RESEARCH ARTICLE

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Enhancing Photosynthesis Efficiency of Hydrogen Peroxide

by Modulating Side Chains to Facilitate Water Oxidation at
Low-Energy Barrier Sites
Huijie Yan, Yuan Peng, Yuyan Huang, Minhui Shen, Xiaoqian Wei, Weixin Zou,
Qing Tong, Ningbo Zhou, Jianqiao Xu, Yuxia Zhang,* Yu-Xin Ye,* and Gangfeng Ouyang*

1. Introduction
Hydrogen peroxide (H2 O2 ) is a crucial oxidant in advanced oxidation
processes. In situ, photosynthesis of it in natural water holds the promise of Hydrogen peroxide (H2 O2 ) can be activated
to form highly oxidative species, making it
practical application for water remediation. However, current photosynthesis
a prominent oxidant frequently employed
of H2 O2 systems primarily relies on oxygen reduction, leading to limited in water treatment for the removal of en-
performance in natural water with low dissolved oxygen or anaerobic vironmental pollutants. However, the per-
conditions found in polluted water. Herein, a novel photocatalyst based on sistent requirement of substantial amounts
conjugated polymers with alternating electron donor–acceptor structures and of H2 O2 , results in exorbitant costs, render-
electron-withdrawing side chains on electron donors is introduced. ing it impractical for in situ remediation of
surface water. Recently, the photocatalytic
Specifically, carbazole functions as the electron donor, triazine serves as the
synthesis method of H2 O2 has emerged as
electron acceptor, and cyano acts as the electron-withdrawing side chain. a rapidly developing alternative.[1–3] With
Notably, the photocatalyst exhibits a remarkable solar-to-chemical conversion sustainable solar energy, H2 O2 can be
of 0.64%, the highest reported in natural water. Furthermore, even in synthesized in situ by simply utilizing
anaerobic conditions, it achieves an impressive H2 O2 photosynthetic O2 and water.[4–7] This technique offers a
highly efficient sustainable and low-cost
efficiency of 1365 μmol g−1 h−1 , surpassing all the reported photosynthetic
in situ method of producing H2 O2 , thus
systems of H2 O2 . This remarkable improvement is attributed to the effective expanding the potential applications of
relocation of the water oxidation active site from a high-energy carbazole to a H2 O2 in in situ surface water remediation.
low-energy acetylene site mediated by the side chains, resulting in enhanced However, current photosynthetic sys-
O2 or H2 O2 generation from water. This breakthrough offers a new avenue for tems of H2 O2 predominantly utilize the
efficient water remediation using advanced oxidation technologies in oxygen reduction half-reaction, failing
to fully exploit the water oxidation half-
oxygen-limited environments, holding significant implications for
reaction.[8–12] This severely hinders the
environmental restoration. application of this techology in natural

H. Yan, Y.-X. Ye, G. Ouyang Y. Huang, M. Shen, J. Xu, G. Ouyang

School of Chemical Engineering and Technology Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of
IGCME Education
Sun Yat-sen University and Southern Marine Science and Engineering LIFM
Guangdong Laboratory School of Chemistry
Zhuhai 519082, China IGCME
E-mail: yeyuxin5@sysu.edu.cn; cesoygf@mail.sysu.edu.cn Sun Yat-Sen University
Y. Peng, N. Zhou, Y. Zhang Guangzhou 510275, China
Key Laboratory of Hunan Province for Advanced Carbon-based Functional X. Wei, W. Zou
Materials State Key Laboratory of Pollution Control and Resource Reuse
School of Chemistry and Chemical Engineering School of the Environment
Hunan Institute of Science and Technology Jiangsu Key Laboratory of Vehicle Emissions Control
Yueyang 414006, China Nanjing University
E-mail: zyxia2010@126.com Nanjing 210023, China
Q. Tong
Center of Modern Analysis
Jiangsu Key Laboratory of Vehicle Emissions Control
The ORCID identification number(s) for the author(s) of this article
Nanjing University
can be found under https://doi.org/10.1002/adma.202311535
Nanjing 210023, China
DOI: 10.1002/adma.202311535

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Scheme 1. The mechanism underlying the differential performance in H2 O2 photosynthesis by TPT-Cz-phCN and TPT-Cz-phOMe.
water, where the dissolved oxygen concentration is typically be-
low 10 mg L−1 and even lower in polluted water. To address this
issue, enhancing the efficiency of water oxidation reaction (WOR)
to generate O2 or directly generate H2 O2 becomes a practical so-
lution. Nevertheless, existing organic photocatalysts exhibit lim-
ited water oxidation capability and yield negligible amounts of
H2 O2 in anaerobic conditions.[13–17] This is because the WOR
involves a two or four-electron process with sluggish kinetics,
including the dissociation of O─H bonds and the formation of
O─O bonds.[18,19] Therefore, to improve the photosynthetic effi-
ciency of H2 O2 , addressing the kinetics limitations of WOR is
crucial.
The kinetic obstacle in WOR is the surface reaction between
the photo-induced holes and H2 O, which takes milliseconds to
occur, much longer than the picoseconds for hole generation
and transfer to the surface.[20] To accelerate the reaction between
holes and H2 O, the key lies in identifying an active site with a
lower energy barrier of WOR and ensuring the holes are local-
ized at these specific sites.[21] Nevertheless, pure organic poly-
mers have a wide distribution of holes on different atoms, which
have varying energy barriers for the water oxidation process.[5]
Up to the present, there remains a dearth of efficacious strate-
gies for effectively regulating the sites for hole distribution.
Herein, we successfully achieved the localization of holes
at low-energy barrier sites. We constructed alternately linked
electron donor–acceptor conjugated polymers with electron-rich
carbazole moieties serving as donors and high-electron-affinity
triazine moieties acting as acceptors (Scheme 1). The acety-
lene moieties functioned as electron bridges, while the electron-
withdrawing cyano moieties modified the electron donors. The
efficiency of photocatalytic H2 O2 synthesis was increased twofold
to 2534 μmol−1 g−1 h−1 (100 mW cm−2 , air, pure water), with
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a remarkable solar-to-chemical conversion efficiency of 0.64%
in natural water. Notably, this efficiency was maintained at one-
half even under anaerobic conditions without sacrificial agents.
This was achieved by effectively shifting the primary hole local-
ization from the high-energy-barrier carbazole to the low-energy-
barrier acetylene through the electron-withdrawing effect of the
side chains. The modifications in the active sites responsible for
WOR were clarified at the molecular levels employing TD-DFT
calculations and in situ infrared characterization. This active site
modulation strategy for enhancing the photosynthesis of H2 O2
holds enormous potential in facilitating the actual utilization of
photocatalysis for in situ remediation of surface water.
2. Results and Discussion
2.1. Chemical and Physical Characterization of CBCPs
Three types of carbazole-based conjugated polymers (CBCPs)
were synthesized using the classic Sonogashira-Hagihara Cross-
Coupling reaction.[22] These polymers were designed to incor-
porate carbazole units (Cz) with side chains containing either
electron-donating (OMe) or electron-withdrawing (CN) groups as
donors. Additionally, triazine moieties (referred to as TPT) were
included as electron acceptors, with acetylene moieties serving as
connectors (Figure 1a). The identification of the electron donor
and acceptor is contingent upon the spatial distribution of their
highest occupied molecular orbital (HOMO) and lowest unoc-
cupied molecular orbital (LUMO) within their optimized struc-
tures. As illustrated in Figure S1 (Supporting Information), the
HOMO was chiefly situated in Cz, whereas the LUMO exhibited
primary localization in the TPT moieties. This discernment led
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Figure 1. Structure and photocatalytic performance of CBCPs. a) Molecular structures of CBCPs. b) Schematic illustration of the electronic structure
of CBCPs. c) Photocatalytic production of H2 O2 by CBCPs in open air and pure water. d) UV–vis diffuse reflectance spectra of CBCPs and the AQY of
TPT-Cz-phCN at 420, 470, and 620 nm. e) Activity comparison between TPT-Cz-phCN and other reported photocatalysts for H2 O2 production in the
absence of oxygen.

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to the classification of Cz as the electron donor and designated
the LUMO as the electron acceptor.
The Fourier-transform infrared (FTIR) spectra of all CBCPs
displayed three intense peaks at 1504, 1403, and 1352 cm−1 ,
which were attributed to the stretching and breathing modes of
aromatic C─N, indicating the presence of triazine structures.[23]
This finding was corroborated by the assignment of peaks at
170.73, 170.43, and 170.61 ppm to the sp2 carbons in the triazine
structures of TPT-Cz-ph, TPT-Cz-phCN, and TPT-Cz-phOMe,
respectively.[24,25] In addition, the existence of triazine structures
in all CBCPs was confirmed by X-ray photoelectron spectroscopy
(XPS) spectra, which showed a peak at ≈286.8 eV deconvoluted
from the C 1s peak and a prominent peak at 398.8 eV in the N
1s deconvolution.[24] The presence of alkynyl groups in all CBCPs
was demonstrated by the appearance of a peak at 2190 cm−1 in the
FTIR spectra, a peak at 2203 cm−1 in the Raman spectra, and char-
acteristic peaks at ≈91 ppm in the nuclear magnetic resonance
(NMR) spectra.[26] Furthermore, XPS spectra confirmed the suc-
cessful incorporation of acetylene into the CBCPs, with a peak
at ≈285.4 eV deconvoluted from the C 1s peak.[27] TPT-Cz-phCN
and TPT-Cz-phOMe showed new peaks at 2226 and 1250 cm−1 in
FTIR spectra, respectively, which were attributed to the cyano and
methoxy groups originating from their respective precursor com-
pounds. These groups were further supported by the characteris-
tic peak at 54.39 ppm in the NMR spectra for the methoxy group
in TPT-Cz-phOMe and the peak at 399.4 eV in the N 1s deconvo-
lution for the N atoms in cyano groups in TPT-Cz-phCN.[5] Taken
together, these chemical characterizations provided robust evi-
dence for the successful synthesis of the corresponding CBCPs
(Figures S2–S5, Supporting Information).
The Power X-ray diffraction patterns revealed that all CBCPs
were amorphous, displaying a broad diffraction peak at 2𝜃 = 21°
(Figure S6, Supporting Information).[28] This indicated the for-
mation of graphitic 2D layers with similar characteristics. The
irregularly stacked blocks in the CBCPs were confirmed by the
scanning electron microscopy images (Figure S7, Supporting In-
formation) and transmission electron microscopy images (Figure
S8, Supporting Information), which were consistent with the
XRD results. The Brunauer–Emmett–Teller (BET) surface areas
of TPT-Cz-ph, TPT-Cz-phCN, and TPT-Cz-phOMe were deter-
mined to be 37.3, 51.2, and 35.2 m2 g−1 , respectively. The cor-
responding average pore sizes of TPT-Cz-ph, TPT-Cz-phCN, and
TPT-Cz-phOMe were found to be 0.91, 1.26, and 0.92 nm, re-
spectively (Figure S9, Supporting Information). The introduction
of cyano groups in TPT-Cz-phCN increased its BET surface area
and pore size, offering more active sites for photocatalysis com-
pared to TPT-Cz-ph. Moreover, the thermogravimetric analysis
demonstrated that all CBCPs had excellent thermal stability, re-
taining 95% of their weight at 400 °C (Figure S10, Supporting
Information).
The appropriate range of electronic structure is of vital impor-
tance to the overall photosynthesis of H2 O2 .[13,29] The electronic
structures of the CBCPs were determined by Mott–Schottky tests
and XPS valence band (VB) spectra.[30,31] According to the Mott-
Schottky tests, the flat-band potentials of TPT-Cz-ph, TPT-Cz-
phCN, and TPT-Cz-phOMe were found to be −0.44, −0.59, and
−0.41 eV versus RHE, respectively (Figure S11, Supporting Infor-
mation). Moreover, the slopes of the CBCPs were positive, indi-
cating that they were n-type semiconductors. Therefore, the con-
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duction band potentials of TPT-Cz-ph, TPT-Cz-phCN, and TPT-
Cz-phOMe were calculated to be −0.54, −0.69, and −0.51 eV,
respectively. The position of the valence band potential was de-
termined by the equation EV = Φ + VBmax − 4.44, where Φ is
the work function of semiconductors, VBmax is the VB maxima,
4.44 is the value of absolute potential of the standard hydrogen
electrode.[32] The VB-XPS spectra showed that the VB maxima
(VBM) of TPT-Cz-ph, TPT-Cz-phCN, and TPT-Cz-phOMe were
2.25, 2.2, and 2.4 eV, respectively (Figure S12, Supporting In-
formation). The work functions were detected by a Kelvin Probe
Force Microscope (KPFM), revealing that the work functions of
TPT-Cz-ph, TPT-Cz-phCN, and TPT-Cz-phOMe were 4.22, 4.22,
and 4.18 eV, respectively (Figure S13, Supporting Information).
VB-XPS was employed to ascertain the energy level difference
from the Valence Band Maximum (VBM) to the Fermi level, while
KPFM was utilized to determine the energy level difference from
the Fermi level to the vacuum level. The numerical value obtained
from the VBM to the vacuum level, minus 4.44, can be converted
to the VBM in standard hydrogen electrode units. Consequently,
the valence band potentials of TPT-Cz-ph, TPT-Cz-phCN, and
TPT-Cz-phOMe were determined to be 1.97, 1.92, and 2.08 eV,
respectively. The electronic structures of the CBCPs are depicted
in Figure 1b, which indicates that all CBCPs are thermodynami-
cally sufficient for the photosynthesis of H2 O2 via both the WOR
and ORR pathways.[33,34]
2.2. Photocatalytic Performance
The photocatalytic performance of the CBCPs was evalu-
ated in pure water and open air under visible-light irradia-
tion (𝜆 > 400 nm, 100 mW cm−2 ). Figure 1c demonstrated
that the electron donor side chains significantly influenced
the photosynthetic efficiency of H2 O2 . Notably, TPT-Cz-phCN,
which contains electron-withdrawing groups, exhibited a re-
markably enhanced performance, with a production rate of
2534 μmol g−1 h−1 , whereas TPT-Cz-phOMe, which contains
electron-donating groups on side chains, displayed a reduced pro-
duction rate of 1017 μmol g−1 h−1 . Moreover, the calculated ap-
parent quantum yields (AQYs) of TPT-Cz-phCN were 19.1%, 8%,
and 3.3% at 420, 470, and 620 nm, respectively (Figure 1d). Con-
versely, the AQYs of TPT-Cz-ph and TPT-Cz-phOMe were only
15.7% and 8% at 420 nm (Figure S14, Supporting Information).
Furthermore, the performance of H2 O2 photosynthesis in nat-
ural water using TPT-Cz-phCN was even better, achieving pro-
duction rates of 3221 and 2966 μmol g−1 h−1 in river water and
seawater, respectively (Figure S15, Table S1, Supporting Informa-
tion). The solar-chemical-conversion (SCC) efficiency of TPT-Cz-
phCN was 0.64%, which is the highest reported in natural water
(Table S2, Supporting Information) and is 6 times higher than the
average solar-to-biomass conversion efficiency of typical plants
(≈0.1%). Remarkably, TPT-Cz-phCN retained one-half of its ac-
tivity in H2 O2 generation even under argon conditions (Figure
S16, Supporting Information). This significantly surpasses the
performance reported in previous studies listed in Figure 1e and
Table S3 (Supporting Information).
Additionally, TPT-Cz-phCN exhibited consistent photosyn-
thetic rates of H2 O2 , chemical structures, and morphologies af-
ter five consecutive runs, as shown in Figure S17 (Supporting
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Information). Moreover, all CBCPs exhibited minimal degrada-
tion of H2 O2 during the photocatalytic reactions (Figure S18,
Supporting Information). The above results demonstrated that
TPT-Cz-phCN exhibited high efficiency in synthesizing H2 O2 ,
exceptional stability, and resistance to interference form complex
matrices in natural water. These findings indicated its potential
application for in situ remediation of natural water.
2.3. Pathways for Photosynthesis of H2 O2
In order to investigate the pathways for generating H2 O2 in pho-
tosynthesis, a series of control experiments and electrochemi-
cal measurements were performed. The average electron trans-
fer number in the ORR process was investigated using rotat-
ing disk electrodes and linear sweep voltammetry curves were
obtained with different rotating speeds. The Koutecky–Levich
(K–L) plots were then fitted, revealing that the average elec-
tron transfer numbers of TPT-Cz-ph, TPT-Cz-phCN, and TPT-
Cz-phOMe were 2.14, 2.08, and 2.18, respectively, which were
close to the theoretical value for reducing O2 to H2 O2 (Figure
S19, Supporting Information).[35] Photocatalytic yields of H2 O2
in CBCPs were greatly increased after switching air to satu-
rated O2 , demonstrating that ORR participated in the H2 O2 gen-
eration (Figure S16, Supporting Information). Furthermore, in
the presence of silver nitrate (AgNO3 ) as an electron sacrificial
agent or 2,2,6,6-tetramethyl-1-piperidinyl oxy (TEMPO) as ·O2 −
sacrificial agents, the photocatalytic yields of H2 O2 in CBCPs
significantly decreased (Figure S20, Supporting Information).[6]
Electron paramagnetic spectroscopy experiments, using 5,5-
dimethyl-1-pyrroline N-oxide (DMPO) as the spin-trap agent,
confirmed that ·O2 − is the critical intermediate in the photosyn-
thesis of H2 O2 (Figure S21, Supporting Information).[36] With
the existence of MeOH as a hole scavenger and TEMPO as ·O2 −
sacrificial agents, all CBCPs exhibited the capability to generate
H2 O2 (Figure S22, Supporting Information). These results col-
lectively indicated that all CBCPs followed both a 1e− two-step
ORR and 2e− one-step ORR pathway for H2 O2 production. Addi-
tionally, photocatalytic hydrogen production experiments eluci-
dated the incapacity of all three materials to generate hydrogen.
This implied that all CBCPs primarily produce hydrogen perox-
ide through oxidation reactions.
The WOR process was also found to be important for the pho-
tosynthesis of H2 O2 , with all CBCPs maintaining almost one-
half of the activities in H2 O2 generation after substituting argon
for air (Figure S16, Supporting Information). In order to further
explore the WOR pathway for H2 O2 production, an isotopic ex-
periment was conducted by using H2 18 O (Figure S23, Support-
ing Information).[12] It was evident that when isotopically labeled
water (H2 18 O) was employed in the photocatalytic reaction in-
stead of conventional water (H2 16 O), and the subsequently gener-
ated H2 O2 was converted to O2 by MnO2 , a distinct isotopic peak
corresponding to 18 O2 was clearly observed. This observation ef-
fectively demonstrated the evolution of H2 O2 through the WOR
pathway. All CBCPs generated H2 O2 in photocatalytic reaction
under Ar and silver nitrate as electron sacrificial agents, demon-
strating a direct 2e− water oxidation pathway for photosynthesis
H2 O2 (Figure S24, Supporting Information).[37] H2 O2 can also
be generated through the indirect two-electron pathway of water
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oxidation. There are two branches in the indirect pathway: one in-
volves the oxidation of H2 O to form hydroxyl radicals (·OH), and
the other involves the oxidation of hydroxyl (OH− ) to form hy-
droxyl radicals (·OH), followed by the reaction of two ·OH to yield
hydrogen peroxide. The oxidation potential for the first branch is
as high as 2.73 V versus NHE. However, the valence band en-
ergies (VB) for TPT-Cz-ph, TPT-Cz-phCN, and TPT-Cz-phOMe
were measured at 1.97, 1.92, and 2.08 V, respectively, render-
ing them insufficient to drive the oxidation reaction of ·OH/H2 O
(2.73 V vs NHE).[38] Although the valence band energies of TPT-
Cz-ph and TPT-Cz-phOMe theoretically allowed for the oxidation
reaction of ·OH/OH− (1.99 V vs NHE), ESR experiments revealed
no detectable ·OH signals (Figure S25, Supporting Information).
Consequently, all CBCPs facilitated the formation of H2 O2 via the
direct two-electron pathway of water oxidation.
The rotating ring-disk electrode measurements further re-
vealed that both O2 and H2 O2 were the potential products for
WOR, with TPT-Cz-phCN exhibiting better WOR performance
than TPT-Cz-ph and TPT-Cz-phOMe (Figure S26, Supporting
Information).[5] The introduction of electron-withdrawing cyano
moieties as side chains into the electron donor greatly improved
the capacity of WOR, as demonstrated by the comparison ex-
periments. Overall, these findings suggested that both ORR and
WOR play important roles in the photosynthesis of H2 O2 , with
the two-electron pathway being the predominant route for ORR
and the introduction of cyano moieties improving the capacity of
WOR.
2.4. Active Sites for Both ORR and WOR
Density functional theory (DFT) calculations were employed to
further investigate the active sites responsible for the photosyn-
thesis of H2 O2 . To simplify the model, we adopted one elec-
tron donor and one acceptor unit to construct the theoretical
computational model. We first calculated the value of oscilla-
tor strength (f) in different transitions, which reflects the tran-
sition probability.[17] The result indicated that the main transi-
tion of all CBCPs was S0 →S1 (Table S4, Supporting Informa-
tion). Therefore, we further investigated the distribution of holes
and electrons in the transition of S0 →S1. According to time-
dependent DFT (TD-DFT), the photoinduced holes of excited
TPT-Cz-ph, TPT-Cz-phCN, and TPT-Cz-phOMe were primarily
situated at the carbazole and acetylene sites, while the photoin-
duced electrons were located at the triazine sites (Figure S27,
Supporting Information).[39] These computational investigations
revealed that the triazine sites were the ORR active sites, while
the carbazole and acetylene sites were the WOR active sites.
Thus, we examined the contribution of non-hydrogen atoms
to holes and electrons in excited state CBCPs (Figure 2; Figure
S28, Tables S5–S7, Supporting Information). Comparing TPT-
Cz-phCN with TPT-Cz-ph, we observed that the hole occupancy
on TPT-Cz-phCN increased for acetylene moieties and decreased
for carbazole moieties, whereas the hole occupancy on TPT-Cz-
phOMe changed in the opposite direction to TPT-Cz-phCN, de-
creasing for acetylene moieties and increasing for carbazole moi-
eties. These findings indicated that the introduction of electron-
withdrawing side chains to the electron donor effectively al-
tered the dominant hole occupancy. The primary hole occupancy,
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Figure 2. The distribution of electrons and holes. The contribution of non-hydrogen atoms to holes and electrons in excited state TPT-Cz-ph (a), TPT-
Cz-phCN (b) and TPT-Cz-phOMe (c).
intricately associated with the active sites for WOR, plays a pivotal
role in the essential process of H2 O2 production.
The active sites for ORR and WOR were further elucidated
by in situ diffuse reflectance infrared Fourier transform spec-
troscopy (DRIFTS) measurements (Figure 3a–c). The new peaks
at ≈1267 and 1203 cm−1 emerged during the photocatalytic pro-
cess in the presence of H2 O and O2 , corresponding to the weak
infrared absorption of ─OH from generated H2 O2 .[16] The spec-
tral features appearing ≈1408 and 1376 cm−1 were attributed to
the stretching and breathing modes of the triazine structures.[23]
The peak intensity corresponding to the triazine structures de-
creased under irradiation, in combination with the analysis of
the distribution of the excited state electrons, indicating that the
triazine structures were involved in H2 O2 production via ORR
reaction.
To further elucidate the active sites in water oxidation, in situ
infrared testing was conducted under H2 O and He conditions
(Figure 3d–f). The peak at ≈2211 cm−1 , assigned to the stretch-
ing vibration of C≡C bonds, showed a gradual enhancement un-
der irradiation in TPT-Cz-phCN, indicating acetylene moieties
as active sites in the WOR.[27] In contrast, the N─O bonds were
formed at ≈1560, 1510, and 1488 cm−1 under irradiation for TPT-
Cz-ph and TPT-Cz-phOMe, with no discernible alteration in the
intensity of the C≡C bonds, indicating that carbazole moieties
served as active sites for the water oxidation reaction.[16,40,41] Ad-
ditionally, in situ infrared testing under O2 conditions revealed
negligible variation in the peak associated with C≡C bonds in
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TPT-Cz-phCN, indicating specific interactions between acetylene
moieties and H2 O. For TPT-Cz-phOMe and TPT-Cz-ph, peaks
corresponding to N─O bonds demonstrated minimal changes,
suggesting specific interactions between carbazole moieties and
H2 O (Figure S29, Supporting Information). These results high-
lighted differences in active sites for water oxidation reactions
among the three CBCPs: acetylene moieties as primary active
sites in TPT-Cz-phCN and carbazole moieties in TPT-Cz-ph and
TPT-Cz-phOMe.
After clarifying the distinctions in active sites, a more in-depth
analysis was conducted to understand the factors contributing to
the performance variations caused by these active sites. This anal-
ysis involved investigating the free energy of each intermediate
in WOR at both acetylene and carbazole sites on CBCPs using
first principles, providing insights into the mechanism underly-
ing the superior WOR performance of TPT-Cz-phCN (Figure 4).
For the two-electron water oxidation pathway, *OH serves as the
exclusive reaction intermediate.[42] The results showed that the
Gibbs free energy (G) for *OH formation was much smaller in
acetylene sites than in carbazole sites on all CBCPs, indicating
that acetylene sites were more likely to serve as active sites for
the two-electron WOR.[5] Compared to the other CBCPs, TPT-
Cz-phCN exhibited the lowest Gibbs free energy for *OH forma-
tion at acetylene sites, indicating that the two-electron water ox-
idation to H2 O2 occurred more readily in TPT-Cz-phCN (Figure
S30, Supporting Information). A similar trend was observed
for the four-electron water oxidation pathway. The four-electron
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Figure 3. Active sites of CBCPs for H2 O2 production. In situ DRIFTS spectra under H2 O and O2 of TPT-Cz-ph (a), TPT-Cz-phCN (b), and TPT-Cz-phOMe
(c); In situ DRIFTS spectra under H2 O and He of TPT-Cz-ph (d), TPT-Cz-phCN (e), and TPT-Cz-phOMe (f).

water oxidation process is governed by the binding of three
pivotal intermediates: O*, OH*, and OOH*.[43] For all three
CBCPs, O* and OH* tended to preferentially form at acety-
lene sites, while for OOH*, the Gibbs free energy difference re-
quired for formation showed minimal variation between acety-
lene and carbazole sites. Thus, acetylene sites effectively reduced
the Gibbs free energy associated with the formation of interme-
diates for both two-electron and four-electron water oxidation for
all CBCPs, enhancing the propensity for the occurrence of the
water oxidation reaction.
From the calculated free energy diagrams, it can be observed
that the rate-determining steps for two-electron water oxidation
and four-electron water oxidation are different on acetylene and
carbazole active sites. To compare the dynamics of these two

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Figure 4. Investigation of active sites for WOR through free energy diagrams. Calculated free energy diagrams and overpotentials depict two-electron
water oxidation pathways on acetylene and carbazole sites of TPT-Cz-ph (a), TPT-Cz-phCN (b), and TPT-Cz-phOMe (c). Additionally, free energy diagrams
and overpotentials illustrate four-electron water oxidation pathways on acetylene and carbazole sites of TPT-Cz-ph (d), TPT-Cz-phCN (e), and TPT-Cz-
phOMe (f).

reactions, it is possible to compute the overpotentials separately
for two-electron and four-electron water oxidation reactions on
different active sites.[44] Lower overpotentials generally indicate
faster reaction kinetics. By comparing the overpotentials, one can
assess the relative rates of the two reactions on acetylene and car-
bazole active sites.
For 2e− WOR, *OH serves as the exclusive reaction inter-
mediate. The ideal ΔG*OH for H2 O2 production is ≈1.76 V,
resulting in a zero overpotential. Thus, the overpotentials for
2e− WOR can be determined by subtracting 1.76 V from the
thermodynamic equilibrium potential.[45] Examining overpoten-
tial values at acetylene sites for TPT-Cz-ph, TPT-Cz-phCN, and
TPT-Cz-phOMe revealed −0.44, −0.61, and −0.44 V, respectively.
Conversely, at carbazole sites, the corresponding values were
0.27, 0.25, and 0.93 V. These results indicate lower overpoten-
tials and faster kinetics at the acetylene sites in the 2e− WOR.
For 4 e− WOR, the OER process involves a complicated four-
electron reaction with the formation of *OH, *O, and *OOH
intermediates successively. The overpotential was calculated as
𝜂 OER = max{ΔGi }/e − 1.23, where e is the electron charge
and ΔGi refers to the Gibbs free energy change in each re-
action step.[46] The overpotential values at acetylene sites for
TPT-Cz-ph, TPT-Cz-phCN, and TPT-Cz-phOMe were 0.82, 0.97,
and 1.1 V, respectively. Conversely, at carbazole sites, the corre-
sponding values were 1.49, 1.47, and 1.49 V, indicating lower
overpotentials and faster kinetics at the acetylene sites in the
4e− WOR. Hence, both the 2e− WOR and 4e− WOR demon-
strated lower overpotentials and faster kinetics at the acetylene
sites.
Thus, acetylene sites were the low-barrier active sites for both
two-electron and four-electron water oxidation for all CBCPs, and
mediating the WOR active sites from high-energy barrier car-
bazole to low-energy barrier acetylene through the introduction
of electron-withdrawing side chains to the electron donor in TPT-
Cz-phCN was the underlying reason for the effective improve-
ment of photocatalytic performance. Based on all the experimen-
tal and computational results, we propose the main process of
TPT-Cz-phCN photocatalytic H2 O2 generation as follows: under
visible-light irradiation, photogenerated electrons were located
on triazine sites, while holes mainly accumulated on low-energy-
barrier acetylene sites. H2 O2 was generated by two-electron ORR
on triazine sites and the two-electron WOR to H2 O2 or four-
electron WOR to O2 at low energy barrier acetylene sites.
2.5. Photophysical Process
After elucidating the processes in ORR and WOR, the inves-
tigation proceeded to explore the charge separation efficiency
and kinetic processes of CBCPs. The photocurrent response
is closely linked to the rate of electron and hole separation,
as demonstrated in Figure S31 (Supporting Information).[47]
The photocurrent density of TPT-Cz-phCN was significantly
higher than that of TPT-Cz-ph and TPT-Cz-phOMe, indicat-
ing that TPT-Cz-phCN had more usable carriers in the pho-
tocatalytic reaction. To understand the mechanism underlying
this finding, the dissociation of an exciton was explored. The
fluorescence quantum yield of TPT-Cz-ph, TPT-Cz-phCN, and

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Figure 5. Investigation of charge separation efficiency in CBCPs. Evolution of photoluminescence intensity as a function of temperature (insert:
temperature-dependent PL spectra) for TPT-Cz-ph (a), TPT-Cz-phCN (b), and TPT-Cz-phOMe (c). Electrostatic potential maps for (d) TPT-Cz-phCN.
TPT-Cz-phOMe was found to be 1.4%, 2.7%, and 2.2%, respec-
tively, indicating that radiative recombination of carbazole-based
CPs was greatly suppressed.[26] Temperature-dependent photo-
luminescence spectra measurements were also conducted to in-
vestigate the reason for efficient exciton dissociation.[48,49] A se-
ries of temperature-dependent photoluminescence curves from
200 to 300 K were obtained, which showed an obvious decrease
in PL intensities with increasing temperature for all carbazole-
based CPs, owing to temperature-activated exciton dissociation.
The exciton activation (Ea ) of the photoluminescence quenching
process was calculated using the Arrhenius equation, I (T) =
E
I0 ∕[1 + Aexp(− kBTa )], and found to be 197, 168, and 224 meV
for TPT-Cz-ph, TPT-Cz-phCN, and TPT-Cz-phOMe, respectively
(Figure 5a–c).[50] The lower Ea of TPT-Cz-phCN indicated that the
separation of excitons was much easier than in the other two ma-
terials. It can be speculated that the incorporation of electron-
withdrawing cyano moieties as side chains to the electron donor
is beneficial to the photocatalytic reaction for enhancing exciton
dissociation by reducing exciton activation (Ea ).
To further investigate the ingrained mechanism behind the
charge separation, DFT calculations were employed. All CBCPs
demonstrated optimal space charge separation, with the lowest
unoccupied orbitals mainly located in the TPT moieties and the
highest occupied orbitals predominantly in the carbazole moi-
eties (Figure S1, Supporting Information).[51] The electrostatic
potential maps depicted the electrical distribution of materials,
showing a dominant negative electron charge surface (blue color)
on the TPT moieties and a main positive charge surface (red
color) on the carbazole moieties for all CBCPs (Figure S32, Sup-
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porting Information).[52] The locations of the distribution of the
positive and negative charges were consistent with those of the
HOMO and LUMO. Furthermore, due to the introduction of
cyano, TPT-Cz-phCN had more positive charges on the carbazole
group, which made it more delocalized compared to TPT-Cz-ph
and TPT-Cz-phOMe (Figure 5d). In addition, the dihedral angles
of TPT-Cz-ph, TPT-Cz-phCN, and TPT-Cz-phOMe were 3.05°,
0.99°, and 1.58°, respectively (Figure S33, Supporting Informa-
tion). The introduction of electron-withdrawing side chains in
the electron donor greatly facilitated the coplanarity of the elec-
tron acceptor and electron donor, thus promoting photocatalytic
performance.
Subsequently, time-resolved photoluminescence spectra of
CBCPs were researched (Figure S34, Table S8, Supporting Infor-
mation). All CBCPs showed significantly reduced fluorescence
lifetimes compared to the literature, suggesting the possibil-
ity of faster separation efficiency of photoinduced electron–hole
pairs.[9,12] Femtosecond transient absorption (TA) spectroscopy
is a powerful technique for investigating the dynamics of photo-
generated charge.[53–55] Upon excitation by a 380 nm pump pulse,
all CBCPs showed no stimulated emission peak, indicating that
the photocatalysts had weak radiative recombination,[56] consis-
tent with their fluorescence quantum yields. All CBCPs exhib-
ited broad positive signals in the range of 500–780 nm, which
were assigned to polarons. This assignment was based on their
amplitude decrease regardless of the addition of AgNO3 as elec-
tron scavengers or EDTA-2Na as hole scavengers (Figure S35,
Supporting Information).[57] Because the polarons are pairs of
more loosely bound charges by Coulomb attraction forces, when
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Figure 6. Analysis of Photogenerated Charge Dynamics in CBCPs. TA spectra in the near-infrared light region for TPT-Cz-ph (a), TPT-Cz-phCN (b), and
TPT-Cz-phOMe (c). TA kinetic traces recorded in H2 O at 1050 nm for TPT-Cz-ph (d), TPT-Cz-phCN (e), and TPT-Cz-phOMe (f).
a charge is accelerated for extraction, the separation of polarons
is accelerated.[58,59] The polaron kinetics of CBCPs were probed
at 650 nm, and the lifetime of TPT-Cz-ph, TPT-Cz-phCN, and
TPT-Cz-phOMe was found to be 333, 325, and 256 ps, respec-
tively (Figure S36, Table S9, Supporting Information). These re-
sults indicated that the introduction of electron-withdrawing side
chains onto the electron donor had little effect on the separation
of polarons.
Furthermore, the dynamics of the photoinduced hole at differ-
ent active sites were investigated through femtosecond TA spec-
troscopy. The TAS signals from 900–1200 nm were assigned to
holes, supported by the amplitude decrease in the presence of
EDTA-2Na as hole scavengers and a slight decrease in the pres-
ence of AgNO3 as electron scavengers (Figure 6a–c; Figure S37,
Supporting Information). The lifetime of the hole in TPT-Cz-
phCN probed at 1050 nm was 319 ps, which is much shorter
than that of TPT-Cz-ph (846 ps) and TPT-Cz-phOMe (994 ps)
(Figure 6d–f, Table S10, Supporting Information). The much
shorter lifetime of the hole in TPT-Cz-phCN demonstrated the
accelerated WOR on low-barrier active sites, thereby improving
the overall photocatalytic activity.
3. Conclusion
We have synthesized a series of electron donor–acceptor con-
jugated carbazole-based polymers for photosynthetic H2 O2 by
introducing different electrical moieties as side chains of elec-
tron donors. Our investigations have shown that the addition
of electron-withdrawing side chains cyano moieties to the elec-
tron donor effectively shifted the primary hole localization from
the high-energy-barrier carbazole to the low-energy-barrier acety-
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lene. This incorporation of electron-withdrawing side chains
also reduced the exciton activation energy, promoting exciton
dissociation. Shifting the primary hole localization partly from
the high-energy-barrier carbazole sites to the low-energy-barrier
acetylene sites, accelerated the water oxidation rate, thus en-
hancing the overall photocatalytic performance. As a result, the
donor–acceptor polymer with electron-withdrawing side chains
in electron donors exhibited excellent and stable photosynthesis
of H2 O2 activity. This strategy of regulating the hole location to
accelerate the water oxidation rate provides a reasonable direc-
tion for the design of photocatalysts for H2 O2 production in nat-
ural water, effectively advancing the photosynthesis of H2 O2 for
in situ remediation of natural water.
Supporting Information
Supporting Information is available from the Wiley Online Library or from
the author.
Acknowledgements
H.Y. and Y.P. contributed equally to this work. This work was sup-
ported by the National Natural Science Foundation of China (22206209,
22336007, and 22176053) and the Natural Science Foundation of Guang-
dong Province 2022A1515011953. The authors thank Xiaoqian Wei, Weixin
Zou, and Qing Tong from the Center of Modern Analysis at Nanjing Uni-
versity for their assistance with in situ DRIFTS technology.
Conflict of Interest
The authors declare no conflict of interest.
© 2024 Wiley-VCH GmbH

www.advancedsciencenews.com
Data Availability Statement
The data that support the findings of this study are available from the
corresponding author upon reasonable request.
Keywords
environmental chemistry, hydrogen peroxide, photocatalysis, water oxida-
tion reactions
Received: November 1, 2023
Revised: January 13, 2024
Published online:
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