RESEARCH ARTICLE | ENVIRONMENTAL SCIENCES

Dynamic defects boost in-­situ H2O2 piezocatalysis for water

cleanup
Maoxi Rana,b,c, Bibai Dub, Wenyuan Liua , Zhiyan Lianga, Lihong Lianga, Yayun Zhangd , Lixi Zengb,1 , and Mingyang Xinga,c,1

Edited by Alexis Bell, University of California, Berkeley, CA; received October 8, 2023; accepted January 3, 2024

Creating efficient catalysts for simultaneous H2O2 generation and pollutant degradation
is vital. Piezocatalytic H2O2 synthesis offers a promising alternative to traditional meth- Significance
ods but faces challenges like sacrificial reagents, harsh conditions, and low activity. In this
study, we introduce a cobalt-­loaded ZnO (CZO) piezocatalyst that efficiently generates Efficient in-­situ H2O2 yield was
H2O2 from H2O and O2 under ultrasonic (US) treatment in ambient aqueous condi- attributed to the generation of
tions. The catalyst demonstrates exceptional performance with ~50.9% TOC removal dynamic defects promoting the
of phenol and in situ generation of 1.3 mM H2O2, significantly outperforming pure adsorption and activation of
ZnO. Notably, the CZO piezocatalyst maintains its H2O2 generation capability even oxygen, which were caused by
after multiple cycles, showing continuous improvement (from 1.3 mM to 1.8 mM). This cobalt deposition, enhancing
is attributed to the piezoelectric electrons promoting the generation of dynamic defects piezoelectric activity during the
under US conditions, which in turn promotes the adsorption and activation of oxygen,
US process and activating lattice
thereby facilitating efficient H2O2 production, as confirmed by EPR spectrometry, XPS
oxygen with more piezoelectric
analysis, and DFT calculations. Moreover, the CZO piezocatalysts maintain outstanding
performance in pollutant degradation and H2O2 production even after long periods of electrons. More importantly,
inactivity, and the deactivated catalyst due to metal ion dissolution could be rejuvenated the inevitable issue of catalyst
by pH adjustment, offering a sustainable solution for wastewater purification. deactivation due to metal ion
dissolution not only got resolved
H2O2 in-­situ generation | dynamic defects | O2 activation | piezocatalytic performance | by pH adjustment, but even
water remediation
showed significant in situ
H2O2 yield. Additionally, CZO
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Refractory pollutants pose a threat to human health and environmental ecosystems once piezocatalyst containing defects
discharged into natural water bodies (1–4). Conventional wastewater treatment methods,
could be repeatedly utilized,
such as adsorption, can only transfer pollutants without complete degradation, while
membrane processes suffer from high costs and membrane fouling. Currently, hydrogen maintaining high H2O2
peroxide (H2O2), an environmentally friendly green oxidant, releases highly reactive free production, and simultaneously
radicals to remove pollutants (5). The anthraquinone oxidation (AO) method, which achieving advanced degradation
involved the Pd-­catalyzed cyclic hydrogenation and oxidation of alkyl-­anthraquinones in of pollutants due to their robust
organic solvents, was commercially employed for H2O2 production (6, 7). However, this self-­repair capabilities.
process was associated with significant energy consumption and environmental impacts
and safety concerns regarding H2O2 transportation and storage. Therefore, developing a
cost-­effective and environmentally friendly in situ H2O2 production and activation cascade
reaction is a sustainable strategy in the field of pollutant removal.
Piezoelectric catalysis has attracted widespread research interest in wastewater treatment
due to its simplicity, cleanliness, and high efficiency (8, 9). It is considered a potential
sustainable alternative to AO method for the production of H2O2. Similar to photocat­
alytic processes, under ultrasonic (US) activation, polarization, and built-­in electric fields
are generated in piezoelectric materials, allowing continuous separation of electrons and
holes and attracting them to opposite surfaces (10). In aqueous solutions, surface charge
carriers can react with water or dissolved oxygen to generate reactive oxygen species (ROS)
for wastewater treatment, achieving the conversion of mechanical energy into chemical
Author contributions: M.X. and L.Z. designed research;
energy (O2 + e− → •O2–, •O2– + e− + 2H+ → H2O2; 2H2O + 2h+ → H2O2 + 2H+). M.R. performed research; Y.Z. contributed analytic tools;
Currently, varieties of piezoelectric semiconductors, e.g., BaTiO3 (11), g-­C3N4 (12), M.R., B.D., W.L., Z.L., L.L., L.Z., and M.X. analyzed data;
and M.R., L.Z., and M.X. wrote the paper.
BiVO4 (13), MoS2 (8), ZnO (14), BiO2-­x (15), and CdS (16) have been widely developed.
For example, Wei et al. developed an efficient piezocatalytic system of in situ The authors declare no competing interest.
piezo-­generation and utilization of H2O2 over Fe/BiVO4, significantly promoting the This article is a PNAS Direct Submission.

production of powerful oxidizing hydroxyl radicals (•OH) (17). Lin et al. revealed the Copyright © 2024 the Author(s). Published by PNAS.
This article is distributed under Creative Commons
piezoelectric effect and piezocatalytic mechanism of oxygen-­vacancy-­rich BiO2−x NSs Attribution-­NonCommercial-­NoDerivatives License 4.0
triggered by low frequency ultrasound (15). Particularly, ZnO, as a commonly used pie­ (CC BY-­NC-­ND).
zoelectric material, has found extensive applications in fields such as water splitting and 1
To whom correspondence may be addressed. Email:
lxzeng@jnu.edu.cn or mingyangxing@ecust.edu.cn.
water remediation, due to its excellent piezoelectric properties, availability, high chemical
This article contains supporting information online at
stability, and environmental friendliness (18). However, ensuring efficient piezoelectric https://www.pnas.org/lookup/suppl/doi:10.1073/pnas.​
catalytic performance (such as in situ piezo-­generation and utilization of H2O2 and pol­ 2317435121/-­/DCSupplemental.
lutant removal) in practical applications remains a challenge, primarily due to the rapid Published February 20, 2024.

PNAS 2024 Vol. 121 No. 9 e2317435121 https://doi.org/10.1073/pnas.2317435121 1 of 11

 recombination of piezoelectric electron–hole pairs. In order to
optimize the piezocatalytic performance of ZnO, researchers have
explored various strategies, including metal or non-­metal doping,
defect engineering, and heterostructure construction. For instance,
Wang and Zheng groups have both chosen the approach of doping
metal ions to enhance the piezoelectric effect (19, 20). Wang et al.
demonstrated that V-­doped NaNbO3 single crystals improved the
catalytic efficiency via enriched active sites and enhanced polari­
zation field under US vibration (21). Additionally, metal deposi­
tion has been widely applied as an effective method to enhance
carrier separation efficiency. For example, Huang et al. developed
Ag single atoms (SAs) and clusters co-­anchored on carbon nitride
(AgSA+C-­CN) to serve as the multifunctional sites for efficient
two-­electron water splitting (22). In addition to enhancing carrier
separation efficiency, increasing oxygen adsorption to accelerate
the oxygen reduction reaction (ORR) process is also a key factor
in improving H2O2 yield. Therefore, introducing defect engineer­
ing based on the aforementioned regulation strategies, with a focus
on adjusting the electronic structure and enriching active/adsorp­
tion sites, becomes crucial. So far, there have been relatively few
studies on ZnO with dynamic oxygen defects in piezocatalysis.
Consequently, the combined use of metal deposition and defect
engineering can significantly promote H2O2 production, while
activating H2O2 to generate ROS for enhanced pollutant removal
performance. This approach holds great research significance in
emerging fields.
Here, we successfully prepared a Co loaded-­ZnO (CZO) pie­
zocatalyst by combining a straightforward hydrothermal process
with a photo-­deposition approach. This catalyst exhibited excel­
lent capability for refractory pollutants removal and notable
non-­sacrificial H2O2 production (pure water). After 3 h of US
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treatment, the removal rate of phenol reached 99% and H2O2
production yield reached 1.3 mM. Experiments and characteri­
zation technique were both employed to explore the mechanism.
It was found that CZO piezocatalyst could be used as an excellent
heterogeneous catalyst for H2O2 generation and activation attrib­
uted to the dynamic defects in the process of US. Moreover, the
generation of dynamic defects contributed to the stability and
long-­term degradation performance of the catalyst. Thus, a
piezocatalysis-­self-­Fenton system has been successfully constructed
over CZO piezocatalyst. Compared to pristine ZnO, the CZO
piezocatalyst significantly enhanced the H2O2 production and the
purification efficiency for refractory pollutants. This study pro­
vides insights into the design of piezocatalysts and their applica­
tions in energy conversion and environmental remediation.
Results
Characterizations of the Fabricated Catalysts. A straightforward
one-­step hydrothermal method was used to prepare ZnO microrods
(ZO), followed by photo-­deposition to synthesize Co-­ZnO-­X
composites (CZO-­X, X = 0, 0.5, 2, 4). The scanning electron
microscopy (SEM) and transmission electron microscopy (TEM)
images of ZO and CZO-­X presented similar microrod structure
with an average length exceeding 2 μm, as shown in SI Appendix,
Figs. S1 and S2 and Fig. 1 A–I. The magnified TEM image of the
circle highlighted in Fig. 1A and the corresponding high-­resolution
TEM (HRTEM) image of ZO (Fig. 1 B and C) displayed ordered
lattice patterns with a spacing of 0.26 nm (002 lattice plane), as
determined by line profile measurements. It could be observed
from the TEM image in Fig. 1D that numerous black dots were
embedded in different domains of ZO. The corresponding energy
dispersive spectroscopy (EDS) elemental mapping and EDS
spectra of CZO-­2 exhibited a uniform distribution of Co, Zn, and
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O (Fig. 1 E and F). Additionally, many small black spots were also
observed on other microrods of CZO-­2 (Fig. 1G). The average
diameter of these black dots was measured to be only ~1.24 nm
(Fig. 1H), demonstrating that the well-­confined Co species mainly
existed in the form of ultrafine clusters. The actual powder state
of these catalysts was depicted in SI Appendix, Fig. S3, with the
color gradually changing from white to yellow. Furthermore, the
results obtained from inductively coupled plasma atomic emission
spectrometry (ICP-­AES) analysis, as shown in SI Appendix,
Table S1, revealed an increase in the loaded content of Co from
0.51 to 0.89% with increasing dosage of cobalt nitrate. This finding
provided additional confirmation of the successful loading of Co.
The crystalline phases of ZO and CZO-­X composite materials were
investigated using X-­ray diffraction (XRD) pattern. In Fig. 1J,
ZO exhibited three strong diffraction peaks at 31.8°, 34.5°, and
36.3°, which correspond to the (100), (002), and (101) crystal
planes of the wurtzite hexagonal ZnO (PDF#75-­0576), while
the XRD pattern of CZO-­X was nearly identical to that of ZO,
indicating that the deposition of Co clusters did not alter the
crystal structure of ZO. It is worth noting that no crystalline phase
of cobalt was detected, likely due to the small quantity and size
of the Co clusters (23). Additionally, the XRD pattern displayed
weak diffraction peaks at 33° and 60°, which were ascribed to
the (213) and (503) crystal planes of Zn(OH)2 (PDF#38-­0356).
This attribution stemmed from the fact that zinc salts inevitably
produced a small amount of Zn(OH)2 during the hydrothermal
synthesis of ZnO. Furthermore, it is noteworthy that varying
material proportions exhibited similar hydroxide profiles in the
XRD pattern. Consequently, the predominant composition of
the catalyst was oxide crystals, allowing for the disregarding of
the impact of this minimal quantity of hydroxides. Raman and
Fourier transform infrared (FT-­IR) spectroscopies were performed
to further characterize the structure of ZO and CZO-­2, as shown
in SI Appendix, Fig. S4. To investigate the chemical state, we
examined the X-­ray photoelectron spectra (XPS), where Fig. 1K
exhibited the Co 2p XPS spectrum of the CZO-­2 sample. The
peaks centered at 780.3 and 795.3 eV were assigned to Co2+ of
Co 2p3/2 and 2p1/2 (24), respectively, while faint peaks observed
at binding energies of 782.1 and 797.4 eV belonged to Co3+ of
Co 2p3/2 and 2p1/2 of Co-­O, respectively. These results collectively
demonstrated the successful introduction of Co and diversity of
Co valence.
Piezoelectricity and Electrochemical Analysis of the Catalysts.
Piezo-­response force microscopy (PFM) was employed to
characterize the piezoelectricity of ZO and CZO-­2 directly. The
application of an AC voltage spanning from −10 to 10 V elicited
a localized hysteresis loop (Fig. 2 A and B), where the applied
external electric field caused continuous deformation of its
surface, accompanied by a significant phase angle shift of 180°.
This unequivocally confirmed the inherent piezoelectricity of ZO
and CZO-­2 material (25). Furthermore, the maximum effective
piezoelectric coefficient (d33) value based on the amplitude loops
for ZO and CZO-­2 were 41.2 and 58.4 pm/V, respectively,
which clarified the piezoelectric response of ZO microrods was
enhanced by Co-­deposition (26). Detailed examinations of the
PFM morphology, 3D morphology, piezo-­response amplitude, and
phase images were presented in SI Appendix, Figs. S5 A–D and S6
A–D. It can be observed that there was a clear contrast in both the
amplitude and phase images of ZO and CZO-­2, demonstrating
the piezoelectric properties of the materials. Theoretically, the cyclic
alteration of the electric field direction in piezoelectric materials
resulting from mechanical vibrations led to a rapid recombination
of piezoelectric charges, exerting a detrimental impact on the
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Fig. 1. (A) TEM image and (B) the corresponding locally enlarged image of ZO; (C) HRTEM image of ZO and the d-­spacing value in the image was measured from
line profile on the Top Right; (D) TEM image, (E) EDS elemental mapping, and (F) EDS spectra of CZO-­2; (G) TEM image and (H) the corresponding locally enlarged
image of CZO-­2; (I) HRTEM image of CZO-­2 and the d-­spacing value in image was measured from line profile on the Top Right; (J) XRD spectra of ZO and CZO-­X;
(K) Co 2p XPS spectrum of CZO-­2.
efficiency of piezocatalysis. Consequently, it became imperative to
enhance both the extended lifetime of piezoelectric charges and the
prompt charge separation in order to optimize the performance of
piezoelectric-­driven redox reactions. We observed from SI Appendix,
Fig. S7 and Table S2 that moderate Co loading significantly
extended the charge carrier lifetime as determined through time-­
resolved photoluminescence (PL) attenuation measurements,
with detailed information provided in SI Appendix, Fig. S7.
Subsequently, the piezo-­generated electrons and holes separation
efficiency of the samples were investigated using electrochemical
impedance spectroscopy (EIS), as shown in Fig. 2C. The smaller arc
radius in the Nyquist plots of EIS for CZO-­X, compared to ZO,
reflected lower resistance, indicating enhanced charge separation
efficiency and improved charge mobility in the Co and ZO phase.
Consequently, this enhanced charge separation efficiency was found
to be highly beneficial for catalytic reactions, similar to the findings
from PL attenuation measurements. Additionally, the charge
densities (Nd) were calculated by Mott–Schottky measurements
from the following formula:
]−1
[1]
Nd = 2∕ e0 𝜀0 𝜀 d 1∕C2 ∕dV ,
( )[ ( )
where e0 represents the electron charge and ε0 and ε are the vacuum
permittivity and dielectric constant of ZnO, respectively (27, 28).
PNAS 2024 Vol. 121 No. 9 e2317435121
As depicted in Fig. 2D, the Mott–Schottky plots of ZO exhibited
a steeper slope compared to CZO-­2 at a frequency of 1 kHz,
indicating that the corresponding Nd of ZO (0.10 × 1022 cm−3)
was smaller than that of CZO-­2 (0.17 × 1022 cm−3). This finding
suggested a faster charge transformation process in CZO-­2, align­
ing with the above-­mentioned results. Furthermore, a compre­
hensive analysis of the plots enabled the determination of the
conduction band (CB) positions of the materials under investiga­
tion. The flat-­band potentials of ZO and CZO-­2 were derived as
approximately −0.93 V and −0.61 V, respectively (vs. saturated
calomel electrode, SCE). Taking into account that the flat-­band
potential typically exceeded the conduction band (CB) potential
by 0.1 to 0.3 V in n-­type semiconductors (29), the estimated ECB
values for ZO and CZO-­2 were −0.79 V and −0.47 V, respectively
(vs. normal hydrogen electrode, NHE).
Piezocatalytic Performance Measurement. Upon ultrasonic
(US) activation, CZO-­2 demonstrated exceptional performance
without additional oxidants, achieving an impressive phenol
oxidation rate of 98.7%, surpassing the capabilities of ZO, which
only achieved a degradation rate of 9.4% (Fig. 3A). Controlled
experiments further highlighted the significance of both US
vibration and the catalyst. Without US, CZO-­2 showed a mere
adsorption rate of 3.3% for phenol, while the degradation rate of
phenol without a catalyst under US treatment was 9.7%. These
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Fig. 2. (A) The butterfly amplitude loop and phase curve of ZO and (B) CZO-­2; (C) Electrochemical impedance spectra (EIS) of the samples; (D) Mott–Schottky
plots of the samples at a frequency of 1 kHz (the Inset shows the electron densities of the samples).
findings underscored the crucial role played by the catalyst and
US activation in facilitating the highly efficient degradation
of phenol. As shown in Fig. 3B, the kinetic constants (kobs) of
phenol oxidation by the CZO-­2 were maximized (0.024 min−1)
compared to other materials. Therefore, CZO-­2 was selected as
the optimal catalyst for subsequent trials. Subsequent research
assessed the influence of US power and catalyst dosage on phenol
removal and investigated the removal efficiency at different phenol
concentrations, with detailed information provided in SI Appendix,
Fig. S8. As widely recognized, solution pH was also a major factor
affecting the degradation of pollutants. Within the initial pH
range of 3 to 9, the degradation rate of phenol was approximately
98.0%, with little variation in the kobs value, initially increasing
and then decreasing (Fig. 3C). These results indicated that the
CZO-­2 piezoelectric system effectively degrades phenol over a
wide pH range. Besides, tap water, Yangtze River, Huangpu River,
and Pearl River had no significant effect on phenol degradation
(Fig. 3D). More importantly, the CZO-­2 material maintained a
remarkable 95.9% removal efficiency of phenol after four cycles
(Fig. 3E), highlighting its sustained high catalytic activity even
after repeated reactions. To demonstrate the versatility of the
CZO-­2/US system, we also selected refractory organic pollutants
other than phenol as target pollutants, including rhodamine B
(RhB), acid orange 7 (AO7), methylene blue (MB), nitrobenzene
(NB), aniline (AB), tetrachlorophenol (4-­CP), sulfadiazine (SD),
and quinoline. It was observed that CZO-­2 exhibited not only
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efficient degradation of phenol but also effective degradation of
RhB, AO7, MB, NB, AB, 4-­CP, SD, and quinoline (Fig. 3F and
SI Appendix, Table S3), highlighting its wide-­ranging applicability
in wastewater treatment.
Activation of O2 and In-­Situ H2O2 Generation by CZO-­2
Piezocatalyst. As shown in Fig. 4 A–D and SI Appendix, Fig. S9,
the radical quenching experiments involving different scavengers
and saturated atmosphere (Ar) were performed to explore the
activation capacity of O2 and the mechanism of H2O2 production
in the CZO-­2/US system. When IPA (as a scavenger of •OH,
k•OH, IPA = 1.9 × 109 M−1 s−1) (30) was added to the CZO-­2 system
(Fig. 4A), the degradation efficiency of phenol declined from
98.7% to 45.1%, which suggested that •OH played a crucial
role in the oxidation process. With the addition of AgNO3 (as
a scavenger of e−) and (NH4)2C2O4 (as a scavenger of h+), there
was a slight inhibition effect on the oxidation of phenol, whereas
significant inhibition of phenol degradation was observed in the
presence of p-­BQ (as a scavenger of •O2−, k •O2–, p-­BQ = 0.9 ×
109 M−1 s−1) (31, 32) or FFA (as a scavenger of 1O2, k1O2, FFA =
1.2 × 108 M−1 s−1) (33). Furthermore, phenol oxidation reaction
was further inhibited by increasing the concentrations of IPA
and FFA (SI Appendix, Fig. S9A). As shown in SI Appendix,
Fig. S9B, a substantial inhibition was observed under Ar-­
saturated conditions. These results verified the significance of O2
activation and the dominant role played by •OH, •O2− and 1O2
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Fig. 3. (A) Phenol removal efficiency in different systems, reaction conditions: [catalyst] = 0.6 g L–1, [phenol]0 = 10 mg/L, and 3 h of US vibration; (B) the
corresponding degradation rate constant of phenol (kobs); (C) effect of initial pH on phenol removal in the CZO-­2 system; (D) the degradation of phenol in real
waters; (E) cycling runs for degradation of phenol in the CZO-­2/US system; (F) degradation of different refractory pollutants by CZO-­2 within 3 h of US.

in phenol oxidation. To clarify the significant impact of 1O2 on
phenol degradation, we referred to our prior research showing
the synergistic effect of 1O2 and •OH in facilitating the ring-­
opening reaction of phenol (34). In our further investigation,
it was observed whether hydroxylation products were present
during the phenol degradation process in the presence of 1O2
scavenger. To avoid interference from the position of the peaks in
the high-­performance liquid chromatography (HPLC), FFA was
replaced with TEMP as 1O2 scavenger. As shown in SI Appendix,
Fig. S10 A and B, the addition of TEMP resulted in a decrease
in phenol degradation efficiency from 98.7 to 11.4%. Moreover,
the liquid chromatography spectrum revealed no significant
hydroxylation products. Conversely, in the CZO-­2/US system,
the accumulation of intermediate products occurred rapidly, and
as the US treatment progressed, phenol gradually underwent
ring opening (SI Appendix, Fig. S10C). This was confirmed by
the detection of small molecules such as fumaric acid through
HPLC (SI Appendix, Fig. S10D) and the high rate of total organic
carbon (TOC) removal, reaching 50.9% (SI Appendix, Fig. S11).
Furthermore, the HPLC–MS results revealed the presence of

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Fig. 4. (A) Radical quenching experiments of the oxidation of phenol and (B) concentration changes of in situ piezo-­generated H2O2 with the additions of
different scavengers and different atmospheres (Ar) in the CZO-­2/US system; (C) energy band diagram of ZO and CZO-­2; (D) concentration changes of •OH
with the additions of different scavengers and different atmospheres (Ar) in the CZO-­2/US system; (E) under air and Ar atmosphere, EPR signals for DMPO-­•OH
(water), DMPO -­•O2− (MeOH), TEMP-­1O2 over CZO-­2 powders under US irradiation; (F) in situ H2O2 production comparison of CZO-­2 with some typical reported
piezocatalysts and photocatalysts.

different intermediates and completely decomposed into CO2 and
H2O in the end (detailed in SI Appendix, Fig. S12). Therefore, the
presence of 1O2 in this system served to promote the hydroxylation
reaction of phenol, which was further attacked by •OH, leading to
ring-­opening. Meanwhile, there was a slight decrease in the peak
intensity of phenol, accompanied by the accumulation of a small
amount of intermediate products in the ZO/US system, which
was consistent with the relatively low TOC removal rate of only
3.7% (SI Appendix, Figs. S11 and S13).
Subsequently, the H2O2 concentration in the CZO-­2/US system
was also detected in pure water by the iodide method using ammo­
nium molybdate. As shown in SI Appendix, Fig. S14, the concen­
tration of H2O2 associated with CZO-­2 reached 1.3 mM under
US irradiation, nearly 6.5-­fold higher than that of ZO. To eliminate
the influence of cobalt ions, cobalt ions were introduced into the
ZO system. Interestingly, it was observed from SI Appendix, Fig. S15
that the concentration of H2O2 did not increase significantly, indi­
cating that the enhanced H2O2 concentration in the CZO-­2 system
was primarily attributed to the faster charge transfer rate and longer
charge lifetime resulting from Co-­deposition. Meanwhile, the con­
centration of H2O2 of the CZO-­2/US system in seawater was also
detected. As shown in SI Appendix, Fig. S16, the results revealed
that the H2O2 yield in seawater was slightly lower compared to that
in pure water, but still reached 0.98 mM. The cumulative •O2− and
•OH production were also quantitatively monitored. Initially, nitro­
tetrazolium blue chloride (NBT) was employed to measure the
concentration of •O2− generated by ZO and CZO-­2 under US
irradiation. As depicted in SI Appendix, Fig. S17, the NBT concen­
tration gradually decreased in both ZO and CZO-­2 samples, indi­
cating the activation of O2 to produce •O2−. By utilizing the
stoichiometric parameter that 1 mole of NBT consumption corre­
sponded to 4 moles of •O2−, the cumulative concentrations of •O2−
in ZO and CZO-­2 were determined to be 0.019 and 0.037 mM,
respectively. Additionally, the terephthalic acid photoluminescence
(TA-­PL) method was used to record the •OH concentration
(SI Appendix, Fig. S18). Similarly, the piezocatalytic production of

6 of 11 https://doi.org/10.1073/pnas.2317435121 pnas.org
 •OH over CZO-­2 was largely enhanced compared with ZO, from
0.016 to 0.034 mM.
According to the above analysis, the pathway of CZO-­2 gener­
ating H2O2 was also investigated. As shown in Fig. 4B, the in situ
generated H2O2 of CZO-­2 with different scavengers and Ar atmos­
phere was detected in pure water under US irradiation. The con­
centrations of H2O2 considerably increased from 1.3 mM (control)
to 1.7 mM (IPA), 1.7 mM (FFA), and 1.6 mM [(NH4)2C2O4].
However, the concentrations of H2O2 considerably decreased to
0.05 mM (AgNO3), 0.02 mM (p-­BQ), and 0.05 mM (Ar-­saturated
condition). These results indicated that H2O2 formation involved
a two-­electron process, and •O2− was an important intermediate
substance for producing H2O2 (O2→•O2−→H2O2). Additionally,
by utilizing UV-­Vis diffuse reflectance spectroscopy (DRS) esti­
mation in SI Appendix, Fig. S19, the optical bandgaps for ZO and
CZO-­2 were determined to be 3.09 eV and 2.93 eV, respectively,
and when combined with the analysis of Mott–Schottky measure­
ment, the corresponding energy band diagrams were illustrated in
Fig. 4C. The suitable CB and valence band (VB) position were
favorable for the oxygen reduction reaction (ORR), thereby initi­
ating the cascade redox reaction. Specifically, piezoelectric electrons
reacted with absorbed O2 to produce •O2−, and the intermediate
•O2− reacted with piezoelectric electrons to generate H2O2, which
could be further decomposed to •OH. The corresponding changes
in •OH radical were in accordance with the abovementioned results
(Fig. 4D). Furthermore, it was observed from SI Appendix, Fig. S20
that while the CZO-­2 catalyst could decompose H2O2 under stir­
ring conditions, it was unable to generate •OH. Moreover, in the
absence of a catalyst, neither US nor stirring could decompose
H2O2, indicating that both US and catalyst were indispensable for
the generation of •OH in this work.
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Additionally, to assess whether Co2+ was involved in the acti­
vation process of H2O2, we introduced Fe2+ into the CZO-­2/US
system, competing with Co2+ in decomposing H2O2. Due to the
faster rate of Fe2+ in decomposing H2O2 compared to Co2+, the
introduction of Fe2+ served as a means to explore whether Co2+
was involved in the activation process of H2O2 during the US
process. If the change in the contents of cobalt ion was more
obvious in the absence of Fe2+ compared to when Fe2+ was added,
it confirmed the participation of Co2+ in the activation process of
H2O2 in the CZO-­2/US system. Thus, from the Co 2p XPS data,
it was observed that, compared to the pure CZO-­2 catalyst, the
post-­reaction Co2+ content decreased from 50.2 to 39.2%, while
the Co3+ content increased from 49.8 to 60.8% (SI Appendix,
Fig. S21A and Table S4). However, when we added Fe2+ into the
CZO-­2/US system (SI Appendix, Fig. S21B and Table S4), it was
found that, in comparison with the pure CZO-­2 catalyst, the
alterations in the contents of Co2+(49.9%) and Co3+(50.1%) after
the reaction were not more obvious than that without adding Fe2+,
demonstrating the involvement of Co2+ in the activation of H2O2.
These results suggested that •OH derived from H2O2 activation
(primary) and H2O oxidation (secondary) through the following
route: O2 → •O2− → H2O2 → •OH and H2O → •OH.
In addition to chemical probes, the main active species that
contributed to the excellent performance of the phenol oxidation
was also confirmed by the EPR characterization, as shown in
Fig. 4E. Under air atmosphere, CZO-­2 piezocatalysis yielded EPR
quadruplet DMPO-­•OH peaks, sextuplet DMPO-­•O2− peaks,
and triplet TEMP-­1O2 peaks with US 10 min, whereas no clear
signal of ROS was observed without US irradiation. Under Ar
atmosphere, weak •OH signal was observed, consistent with the
previous findings, and the signal of •O2− and 1O2 were negligible.
Additionally, upon the addition of p-­BQ or phenol in the presence
of US irradiation, the peak intensity of 1O2 was weakened,
PNAS 2024 Vol. 121 No. 9 e2317435121
suggesting both the evolution of 1O2 from •O2− and its direct
interaction with phenol molecules. Based on these results, we
proposed a mechanism for ROS generation via ultrasound-­driven
piezocatalysis (Eqs. 2–6). Additionally, among various piezocata­
lysts and photocatalysts studied, the CZO-­2/US system exhibited
the highest production of H2O2, as illustrated in Fig. 4F and
SI Appendix, Table S5.
Vibration
� e− + h+ ,
CZO − 2 ���������������→ [2]
O2 + e− → ∙ O2 − , [3]
2 ∙ O2 − + 2H2 O → 2H2 O2 + 2OH− +1 O2 [4]
[5]
H2 O2 + Co2+ → Co3+ + ∙ OH + OH− ,
H2 O + h+ → ∙ OH + H+ . [6]
Investigation on the Mechanism of Enhanced H2O2 Concen­
tration. It was noteworthy that the concentration of H2O2
generated during the US exposure was re-­evaluated using the
CZO-­2 sample after four cycles. Interestingly, there was a
noticeable increase in the H2O2 concentration, as depicted in
Fig. 5A, with concentration rising from 1.3 mM to 1.8 mM. To
investigate this phenomenon, we initially examined the surface
vacancies of different catalysts using EPR characterization. As
shown in Fig. 5B, ZO and CZO-­2 exhibited minimal vacancies
signal prior to the US reaction. However, following the US
reaction, ZO displayed a weak oxygen defects signal peak at g =
2.004. In contrast, CZO-­2 exhibited a significantly enhanced
oxygen defects signal. Apart from the EPR technique, we employed
X-­ray photoelectron spectroscopy (XPS) to examine the alteration
in the surface defect ratio of the material before and after the
reaction. Fig. 5C and SI Appendix, Table S6 revealed the O 1 s
XPS spectrum, which exhibited a splitting into two or three peaks:
lattice oxygen was bonded to metal (Olatt, 529.5 to 530.6 eV),
oxygen deficiency (Odef, 531.0 to 531.8 eV), and the surface
adsorbed molecule H2O (Osurf, 532. 8 eV) (35). The relative ratio
of oxygen deficiency in ZO exhibited no significant change before
[Odef/(Odef + Olatt) = 4.4%] and after reaction [Odef/(Odef + Olatt)
= 3.9%], which was consistent with the previous results.
Conversely, the relative ratio of Odef of CZO-­2 remarkably
increased from 6.4 to 29.1% after reaction, and the surface oxygen
content dwindled from 62.4 to 51.0%, providing strong evidence
for the occurrence of dynamic oxygen vacancies during the CZO-­2
US stress. Thus, we speculated that the formation of dynamic
oxygen defects of CZO-­2 material during the US process might
have been either due to the deposition of cobalt, which enhanced
piezoelectric activity, activating lattice oxygen by more piezoelectric
electrons during migration, ultimately leading to the formation
of oxygen defects, or due to the catalyst generating additional heat
on the surface under US conditions, promoting oxygen overflow.
Therefore, we conducted an experiment in which we subjected
the CZO-­2 catalyst to a 3-­h heat treatment at a temperature
equivalent to that generated under ultrasound. The results from
Fig. 5D showed that no defect signal was observed in the CZO-­2
after the heat treatment. Following this, we introduced AgNO3
into the reaction process and observed a substantial decrease in
the defect signal by examining the EPR signal of the catalyst after
reaction. This finding served as strong evidence for the pivotal role
of piezoelectric electrons in the formation of dynamic defects.
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Fig. 5. (A) Time dependence for yield of CZO-­2 and fourth-­CZO-­2 under US irradiation; (B) EPR spectra of the samples; (C) O 1 s XPS spectrum of ZO and CZO-­2
fresh and after the reaction; (D) EPR spectra of the samples; (E) formation energy of oxygen vacancy over ZO-­OV, CZO-­OV, and CZO-­OV-­adding electrons; (F) the
charge density difference of the O2 molecule on CZO with different oxygen vacancy concentrations (the yellow electronic cloud represents the loss of electrons,
and the blue electronic cloud represents the gain of electrons; the isosurface is set to 0.0005 eV).

Furthermore, the formation energy of a single oxygen defect over
CZO was studied by DFT calculations, as shown in Fig. 5E.
Results indicated that oxygen vacancy on surface of CZO (EOV =
3.49 eV) was obviously lower than that of ZO (EOV = 3.94 eV),
suggesting that the oxygen vacancies more easily formed on the
surface of CZO due to cobalt deposition. Additionally, by
introducing additional electrons into the CZO-­OV model to
bolster the reducing atmosphere, a noteworthy reduction in defect
formation energy was observed, decreasing from 3.49 eV to 2.25
eV. This compelling finding unequivocally established the intricate
connection between defect formation and electron density. Thus,
these results indicated that the formation of dynamic defects was
not caused by the thermal effects during the US process but rather
by the activation of lattice oxygen through piezoelectric electrons.
Additionally, we could further observe from Fig. 5B that after
undergoing four cycles, the catalyst exhibited a stronger defect
signal. Simultaneously, the in situ generated H2O2 concentration
also increased further, indicating a positive correlation between
the amount of H2O2 and the defect concentration. To investigate
how the catalyst maintained excellent piezoelectric activity under
conditions of continuous defect generation, the post-­reaction
catalyst was stored in ambient air for a period of time. It was found
from Fig. 5D that the defect signal of first-­CZO-­2-­used-­storage
noticeably weakened. This indicated that the CZO-­2 catalyst
possessed self-­repair capabilities, allowing it to maintain out­
standing stability during multiple cyclic tests. Additionally, since
the production of H2O2 was derived from the ability of the catalyst
to adsorb and activate dissolved oxygen, we initiated the process
by increasing aeration, thereby maximizing the concentration of
dissolved oxygen. The results revealed that, after 1 h of aeration,
the H2O2 concentration increased from 1.3 mM to 1.6 mM
(SI Appendix, Fig. S22). Subsequently, to gain a deeper under­
standing of the interaction between O2 molecules and piezocatalysts
with different concentrations of oxygen defects at a molecular
level, DFT simulation has been employed (36, 37). Based on
experimental characterization, we theoretically modeled the
optimal geometric structure of CZO (002) and confirmed the
optimal adsorption site of the O2 molecules (SI Appendix,
Fig. S23). As shown in Fig. 5F, CZO samples with varying oxygen
vacancies (from OV0 to OV3) exhibited strong O2 molecule

8 of 11 https://doi.org/10.1073/pnas.2317435121 pnas.org
 adsorption with a negative adsorption energy ranging from
approximately −3.05 eV to −3.24 eV, accompanied by a charge
transfer ranging from 0.645 e− to 0.657 e−, indicating that the
more defect sites exposed on the catalyst surface, more electron
transfer occurs from ZO-­OV to Co clusters, leading to electron-­
enriched Co clusters and thereby promoting the adsorption and
activation of the O2 molecule. Meanwhile, SI Appendix, Figs. S21
and S24 revealed the electron cloud density of Co increased, while
that of Zn decreased in CZO-­2 after the reaction (detailed
information was shown in SI Appendix, Fig. S24 and Tables S4
and S7), indicating that the large number of defects as electron
traps produced by CZO-­2 in the piezoelectric reaction process,
effectively impeding the recombination of both piezoelectric holes
and electrons and promoting the charge transfer of ZO to Co
clusters by the Zn-­O-­Co electron transfer chain, thus obtaining
electron rich structure. Thus, we speculated that Co clusters acted
as active sites for electron enrichment, facilitating the activation
of O2 to produce H2O2 and then be further activated to •OH.
Besides, we introduced iron into ZnO (Fe-­ZnO) using the same
photo-­deposition method, and its XRD spectrum closely
resembled that of CZO-­2 (SI Appendix, Fig. S25A), displaying
prominent characteristic peaks of ZnO. Moreover, Fe-­ZnO
exhibited excellent piezoelectric catalytic performance, with a
phenol degradation rate of 87% and a H2O2 production rate of
1.46 mM after US treatment for 3 h (SI Appendix, Fig. S25B). To
exclude the potential interference of Fe3+ produced during the US
process to the detection of H2O2 by iodometry, we mixed the
reaction solution obtained after 3 h of ultrasound with an equal
amount of potassium thiocyanate (10 mg mL−1). The UV-­visible
spectrum analysis of Fe3+ content in the solution, as shown in
SI Appendix, Fig. S25C, revealed the absence of Fe3+. Simult­
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aneously, the leaching of 0.068 mg L−1 Fe from the Fe-­ZnO
solution after 3 h of US was analyzed using ICP-­AES. Assuming
this was equivalent to the concentration of Fe3+, it was observed
that the reaction of Fe3+ with potassium iodide at this concentration
did not exhibit a peak at 351 nm (SI Appendix, Fig. S25D).
Consequently, in the Fe-­ZnO/US system, the iodometric detection
of H2O2 concentration was deemed reasonable. As a result, similar
results could be achieved by substituting cobalt with alternative
metals through the application of the same photo-­deposition
method, thereby overcoming the inherent constraints associated
with this approach.
In order to study the effect of background material and poten­
tial application of CZO-­2 material, the impact of typical anions
(Cl−, NO3−, HCO3−, and SO42−) and dissolved organic matter
(DOM) on phenol degradation was investigated separately. As
depicted in Fig. 6A, in the presence of Cl−, NO3−, HCO3−, SO42−,
and DOM, the oxidation efficiencies of phenol were 88.6%,
97.5%, 97.0%, 91.5%, and 91.4%, respectively (in 180 min).
Although the degradation efficiency was not significantly affected,
the degradation rate exhibited sensitivity, particularly in the pres­
ence of Cl− ions. This was because Cl− could induce a competing
reaction with phenol oxidation by utilizing •OH. Material stabil­
ity was also an important indicator for evaluating potential appli­
cations of catalysts, we performed comprehensive investigations,
including characterizing the catalyst after reaction, assessing the
degradation efficiency of catalysts stored for varying time dura­
tions, evaluating their capacity for in situ H2O2 generation, and
examining their long-­term pollutant degradation capabilities.
First, the SEM images (SI Appendix, Fig. S26 A and B), XRD
pattern (SI Appendix, Fig. S26C), and FT-­IR spectra (SI Appendix,
Fig. S26D) of CZO-­2 after reaction were nearly identical to those
of the initial sample, indicating that CZO-­2 demonstrated robust
structural stability following the reaction, attributable to its
PNAS 2024 Vol. 121 No. 9 e2317435121
remarkable self-­healing capabilities. Next, the phenol degradation
performance and H2O2 generation ability of the catalyst were
tested after it had been placed for 2 mo and 5 mo. As depicted in
Fig. 6B, it was observed that even after 3 h of US irradiation,
phenol degradation was nearly complete. Moreover, the concen­
tration of H2O2 remained at 1.2 mM and 1.0 mM in pure water,
respectively, indicating that the capability of the catalyst to degrade
phenol and produce H2O2 did not significantly decline over the
extended period. Additionally, based on the ion dissolution results
obtained from ICP-­AES analysis (Fig. 6C), it could be observed
that, with prolonged US time in the CZO-­2/US system, the con­
centrations of cobalt ions and zinc ions increased from 0.58 mg/L
to 0.75 mg/L and from 4.2 mg/L to 7.4 mg/L, respectively.
Subsequently, after the reaction solution underwent treatment
with a cation exchange resin, the concentrations of cobalt ions
and zinc ions significantly decreased to 0.085 mg/L and 0.06
mg/L, respectively, which was far lower than the emission standard
and effectively prevented secondary pollution. Simultaneously,
the pH of the reaction solution after 3 h of ultrasound was adjusted
to 10 with NaOH. Following a subsequent aging period, the dis­
solution concentrations of cobalt and zinc ions decreased signifi­
cantly, from 0.75 mg/L to less than 0.01 mg/L and 7.4 mg/L to
0.019 mg/L, respectively. The dissolved metal ions formed hydrox­
ide precipitates, allowing for their effective reuse. Consequently,
it was observed that H2O2 yield increased with prolonged US
exposure in pure water within the CZO-­2/US system (Fig. 6D).
However, after further extension of the time, the H2O2 production
rate eventually fell below the H2O2 decomposition rate, resulting
in a gradual decrease of H2O2 yield. Nevertheless, adjusting the
pH of the above solution to 10 and allowing for an aging period
led to an increase in H2O2 yield again, which demonstrated that
the deactivated catalyst due to metal ion dissolution could be
rejuvenated by pH adjustment, ensuring the long-­term stability
for in situ H2O2 production of the CZO-­2/US system.
Furthermore, long-­term continuous degradation of phenol was
examined under US exposure (Fig. 6E). The performance was
evaluated after 60 h of US treatment with eight rounds of phenol
supplementation. Although the degradation rate gradually slowed
down, CZO-­2 maintained a high phenol degradation efficiency
of 92%, showcasing its remarkable stability.
Conclusions
Piezocatalysis proved to be an exceptionally attractive and effective
technology in the field of wastewater treatment. However, the
major obstacles encountered in the development of piezocatalytic
reaction primarily revolved around the dual aspects of H2O2 gen­
eration and activation without introducing additional oxidants,
which were indispensable for producing sustainable ROS capable
of achieving thorough purification of wastewater. In this study,
the CZO piezocatalysts prepared by the hydrothermal method
combined with the photo-­deposition method demonstrate excep­
tional efficacy in wastewater treatment and in situ generated
H2O2, attributed to fast charge separation efficiency and extended
charge lifetime brought by Co-­deposition and the existence of
dynamic defects, as confirmed by EPR and XPS analysis. More
importantly, the catalysts placed for longer periods (over 2 mo)
continue to perform superior H2O2 production (~1.2 mM) and
contaminant removal capabilities. This observation not only
underscores the substantial potential of CZO piezocatalysts in
practical wastewater treatment applications but also serves as a
reference for future studies on improving H2O2 production by
facilitating the generation of dynamic vacancies through metal
deposition.
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Fig. 6. (A) Removal efficiencies and the corresponding kobs value of phenol oxidation (US for 3 h) in the presence of different water quality constituents [(anion) =
10 mg L−1, (DOM) = 10 mg L−1]; (B) under US irradiation, time dependence for phenol removal efficiency and H2O2 yield of CZO-­2 after 2 and 5 mo of placement; (C)
variation of ion concentration in the CZO-­2/US (0.6 g L–1) system (treatment-­1: cation-­exchange resin was used for adsorption of dissolved metal ions; treatment-­2:
adjusting pH = 10 with NaOH); (D) time dependence for H2O2 yield of CZO-­2. (E) Time dependence for phenol removal efficiency of CZO-­2.

Materials and Methods
Preparation of Catalysts. The ZnO microrods were synthesized using a hydro-
thermal method. Specifically, a mixture of 10 mmol Zn(NO3)2·6H2O, 10 mmol
urotropin, and 48 mL of ultrapure water was stirred until homogenous. The result-
ing solution was transferred to a 100-­mL hydrothermal reactor and maintained
at 95 °C for 24 h. After completion, the solution was filtered, washed, and dried
at 60 °C to obtain purified ZnO microrods (referred to as ZO).
To prepare Co-­ZnO-­X composites (where X represents the concentra-
tion of Co(NO3)2·6H2O, X = 0, 0.5, 2, 4 mM), a light deposition method
was employed. A mixture containing 0.2 g ZO, varying amounts of
Co(NO3)2·6H2O, and 100 mL of ultrapure water was stirred under xenon
lamp irradiation for 20 h. Subsequently, the solution was filtered, washed,
and dried at 60 °C in a vacuum oven, resulting in the formation of Co-­ZnO-­0
(CZO-­0), Co-­ZnO-­0.5 (CZO-­0.5), Co-­ZnO-­2 (CZO-­2), and Co-­ZnO-­4 (CZO-­4)
composites.

10 of 11 https://doi.org/10.1073/pnas.2317435121 pnas.org
 Iodometric Method for Detecting H2O2. The concentration of H2O2 produced
was detected by the iodometric method according to the literature following
the steps below: Ammonium molybdate tetrahydrate (H24Mo7N6O24·4H2O) was
dissolved in 5 mL of deionized water to prepare a 0.01 M solution, while potas-
sium iodide (KI) was dissolved in 10 mL of deionized water to prepare a 0.1
M KI solution. During different intervals of ultrasonic irradiation, 0.5 mL of the
reaction solution was collected and mixed with 2 mL of the KI solution, along
with 50 μL of ammonium molybdate tetrahydrate solution. The resulting mixture
was vigorously shaken, allowed to stand for 10 min, and subsequently analyzed
using a UV-­Vis spectrophotometer at a maximum absorption wavelength of 351
nm. The concentration of H2O2 was determined using a standard curve method.
Degradation of Organic Pollutants. The degradation efficiency of different pollut-
ants [including phenol, nitrobenzene (NB), aniline (AB), sulfadiazine (SD), p-­chloro-
phenol (4-­CP), quinoline, rhodamine B (RhB), methylene blue (MB), and acid orange
7 (AO7)] was assessed by determining their concentrations using HPLC and UV-­Vis
spectrophotometer. At specified time intervals, a 1 mL aliquot of the sample was taken
and passed through a 0.22-­μm membrane to remove solid catalyst. The injection vol-
ume for HPLC analysis was 20 μL. The flow rate was set at 1 mL min−1, and the column
temperature was maintained at 30 °C. The specific HPLC methods used for analyzing
different pollutants could be found in SI Appendix, Table S3. Additionally, the solution
samples were analyzed for total organic carbon (TOC) content using a TOC analyzer.
Statistical Analysis. All data were gained directly from the source experiment
and processed using Origin. All experiments were carried out in duplicate.
1. S. Li et al., Incorporating oxygen atoms in a SnS2 atomic layer to simultaneously stabilize atomic
hydrogen and accelerate the generation of hydroxyl radicals for water decontamination. Environ. Sci.
Technol. 56, 4980–4987 (2022).
2. Y. Zhang et al., Highly efficient removal of U (VI) by the photoreduction of SnO2/CdCO3/CdS
nanocomposite under visible light irradiation. Appl. Catal. B 279, 119390 (2020).
3. S. Zhou et al., Self-­regulating solar steam generators enable volatile organic compound removal
Downloaded from https://www.pnas.org by 171.252.154.204 on March 29, 2024 from IP address 171.252.154.204.
through in situ H2O2 generation. Environ. Sci. Technol. 56, 10474–10482 (2022).
4. Y. Chen et al., Selective recovery of precious metals through photocatalysis. Nat. Sustain. 4, 618–626
(2021).
5. J. Ji et al., Defects on CoS2−x: Tuning redox reactions for sustainable degradation of organic
pollutants. Angew. Chem. Int. Ed. 133, 2939–2944 (2021).
6. Q. Chen, Development of an anthraquinone process for the production of hydrogen peroxide
in a trickle bed reactor-­From bench scale to industrial scale. Chem. Eng. Process. 47, 787–792
(2008).
7. Y. Zhang et al., H2O2 generation from O2 and H2O on a near-­infrared absorbing porphyrin
supramolecular photocatalyst. Nat. Energy 8, 361–371 (2023).
8. W. Liu et al., Efficient hydrogen production from wastewater remediation by piezoelectricity
coupling advanced oxidation processes. Proc. Natl. Acad. Sci. U.S.A. 120, e2218813120 (2023).
9. M. Ran et al., Selective production of CO from organic pollutants by coupling piezocatalysis and
advanced oxidation processes. Angew. Chem. Int. Ed. 135, e202303728 (2023).
10. H. Huang et al., Macroscopic polarization enhancement promoting photo-­and piezoelectric-­
induced charge separation and molecular oxygen activation. Angew. Chem. Int. Ed. 56,
11860–11864 (2017).
11. P. Zhu et al., Piezocatalytic tumor therapy by ultrasound-­triggered and BaTiO3-­mediated
piezoelectricity. Adv. Mater. 32, 2001976 (2020).
12. C. Hu et al., Exceptional cocatalyst-­free photo-­enhanced piezocatalytic hydrogen evolution of
carbon nitride nanosheets from strong in-­plane polarization. Adv. Mater. 33, 2101751 (2021).
13. F. Wang et al., Unveiling the effect of crystal facets on piezo-­photocatalytic activity of BiVO4.
Nano Energy 101, 107573 (2022).
14. Q. T. Hoang et al., Piezoelectric Au-­decorated ZnO nanorods: Ultrasound-­triggered generation of
ROS for piezocatalytic cancer therapy. Chem. Eng. J. 435, 135039 (2022).
15. L. Yang et al., Oxygen-­vacancy-­rich piezoelectric BiO2−x nanosheets for augmented piezocatalytic,
sonothermal and enzymatic therapies. Adv. Mater. 35, 2300648 (2023).
16. Q. Zhao et al., The collaborative mechanism of surface S-­vacancies and piezoelectric polarization for
boosting CdS photoelectrochemical performance. Chem. Eng. J. 433, 133226 (2022).
17. Y. Wei et al., In-­situ utilization of piezo-­generated hydrogen peroxide for efficient p-­chlorophenol
degradation by Fe loading bismuth vanadate. Appl. Surf. Sci. 543, 148791 (2021).
18. J. Ma et al., High efficiency bi-­harvesting light/vibration energy using piezoelectric zinc oxide
nanorods for dye decomposition. Nano Energy 62, 376–383 (2019).
19. S. Cheng et al., The highly effective therapy of ovarian cancer by Bismuth-­doped oxygen-­deficient
BaTiO3 with enhanced sono-­piezocatalytic effects. Chem. Eng. J. 442, 136380 (2022).
PNAS 2024 Vol. 121 No. 9 e2317435121
Full details for DFT computations, control experiments, and materials character-
izations were introduced in SI Appendix.
Data, Materials, and Software Availability. All study data are included in the
article and/or SI Appendix.
ACKNOWLEDGMENTS. This work was supported by the National Natural Science
Foundation of China (No. 22325602, 22276071, 52000101, 22176060, and
22076064) and sponsored by Program of Shanghai Academic/Technology Research
Leader (23XD1421000). Project supported by Shanghai Municipal Science and
Technology Major Project (Grant No. 2018SHZDZX03), the Program of Introducing
Talents of Discipline to Universities (B16017), and the Science and Technology
Commission of Shanghai Municipality (20DZ2250400). Authors thank Research
Center of Analysis and Test of East China University of Science and Technology for
the help on the characterization.
Author affiliations: aKey Laboratory for Advanced Materials and Joint International
Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel
Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and
Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University
of Science and Technology, Shanghai 200237, People’s Republic of China; bGuangdong
Key Laboratory of Environmental Pollution and Health, School of Environment, Jinan
University, Guangzhou 511443, People’s Republic of China; cKey Laboratory for Advanced
Materials and Institute of Fine Chemicals, School of Resources and Environmental
Engineering, East China University of Science and Technology, Shanghai 200237, People’s
Republic of China; and dState Key Laboratory of Chemical Engineering, East China
University of Science and Technology, Shanghai 200237, People’s Republic of China
20. B. Li et al., Ultrasound-­remote selected activation mitophagy for precise treatment of rheumatoid
arthritis by two-­dimensional piezoelectric nanosheets. ACS Nano 17, 621–635 (2022).
21. Y. Li et al., Robust route to H2O2 and H2 via intermediate water splitting enabled by capitalizing on
minimum vanadium-­doped piezocatalysts. Nano Res. 15, 7986–7993 (2022).
22. C. Hu et al., Orthogonal charge transfer by precise positioning of silver single atoms and clusters
on carbon nitride for efficient piezocatalytic pure water splitting. Angew. Chem. Int. Ed. 61,
e202212397 (2022).
23. J. Chen et al., Nickel clusters accelerating hierarchical zinc indium sulfide nanoflowers for
unprecedented visible-­light hydrogen production. J. Colloid Interface Sci. 608, 504–512 (2022).
24. Q. Yan et al., Constructing an acidic microenvironment by MoS2 in heterogeneous Fenton reaction
for pollutant control. Angew. Chem. Int. Ed. 60, 17155–17163 (2021).
25. H. You et al., Harvesting the vibration energy of BiFeO3 nanosheets for hydrogen evolution. Angew.
Chem. Int. Ed. 131, 11905–11910 (2019).
26. C. Zhang et al., Piezo-­photocatalysis over metal-­organic frameworks: Promoting photocatalytic
activity by piezoelectric effect. Adv. Mater. 33, 2106308 (2021).
27. S.-­H. Chiou et al., Plasmonic gold nanoplates-­decorated ZnO branched nanorods@ TiO2 nanorods
heterostructure photoanode for efficient photoelectrochemical water splitting. J. Photochem.
Photobiol. A 443, 114816 (2023).
28. C. Tiwari et al., Precursor mediated and defect engineered ZnO nanostructures using thermal
chemical vapor deposition for green light emission. Thin Solid Films 762, 139539 (2022).
29. J. Zheng et al., Incorporation of CoO nanoparticles in 3D marigold flower-­like hierarchical
architecture MnCo2O4 for highly boosting solar light photo-­oxidation and reduction ability.
Appl. Catal. B 237, 1–8 (2018).
30. E. J. Rosenfeldt et al., Degradation of endocrine disrupting chemicals bisphenol A, ethinyl estradiol,
and estradiol during UV photolysis and advanced oxidation processes. Environ. Sci. Technol. 38,
5476–5483 (2004).
31. Y. Bu et al., Peroxydisulfate activation and singlet oxygen generation by oxygen vacancy for
degradation of contaminants. Environ. Sci. Technol. 55, 2110–2120 (2021).
32. X. Chen et al., Photocatalytic free radical-­controlled synthesis of high-­performance single-­atom
catalysts. Angew. Chem. Int. Ed. 62, e202312734 (2023).
33. C. Qi et al., Activation of peroxymonosulfate by base: Implications for the degradation of organic
pollutants. Chemosphere 151, 280–288 (2016).
34. H. Yu et al., Singlet oxygen synergistic surface-­adsorbed hydroxyl radicals for phenol degradation in
CoP catalytic photo-­Fenton. Chinese J. Catal. 43, 2678–2689 (2022).
35. W. Wang et al., The confined interlayer growth of ultrathin two-­dimensional Fe3O4 nanosheets with
enriched oxygen vacancies for peroxymonosulfate activation. ACS Catal. 11, 11256–11265 (2021).
36. S. Wang et al., Targeted NO oxidation and synchronous NO2 inhibition via oriented 1O2 formation
based on lewis acid site adjustment. Environ. Sci. Technol. 57, 12890–12900 (2023).
37. J. Cao et al., Tailoring the asymmetric structure of NH2-­UiO-­66 metal-­organic frameworks for
light-­promoted selective and efficient gold extraction and separation. Angew. Chem. Int. Ed. 62,
e202302202 (2023).
https://doi.org/10.1073/pnas.2317435121 11 of 11