pubs.acs.

org/acscatalysis Research Article

Rational Design of Conjugated Microporous Polymer Photocatalysts

with Definite D−π−A Structures for Ultrahigh Photocatalytic
Hydrogen Evolution Activity under Natural Sunlight
Changzhi Han, Sihui Xiang, Shenglin Jin, Chong Zhang,* and Jia-Xing Jiang*
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ABSTRACT: Organic polymers with conjugated architectures have been widely exploited
as photocatalyst materials for hydrogen generation. However, it is still an enormous
Downloaded via UPPSALA UNIV on September 6, 2023 at 11:19:46 (UTC).

challenge to develop photocatalysts with high hydrogen generation activity under natural
sunlight, which is pretty significant for practical applications. Herein, two conjugated
microporous polymer photocatalysts with definite D−π−A structures are designed and
prepared using dibenzo[g,p]chrysene or pyrene with planar conjugated architecture as
electron donors, thiophene as a π-spacer, and dibenzo[b,d]thiophene-S,S-dioxide as an
electron acceptor. Benefiting from the efficient separation of light-generated electrons/
holes due to the definite D−π−A structure and the broad light absorption range, the bare
polymer Py-TP-BTDO could deliver a high photocatalytic hydrogen evolution rate (HER)
of 115.03 mmol h−1 g−1 upon exposure to visible light (λ > 420 nm). Impressively, the
outdoor photocatalytic experiment reveals that abundant and continuous hydrogen bubbles
could be produced fast and visually observed under natural sunlight by the Py-TP-BTDO
polymer film with a large active area of 120 cm2. A water-drainage experiment further
demonstrates that 1224 mL of hydrogen gas could be produced by 25 mg of a polymer photocatalyst with 3 wt % Pt cocatalyst under
natural sunlight in 7 h, corresponding to a high HER of 312.24 mmol h−1 g−1, which represents the state of the art of organic
photocatalyst materials to date. The high photocatalytic activity under natural sunlight suggests the potential of the developed Py-
TP-BTDO polymer photocatalyst in the practical applications for photocatalytic hydrogen production.
KEYWORDS: conjugated microporous polymer, D−π−A structure, dibenzo[b,d]thiophene-S,S-dioxide acceptor,
photocatalytic hydrogen production, natural sunlight

■ INTRODUCTION
The technology for converting inexhaustible solar energy into
renewable and clean hydrogen energy is a widely accepted
ideal approach to produce green fuel, where the type of
semiconductive photocatalyst materials greatly affects the
hydrogen evolution efficiency.1−3 Nowadays, a variety of
photocatalyst materials including inorganic photocatalysts4−6
and organic metal-free polymer photocatalysts7−10 have been
developed for hydrogen production. Compared to inorganic
photocatalysts, organic photocatalysts with conjugated archi-
tectures have aroused enormous interests due to their
outstanding structure stability, tunable energy levels, and
flexible molecular design. Among these developed organic
photocatalysts, dibenzo[b,d]thiophene-S,S-dioxide (BTDO)
containing polymer photocatalysts show great potential for
solar-to-hydrogen conversion since the strong electron-with-
drawing ability and high hydrophilicity of BTDO endow the
photocatalysts with enhanced charge separation ability and
effective contact with water molecules. However, the real-
world application of organic photocatalysts for photocatalytic
hydrogen generation is still severely restricted by the low
photocatalytic performance under natural sunlight and poor
long-term photocatalytic stability of photocatalyst materials.
To upgrade the photocatalytic activity of organic photo-
catalysts with conjugated frameworks, various strategies have
been put forward, such as expanding the optical absorption
range,11−14 designing organic−inorganic or organic−organic
heterojunctions,15−18 constructing donor−acceptor (D−A) or
donor−π−acceptor (D−π−A) structures19−23 and enhancing
the hydrophilicity.24−27 Among these strategies, building D−A
or D−π−A type polymer photocatalysts has attracted great
attention, since the intrinsic electron push−pull effect between
donor units and acceptor units is advantageous in facilitating
the photo-induced charge separation and thus increasing the
photocatalytic activity of the polymer photocatalysts. For
Received: October 10, 2022
Revised: December 3, 2022
Published: December 13, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acscatal.2c04993

204 ACS Catal. 2023, 13, 204−212
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Scheme 1. Synthetic Routes of Dc-TP-BTDO and Py-TP-BTDO (Insets: Photographs of the As-Synthesized Dc-TP-BTDO
and Py-TP-BTDO)
example, Li and co-workers developed a D−A type porous
organic photocatalyst of BTT-CPP with conjugated frame-
works using benzo[1,2-b:3,4-b′:5,6-b″]trithiophene as the
electron donor and BTDO as the electron acceptor. Benefiting
from the D−A structure, BTT-CPP obtained a high hydrogen
evolution rate (HER) of 37.87 mmol h−1 g−1 under UV−Vis
light.28 Wang and co-workers synthesized a high-performance
D−A type linear polymer of PDBTSO-T by coupling
thiophene as the donor unit and BTDO as the acceptor,
realizing an outstanding HER of 147 mmol h−1 g−1 under UV−
Vis light.29 We developed a narrow band gap dithieno[3,2-
b:2′,3′-d]thiophene-S,S-dioxide, a derivative of BTDO, as the
acceptor unit, which enabled the resulting polymer of
PyDTDO-3 to show a high HER of 16.32 mmol h−1 g−1
under visible light.30 To extend the conjugation degree of the
polymer chains and tune the chemical composition of D−A
polymer photocatalysts, D−π−A type conjugated polymer
photocatalysts have been exploited by inserting a π bridge
between the donor and acceptor units.19,20,31 However, most
D−π−A type polymer photocatalysts with outstanding photo-
catalytic performance were synthesized by ternary statistical
copolymerization, which commonly leads to the complexity
and uncertainty of the polymer structure since there might
exist considerable D−π−D and A−π−A structures in the
resulting polymers from ternary statistical copolymerization,
which might hinder the separation of light-induced charge
carriers, thus restricting the effect of D−π−A structure on
boosting the photocatalytic activity.
To further get insight into the influence of the polymer
structure on photocatalytic activity and exclude the effect of
D−π−D and A−π−A structures, we designed and prepared
two CMP photocatalysts with definite D−π−A structure using
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planar pyrene (Py) and dibenzo[g,p]chrysene (Dc) as the
electron donors, thiophene (TP) as the π-spacer, and BTDO
with strong electron-withdrawing attribute as the electron
acceptor. To avoid the formation of D−π−D and A−π−A
structures during the polymerization, the π-spacer of TP was
precoupled with the electron donors of Py and Dc units,
respectively. Then, the polymerization reaction was conducted
by the Pd(0)-catalyzed Suzuki−Miyaura coupling reaction
from the two derivatives with the BTDO acceptor to produce
alternative polymers with a definite D−π−A structure (Scheme
1). The photocatalytic hydrogen evolution experiment
demonstrated that both polymers show high photocatalytic
activity due to the efficient separation of light-generated
electrons/holes benefited from the definite D−π−A structure,
while the polymer photocatalyst of Py-TP-BTDO with pyrene
donors exhibits higher photocatalytic activity than Dc-TP-
BTDO with the dibenzo[g,p]chrysene donor, attributed to the
narrower band gap and broader light absorption range of Py-
TP-BTDO. An ultrahigh HER of 331.37 mmol h−1 g−1 could
be obtained by Py-TP-BTDO with 3 wt % Pt under UV−Vis
light (λ > 300 nm) at a low polymer concentration of 50 mg
L−1. More importantly, Py-TP-BTDO also demonstrates an
impressive photocatalytic activity with an average HER of
312.24 mmol h−1 g−1 outdoor under natural sunlight,
demonstrating the potential of Py-TP-BTDO for practical
applications.
■ EXPERIMENTAL SECTION
Chemicals. The compounds of dibenzo[b,d]thiophene-S,S-
dioxide, 1,3,6,8-tetrabromopyrene, 2,7,10,15-
tetrabromodibenzo[g,p]chrysene, Pd(PPh3)4, ascorbic acid
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Figure 1. (a) FT-IR spectra. (b) Solid-state 13C NMR spectra and the assignment of carbon atoms in the polymers. (c) Nitrogen adsorption/
desorption isotherms at 77.3 K. (d) UV−Vis absorption spectra. (e) Fluorescence emission spectra. (f) Energy band positions.
(AA), and DMF were obtained from Innochem, EXTEN-
SION, and Acros and used as received without further
purification. The 2,7,10,15-tetrakis(5-bromothiophen-2-yl)-
dibenzo[g,p]chrysene (M1), 1,3,6,8-tetrakis(5-bromothio-
phen-2-yl)pyrene (M2) and 3,7-bis(4,4,5,5-tetramethyl-1,3,2-
dioxaborolan-2-yl)dibenzo[b,d]thiophene-S,S-dioxide (M3)
were prepared according to the reported methods in the
literature.32,33 The 1H NMR spectrum for 2,7,10,15-tetra-
(thiophen-2-yl)dibenzo[g,p]chrysene, the intermediate of M1,
is shown in Figure S1. Considering that M1 and M2 are
insoluble in common solvents, we presented their mass spectra
in Figures S2 and S3, respectively.
Synthesis of Dc-TP-BTDO. First, M1 (486.2 mg, 0.5
mmol), M3 (468.2 mg, 1.0 mmol), and Pd(PPh3)4 (20.0 mg,
17.3 μmol) were added into a 100 mL double-neck flask filled
with N2, and then, 20 mL of dry DMF and 4 mL of K2CO3
aqueous solution (2.0 M) were injected into the flask. The
mixture reacted at 150 °C with stirring for 48 h. After cooling
down, the precipitate was obtained by filtrating and washed
with dichloromethane, methanol, and deionized water several
times. After drying in a vacuum at 120 °C for 48 h, Dc-TP-
BTDO was obtained as insoluble orange polymer powder
(yield: 89.91%). Anal. calcd for (C66H32O4S6)n (%): C 73.31,
H 2.98, S 17.79; found: C 69.00, H 3.56, S 14.91.
Synthesis of Py-TP-BTDO. M2 (423.2 mg, 0.5 mmol), M3
(468.2 mg, 1.0 mmol), 4 mL of K2CO3 aqueous solution (2.0
M), and 20 mL of DMF and Pd(PPh3)4 (20.0 mg, 17.3 μmol)
were used in this polymerization. Besides the dosages of
chemicals, the synthesis of Py-TP-BTDO and Dc-TP-BTDO
shares the same protocol. The polymer Py-TP-BTDO was
obtained as insoluble red polymer powder (yield: 97.6%).
Anal. calcd for (C56H26O4S6)n (%): C 70.41, H 2.74, S 20.14;
found: C 67.21, H 3.62, S 19.08.
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Photocatalytic Experiment. The photocatalytic H2
generation experiment was conducted on an all-glass automatic
online trace gas analysis system (Labsolar-6A, Beijing Perfect-
light Technology Co., Ltd.) according to our previously
reported procedures.34
■ RESULTS AND DISCUSSION
The resulting CMPs were obtained as orange (for Dc-TP-
BTDO) and red (for Py-TP-BTDO) insoluble solid powders.
The structure characterization of Dc-TP-BTDO and Py-TP-
BTDO was carried out by Fourier-transform infrared (FT-IR)
and solid-state 13C nuclear magnetic resonance (NMR)
spectra, as shown in Figure 1. The characteristic peaks for
the sulfone group in the BTDO unit are located at 1306 and
1154 cm−1 in the FT-IR spectra,35−37 and the peaks at 1598
and 1464 cm−1 originate from the C�C bonds in the aromatic
rings (Figure 1a). Additionally, the weak peaks at around 500
cm−1 correspond to the unreacted C−Br end group in Dc-TP-
BTDO and Py-TP-BTDO (Figure 1a),38 which might be
responsible for the discrepancy between the calculated and
found elemental analysis for the two resulting polymers as
presented in the experimental section.39,40 As shown in Figure
1b, the signal at the highest chemical shift of around 141 ppm
corresponds to the carbon atoms linking with sulfur atoms in
thiophene and BTDO units.41−43 Powder X-ray diffraction
patterns demonstrated the amorphous feature for Dc-TP-
BTDO and Py-TP-BTDO, as supported by their broad and
weak diffraction peaks (Figure S4). The N2 sorption
measurement at 77.3 K revealed a high N2 uptake at a low
relative pressure (P/P0 < 0.01) for both polymers, indicating
abundant micropores in both Dc-TP-BTDO and Py-TP-
BTDO (Figure 1c). The obtained specific surface areas are 189
and 306 m2 g−1 for Dc-TP-BTDO and Py-TP-BTDO,
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Table 1. Photophysical Properties and HERs for the CMP Photocatalysts

polymer Ega (eV) HERb (mmol h−1 g−1) HERc (mmol h−1 g−1) HERd (mmol h−1 g−1) HERe (mmol h−1 g−1)
Dc-TP-BTDO 2.24 82.12 110.94 86.27 113.14
Py-TP-BTDO 1.98 115.03 141.61 182.78 245.79
a
Calculated from the absorption edge. b10 mg of bare polymer under visible light (λ > 420 nm). c10 mg of bare polymer was irradiated by UV/Vis
light (λ > 300 nm). d10 mg of polymer with 3 wt % Pt under visible light. e10 mg of polymer with 3 wt % Pt under UV/Vis light.

Figure 2. Time course of hydrogen evolution for Dc-TP-BTDO and Py-TP-BTDO under the irradiation of (a) visible light (λ > 420 nm) and (b)
UV−Vis light (λ > 300 nm) loading 3.0 wt % Pt. (c) SPV spectra. (d) Photocurrent curves.

respectively, calculated based on the adsorption branches in
the N2 adsorption isotherms. Pore size distribution manifested
that Dc-TP-BTDO mainly possesses slightly bigger micropores
with a diameter centered at around 1.38 nm than that of Py-
TP-BTDO (1.19 nm), attributed to the larger size of
dibenzo[g,p]chrysene than that of pyrene (Figure S5). The
hydrophilicity for Dc-TP-BTDO and Py-TP-BTDO was
evaluated by the water contact angle measurement (Figure
S6), where the two polymers show similar water contact angles
of 92.3° and 100.8° for Dc-TP-BTDO and Py-TP-BTDO,
respectively, demonstrating their similar hydrophilicity. The
scanning electron microscopy (SEM) images revealed that
both the CMPs possess even rod morphology, while Dc-TP-
BTDO rod was smaller than the Py-TP-BTDO rod (Figure
S7).
The UV−Vis absorption spectra and fluorescence emission
spectra were adopted to illustrate the photophysical properties
of Dc-TP-BTDO and Py-TP-BTDO in the solid state. As
shown in Figure 1d, Py-TP-BTDO shows a red-shifted light
absorption edge compared with Dc-TP-BTDO, indicating that
more visible light can be absorbed by Py-TP-BTDO during the
photocatalytic process. The calculated optical band gaps are
2.24 eV for Dc-TP-BTDO and 1.98 eV for Py-TP-BTDO
(Figure S8). Py-TP-BTDO also manifests a red-shifted
fluorescence emission peak at 651 nm compared with Dc-
TP-BTDO (592 nm), which is similar to that of the UV−Vis
207
absorption. The weaker emission intensity of Py-TP-BTDO
than that of Dc-TP-BTDO implies less radiative recombination
of the light-induced electrons and holes in Py-TP-BTDO
(Figure 1e). The energy band levels of Py-TP-BTDO and Dc-
TP-BTDO were determined by combining cyclic voltammo-
gram (CV) measurements (Figure S9) and their optical band
gaps. Both the CMPs possess sufficiently high lowest
unoccupied molecular orbital (LUMO) energy levels that
could provide enough driving force for reducing protons to
hydrogen gas (Figure 1f).
The photocatalytic properties of Dc-TP-BTDO and Py-TP-
BTDO were initially assessed by the photocatalytic hydrogen
evolution experiment on a photocatalytic reaction system
(Labsolar-6A, Beijing Perfectlight), where 10 mg of the
photocatalyst was suspended in 100 mL of mixed aqueous
solution containing AA sacrificial agent and N,N-dimethylfor-
mamide (DMF) dispersant. Both polymer photocatalysts
deliver outstanding photocatalytic activities under various
test conditions (Table 1 and Figure S10−S12). The HERs
of the bare Dc-TP-BTDO and Py-TP-BTDO could reach
82.12 and 115.03 mmol h−1 g−1 under visible light, respectively
(Figure 2a). When 3 wt % Pt was loaded, the HER of Py-TP-
BTDO was upgraded to 245.79 mmol h−1 g−1 under UV−Vis
light (Figures 2b and S11), which represents the state-of-the-
art organic photocatalysts (Table S1). The inductively coupled
plasma optical emission spectrometry (ICP-OES) revealed that
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Figure 3. (a) AQY of Py-TP-BTDO. (b) HERs of Py-TP-BTDO with different qualities in 100 mL of photocatalytic solution. (c) Time course of
hydrogen evolution for Py-TP-BTDO loading 3 wt % Pt from different batches under UV−Vis light (λ > 300 nm). (d) Stability test of bare Py-TP-
BTDO under visible light (λ > 420 nm) with intermittent degassing (black dashed lines).

Dc-TP-BTDO has a higher residual Pd content of 0.35% than
Py-TP-BTDO (0.22%) (Figure S13), which might be
responsible for the relatively weak role of the Pt cocatalyst
on boosting the photocatalytic activity of Dc-TP-BTDO
(Figure 2a,b), since Pd could also function as a cocatalyst
facilitating the photocatalytic HER.44 Notably, Py-TP-BTDO
shows a much higher photocatalytic activity than its counter-
part polymer Py-T-BTDO-3 (127.9 mmol h−1 g−1) prepared
by ternary statistical copolymerization,19 demonstrating that
the definite D−π−A structure design is an efficient strategy to
boost the photocatalytic activity since there might exist D−π−
D and A−π−A structures in Py-T-BTDO-3 from ternary
statistical copolymerization,19 which lead to the low photo-
catalytic activity of Py-T-BTDO-3. There is no doubt that the
wider optical absorption scope and less radiative recombina-
tion of light-induced charges of Py-TP-BTDO as discussed
above conduce to its higher HER than Dc-TP-BTDO. To
further illustrate the difference between the photocatalytic
activity of Py-TP-BTDO and Dc-TP-BTDO, the surface
photovoltage (SPV) and photocurrent tests were conducted.
The SPV spectra revealed that Py-TP-BTDO displays higher
photovoltage than Dc-TP-BTDO, indicative of stronger charge
separation capability for Py-TP-BTDO (Figure 2c), attributed
to its narrower band gap that facilitates the transfer of light-
induced charges, which is also consistent with the fluorescence
emission spectra. In addition, the electrochemical impedance
spectroscopy (EIS) measurement was also conducted to
explore the interfacial charge transfer kinetics of the two
polymers. It manifested that Py-TP-BTDO displays a higher
interfacial charge transfer resistance than Dc-TP-BTDO, as
revealed by the larger diameter in the Nyquist plot of Py-TP-
BTDO (Figure S14), which could be attributed to the lower
hydrophilicity of Py-TP-BTDO (Figure S6). As shown in the
208
photocurrent curves (Figure 2d), the higher photocurrent
intensity of Py-TP-BTDO implies that more light-induced
charges can be generated in Py-TP-BTDO than that in Dc-TP-
BTDO upon the optical irradiation, which could be explained
by the broader light absorption range that enables Py-TP-
BTDO to absorb more photons as well as the more efficient
separation of light-induced charge carriers of Py-TP-BTDO,
supporting well the higher photocatalytic activity of Py-TP-
BTDO.
Inspired by the high photocatalytic activity, we also explored
the photocatalytic performance of Py-TP-BTDO in pure water
and the photocatalytic solutions with different sacrificial
reagents under UV/Vis light irradiation (λ > 300 nm). As
shown in Figure S15, no hydrogen could be detected in pure
water. When using triethanolamine (TEOA) and triethylamine
(TEA) as the sacrificial agents, Py-TP-BTDO could deliver the
HERs of 3.25 and 30.98 mmol h−1 g−1, respectively (Figure
S15). These values are much lower than 245.79 mmol h−1 g−1
when using AA as the sacrificial reagent, which was also
observed in other organic polymer photocatalysts.11,20 The
photocatalytic activity for oxygen evolution was also assessed
using AgNO3, Co(OH)2, and La2O3 as the electron scavenger,
co-catalyst, and pH buffer agent, respectively, according to the
reported method.45 It revealed that Py-TP-BTDO could also
manifest a high photocatalytic oxygen evolution activity under
visible light with an average oxygen evolution rate of 90.09
μmol h−1 g−1 (Figure S16).
The high apparent quantum yield (AQY) of 39.13% was
achieved at 520 nm for Py-TP-BTDO, indicating a high solar-
to-hydrogen conversion efficiency under visible light (Figure
3a), which also exceeds that of most previously reported
organic photocatalysts (Table S1). Furthermore, the influence
of the polymer photocatalyst concentration, including 50 mg
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Figure 4. (a) Py-TP-BTDO film for hydrogen generation under natural light. (b) Home-made equipment for water-drainage and gas-gathering
experiments under natural light. (c−g) Time course of hydrogen evolution for Py-TP-BTDO with 3 wt % Pt under natural sunlight in five days
(data recorded per 30 min).

L−1 (5 mg in 100 mL), 100 mg L−1 (10 mg in 100 mL), 150
mg L−1 (15 mg in 100 mL), and 200 mg L−1 (20 mg in 100
mL), on their photocatalytic activity was evaluated. It reveals
that the HER value of Py-TP-BTDO decreased with increasing
concentration (Figure 3b). It should be noted that the absolute
amount of the produced hydrogen gas increased with
increasing concentration of Py-TP-BTDO from 50 to 100
mg L−1 and then remained relatively stable with an increase in
209
concentration, suggesting the saturation effect of the polymer
photocatalyst, which is also observed in the previous
research.28,46,47 Of note, an ultrahigh HER of 331.37 mmol
h−1 g−1 was realized by Py-TP-BTDO (Figure 3b) at a low
concentration of 50 mg L−1. Confocal laser scanning
microscopy (CLSM) measurement was conducted to reveal
the dispersion of Py-TP-BTDO in the photocatalytic solution.
As the polymer concentration increased from 50 to 200 mg
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L−1, there is no obvious change in the dispersion size of Py-TP-
BTDO, while Py-TP-BTDO indeed got aggregated (Figure
S17). This aggregation not only hinders the contact of Py-TP-
BTDO with the photocatalytic solution but restricts the
effective absorption of the incident light, resulting in the low
utilization ratio of the active sites in Py-TP-BTDO. As a result,
the absolute amount of generated hydrogen gas will reach a
stable value with the increase in the polymer concentration.
Considering the ultrahigh HER value of Py-TP-BTDO, we
synthesized other two batches of Py-TP-BTDO and measured
their photocatalytic activity under identical reaction conditions
to assess the reproducibility of the Py-TP-BTDO photo-
catalyst. Satisfactorily, all the three batches of Py-TP-BTDO
show similar photocatalytic activity (Figure 3c), demonstrating
the excellent reliability of Py-TP-BTDO as the photocatalyst
for hydrogen production. In addition, Py-TP-BTDO also
exhibits high photocatalytic stability for continuous hydrogen
evolution without significant attenuation in the photocatalytic
activity during the cycling photocatalytic experiment lasting for
14 h (Figures 3d and S18). The structure stability of Py-TP-
BTDO was evaluated by FT-IR, solid-state 13C NMR, UV−Vis
absorption, and fluorescence emission spectroscopy on the
recollected sample after the photocatalytic hydrogen evolution
experiment. The characterization results manifested no
noticeable change in the chemical structure of Py-TP-BTDO
after the photocatalytic experiment (Figure S19), indicating
the superior structural stability of Py-TP-BTDO.
For real-world applications, it is necessary to assess the
photocatalytic hydrogen evolution performance under natural
sunlight. To this end, we carried out the photocatalytic
hydrogen evolution experiment outdoor under natural sunlight
using the Py-TP-BTDO photocatalyst. We first implemented
the photocatalytic test outdoor using polymer film, which was
prepared by loading 35 mg of bare polymer on a rectangular
glass substrate with a size of 12 cm × 10 cm. Remarkably,
abundant hydrogen bubbles generated from the surface of the
polymer film could be visually observed under natural sunlight
(Figure 4a and Supporting Video 1), which was rarely achieved
by the reported polymer photocatalysts, verifying the high
photocatalytic performance of Py-TP-BTDO. In order to
quantitatively obtain the photocatalytic HER of Py-TP-BTDO
under natural sunlight, we further performed the water-
drainage and gas-gathering experiment using the polymer
suspension (Figure 4b). Impressively, 1224 mL of hydrogen
gas could be totally produced by 25 mg Py-TP-BTDO with 3
wt % Pt in 500 mL of photocatalytic reaction solution
irradiated by natural sunlight for 7 h, corresponding to an
average HER of 312.24 mmol h−1 g−1, which demonstrates that
the high photocatalytic activity of Py-TP-BTDO could be well
maintained under natural sunlight (Figure 4c and Supporting
Video 2). Considering that the concentration of the polymer
photocatalyst is identical (50 mg L−1) in both cases, the similar
HER values obtained from different approaches demonstrated
the reliability of the results. In addition, Py-TP-BTDO also
demonstrates outstanding photocatalytic stability under natural
sunlight, as evidenced by the tiny attenuation of photocatalytic
activity during the outdoor photocatalytic experiment lasting
for 5 days (Figure 4c−g), which is significant for the practical
application. The fluctuation in the photocatalytic activity
during the photocatalytic experiment outdoor should be
related to the change of light intensity, as shown in Figure
4c−g. The high photocatalytic activity and stability of Py-TP-
BTDO under natural sunlight demonstrated that it has a great
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Research Article
potential in the practical application for hydrogen evolution,
although a more comprehensive and systematic assessment for
hydrogen evolution needs to be done outdoor, in which a set
of special equipment might need to be designed and
assembled, and the related work is currently underway in our
laboratory.
■ CONCLUSIONS
In summary, we demonstrated the importance of polymer
structure design for organic polymer photocatalysts, and the
definite D−π−A structure indeed has a positive influence on
boosting the photocatalytic activity for hydrogen evolution.
Unlike the other reported D−π−A containing polymers
produced from ternary statistical copolymerization that could
generate considerable D−π−D and A−π−A structures, the
sole and definite D−π−A structure in the newly developed
polymer photocatalysts could further enhance the transmission
and separation of light-induced charge carriers. A high HER of
331.37 mmol h−1 g−1 under UV−Vis light could be obtained
by Py-TP-BTDO with an optimized polymer structure
showing a broad light absorption range and efficacious charge
separation. Remarkably, the outdoor photocatalytic experiment
also revealed the high photocatalytic activity of Py-TP-BTDO
under natural sunlight in both polymer film and polymer
suspension, where an ultrahigh HER of 312.24 mmol h−1 g−1
could be obtained as evidenced by a water-drainage experiment
performed outdoor. This work reveals the positive effect of the
D−π−A structure on the photocatalytic hydrogen evolution
performance for hydrogen generation and provides an efficient
strategy to develop high-performance organic photocatalysts
for the practical application of photocatalytic hydrogen
generation.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscatal.2c04993.
Details for monomer synthesis and characterizations of
the polymers; powder X-ray diffraction patterns; CV
curves; water contact angle images; CLSM images; and
SEM images (PDF)
Abundant hydrogen bubbles generated from the surface
of polymer film visually observed under natural sunlight
(MP4)
High photocatalytic activity of Py-TP-BTDO well
maintained under natural sunlight (MP4)
■ AUTHOR INFORMATION
Corresponding Authors
Chong Zhang − Key Laboratory for Macromolecular Science
of Shaanxi Province, Shaanxi Key Laboratory for Advanced
Energy Devices, School of Materials Science and Engineering,
Shaanxi Normal University, Xi’an 710062, P.R. China;
Email: chongzhangabc@snnu.edu.cn
Jia-Xing Jiang − Key Laboratory for Macromolecular Science
of Shaanxi Province, Shaanxi Key Laboratory for Advanced
Energy Devices, School of Materials Science and Engineering,
Shaanxi Normal University, Xi’an 710062, P.R. China; Key
Laboratory of Optoelectronic Chemical Materials and Devices
(Ministry of Education), School of Optoelectronic Materials
& Technology, Jianghan University, Wuhan 430056, P.R.
https://doi.org/10.1021/acscatal.2c04993
ACS Catal. 2023, 13, 204−212
ACS Catalysis pubs.acs.org/acscatalysis
China; orcid.org/0000-0002-2833-4753;
Email: jiaxing@snnu.edu.cn
Authors
Changzhi Han − Key Laboratory for Macromolecular Science
of Shaanxi Province, Shaanxi Key Laboratory for Advanced
Energy Devices, School of Materials Science and Engineering,
Shaanxi Normal University, Xi’an 710062, P.R. China
Sihui Xiang − Key Laboratory for Macromolecular Science of
Shaanxi Province, Shaanxi Key Laboratory for Advanced
Energy Devices, School of Materials Science and Engineering,
Shaanxi Normal University, Xi’an 710062, P.R. China
Shenglin Jin − Key Laboratory for Macromolecular Science of
Shaanxi Province, Shaanxi Key Laboratory for Advanced
Energy Devices, School of Materials Science and Engineering,
Shaanxi Normal University, Xi’an 710062, P.R. China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acscatal.2c04993
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work was financially supported by the National Natural
Science Foundation of China (22175110 & 52103264), the
Fundamental Research Funds for the Central Universities
(GK202102005 and GK202003045), and the Young Scientist
Innovation Project of School of Materials Science and
Engineering at Shaanxi Normal University (2022YSIP-MSE-
SNNU002).
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