RESEARCH ARTICLE
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Covalent Furan-Benzimidazole-Linked Polymer Hollow Fiber
Membrane for Clean and Efficient Photosynthesis of
Hydrogen Peroxide
Tao Yang, Yaowei Jin, Yingchu Wang, Aiguo Kong,* Yue Chen, Yingying Zou, Chao Liu,
Guangfeng Wei,* and Chengzhong Yu*
Photocatalytic H2 O2 production by conversion of O2 in aqueous solution is
often challenged by the use of sacrificial agents, the separation of powdery
photocatalysts, solution, and contaminants, and low activity of photocatalyst.
Herein, a membrane of covalent furan-benzimidazole-linked polymer
(Furan-BILP) with both O- and N-containing heterocycles bonded via
O–C–C=N is reported for the first time as a photocatalyst to harvest clean
H2 O2 in pure water with high-performance. A coordination-polymer hard
template strategy is developed to produce Furan-BILP hollow microfibers that
can be further assembled into membranes with desired sizes. The resultant
Furan-BILP membrane directly delivers clean H2 O2 solution as the product
with a high H2 O2 production rate of 2200 μmol g−1 h−1 in pure water. Density
functional theory calculations and experiment results indicate that the C atom
from Furan ring on the linkage binds to the adsorbed OOH* , the H atom of
OOH* forms a hydrogen bond with the N atom in the benzimidazole ring,
thus the intermediate six-membered ring structure stabilizes the OOH* and
favors 2e-ORR. The strategy using both molecular engineering to tune the
electronic structure and macrostructural engineering to shape the
morphology may be applied to design other coordination organic polymer
photocatalysts with further improved performance.
1. Introduction
Hydrogen peroxide (H2 O2 ) is a green oxidant and widely
used in industrial bleaching, chemical synthesis, environmen-
tal cleaning, medical disinfection, and energy applications.[1]
T. Yang, Y. Wang, A. Kong, Y. Chen, Y. Zou, C. Liu, C. Yu
School of Chemistry and Molecular Engineering
East China Normal University
Shanghai 200241, P. R. China
E-mail: agkong@chem.ecnu.edu.cn; c.yu@uq.edu.au
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.202300714
© 2023 The Authors. Advanced Functional Materials published by
Wiley-VCH GmbH. This is an open access article under the terms of the
Creative Commons Attribution-NonCommercial License, which permits
use, distribution and reproduction in any medium, provided the original
work is properly cited and is not used for commercial purposes.
DOI: 10.1002/adfm.202300714
Adv. Funct. Mater. 2023, 33, 2300714 2300714 (1 of 10)
Currently, the anthraquinone process is still
dominant for the industrial-scale produc-
tion of H2 O2 , which generates considerable
pollutants.[2] Therefore, environmentally
benign and on-site synthesis approaches of
H2 O2 have attracted continuous attention,
such as electrocatalytic or photocatalytic
H2 O2 production with oxygen (O2 ) and wa-
ter (H2 O) as sources.[3] Compared to the
electricity-consuming electrocatalysis, the
photocatalytic process using inexhaustible
solar as energy input is more promising for
H2 O2 production especially via 2e- oxygen
reduction (2e-ORR) pathway[3b,4] Typically,
photocatalysts usually in powder forms
are dispersed in a suspension contain-
ing sacrificial reagents.[5] While the pho-
tocatalyst efficiency of H2 O2 generation is
an important topic,[5a] the requirement of
clean H2 O2 solution is another crucial as-
pect, because additional separation of cat-
alysts and/or sacrificial reagents is time
and energy consuming, which even causes
decomposition of the generated H2 O2 .[6]
Therefore, the design of 2e-ORR photocat-
alysts with both high activity and free of
product separation is of great significance.
Visible light-responsive and sacrificial agent-free photocata-
lysts hold promise for effective and green synthesis of H2 O2 . As
a metal-free porous material with tunable components and struc-
tures, and good stability, covalent organic polymers (COPs) stand
Y. Jin, G. Wei
Shanghai Key Laboratory of Chemical Assessment and Sustainability,
School of Chemical Science and Engineering
Tongji University
Shanghai 200092, P. R. China
E-mail: weigf@tongji.edu.cn
C. Yu
Australian Institute for Bioengineering and Nanotechnology
The University of Queensland Brisbane
Queensland 4072, Australia
© 2023 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH

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Figure 1. Illustration of the synthesis of hollow Furan-BILP microfiber
photocatalytic membrane.
out from various organic and inorganic photocatalysts including
metal-organic frameworks.[7] In particular, nitrogen-containing
COPs, e.g., with melamine, triazines, imines, and diarylamino
benzene as building blocks, have shown excellent photocatalytic
H2 O2 production performance.[4,7c,d,8] Nevertheless, the reported
COP-based photocatalysts were mainly used in a suspension sys-
tem during the H2 O2 photogeneration process, and organic addi-
tives were often needed to improve the wettability of hydrophobic
COP catalysts.[4,5b] The separation of catalysts and organic sol-
vents is required for clean production of H2 O2 . Moreover, most
reported COPs are micropore-dominant spheres, irregular parti-
cles, and plates,[7c,9] which may limit the active sites exposure,
mass transportation, and thus the production rate of H2 O2 . It
is challenging to prepare COP-based photocatalysts for directly
harvesting clean H2 O2 with high-performance and free of post-
synthesis separation.
Benzimidazole-linked polymers (BILPs) are a class of N-
containing heterocyclic organic semiconductors with narrow
bandgap and good thermal and chemical stability,[10] usu-
ally used in ion adsorption, gas separation, but rarely as
photocatalysts.[10a,11] By introducing another heterocyclic unit
such as porphyrin and pyridine into BILP frameworks, the re-
sultant COPs showed efficient photocatalytic activity in selec-
tive oxidation of thioanisole, sonogashira coupling, and CO2
photoreduction.[12] Nevertheless, the reported BILP-based photo-
catalysts have predominantly N-substituted heterocycles in com-
position, and there are rare reports on their applications in 2e-
ORR photocatalytic generation of H2 O2 .
In this work, a novel furan-benzimidazole-linked polymer
(Furan-BILP) membrane is reported as a high-performance 2e-
ORR photocatalyst for clean production of H2 O2 , free of sacrifi-
cial reagent or complicated catalyst separation process. As shown
in Figure 1, furan-2,5-dicarbaldehyde (Furan) and 2,3,6,7,10,11-
hexaminotriphenylene (HATP) were chosen as precursors to
form a visible light responsive strong 𝜋–𝜋 conjugation struc-
ture. Different from most reported BILPs containing only N-
substituted heterocycles, the Furan-BILP framework has both N-
and O-containing heterocycles linked via an O–C–C=N bond.
Density functional theory calculations suggest that the C atom
from Furan ring on the linkage is the active site that binds to the
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O atom of OOH* , and the H atom of OOH* forms a hydrogen
bond with the N atom in the benzimidazole ring on the linkage
(O–C–C=N). The double heterocyclic structure in Furan-BILP is
advantageous for the stabilization of the OOH* with an inter-
mediate six-membered ring structure. The bandgap calculation
and experimental observations further support that photoelec-
tron generation and 2e-ORR occur on the Furan-containing hete-
rocycle by indirect two-electron oxygen reduction. Moreover, the
morphology of Furan-BILP is controlled as hollow microfiber for
enhanced mass transportation and membrane-forming charac-
teristics, by using a newly developed Al-diethylenetriamine pen-
taacetic acid (Al-DTPA) coordination polymer hard templating
method. After removing the hard templates and vacuum-assisted
deposition of Furan-BILP hollow microfibers on carbon cloth,
a flexible and hydrophilic Furan-BILP membrane consisted of
hollow fibers can be obtained and readily used as a photocata-
lyst for producing clean H2 O2 solutions. The membrane catalyst
gives a high H2 O2 production rate of 2200 μmol g−1 h−1 in O2 -
presaturated pure water and long-time durability. Our strategy
using both molecular engineering to tune the electronic structure
and macrostructural engineering to shape the morphology may
be applied to design other coordination organic polymer photo-
catalysts.
2. Results and Discussion
To synthesize Furan-BILP membrane, the design of hollow mi-
crofibers as building blocks is the key. This is achieved by a
hard templating method, using Al-DTPA coordination polymer
microfibers as templates to prepare the hollow Furan-BILP mi-
crofibers (Figure S1, Supporting Information). First, the Al-
DTPA coordination polymer microfibers previously reported
by us (Figure S2, Supporting Information) were prepared as
the hard templates.[13] As shown in transmission electron mi-
croscopy (TEM) and scanning electron microscope (SEM) im-
ages of Al-DTPA in Figure 2a and Figure S2 (Supporting In-
formation) , the Al-DTPA microfibers with an average length
of 30–100 μm and diameter of ≈500 nm were obtained. The
Al-DTPA microfibers can be well dispersed in organic solvents
such as N,N-dimethylformamide (DMF) to form a suspension
at room temperature (Figure S3, Supporting Information). Af-
ter adding Furan and HATP precursors, heterogeneous nucle-
ation and growth of Furan-BILPs on the surface of Al-DTPA mi-
crofibers (named as Furan-BILP@Al-DTPA) may be triggered by
the electrostatic and/or Van der Waals interaction between sur-
face carboxylate of Al-DTPA and amino groups of HATP, as ev-
idenced by Fourier transform infrared (FT-IR) spectra, powder
X-ray powder diffraction (PXRD) and TEM studies (Figure S4,
Supporting Information). Therefore, by optimizing the ratio and
the adding method of Al-DTPA and Furan-BILP precursors (Fig-
ure S5, Supporting Information), Furan-BILP hollow microfibers
were finally obtained by etching off Al-DTPA templates in 0.1 m
KOH. TEM and SEM images show the resultant Furan-BILP ma-
terial has a hollow fiber morphology (Figure 2b–g). The length,
diameter, and shell thickness were estimated to be ≈30–100 μm,
500 and 35 nm, respectively (Figure 2b–d) and TEM (Figure 2e–
g). Some long ribbons are also observed, which might be resulted
from the incomplete enclosing of Furan-BILP polymers on Al-
DTPA templates. The high-resolution TEM (HRTEM) image
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Figure 2. a) SEM images of Al-DTPA templates. b–d) SEM images of the prepared Furan-BILP hollow microfibers. e–g) TEM images of the prepared
Furan-BILP hollow microfibers. h) HRTEM images of Furan-BILP. i) EDS elemental mapping images of Furan-BILP.
reveals an amorphous framework of Furan-BILP (Figure 2h). The
energy dispersive spectroscopy (EDS) element mapping images
(Figure 2i) illustrate C, N, and O signals, in accordance with the
composition of the Furan-BILP microfibers.
The crystalline structures and porosities of Furan-BILP were
also investigated. The PXRD pattern of Furan-BILP (Figure S4a,
Supporting Information) indicated an amorphous nature. The
N2 -sorption analysis of Furan-BILP revealed a type-IV isotherm
with a H3-type hysteresis loop in a broad relative pressure range
(Figure 3a). The Brunauer-Emmett-Teller (BET) specific surface
area of Furan-BILP was calculated to be 807 m2 g−1 . From
the pore size distribution curves, a micropore size centered at
≈1.8 nm was determined with a broad distribution (Figure S6,
Supporting Information). To demonstrate the role of Al-DTPA,
one Furan-BILP control sample was synthesized without us-
ing Al-DTPA templates, which showed an irregular morphology
(named as Furan-BILP-I, Figure S5, Supporting Information). It
is noted that Furan-BILP-I exhibited a low specific surface area
of ≈26 m2 g−1 without obvious micropores (Figure 3a; Figure S6,
Supporting Information), suggesting that the interfacial assem-
bly of Furan-BILP on the surface of Al-DTPA is essential to create
abundant porosities in Furan-BILP.
The molecule structures of Furan-BILP were also studied
by FT-IR, solid-state 13 C nuclear magnetic resonance spec-
troscopy (13 C NMR), and X-ray photoelectron spectroscopy (XPS).
Compared to Furan and HATP precursors, the FT-IR spec-
trum of Furan-BILP presented new vibration bands at 1620 and
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1287 cm−1 , typical of the C=N units,[4,9b] and the symmetric
stretching mode of C–N of the benzimidazole rings.[14] The peak
observed at 1022 cm−1 is attributed to C–O–C on Furan rings.
The chemical shifts at 144, 134 and 127 ppm in the 13 C NMR
spectrum of Furan-BILP were respectively attributed to the car-
bon atoms on benzimidazole rings or at the Furan ring edge (see
index in Figure 3c).[15] The peaks at 106 and 112 ppm were as-
signed to carbon atoms at the inner benzene in the triphenylene
and unsubstituted carbon atoms at the phenyl edges.[15] The XPS
survey scan spectrum of Furan-BILP (Figure 3d) demonstrated
the existence of C, N, and O, in agreement with the results of
EDS element mapping results (Figure 2i). The high-resolution C
1s XPS spectrum (Figure 3e) indicated the C–C or C=C signals of
triphenylene at 284.8 eV, while the XPS signals at 285.6 (C-NH),
288.5(C=N), and 286.7 eV (C–O) corresponded to the C atoms on
benzimidazole and Furan rings.[10c,16] The N 1s XPS spectroscopy
of Furan-BILP (Figure 3f) could be deconvoluted into two peaks
at 399 and 400.5 eV, attributing to C–N and C–NH of benzim-
idazole on Furan-BILP.[9b,17] The O 1 s spectrum (Figure 3g) of
Furan-BILP also revealed two peaks at 534.5 and 532.7 eV. The
former was the signal of the O atoms in the Furan ring, while
the latter corresponded to the adsorbed water or O2 species on
polymer.[18] Collectively, the above characterizations demonstrate
that a highly porous furan-benzimidazole-linked polymer has
been successful prepared via a hard templating approach.
The UV–vis diffuse reflectance spectrum (UV–vis DRS) of
Furan-BILP is presented in Figure 3h, showing strong light
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Figure 3. a) Nitrogen adsorption-desorption isotherms of Furan-BILP prepared with or without Al-DTPA. b) FT-IR of Furan-BILP and corresponding
monomers. Solid-state 13 C NMR (c) and XPS survey spectra (d) of the prepared Furan-BILP fibers. High-resolution XPS spectra of Furan-BILP for (e) C
1s, (f) N 1s, and (g) O1s. h) UV−vis diffuse reflectance spectra of Furan-BILP (Inset shows the corresponding bandgap energy Tauc plot). i) Schematic
illustration of the band structures of Furan-BILP.

adsorption between 300 and 650 nm. From the corresponding
Tauc plots, the bandgap of Furan-BILP was estimated to be
2.19 eV.[19] The narrow bandgap of Furan-BILP should be at-
tributed to its strong 𝜋–𝜋 conjugation structure. The valance
band maximum (VBM) value of Furan-BILP determined by ul-
traviolet photoelectron spectroscopy (UPS) was −5.86 eV (vs vac-
uum level, Evacum ) by subtracting the width of the He I UPS
spectra from the excitation energy (21.22 eV),[20] as shown in
Figure S7 (Supporting Information). Based on above results,
the band structure including VBM and conduction band min-
imum (CBM) edges of Furan-BILP is shown in Figure 3i. The
CBM value (−0.77 V vs normal hydrogen electrode (NHE) at
pH 0) were more negative than the redox potential of O2 /·O2 −
(−0.33 V vs NHE at pH 0), while the VBM value (+1.42 V NHE
at pH 0) was more positive than that of O2 /H2 O (+1.23 V vs
NHE at pH 0).[3b,21] The band structure diagram indicated that
the electron (e− )-hole (h+ ) pair photogenerated on Furan-BILP
photocatalysts could produce sufficient thermodynamic driving
forces to conversing O2 to H2 O2 in pure water, together with
4-electron water oxidation reaction (4e-WOR). The steady-state
photoluminescence (PL) spectroscopy of Furan-BILP illustrated
a very weak fluorescence emission signal (Figure S8, Supporting
Information), indicating efficient charge separation of photoex-
cited electron-hole pairs in Furan-BILP containing both O- and
N-heterocycles.[22]
To achieve clean production of H2 O2 solution, Furan-BILP
membrane was constructed by simply filtration of the Furan-
BILP hollow microfibers on top of hydrophilic carbon cloth un-
der vacuum (Figure 4a). As shown in Figure 4b,c, yellow-colored
Furan-BILP membrane can be formed by dipping ≈0.5 mg of
Furan-BILP fibers on top of carbon cloth of 3 cm diameter
(≈7 cm2 ). The Furan-BILP membrane displayed a hydrophilic
property with a water contact angle of ≈35°. The membrane
thickness could be adjusted by using different amounts of Furan-
BILP fibers. When the mass density of Furan-BILP fibers on car-
bon cloth reached ≈4 mg 7cm−2 , the resultant membrane could
be peeled off from carbon cloth and became a self-supported
membrane (Figure S9, Supporting Information) with the inter-
weaved microfibers observed in SEM images. The size of Furan-
BILP membrane could also be enlarged by using carbon cloth

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Figure 4. a) A typical preparation of the photocatalytic Furan-BILP hollow microfiber membrane. b) Photo and SEM images of the hydrophilic carbon
cloth. c) Photo and SEM images of the hollow Furan-BILP hydrophilic membrane on carbon cloth (Inset is the corresponding contact angle image).

Figure 5. a) Time-dependent production of H2 O2 in N2 - or O2 -presaturated neat water under visible light irradiation using Furan-BILP. b) Comparison of
H2 O2 production rate of Furan-BILP with previous reports. c) Test mode of transient H2 O2 photocurrent response with Pt-ring as the working electrode.
d) The transient H2 O2 photocurrent response of the Furan-BILP in N2 - or O2 -presaturated 0.1 m Na2 SO4 solution under irradiation of visible light
(𝜆>420 nm) at a bias of 1.2 V (vs RHE). e) ESR spectra of Furan-BILP for DMPO- ·O2 − .

with a larger size, like a membrane with 9 cm diameter shown in
Figure S9b (Supporting Information).
The photocatalytic performance of Furan-BILP membrane
was first evaluated in O2 -presaturated pure water. The time-
dependent curves of the generated H2 O2 amount (Figure 5a)
revealed approximately a linear increase. The H2 O2 production
amount reached 2.2 μmol using a membrane composed of 0.5 mg
Furan-BILP hollow microfibers at 2 h, giving an H2 O2 production
rate of 2200 μmol g−1 h−1 , higher than most of the reported sac-
rificing reagents-free catalysts (Figure 5b; Table S1, Supporting
Information). For comparison, the Furan-BILP-I prepared with-
out using Al-DTPA templates gave a lower production rate of
355 μmol g−1 h−1 (Figure S10, Supporting Information), about
five times lower than Furan-BILP membrane. The higher H2 O2
production rate of Furan-BILP hollow fibers may be ascribed to
the more negative CBM value with stronger reduction ability,

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improved charge transportation, and separation efficiency as de-
termined by transient photocurrent response and electrochem-
ical impedance spectroscopy (EIS) measurements (Figure S11,
Supporting Information), and hollow tubular morphology with
high specific surface area, enhanced active exposure and mass
transfer. Moreover, to investigate whether the produced H2 O2 can
be decomposed by the photocatalyst, the Furan-BILPs were added
into 0.1 mm H2 O2 aqueous solution and the H2 O2 concentration
change was recorded under visible light radiation within 2 h (Fig-
ure S12, Supporting Information). The H2 O2 decomposition in-
duced by Furan-BILP microfibers was negligible, indicating an
intrinsically low catalytic decomposition capability for H2 O2 .
In principle, the photoproduction of H2 O2 in O2 -saturated
pure water can be contributed by direct 2e-ORR (Equation.
(1)), indirect two-step single-electron 2e-ORR process (Equations.
(2,3)), and/or 2-electron WOR (Equation. (4), 2e-WOR):[17c,21]
O2 + 2H+ + 2e− → H2 O2 (E Φ = +0.68 V vs NHE at pH 0) (1)
O2 + 2e− → ∙ O−2 (E Φ = −0.33 V vs NHE at pH 0) (2)
∙
O−2 + 2H+ + e− → H2 O2 (E Φ = +1.44 V vs NHE at pH 0) (3)
2H2 O → H2 O2 + 2H+ + 2e− (E Φ = +1.76 V vs NHE at pH 0) (4)
Considering that the CBM edge values for Furan-BILP were
<−0.33 V (vs NHE at pH 0), both the direct 2e-ORR and in-
direct 2e-ORR pathways are thermodynamically favorable for
H2 O2 production.[3b,23] To gain more insight, the generated H2 O2
amount over Furan-BILP membrane was measured in continu-
ously bubbling N2 pure water that could remove O2 (including O2
generated from 4e-WOR). There was almost no hydrogen perox-
ide detected in this control experiment (<0.1 μmol), suggesting
the 2e-WOR pathway is not feasible in our system, consistent
with the CBM edges of Furan-BILP (<1.76 V vs NHE at pH 0).
However, 0.4 μmol of H2 O2 was detected at 2 h in N2 -presaturated
water without continuous bubbling (Figure 5a), suggesting that
the 4e-WOR pathway is still possible that generates O2 for fur-
ther production of H2 O2 via the 2e-ORR pathway. Considering
that 2.2 μmol of H2 O2 was harvested in O2 -presaturated water,
the above control experiments indicate that the 2e-ORR pathway
is dominant in the photocatalytic H2 O2 production over Furan-
BILP membrane.
To further understand the mechanism, the transient H2 O2
photocurrent response curves were measured on rotating ring-
disc electrode (RRDE) in N2 - or O2 -saturated 0.1 m Na2 SO4 so-
lution under irradiation of visible light (𝜆>420 nm) at a bias of
1.2 V (vs reversible hydrogen electrode (RHE)). The test mode
is displayed in Figure 5c. Under the irradiation of visible light,
the produced H2 O2 on Furan-BILP coated on rotating disk elec-
trode could diffuse to the Pt-ring electrode at a rotation rate of
1600 rpm. When the Pt-ring on RRDE was used as the work-
ing electrode, the detected photocurrent signals in direct pro-
portion to the transiently generated H2 O2 amount would be ob-
served. The photocurrent density in N2 -saturated 0.1 m Na2 SO4
solution was smaller than in O2 -saturated solution (Figure 5d),
showing the same trend as in Figure 5a. To understand the spe-
cific pathway of 2e-ORR, the presence of superoxide radical in-
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Figure 6. DFT calculated free energy diagrams of O2 reduction pathways
toward H2 O2 generation on different active sites in Furan-BILP. The opti-
mized structures of OOH* states are shown in inserted dashed rectangles
in corresponding colors.
termediate (·O2 − ) signal for the indirect two-step single-electron
O2 reduction could be captured by 5,5-dimethyl-pyrroline N-oxide
(DMPO). The typical DMPO- ·O2 − signals for Furan-BILP could
be well identified in spin-trapping electron spin resonance (ESR)
spectra (Figure 5e),[5b,24] suggesting that the indirect 2e-ORR
pathway could contribute to the photoproduction of H2 O2 .
The active sites of Furan-BILP in the photocatalytic 2e-ORR
process is an important research question. The activation of O2
molecule is the critical step for the formation of H2 O2 , therefore
the first electron transfer to the O2 (O2 + H+ + e− → OOH, gen-
erating adsorbed OOH* ) is utilized to evaluate the activity of dif-
ferent possible reactive sites of Furan-BILP for 2e-ORR. The free
energy cost of OOH* on different sites of Furan-BILP has been
calculated based on density functional theory (DFT). As shown
in Figure 6, the free energy cost for the OOH* formation on the
linkage C atoms on Furan ring is lower than that on other sites.
The lowest free energy cost for the formation of OOH* on Furan-
BILP is 0.22 eV at 0 V versus standard hydrogen electrode. This
is because when the O atom of OOH* bonds to the carbon atom
next to the Furan O atom, the H atom of OOH* forms a hydrogen
bond with the nitrogen atom of the C=N bond in the benzimi-
dazole ring. It is inferred that the double heterocyclic structure
in Furan-BILP is advantageous for the stabilization of the OOH*
with an intermediate six-membered ring structure, which even-
tually favors the H2 O2 generation.
The pre-adsorption of O2 was also investigated. The minimum
adsorption-free energy of adsorbed O2 after considering the sol-
vation effect on Furan-BILP is still positive (0.10 eV). suggesting
the molecular O2 adsorption on Furan-BILP is thermodynami-
cally prohibited. It is found that the most stable O2 adsorption
site is also located adjacent to the Furan ring, as shown in Figure
S13 (Supporting Information), which is consistent with the most
stable OOH* adsorption site identified in Figure 6. This observa-
tion further indicates that the linkage C atoms on the Furan ring
are the active sites for ORR.
To gain deep insights into the origin of the enhanced 2e-
ORR performance, Heyd–Scuseria–Ernzerhof (HSE06) hybrid
functional calculations were applied to investigate the elec-
tronic structures of Furan-BILP accurately. The electronic band
structures (Figure S14, Supporting Information) indicated that
Furan-BILP has a direct bandgap of 2.39 eV, close to the experi-
mental value. The density of states (DOS) and projected density of
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Figure 7. a) Total density of states (DOS) and projected DOS (pDOS) for
Furan-BILP. The energy of Fermi level (Ef ) is set to 0 eV. b) HOMO and
LUMO isosurfaces for Furan-BILP.
states (pDOS) on to C, N, and O atoms of Furan-BILP are plotted
in Figure 7a. The highest occupied molecular orbital (HOMO) is
contributed predominately by the 2p orbitals of C and N atoms,
while the lowest unoccupied molecular orbital (LUMO) is mainly
contributed by the 2p orbital of C and Furan O atoms. This is also
reflected on the isosurfaces of the HOMO and LUMO of Furan-
BILP (Figure 8b), where the HOMO orbital is mainly distributed
in the large conjugated system composed of C and N atoms, while
the LUMO orbitals tend to be distributed on the Furan group.
These DFT results imply that the excited photoelectrons are more
likely to transfer toward the Furan O atoms during the photocat-
alytic conversion of O2 . The O2 reduction (forming OOH* ) can
more easily to take place on the C site close to the Furan O atoms.
The photocatalytic stabilities for organic semiconductors are
often insufficient, owing to the attacking for active sites by ·O2 −
and hole(+).[25] The H2 O2 photosynthesis on Furan-BILP cata-
lysts was tested for five cycles in a suspension system contain-
ing 5 mg of Furan-BILP photocatalysts (Figure 8a). The photocat-
alytic performance of Furan-BILP experienced a slight decrease
in the second cycle, then remained almost constant in the fol-
lowing cycles. The H2 O2 photoproduction durability of Furan-
BILP fiber membrane (4 mg 7 cm−2 ) was also tested by a con-
tinuous long-time experiment in pure water (Figure 8b and Fig-
ure S15, Supporting Information). Although the catalyst amount
of Furan-BILP on membrane was only 4 mg, the continuously
increased H2 O2 amount was still observed within 54 h in pure
water.
It has been found by Cooper et al that the activity decay of
imine conjugated polymers was mainly attributed to imine ox-
idation to amide and the loss of extended conjugation in a long-
time stability test.[7c] To study the possible structural change in
our case, the Furan-BILP catalyst after long-time irradiation ex-
periments was also collected and studied by FT-IR, C 1s, N 1s,
and O 2p XPS spectra (Figure 8 c–e; Figure S16, Supporting In-
formation). The changes in FT-IR signals of C=N and C–N (at
1620 and 1287 cm−1 ) on the benzimidazole rings was hardly ob-
served. There was neither obvious change in the C 1s nor C-NH
units (400.5 eV) in the XPS spectrums. Nevertheless, the signal
Adv. Funct. Mater. 2023, 33, 2300714 2300714 (7 of 10)
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intensity of the N 1s of imine (C=N) at 399.0 eV on benzimi-
dazole ring and the O 1s at ≈534 eV from C–O on Furan ring
decreased slightly. In addition, there is no obvious change of O1s
XPS signal for absorbed O2 or water, and signals at ≈403.8 eV
assigning to amide groups are not found. These experimental re-
sults are in accordance with the DFT calculation. When imine
groups are covalently linked to benzimidazole rings, the photoex-
citation is mainly located at the O–C–C=N linkage. Long-term
exposure to photogenerated holes or reactive oxygen species may
cause linkage breakage to a small extent. Nevertheless, oxidation
from imine to amide is not evident on Furan-BILP photocatalyst
within the investigated experimental conditions. The Furan-BILP
fiber morphology after undergoing the photocatalytic reaction of
10 h showed negligible changes, as shown in SEM and TEM im-
ages (Figures S17 and S18, Supporting Information).
Finally, a Furan-BILP membrane with a larger diameter of
9 cm and ≈20 mg of Furan-BILP hollow microfibers was put into
a quartz pond in summer under sunlight irradiation containing
high energy light of <420 nm (Figure S19, Supporting Informa-
tion). The H2 O2 concentration observed from 8:30 am to 4:30 pm
at outside (north latitude 31.1°, east longitude 121.3°) recorded a
processive increase of H2 O2 (Figure 8f), suggesting a good sta-
bility of Furan-BILP under natural sunlight. A 50 mL clean H2 O2
solution of ≈28 μmol within 8 h was directly harvested.
3. Conclusion
Benzimidazole N-heterocycles and Furan O-heterocycles were
conjugated into a unique covalent organic polymer, which can be
fabricated into a hollow microfiber morphology by a hard tem-
plating method. In pure water, the resultant hydrophilic Furan-
BILP photocatalytic membrane converted O2 into clean H2 O2 so-
lution by an indirect 2e-ORR pathway, with a high photocatalytic
production rate of 2200 μmol g−1 h−1 . The active sites, the origin
of high activity, and stability have been investigated by both ex-
periments and DFT calculation. This work provides an attractive
new COP-based membrane for directly producing clean H2 O2 so-
lution, and inspiration for the design of high-efficiency photocat-
alysts via both molecule and macrostructural engineering.
4. Experimental Section
Synthesis: The synthesis of Furan-BILP hollow microfibers were typi-
cally prepared by a coordination polymer microfiber template method. The
Al-diethylenetriamine pentaacetic acid (Al-DTPA) microfibers were pre-
pared according to the reported synthesis method, which were used as
hard templates for the preparation of Furan-BILP hollow microfibers.[13]
In a typical synthesis, 0.2 g dried Al-DTPA microfibers were dispersed into
60 mL N, N-dimethylformamide (DMF) containing 54.0 mg 2,3,6,7,10,11-
hexaminotriphenylene hexahydrochloride (HATP·6HCl) in N2 atmosphere
at room temperature. And then 20 mL DMF solution with 18.6 mg Furan-
2,5-dicarbaldehyde was dropped into the suspension above. The amine
aldehyde condensation reaction transiently happened at room tempera-
ture in the existence of Al-DTPA templates. After the mixtures above were
stirred for 4 h, 0.3 g zinc acetate (Zn (Ac)2 ·2H2 O) was added gently ad-
justing the pH value. The resultant mixtures were further reacted for an-
other 4 h. The solid products were collected by filtrating and washing with
ethanol. The yellow Furan-BILP hollow microfibers were finally obtained by
etching off Al-DTPA with 0.1 m KOH at room temperature.
© 2023 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH

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Figure 8. a) Recycling test of Furan-BILP in suspension system (5 mg Furan-BILP, 40 mL pure water and irradiation for 1h). b) Long-time photocatalytic
H2 O2 production of Furan-BILP under >420 nm irradiation. c) FT-IR, d) O 1s, and e) N 1s XPS spectra of Furan-BILP before and after irradiation. f)
Photocatalytic H2 O2 production of Furan-BILP under natural sunlight irradiation in summer.
Characterization: Fourier transform infrared (FT-IR) spectra were
recorded on a Thermal Nicolet iS50 spectrometer using samples embed-
ded in potassium bromide (KBr) pellets. Powder X-ray powder diffraction
(PXRD) patterns were performed on a Bruker D8 Advanced X-ray diffrac-
tometer with Cu K𝛼 radiation (𝜆 = 0.154 nm). X-ray photoelectron spec-
troscopy (XPS) measurements were performed on an Axis Ultra DLD using
C 1s (284.8 eV) as a reference to correct the binding energy. Photolumines-
cence (PL) spectroscopy was undertaken using a fluorescence spectropho-
tometer (SHIMADZU RF-6000 fluorophotometer). Transmission electron
microscopy (TEM) images were obtained on a JEOL-2010 transmission
electron microscope at an acceleration voltage of 200 kV. A Hitachi ST-
4800 scanning electron microscope (SEM) and FEI-Nova Nano SEM 450
scanning electron microscope were used to determine the catalyst mor-
phology. The porous structure and surface area were analyzed at 77 K on
an Autosorb-iQ gas-sorption analyzer (Quantachrome, USA). Ultraviolet
photoelectron spectroscopy (UPS) measurements were performed on an
ESCALAB 250Xi electron spectrometer (Thermo Fisher Scientific) with He
I (21.22 eV) as the monochromatic light source. Solid-state 13 C CP/MAS
NMR measurement was recorded using a Bruker AVANCE III 400 WB spec-
trometer at a MAS rate of 5 kHz and a CP contact time of 2 ms. Elec-
tron spin resonance (ESR) spectra were recorded using a Bruker EMX plus
model spectrometer.
H2 O2 Production on Furan-BILP Photocatalytic Membrane: 1.0 mL
ethanol suspension solution containing 0.5 mg Furan-BILP hollow mi-
crofibers was dipping on circular hydrophilic carbon cloth and followed
by suction filtration with vacuum pump. The membrane was finally ob-
tained by naturally drying at room temperature. The prepared Furan-BILP
membrane was soaked into the bottom of a quartz tank with 15 mL deion-
ized water. The flowed O2 was bubbled into the suspension for 30 min in
dark. A 300 W Xe lamp (𝜆 > 420 nm) fitted with a 420 nm cutoff filter was
used as the light source. At given time intervals, 500 μL solution filtrated
with a 0.22 μm filter was added into 1 mL potassium hydrogen phthalate
(C8 H5 KO4 ) solution (0.1 m ) and 1 mL potassium iodide (KI) solution
(0.4 m) and kept for 30 min in dark. H2 O2 molecules would react with I−
to generate I3 − , and the amount of I3 − was measured by a UV spectropho-
Adv. Funct. Mater. 2023, 33, 2300714 2300714 (8 of 10)
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tometer at its characteristic absorbance peak (350 nm). For excluding the
affection of O2 in iodometry method, the concentration of H2 O2 was de-
termined by subtracting the initial background in the O2 saturated solution
at 0 min.
Photoelectrochemical Measurements: A traditional transient photocur-
rent test was carried out in a standard three-electrode cell system in 0.1 m
Na2 SO4 solution, employing Ag/AgCl electrode and Pt wire as the refer-
ence and counter electrodes. A 300 W xenon lamp (> 420 nm) was used as
the light source. The working electrode was prepared by coating catalyst
slurry on indium-doped tin oxide (ITO, 1 cm2 ). The slurry was obtained
by dispersing catalyst powder (10 mg) in 10% Nafion solution (40 μL).
The corresponding electrochemical impedance spectroscopy (EIS) of cat-
alyst on ITO was recorded in this system with the frequency range of 0.01–
106 Hz.
In addition, a transient H2 O2 photocurrent measurement was also con-
ducted with a similar three-electrode system,[26] by replacing catalyst/ITO
working electrode above with catalyst/rotating ring-disk electrode (RRDE)
(Pine Research Instrumentation, USA) under irradiation of visible light
(𝜆>420 nm). 5 mg Furan-BILP samples were dispersed into the mixture
solution consisting of 0.5 mL ethanol and 10 μL Nafion under ultrasonic
treatment to obtain an ink suspension. The disk electrodes were polished
with 0.03 μm Al2 O3 power. The ink suspension of 15 μL was uniformly
coated onto the disk electrodes and dried under an infrared lamp. The O2 -
saturated 0.1 m Na2 SO4 aqueous solution was used as the electrolyte. In
the transient H2 O2 photocurrent test, the photogenerating H2 O2 species
on Furan-BILP-modified disk electrode at the rotating speed of 1600 rpm
could diffuse to Pt-ring, and give a current signal of H2 O2 decomposition
at the Pt-ring working electrode with a constant potential of 1.2 V versus
RHE.[27]
Computational Methods: Density functional theory (DFT) calculations
were performed using VASP 6.2.1 packages[28] with projected augmented
wave (PAW) pseudo-potentials.[29] The exchange-correlation energy was
treated based on the generalized gradient approximation (GGA) by
using Perdew–Burke–Ernzerhof (PBE) functional.[30] The plane-wave cut-
off energy was set to 450 eV. The DFT-D3(BJ) method of Grimme[31] was
© 2023 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH

www.advancedsciencenews.com
employed to describe long-range VDW interactions. The Monkhorst–Pack
scheme with a k-point separation length of 0.05 Å−1 was utilized for sam-
pling the first Brillion zone.[32] To correct the zero-point energy for reac-
tion barrier, the vibrational frequency calculations were performed via the
finite-difference approach. To simulate both long-range and short-range
solvation effects, the same approach was followed as used in the pre-
vious study.[33] Specifically, the first solvation shell surrounding OOH*
was modelled by explicit H2 O molecules, and the rest of the solution was
represented by the implicit solvation model implemented in the VASPsol
package.[34,35] All atoms are fully relaxed in the calculations. The Quasi-
Newton l-BFGS method was used for geometry relaxation until the max-
imal force on each degree of freedom less than 0.01 eV Å−1 . Heyd–
Scuseria–Ernzerhof (HSE06) hybrid functional[36,37] calculations were ap-
plied to obtain a more accurate understanding of the electronic structures.
To derive the free energy reaction profiles, the same approach was followed
as the previous work.[38] The standard thermodynamic data[39] were uti-
lized to obtain the temperature and pressure contributions. The free en-
ergy of gaseous O2 was derived as G[O2] = 4.92 eV + 2G[H2O] – 2G[H2] by
utilizing the oxygen evolution reaction equilibrium at the standard condi-
tions.
Supporting Information
Supporting Information is available from the Wiley Online Library or from
the author.
Acknowledgements
T.Y. and Y.J. contributed equally to this work. This work was sup-
ported by the National Natural Science Foundation of China (Grant NO.
22173069), Shanghai Municipal Natural Science Foundation (Grant NO.
21ZR1419500, 21ZR1467800), and the Fundamental Research Funds for
the Central Universities.
Open access publishing facilitated by The University of Queensland, as
part of the Wiley - The University of Queensland agreement via the Council
of Australian University Librarians.
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available from the cor-
responding author upon reasonable request.
Keywords
furan-benzimidazole-linked polymers, hollow microfibers, hydrogen per-
oxide, membranes, photosynthesis
Received: January 18, 2023
Revised: March 25, 2023
Published online: May 8, 2023
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