq (S2))[26]. The high compo­
sition and crystallinity of β phase in SCP are crucial to drive
mechanical-to-chemical transformations. Additionally, the hybrid
design incorporating CNT as conductive fillers also enhances the charge
carrier concentration (Fig. S7) and improves the wettability of the
composite for better interaction with aqueous reaction medium during
piezo-catalysis (Fig. S3). Moreover, as the composition of conductive
CNT increases, the surface carrier concentration of CNT/PVDF com­
posites also increases. This observation is supported by a gradual drop in
their impedance value, as evident in Fig. S3.
3.3. Piezo-catalytic activity
3.3.1. Piezo-catalytic catalytic degradation
The SCP ensembles are subsequently employed as piezo-catalysts for
the degradation of organic pollutants as well as H2O2 generation using
ultrasound as a source of mechanical energy. We select rhodamine B
(RhB), crystal violet (CV), methylene blue (MB), tetracycline hydro­
chloride (TC), and methyl orange (MO) as model organic pollutants
because they are common water pollutants with severe toxicity and
mutagenic effects[27]. The reaction is performed by first adding SCP to
the aqueous pollutant solution and placed in dark for 30 min to achieve
adsorption/desorption equilibrium. The piezo-catalysis is then initiated
by activating the ultrasonication (240 W). At pre-defined intervals of
30 min, aliquots of the reaction solution are extracted to quantify the
concentration of the pollutants left in the reaction solution.
To optimize the piezo-catalytic reactions, we conduct systematic
studies on the effects of CNT composition (0–2 wt%) and ultrasonication
power on the piezo-catalytic performance of the SCP hybrid. First, we
observe that increasing CNT content from 0 wt% to 1.5 wt% leads to a
gradual improvement in the degradation efficiency of RhB (40 mg/L)
from 50% to 98.1% (Fig. 3a), respectively. However, when the CNT
content exceeds 1.5 wt% (i.e., SCP2.0), the degradation efficiency drops
significantly to ~50.6%. Notably, the degradation efficiency achieved
by SCP1.5 is 114% and 581% higher than the original PVDF and the
blank experiment (without catalyst; Fig. S8), also beyond other reports
[28–32], respectively. The self-degradation of RhB in the blank experi­
ment is mainly driven by the cavitation effect under ultrasonication[33].
The observed initial rise in degradation efficiency is attributed to the
increase in surface carrier concentration facilitated by CNT, whereas
subsequent decline is due to the excessive increase in the composite’s
Y. Zhang et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 677 (2023) 132412

Fig. 2. (a) Scheme depicting the as-fabricated SCP. SEM images of (b) self-polarized PVDF (SCP0) and (c) self-polarized CNT/PVDF nanocomposites (SCP1.5). (d)
High-resolution XPS O 1 s core-level spectrum of CNT. (e) FTIR spectra of original PVDF, SCP0 and SCP1.5 and (f) the related calculated β phase content. (g) DSC
heating curves and (h) cooling curves of original PVDF, SCP0 and SCP1.5 and (i) the corresponding calculated crystallinity.

internal conductivity which promotes charge recombination. Using a
pseudo-first order reaction kinetics (Eq. 2), we also observe that SCP1.5
exhibits the highest rate constant (k; Fig. 3b) of 0.023 min− 1 when
compared to other CNT compositions. Hence, we select the optimized
SCP1.5 for further investigations in piezo-catalysis[34].
ln(C0 /C = kt)
In the investigation of the effect of ultrasonication power, we
conduct degradation experiments using SCP1.5 at different ultrasound
power levels (120–360 W). The results of the time-dependent in­
vestigations highlight that an optimal degradation efficiency of ~90% is
achieved after two hours when the ultrasound power is ≥ 240 W
(Fig. 3c). Furthermore, the SCP1.5 exhibits versatility in degrading
various organic pollutants, such as MB (10 mg/L, Fig. 3d), CV (20 mg/L,
Fig. 3d), MO and TH (5 mg/L, Fig. S9). For instance, the SCP1.5 effi­
ciently degrades positively charged RhB, MB and CV at > 95% effi­
ciency. The degradation efficiency of MO and TC is lower at < 68%
owing to the electrostatic repulsion between the negatively charged CNT
and negatively charged molecules, thereby hindering effective reactant-
catalyst interactions[35]. Nevertheless, this comparison again high­
lights the importance of incorporating CNT into the SCP ensemble to
facilitate their interactions with positively charged molecules, a vital
pre-requisite for efficient catalysis.
We proceed to evaluate the reusability of our piezo-catalyst and its
(2)
performance- under different aqueous environments, including various
(1) pH conditions, (2) environment temperatures, and (3) water quali­
ties. Our SCP1.5 demonstrates high reusability, attaining a consistent
degradation efficiency of ~95% over three successive cycles (Fig. 3e)
while maintaining its structural integrity and high β phase content
(Fig. S10). The SCP1.5 also exhibits high RhB degradation efficiency of
~95% even when subjected to a wide range of pH conditions, from
strongly acidic (pH 1) to weakly basic (pH 10). The efficiency only
slightly decreases to ~79% under strongly alkaline condition (pH 13),
denoting that SCP1.5 is compatible with a broad range of pH environ­
ments (Fig. S11). Our SCP1.5 also performs well under ambient to
slightly elevated temperature conditions (20 – 40 ℃), while a lower

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Y. Zhang et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 677 (2023) 132412

Fig. 3. Piezo-catalytic degradation of organic pollutants using SCP. Time-dependent plot of (a) normalized RhB concentration (C/C0) and (b) ln (C0/C) using SCP
containing different CNT composition. Time-dependent plot of normalized concentration under (c) different ultrasonication power and (d) different organic pol­
lutants. (e) Degradation ratios of RhB over three repeated cycles. (f) Time-dependent plot of normalized RhB concentration and (g) corresponding degradation ratios
of RhB when in the presence of different scavengers. ESR spectra of (h) DMPO-•OH and (i) DMPO-⋅O-2 obtained from SCP1.5 with different ultrasonication time.

degradation efficiency of ~54% is obtained under low-temperature
condition (10 ℃; Fig. S12). This observation signifies the stability and
suitability of SCP1.5 for degrading water pollutants in (sub)tropical
areas. Moreover, SCP1.5 maintains its high catalytic performance in DI
water and tap water, only experiencing a slight decrease of efficiency to
~77% in the presence of harsh sea water conditions (Fig. S13). Collec­
tively, our SCP1.5 clearly exhibits excellent recyclability, high stability in
various environmental conditions, and the ability to perform effectively
in various aqueous media.
To unravel the molecular mechanism behind the superior degrada­
tion efficiency of SCP1.5, we employ EDTA-2Na, AgNO3, IPA and BQ as
scavengers for hole (h+), electron (e-), hydroxyl radical (•OH), and su­
peroxide anion (•O-2), respectively. These comparisons are crucial for
identifying the active species and their contributions in the degradation
process (Figs. 3f, 3g)[29]. We observe that both IPA and BQ significantly
inhibit the piezo-catalytic degradation, demonstrating that •OH and •O-2
are the primary active species generated by our SCP1.5 to break down
organic pollutants. We further confirm the generation of ⋅OH and •O-2
species using electron paramagnetic resonance spectroscopy (ESR), as
shown in Fig. 3h-i and Fig. S14. Upon introducing ultrasound, we
observe the gradual increases in the peak intensities of both •OH and
•O-2 species from 0 to 15 min. In contrast, in the absence of ultra­
sonication, no characteristic peaks of •OH and •O-2 are observed. This
finding highlights that our mechanically driven piezo-catalyst is
responsible for the cascade generation of •OH and⋅O-2 species that are
subsequently utilized to degrade organic pollutants.
3.3.2. Piezo-catalytic H2O2 production
In addition to the excellent piezo-catalytic degradation performance,
we also evaluate the ability of SCP to produce H2O2 under different CNT
content (0 – 2.0 wt%; Fig. 4a) and various ultrasonication powers. In
brief, we add SCP to an ethanolic aqueous solution (20% ethanol in
water) and subject it to ultrasonication treatment at 300 W for 2 h[36].
At pre-defined time intervals, we extract the reaction solution to

6
Y. Zhang et al.
Fig. 4. H2O2 generation by SCP piezo-catalysis under different conditions. (a) H2O2 productions by SCP containing different CNT content (0.25–2 wt%) under 300 W
ultrasound. (b) Concentration of H2O2 generated after 2 h. (c) Generation of H2O2 using SCP1.5 with different ultrasonication power. (d) H2O2 production rate by
SCP1.5 for three successive cycles. Concentration of H2O2 produced in the presence of (e) scavenger and (f) various gas environments for 2 h.
quantify the amount of H2O2 generated using a chromogenic method
and a standard calibration curve based on a characteristic absorption
peak at 350 nm (Fig. S15). Figs. 4a and 4b show an increase in H2O2
concentration generated as CNT content increases from 0 wt% to 1.5 wt
%, whereas further increases in the CNT composition (SCP2.0) results in
a sharp decrease in H2O2 concentration to a level even lower than
SCP0.25. The optimal H2O2 production using SCP1.5 aligns with our
previous observations in the organic pollutant degradation, again sup­
porting that a CNT content of 1.5 wt% in the composite is ideal for
piezo-catalysis. Moreover, we also notice a peak in H2O2 production as
the ultrasonication power varies between 120 W and 360 W (Fig. 4c).
For instance, H2O2 production increases from 39.3 μM to 1013.5 μM
with an input power of 120–300 W, respectively, which is followed by a
sharp decrease to 324.1 μM at a higher power of 360 W. The drastic loss
of H2O2 product at high ultrasonication power (360 W) is possibly due
to its decomposition under high mechanical stress.
By employing the optimized conditions involving SCP1.5 as a piezo-
catalyst and ultrasonication power of 300 W, our design achieves a
1
promising H2O2 production rate of 13.5 mmol g−CNT h− 1 which remains
relatively stable over three cycles. The H2O2 production rate enabled by
our SCP1.5 is notably > 6-fold and > 19-fold higher than SCP0 and
emerging piezo-catalytic designs, respectively (Fig. 4d)[21,37]. It is
worth mentioning that standalone CNT is catalytically inactive, as
evident from the negligible H2O2 production even under identical
ultrasonication conditions (Fig. S16). The self-production of H2O2 in the
blank experiment is mainly driven by the cavitation effect under ultra­
sonication in Fig. S16[33]. Moreover, the SCP0 (i.e., no CNT) also
demonstrates low H2O2 production of 159.1 μM despite having a high β
phase content. The poor piezo-catalytic performance of SCP0 is likely
attributed to the low carrier density on the PVDF surface because
smaller piezoelectric current is generated from SCP0 compared to SCP1.5
(Fig. S17). We observe that SCP1.5 attains a higher piezoelectric current
(ultrasonication power, 240 W; film size, 3 ×2 cm2; mass loading,
7
Colloids and Surfaces A: Physicochemical and Engineering Aspects 677 (2023) 132412
1 mg/cm2) of 1.3 μA, which is ~3-fold better than SCP0 (Fig. S16). The
improvement in piezoelectric current response is attributed to the lower
impedance of SCP1.5 compared to SCP0 (Fig. S5), indicating higher
charge separation and transfer efficiency. Our findings jointly highlight
the crucial role of the synergistic coupling of the PVDF matrix with high
β phase content and conductive CNT filler in imparting SCP1.5 with high
piezo-catalytic activities in pollutant degradation and H2O2 production.
To elucidate the origin and dominant active species responsible for
the superior H2O2 production of SCP1.5, we conduct an additional con­
trol experiment using benzoquinone (BQ) as a •O-2 scavenger[37]. In the
presence of BQ scavenger, the amount of H2O2 generated by SCP1.5 over
a 2-hour duration drastically decreases from 1013.5 μM to 227.5 μM.
This observation provides concrete evidence that •O-2 is the active in­
termediate species responsible for the generation of H2O2 through a
two-step single electron reduction process[6]. Furthermore, we also
investigate the H2O2 generation using SCP1.5 under four different gas
environments, namely (i) air, (ii) O2, (iii) Ar and (iv) N2. Notably, the
presence of O2 environment exhibits the highest H2O2 production of
1422.4 μM (Fig. 4f). Negligible H2O2 is produced by SCP1.5 when the
reaction is performed in Ar or N2 environments, indicating that atmo­
spheric oxygen is the major source of reactant rather than the dissolved
and/or trapped oxygen in the reaction solution. These systematic studies
clearly demonstrate that the main chemical process behind H2O2 gen­
eration involves the reduction reaction of O2 reactant in air or neat O2
gas stream.
3.4. Mechanism discussion
Collectively, our findings highlight that the mechanically-induced
electrical charges generated through ultrasonication play an important
role in the piezo-catalytic (1) degradation of organic pollutants and (2)
H2O2 generation (Fig. 5). When SCP1.5 is subjected to ultrasonication
treatment, it undergoes polarization which leads to the generation of an
Y. Zhang et al.
Fig. 5. Schematic illustration of the proposed mechanism of piezo-catalytic pollutants degradation and H2O2 production.
internal electric field within the composite. This piezo-electric field fa­
cilitates the production and separation of the electron-hole pairs (Fig. 5)
under the influence of shock waves caused by the collapse of the cavi­
tation bubbles. The efficient separation of the electrons and holes is
instrumental in driving subsequent redox reactions (Eq. 5). (1) In the
case of piezo-catalytic degradation of organic molecules, the significant
inhibition of RhB degradation in the presence of IPA and BQ scavengers
indicate that •OH and •O-2 are the main chemical species driving the
degradation processes through the stepwise reactions highlighted in Eq.
3-9. (2) For piezo-catalytic H2O2 production, the reaction uses ethanol as
a sacrificial agent to consume the positively charged holes. Conse­
quently, only the negatively charged electrons generated through
piezoelectric conversion can contribute to H2O2 production. Our
experimental observations affirm O2 as the major reactant for H2O2
generation. During the generation of superoxide radicals from O2, polar
oxygen molecules interact with polar functional groups on the surface of
CNT (e.g., C– – O, C-O-H, etc) which serve as the active sites. These
intermolecular chemical interactions cause oxygen molecules to adsorb
on the surface of CNT, thereby facilitating the transfer of mechanically
driven piezoelectric electrons to the oxygen species via the CNT relay
[38]. Consequently, upon piezoelectric conversion, the generated elec­
tron carriers drive the reduction reaction involving H+ and O2 reactants
to form the H2O2 product. The ethanol is concurrently oxidized by the
h+ to prevent charge accumulation, thereby facilitating the
piezo-catalytic reactions[39].
SCP1.5 + ultrasound→e− + h− (3)
H2 O→OH − + H + (4)
e− + O−2 →⋅O2 − (5)
2H + + O2 + 2e− →H2 O2 (6)
e− + H2 O2 + H + →⋅OH + H2 O (7)
OH − + h+ →⋅OH + e− (8)
⋅OH/⋅O2 − + Pollutants→Oxidation products (9)
H2 O→OH − + H + (4)
e− + O2 → + ⋅O2 − (5)
2H + + O2 + 2e− →H2 O2 (6)
8
Colloids and Surfaces A: Physicochemical and Engineering Aspects 677 (2023) 132412
4. Conclusion
In conclusion, we have successfully developed an efficient piezo-
catalyst through the design of a self-polarized CNT/PVDF (SCP) com­
posite. This composite exhibits a high β phase content achieved via the
nanoscale induction effects by water molecules. Our unique approach
drastically enhances the β phase composition in the SCP to ~95%, which
is 5.8-fold higher than the original PVDF powder. In addition, the
incorporation of CNT filler also improves the composite’s conductivity
and charge carrier density. The SCP demonstrates remarkable efficiency
in degrading various organic pollutants at ≥ 95% efficiency within 2 h
under optimal ultrasonication treatment (240 W). This efficiency is
~5.8-fold better than that of the original PVDF powder. Furthermore,
the nanocomposite also exhibits excellent reusability and adaptability to
different environmental conditions, including reaction temperature and
water quality. More importantly, the best-performing SCP1.5 generates
1
H2O2 at a rate of 13.5 mmol g−CNT h− 1, which is > 6-fold and > 19-fold
more superior to SCP0 and emerging piezo-catalytic platforms, respec­
tively. Mechanistic investigations highlight the crucial role of the syn­
ergistic coupling between the PVDF matrix with high β phase content
and the conductive CNT filler in enhancing the piezo-catalytic activities
of SCP for pollutant degradation and H2O2 production. Our work pro­
vides a unique perspective on designing PVDF-based composites to
enhance their piezoelectric properties and conductivity. This design
strategy aims to expedite mechanically driven catalysis for practical
applications in the environmental, energy, and (bio)chemical fields.
CRediT authorship contribution statement
Yingying Zhang: Conceptualization, Investigation, Validation,
Formal analysis, Writing – original draft. Carice Chong: Conceptuali­
zation, Investigation, Validation, Formal analysis, Writing – original
draft. Wangshu Tong: Investigation, Formal analysis, Visualization,
Resources. Haitao Li: Resources, Writing – review & editing, Funding
acquisition, Supervision. Hiang Kwee Lee: Resources, Writing – review
& editing, Supervision. Jie Han: Resources, Visualization, Writing –
review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Y. Zhang et al.
Data Availability
Data will be made available on request.
Acknowledgements
Haitao Li thanks the financial support from Natural Science Foun­
dation of Shandong Province (ZR2023QF019), Jiangsu Higher Educa­
tion Institutions of China (21KJB430049) and Innovation Technology
Platform Project (YZ2020268) jointly built by Yangzhou City and
Yangzhou University. H.K.L. thanks the funding supports from
Singapore Ministry of Education (RS13/20 and RG4/21), Agency for
Science, Technology and Research, Singapore (A*STAR, A2084c0158),
Center of Hydrogen Innovation, National University of Singapore (CHI-
P2022-05), and Nanyang Technological University start-up grants.
Wangshu Tong thanks the funding supports from the NSFC (52173088).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.colsurfa.2023.132412.
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