Bandgap engineering of novel peryleno[1,12-bcd]thiophene sulfone-based conjugated co-polymers for significantly enhanced hydrogen evolution without co-catalyst

Article abstract of DOI:10.1039/d0ta07286a

Low-cost conjugated polymers as efficient photocatalytic semiconductors for hydrogen evolution have attracted worldwide attention in recent years. However, the narrow visible-light absorption spectrum, fast electron-hole recombination and expensive co-catalysts have limited their large-scale practical application in water splitting. In this work, we first developed the new peryleno[1,12-bcd]thiophene sulfone unit with extended π-conjugation, then prepared a series of sulfone-based hybrid conjugated co-polymers (PS-1-PS-8) by statistically adjusting the molar ratio of the monomer. The experimental results and DFT calculations indicated that with the gradual increase in the peryleno[1,12-bcd]thiophene sulfone contents in the polymer backbone, the optical bandgaps of co-polymers could be fine-tuned from 2.72 eV to 1.58 eV, and showed a red-shift in the visible-light region for improving the light-capturing capability. Besides, the internal charge separation capability along the co-polymers (PS-1-PS-8) was promoted. However, the driving force for proton reduction and the dispersibility of these co-polymers in aqueous solution were gradually decreased. When the molar ratio of dibenzo[b,d]thiophene sulfone to peryleno[1,12-bcd]thiophene sulfone was 19 : 1, the polymerPS-5achieved the highest hydrogen evolution rate (HER), so far, of 7.5 mmol h^?1g^?1without co-catalyst under visible light, with an apparent quantum yield (AQY) of 15.3% at 420 nm. The HER performance was almost 3 times higher than that of the typical dibenzo[b,d]thiophene sulfone-based conjugated polymerP7. This work provides a strategy for maximizing the HERs of organic semiconductors by balancing the bandgap, charge recombination, driving force and wettability.

Full text of DOI:10.1039/d0ta07286a

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Bandgap engineering of a novel peryleno[1,12-bcd] thiophene
sulfone based conjugated co-polymers for significantly enhanced
hydrogen evolution without co-catalyst
Received 00th January 20xx,
Accepted 00th January 20xx
Haonan Ye,a Zhiqiang Wang,b Zhicheng Yang,a Shicong Zhang,a Xueqing Gong b* and Jianli Hua a*
DOI: 10.1039/x0xx00000x
Low-cost conjugated polymers as efficient photocatalytic semiconductor for hydrogen evolution has attracted worldwide
attention in recent years. However, the narrow visible-light absorption spectrum, fast electron-hole recombination and the
expensive co-catalysts have limited their large-scale practical application in water splitting. In this work, we firstly developed
the new peryleno[1,12-bcd] thiophene sulfone unit with extended π–conjugation, then prepared a series of sulfone-based
hybrid conjugated co-polymers (PS-1~PS-8) by statistically adjusting the molar ratio of the monomer. The experimental
results and DFT calculation indicated with the gradually increasing of peryleno[1,12-bcd] thiophene sulfone contents in
polymer backbone, the optical bandgap of co-polymers could be fine-tuned from 2.72 eV to 1.58 eV, which showed a red-
shift trend in the visible-light region for improving the light capture capability. Besides, the internal charge separation
capability along the co-polymers (PS-1~PS-8) could be promoted. However, the driving force for proton reduction and
dispersibility in aqueous solution of these co-polymers were gradually decreased. When the molar ratio of
dibenzo[b,d]thiophene sulfone to peryleno[1,12-bcd] thiophene sulfone was 19:1, the polymer PS-5 achieved so far highest
hydrogen evolution rates (HERs) of 7.5 mmol h -1 g -1 without co-catalysts under visible light, whose an apparent quantum
yield (AQY) was up to 15.3 % at 420 nm. The performance of HERs is almost 3 times higher than that of the typical dibenzo[b,
d]thiophene sulfone-based conjugated polymer P7. This work provided a strategy for maximizing the HERs of organic
semiconductor by balancing band gap, charge recombination, driving force and wettability.
26
microporous polymers (CMPs),25,
conjugated organic
28
frameworks (COFs),27,
and covalent triazine frameworks
1. Introduction
(CTFs)29-31 as photocatalytic materials. Compared to inorganic
semiconductors, organic photocatalysts have the advantages of
adjustable energy levels, electronic structures and numerous
modification sites according to various monomers and synthesis
methods.32-38
As a clean energy source, the hydrogen has high energy density,
and also is raw material for many industrial products.1-5
Besides the commonly used industrial methods for hydrogen
production,6 photocatalytic water-spitting for hydrogen
evolution has attracted researchers' attention due to the
advantage of endless solar energy.7-11 Since Fujishima’s
research on the photocatalytic activity of TiO2,12 there were
many semiconductor materials used for photocatalytic
hydrogen generation.13-15 However, most of these materials
were expensive inorganic semiconductors with the moderate
ability to capture visible light.16 In 2009, Wang’s work on
graphitic carbon nitride (g-C3N4) for hydrogen evolution
reawakened the researchers’ passion on various organic
semiconductor,17-20 such as linear polymers,21-24 conjugated
Notably, there are multiple factors that affected the
photocatalytic performance of polymers for hydrogen evolution
found by hundreds of researches, including visible-light
absorption, charge separation and interface chemical
reaction.39, 40 Recently, Cooper et al. developed a library of high-
throughput techniques to synthesize more than 170 co-
polymers, and described several main variables probably
influence the hydrogen evolution rates (HERs)41. Among those
co-polymers, the dibenzo-[b,d]thiophene sulfone units has
attracted the attention due to its strong charge separation
ability and excellent hydrophilicity.21-23, 42-44 In 2016, Cooper et
al. reported a series of conjugated polymers with different band
gaps and HERs, and firstly discovered the co-polymerized
dibenzo-[b,d]thiophene sulfone based polymer (P7) owned the
excellent photocatalytic performance.21 And Liu et al.
investigated the effect of different donor units on the hydrogen
production efficiency of D-A type dibenzo-[b,d]thiophene
sulfone-based conjugated polymers.42 Subsequently, the
a. Key Laboratory for Advanced Materials, Institute of Fine Chemicals, School of
Chemistry and Molecular Engineering, East China University of Science and
Technology, 130 Meilong Road, Shanghai, 200237, China. E-mail:
jlhua@ecust.edu.cn (J. Hua)
b. Key Laboratory for Advanced Materials, Centre for Computational Chemistry and
Research Institute of Industrial Catalysis, School of Chemistry and Molecular
Engineering, East China University of Science and Technology, Shanghai 200237,
P.R. China. E-mails: xgong@ecust.edu.cn (X. Gong)
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
homopolymer of dibenzo[b,d]thiophene sulfone
(P10)
developed by Cooper et al. achieved a high HERs and an
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ARTICLE
Journal Name
excellent external quantum efficiency (11.6 %, 420 nm).22 It is The original compounds of perylene, dibenzo[b,d]thiophene 5,5-
View Article Online
worth noting that lots of dibenzo[b, d]thiophene sulfone-based dioxide
and
1,4-bis(4,4,5,5-tetramethDylO-1I:,310,2.1-0d3io9x/Dab0oTAro0l7a2n8-62A-
conjugated polymers were designed and the photocatalytic yl)benzene were all commercially purchased and used directly
activity for hydrogen production of these semiconductors were without further purification. All reagents and catalysts used in the
at top-performance among the series of Suzuki-polymerization reaction were also purchased commercially and all glassware were
conjugated polymers.39, 45
dried at high temperatures. For efficient chemical reactions, all
However, the absorption spectrum of most dibenzo[b, reactions were vacuumed and operated under nitrogen protection.
d]thiophene sulfone-based conjugated polymers is not strong In addition, the reaction intermediate (peryleno[1,12-bcd]
enough. Moreover, it is necessary to apply expensive noble thiophene) and the monomers (3,7-dibromodibenzo[b,d]thiophene
metal co-catalysts such as platinum to accelerate the hydrogen 5,5-dioxide and 3,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-
evolution, due to the existent of strong trend of charge- yl)dibenzo[b,d]thiophene 5,5-dioxide) were synthesized according to
recombination in the polymer backbone, which is not suitable previous works.47, 48 The synthetic route of 3,10-dibromoperyleno
for practical applications.45 Recently, our group firstly prepared [1,12-bcd]thiophene 1,1-dioxide was described in supporting
N-annulated perylene-based polymer (P3), and the P3/g-C3N4 information.
heterojunction behaved outstanding visible-light capture
ability, leading to significantly increase HER of 13.0 mmol h −1
g
−1 with a recorded AQY of 27.32% even at 520 nm.46 In this work,
we firstly developed the new peryleno[1,12-bcd] thiophene
sulfone unit with extended π–conjugation, and then prepared a
series of sulfone-based conjugated polymers (PS-1~PS-8) via Pd
(0)-catalyzed Suzuki co-polymerization method. The general
synthetic route was shown in Scheme 1. Subsequently, we
further explored the effects of the ratio of peryleno[1,12-bcd]
thiophene sulfone monomers on the optical band gap, energy
level structure, charge separate and photocatalytic
performance of the as-prepared samples. The experimental
results and DFT calculation suggested that, with the increasing
of peryleno[1,12-bcd] thiophene sulfone content in the hybrid
polymer, the absorption spectra of polymers showed a huge
red-shift trend in the visible-light region, and the charge
separation and transfer capability along the polymer backbone
was enhanced. And the polymer PS-5 with a molar ratio of
Scheme 1. General synthetic routes of the PS-1~PS-8
dibenzo[b,d]thiophene
sulfone
to
peryleno[1,12-bcd]
thiophene sulfone (19:1) achieved the highest HERs of 7.5 mmol
h -1 g -1 without co-catalysts loading, with a recorded AQY of 15.3
% under λ = 420 nm monochromatic illumination, to the best of
our knowledge, which was the recorded value among all the
reported liner conjugated polymers. However, with the further
feed ratio of peryleno[1,12-bcd] thiophene sulfone content in
polymer skeleton, the lowest unoccupied molecular
orbital (LUMO) of the sample gradually lied lower in energy
level and got almost closed to H2O/H2 redox potential, leading
the thermodynamic driving force for proton reduction was
decreased. Besides, the dispersibility in aqueous solution of co-
polymers decreased and further decelerating proton reduction
reaction on polymer surface. Hence, a sudden drop in HERs was
observed down the series and the PS-8 almost behaved
negligible photocatalytic performance. This work highlights that
rationally balancing the multifarious factors on photocatalytic
activity is crucial for maximizing the HERs of organic
semiconductor. More importantly, all as-prepared polymers
were not loaded with nanoparticle platinum as co-catalyst for
HERs.
2.2． Synthesis of polymers (PS-1~ PS-8)
As shown in Scheme 1, the conjugated polymers were synthesized
by classical Suzuki–Miyaura polymerization,49, 50 and the starting mat
erials are dibromo arenes and diboronic ester arenes. The general sy
nthesis process of Suzuki–Miyaura polymerization is as follows: To a
mixture solution of diboronic ester arenes monomer (1,4-bis(4,4,5,5
-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (A) or 3,7-bis(4,4,5,5-t
etramethyl-1,3,2-dioxaborolan-2-yl)dibenzo[b,d]thiophene 5,5-dioxi
d--e (B), 1 mmol) and dibromo arenes monomer (3,7-dibromodibenz
o[b,d]thiophene 5,5-dioxide (C) or 3,10-dibromoperyleno[1,12-bcd]t
hiophene 1,1-dioxide (D), 1 mmol) in degassed toluene (15 mL), wer
e added tetrakis(tri-phenylphosphine) palladium (0) (11.5 mg, 0.01
mmol), 2M aqueous solution of potassium carbonate (8 mL, 12 mmo
l)and one drop of Aliquat 336 (methyltrioctylammonium chloride) e
m-ployed as a phase transfer catalyst to promote polymerization re-
action in Schlenk tube. And the mixture solution was first vacuumed
and then heated under nitrogen for 48 h at 110 oC. The reaction pro
-duct was subsequently washed with water (100 mL *3) and methan
2. Experimental Section
2.1. Chemicals and materials
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Fig. 1. (a) FTIR spectra of the PS-1~PS-8 polymers; (b) Solid state 13C NMR of the PS-1~PS-8 polymers; (c) PXRD of the PS-1~PS-8 polymers.
ol (100 mL *3). After Soxhlet extraction for 2 days with acetone and
and corresponding molecular frontier orbitals were calculated
chloroform, and the final product was obtained after drying to give a without symmetry constrains at the B3LYP/6-311+G* level.52-54 To
yield of 53.8 % - 78.8 %. The specific synthesis steps of polymers we study the solvent (water) effect, the self-consistent reaction field
re described in supporting information.
method based on the SMD model was utilized.55
2.3． Photocatalytic hydrogen production and apparent quantum
yield (AQY) experiment
3. Results and discussion
3.1. Synthesis
According to previous work,21,
The photocatalytic hydrogen evolution experiments were carried out
under 300 W xenon lamp (CEL-HXF 300) irradiation in a glass gas-
closed-circulation system (CEL-SPFLU-DFBZN) connected to a Gas
chromatography (GC 2060, TCD detector, and Ar carrier). 25 mg
sample of polymer (PS-1~PS-8) dispersing in deionized water solution
with 20 vol. % triethanolamine as sacrificial agent was employed to
photocatalytic test. Before the test, the whole device was first
vacuumed by a vacuum pump to less than -0.1 Mpa, and
photocatalytic reactor was then placed under visible-light
illumination (300 W xenon lamp, 420 nm ≤ λ ≤ 780 nm) for testing.
Moreover, AQY measurement for H2 generation was performed
under at monochromatic light irradiation (300 W xenon lamp, λ =
420, 435, 475, 500, 520, 550, 630 nm) with 10 % filter film. 12.5 mg
sample of polymer (PS-1~PS-8) dispersing in deionized water solution
with 20 vol. % triethanolamine as sacrificial agent. The calculation
formula of AQY was estimated as Equation:
22
dibenzo[b,d]thiophene sulfone-
based polymers P7 and P10 showed excellent photocatalytic
performance due to their strong charge separation ability and
excellent hydrophilicity. In order to further broaden the light
absorbed range of P7 (named as PS-1 in this work), we designed and
synthesized peryleno[1,12-bcd] thiophene sulfone-based polymer
PS-2 with extended π–conjugation polymer backbone (Series-1 in
Scheme 1). Furthermore, based on the homopolymer of
dibenzo[b,d]thiophene sulfone P10 (named as PS-3 in this work), a
series of hybrid polymers were synthesized by gradually replacing the
dibenzo[b,d]thiophene sulfone unit with peryleno[1,12-bcd]
thiophene sulfone in the skeleton of polymer (PS-4~PS-8 of Series-2
in Scheme 1). These eight polymers were prepared by Pd (0)-
catalyzed Suzuki co-polymerization method in 110 oC for 48 h, in
which the general synthetic route was shown in Scheme 1.
ퟐ ×퐂 ×퐍퐀
AQY (%) = ퟐ × 퐍퐮퐦퐛퐞퐫 퐨퐟 퐞퐯퐨퐥퐯퐞퐝 퐇ퟐ 퐦퐨퐥퐞퐜퐮퐥퐞퐬 ×100 % =
× ퟏퟎퟎ %
훌
퐍퐮퐦퐛퐞퐫 퐨퐟 퐢퐧퐜퐢퐝퐞퐧퐭 퐩퐡퐨퐭퐨퐧퐬
퐒 ×퐏 × 퐭
퐡 ×퐜
3.2. Structural and morphological characterization
Owing to the lack of solubilizing side chains in skeleton, all as-
prepared polymer powders were insoluble in common organic
solvents (DCM, THF, CHCl3, DMSO, acetone). The chemical
structures of samples were evidenced by FTIR spectroscopy and
solid-state 13C NMR. As shown in Fig 1a, the peak at around
1600 cm−1 belonged to the aromatic ring C=C stretching
vibrations, showing that the benzene ring of the polymer was
not damaged during the copolymerization process. The typical
vibration peak at 1145 cm-1 and 1310 cm-1 was attributed to the
where, C is the hydrogen evolution amount (μmol) per hour; NA is
the Avogadro constant (6.022×1023 mol-1); S is the illumination area
(12.56 cm2); P is the light intensity (20.62 W cm-2); t is the illumination
time (3600 s); λ is the wavelength of the monochromatic light (m); h
is the Plank constant (6.626 × 10-34 J s); c is the speed of light (3 × 108
m s-1).
2.4．Computational details
Spin-unrestricted density functional theory (DFT) calculations were
performed using the Gaussian 09 program package.51 All structures
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Fig. 2. UV–vis diffuse reflectance spectra of PS-1 and PS-2 (a); PS-3 to PS-8 (b);
Tauc plots of PS-1 and PS-2 (c); PS-3 to PS-8 (d).
Fig. 3. Cyclic voltammetry measurements of PS-1 to PS-4 (a) and PS-5 to PS-8
(b) in THF solution; (c) Energy levels of PS-1 to PS-8; (d) The colors of PS-1 to
PS-8.
O=S=O
dibenzo[b,d]thiophene
group,
confirming
sulfone
the
or
existence
peryleno[1,12-bcd]
of
obviously underwent red-shift for polymers (PS-4 to PS-7), and
located at around 475 nm and 608 nm for PS-8 (Table 1). And as
shown in Fig. 3d, the prepared polymers showed the
appearance of color ranging from yellow-green (PS-3) to brown
thiophene sulfone unit in polymer backbone. In addition, a
broad peak at 3400 cm−1 was assigned to physically adsorbed
water. The chemical structures of polymers were further
characterized by solid-state 13C NMR (Fig. 1b), and all the solid-
state 13C NMR spectra of resulting the polymers solid-state
exhibited broad peaks ranging from 100 to 160 ppm,
corresponding to signals of aromatic carbons. Besides, the
typical signal of borate groups was not detected, suggesting the
completion of polymerization. The crystal structures of
polymers were characterized by PXRD (Fig. 1c). There were
some hump detecting in PXRD, which might attribute to the π-
π stacking between the polymer backbones and those peaks
were also found in other reported conjugated polymers,
indicating the amorphous or semi-crystalline structure of all
samples.21, 26, 42 And the micromorphology of polymers was
analyzed by Scanning Electron Microscopy (SEM) image (Fig.
S1), in which all as-prepared samples showed nanoparticle-like
shapes.
(
PS-6), and further to black (PS-8). Moreover, the optical gaps
(Eg) of polymers determined from Tauc plots were 2.72 eV for
PS-1 and 2.02 eV for PS-2, respectively. For the series-2, the Eg
gradually became narrower from 2.63 eV (PS-3) to 1.58 eV (PS-
8), and the corresponding data is listed in Table 1. Light
absorption is always regarded as one of the key factors affecting
the photocatalytic activity of the semiconductors. The more
protons the photocatalysts absorb, the more excitons they will
generate for the photocatalytic redox reaction. We found that
polymers obtained
a decreasing optical gaps with the
introduction of peryleno[1,12-bcd] thiophene sulfone in the
polymer backbone, which was beneficial for visible-light
absorption.
3.4. Electrochemical properties and energy level
The electrochemical properties of the as-prepared samples
were further characterized by oxidative half cyclic
voltammograms with a traditional three-electrode system.
Here, the ferrocene/ferrocenium (Fc/Fc+) was employed as an
external potential reference and 0.1M tetra-n-butylammonium
hexafluorophosphate (TBAPF6) in ultra-dry THF was used as
electrolyte solution. The highest occupied molecular orbital
(HOMO) (eV) was determined according to EHOMO (eV) = −4.8 eV
- (E ox_onset (vs SCE)- EoxFc/Fc+ (vs SCE)), and the EoxFc/Fc+ is 0.51 V vs
SCE in this work (Fig. S2). As shown in Fig. 3a and 3b, the Eox_onset
of PS-1 and PS-2 were 1.16 V and 1.25 V versus SCE, and the
corresponding HOMO values were -5.45 eV and -5.54 eV versus
vacuum (Fig. 3c), respectively. For the series-2, the HOMO
values of PS-3 to PS-8 calculated from Eox_onset were -5.57 eV, -
5.60 eV, -5.66 eV, -5.70 eV, -5.76 eV and -5.83 eV versus
vacuum, respectively. With the feed ratio of peryleno[1,12-bcd]
thiophene sulfone in the polymer backbone, the HOMO values
3.3. Optical properties characterization
The optical properties of as-prepared samples were
characterized by UV–vis diffuse reflectance spectra (DRS). As
shown in Fig. 2a, PS-1 behaved poor visible-light response
spectrum and showed a major absorption peak located at
nearby 420 nm, while the PS-2 showed obviously red-shifted
because of the extended π-conjugation degree for
peryleno[1,12-bcd] thiophene sulfone. Similar result was also
observed in series-2 (Fig. 2b), PS-3 exhibited an absorption peak
located at around 440 nm, and with the increasing of
peryleno[1,12-bcd] thiophene sulfone content, the spectra of
polymers (PS-4 to PS-8) showed a new red-shift wide absorption
peak appeared in the visible region. Among them, PS-8 with the
highest content of peryleno[1,12-bcd] thiophene sulfone
achieved almost full visible spectrum absorption. The
corresponding absorption peak located at 440 nm and 520 nm
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Table 1. Maximum absorption wavelength, photophysical properties, and hydrogen evolution rate of the as-prepared polymers
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DOI: 10.1039/D0TA07286A
Contact angleh
λ max a (nm)
in solid
420
LUMO b
(eV)
HOMO c
(eV)
HER e
D[4,3] f
(nm)
D[3,2] g
(nm)
Eg d (eV)
(o)
(mmol h-1 g-1)
PS-1
PS-2
PS-3
PS-4
PS-5
PS-6
PS-7
PS-8
-2.73
-3.52
-2.94
-3.45
-3.54
-3.61
-3.69
-4.25
-5.45
-5.54
-5.57
-5.60
-5.66
-5.70
-5.76
-5.83
2.72
2.02
2.63
2.15
2.12
2.09
2.07
1.58
2.6
4.0
1213.9
1461.8
791.1
832.2
843.7
880.2
895.3
941.2
4052.78
68.81
71.75
58.18
62.21
62.49
63.46
64.01
66.37
450; 568
440
5016.8
830.4
870.3
905.9
958.2
961.3
1176.2
4.5
440; 512
440; 519
440; 523
440; 528
475; 608
6.1
7.5
4.1
2.3
0.025
a The maximum absorption wavelength of polymers in soild. b LUMO energy level calculated from HOMO and optical bandgaps. c HOMO energy level measured
by CV measures. d The optical bandgaps calculated from the UV-vis diffuse reflectance spectra. e 25 mg catalyst without Pt-loading under visible light illumination
(λ > 420 nm). f Volume mean diameter. g Surface area mean diameter (Sauter mean diameter). h Water Contact angle (o)
of polymers gradually lied lower in energy level. In addition, the samples. With the increasing of the peryleno[1,12-bcd]
LUMO energy level were determined according to ELUMO = EHOMO thiophene sulfone content in the hybrid polymer (searie-2), the
+ Eg, and the LUMO values of PS-1 and PS-2 were -2.73 eV and - LUMO of the copolymers got more close to the H2O/H2 redox
3.52 eV versus vacuum (Fig. 3c), respectively. For the series-2, potential, and the driving force for H+ reduction reduced ranged
the LUMO values of PS-3 to PS-8 exhibited a similar trend as from ~ 1.55 eV to ~ 0.15 eV, which might play an important role
their HOMO values, and PS-8 lied the lowest in energy level at - in hydrogen evolution in lots of recent researches.41, 56, 57
4.25 eV versus vacuum (Fig. 3c). The values of HOMO, LUMO
and Eg were listed in Table 1, and the corresponding energy level
diagram was shown in Fig. 3c. Notably, the LUMO of all
3.5. Photocatalytic hydrogen production and stability
polymers lied higher in energy level than the H2O/H2 redox We then investigated the photocatalytic hydrogen evolution
potential(-4.5 eV versus vacuum), suggesting that they have the rates (HERs) of polymers. The 300 W xenon lamp and the TEOA
potential to participate in photocatalytic water-splitting for was employed as light source and sacrificial electron donor for
hydrogen evolution. In addition, the photoluminescence (PL) regeneration of oxidation samples, respectively. The quality of
spectroscopy (λexc = 385 nm) of as-prepared samples in THF the prepared sample employed in the experiment was 25 mg.
solution were shown in Fig. S3-S4.
More importantly, all as-prepared samples were not loaded
Based on the above experiments, a series of sulfone-based with nanoparticle high-price platinum as co-catalyst. Firstly, as
polymers were successfully prepared and a possible mechanism shown in Fig. 4a, upon visible-light illumination (λ > 420 nm), the
for photocatalytic hydrogen production was proposed. Upon average amounts of hydrogen produced by PS-1 and PS-2 were
illumination, photo-generated electron-hole pairs (Frenkel 2.6 mmol h-1 g-1 and 4.0 mmol h-1 g-1, respectively. Compared to
excitons) were created and then migrated to the surface of PS-1, PS-2 showed higher activity of hydrogen evolution due to
polymer. Electrons jump into LUMO from HOMO of the polymer its wider visible-light absorption range. Then for series-2, the
and then reduced H+ to hydrogen, and the holes are reduced by HERs chart of polymers (PS-3 to PS-8) behaved as a volcanic
the TEOA employed as sacrificial electron donor. However, pattern, in which the HERs of photocatalysts firstly rose and
compared to inorganic semiconductor, most organic materials then went down with the further increasing of the
with strong binding energies typically have the trend to undergo peryleno[1,12-bcd] thiophene sulfone content. From PS-3 to
charge recombination and exciton dissociation cannot be PS-5, the HERs of samples increased as the optical gap was red-
carried out easily and spontaneously. Hence in most cases, shifted, and the polymer PS-5 obtained the highest hydrogen
those undissociated electron-hole pairs (Frenkel excitons) evolution rate (7.5 mmol h-1 g-1), which was at top-performance
usually have to migrate to the interface between photocatalyst in the liner conjugated polymers for hydrogen evolution
and aqueous solution, and one of the charge carriers undergo without Pt-loading. However, with the further increasing of the
redox reaction while the remaining one subsequently takes part peryleno[1,12-bcd] thiophene sulfone contents in series-2, the
in another reaction.39 Therefore, those charge carriers must HERs of polymers from PS-5 to PS-8 gradually reduced, which
possess strong thermodynamic driving force for corresponding might be ascribed to the decreasing driving force for H+
reaction, such as proton reduction in hydrogen evolution, and reduction. And the polymer PS-8 with the lowest
the driving force descried here often refers to the energy level thermodynamic driving force (0.25 eV) showed the very poor
offset between the LUMO level of the photocatalyst and the HER (0.025 mmol h-1 g-1), although it behaved the widest visible-
H2O/H2 redox potential. In this work, we successfully employed light absorption capacity among all as-prepared samples. For
bandgap engineering by adjusting the ratio of peryleno[1,12- comparison, the polymers PS-1 and PS-3 showed the
bcd] thiophene sulfone content in polymer backbone to finely approximate performance to P7 and P10 with similar structure
tune the optical properties and energy level structures of
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DOI: 10.1039/D0TA07286A
Fig. 4. (a) Photocatalytic hydrogen evolution rates of PS-1 to PS-8; (b) Photostability for H2 production of PS-1 to PS-4; (c) Photostability for H2 production of PS-
to PS-8; (d) Correlation of the amount of platinum loaded onto polymers with the observed photocatalytic hydrogen evolution rates from
5
water/methanol/triethylamine mixtures under visible light. The amount of platinum in each samples was measured via ICP-AES; (e) Wavelength-dependent AQY
and DRS spectrum of PS-2 (λ = 420, 435, 475, 500, 520, 550 and 630 nm. Reaction conditions: 50 mL deionized water, 12.5 mg photocatalyst, 10 mL TEOA. (f)
Wavelength-dependent AQY and DRS spectrum of PS-5 (λ = 420, 435, 475, 500, 520, 550 and 630 nm. Reaction conditions: 50 mL deionized water, 12.5 mg
photocatalyst, 10 mL TEOA.
reported in the literature,21, 22 indicating the reliability of our λ = 420 nm monochromatic illumination, to the best of our
experiments.
knowledge , which was the recorded AQY value among liner
The long-term experiment of photocatalytic stability was conjugated polymers (P10, AQY420= 11.6 %). The PS-5 also
lasted for 15 hours with each cycle of 5h. As shown in Fig. 4b obtained high AQY values (1.93 %) in the long wave range (λ =
and 4c, the hydrogen producing properties of the polymers did 550 nm).
not significantly decrease after the photocatalytic reaction. The
structural stability of polymers was confirmed by FTIR (Fig. S5-
S6) and DRS (Fig. S7-S8) of post-reaction samples, and all
3.6. Computational and photo-electrochemical studies
polymers didn’t show any significant change in light absorption Promoting the separation of photo-generated electron-hole
range. In addition, polymers (PS-1
~
PS-8) were synthesized via pairs also plays important roles in improving photocatalytic
46
Pd (0)-catalyzed Suzuki polymerization and Pd nanoparticles performance of organic semiconductor.23,
Hence, DFT
could also be employed as co-catalyst for accelerating proton calculations were carried out not only to gain insightful
reduction reaction. Hence, as shown in Fig. 4d, residual information about the trend of bandgap, but also deeply
palladium was characterized by ICP-AES, and their residual explore the electronic structure of co-polymers for better
contents were range from of 0.23 wt% ~2.10 wt% for the co- understanding the relationship between structure and
polymers. However, the amount of residual palladium was not photocatalytic performance. We optimized the structures and
directly related to the HERs of polymers, suggesting the residual obtained the molecular orbital diagrams of the oligomer models
palladium had no obviously effect on the HERs.
(Fig. S10), and the distribution of frontier molecular orbitals of
4) are shown in Fig. 5. Firstly, the energy
To explore the relationship between photocatalytic four models (models 1
~
activity and absorption spectrum of as-prepared samples, AQY level position and band gap of samples calculated by DFT give
measurement was employed under various monochromatic the same trend as the experimental results, in which the Eg
light irradiations with a 10% filter. As shown in Fig. 4e and 4f, a become narrower and the LUMO values lie lower in energy level
good correlation between the AQY value and the absorption
intensity of polymers at different wavelengths was detected,
indicating that the hydrogen evolution was photocatalytic
reaction. Compared to that of PS-1 (4.2 %) (Fig. S9), the AQY
values of PS-2 (11.5 %) with peryleno[1,12-bcd] thiophene
sulfone as acceptor unit were much higher under λ = 435 nm
monochromatic illumination due to its wider visible-light
absorption range. Moreover, the PS-2 even obtained AQY value
at 3.9 % under λ = 550 nm monochromatic illumination,
indicating its high activity in the long wave range. More
importantly, the AQY value of PS-5 with a molar ratio of 19:1 of
dibenzo[b,d]thiophene
thiophene sulfone was up to15.3 % without co-catalysts under
sulfone
to
peryleno[1,12-bcd]
Fig. 5. The distribution of frontier molecular orbitals of four models: (a) Models
1; (b) Models 2; (c) Models 3; (d) Models 4.
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photocatalytic activity. Moreover, the EIS measurement was
View Article Online
DOI: 10.1039/D0TA07286A
employed to study the charge transfer efficiency of polymers
(Fig. 6b). Generally speaking, decreased radius showed the
lower charge transfer resistance as well as higher charge
mobility. In all samples, with the introduction of peryleno[1,12-
bcd] thiophene sulfone unit, the polymers behaved decreased
radius in EIS measurement, and the PS-8 obtained the smallest
radius, suggesting the improved photo-induced charge
conductivity.
The photoluminescence (PL) spectroscopy of polymers was
carried out for studying the charge transfer kinetics. As shown
in Fig. 6c, PS-1 showed strong fluorescent peak at 427 nm due
to the charges recombination. After introducing peryleno[1,12-
bcd] thiophene sulfone unit, PS-2 behaved relatively lower
fluorescent peak at 578 nm, indicating that the charges
recombination was effectively suppressed. Similarly, in series-2,
with the further feed ratio of peryleno[1,12-bcd] thiophene
sulfone content in polymer skeleton, polymers exhibited
Fig. 6. (a) Transient current responses to full time and on–off cycles
photocurrent of illumination on PS-1~PS-8 membrane electrodes, respectively
(0 bias); (b) EIS Nyquist plots of PS-1~PS-8 at open circuit voltage; (c)
Photoluminescence (PL) spectra of PS-1~PS-7 in THF solution; (d) Time-
resolved fluorescence spectroscopy of PS-1~PS-7 in THF solution.
gradually reduced fluorescent strength from PS-3 to PS-7
,
indicating the enhanced charge-separate rate. The time-
resolved fluorescence (TRFS) measurements to quantify the
after introducing peryleno[1,12-bcd] thiophene sulfone unit in lifetimes of the charges are carried out for the electron
polymer backbone. In addition, compared with the model 1 recombination/transfer kinetics analysis. As shown in Fig. 6d,
(oligomer of PS-1), the peryleno[1,12-bcd] thiophene sulfone the relative data of fluorescence lifetimes of samples were 0.97
unit with coplanar structure can markedly contribute to the ns, 0.98 ns, 1.00 ns, 1.01 ns, 1.03 ns, 1.03 ns and 1.04 ns for PS-
LUMO of model 2 (oligomer of PS-2), and model 2 exhibit higher
1~PS-7, respectively. Longer decay lifetime usually means
degree of LUMO-HOMO separation, indicating that the slower electron-holes recombination and higher charge
effective separation of electron-hole pairs existing in the separation. And PS-7 behaved the lowest fluorescent peak and
backbone of model 2. Similarly, it is also clear that the model 4 longest decay lifetime in all polymers, while the fluorescence
also exhibit higher degree of LUMO-HOMO separation than that emission of PS-8 was too low to be detected. All in all, with the
of model 3. The excellent flatness of monomers contributes to increasing of peryleno[1,12-bcd] thiophene sulfone unit, the
the decrease in exciton binding energy,23 and the introduction separation and transfer photogenerated electron-hole pairs
of monomers with extended conjugation into polymer were accelerated, and might further promote proton reduction
backbone, such as perylene or pyrene unit, would be helpful for reaction on polymer surface.
charge separation capability.42,46 Therefore, we speculated that
the introduction of peryleno[1,12-bcd] thiophene sulfone unit
with extended π-conjugation in the polymer could promote the
3.7. Surface dynamics analysis
separation of photo-generated charges, which might benefit for Compare to conjugated polymers containing other monomers,
proton reduction reaction on polymer surface.
sulfone-based polymers showed ultra-high photocatalytic
The speculation was supported by photo-electrochemical hydrogen production performance because the localization of
characterization. Firstly, the transient photocurrent responses water around the hydrophilic sulfone groups in polymer
(I–t) and electrochemical impedance spectra (EIS) were backbone is crucial for interface proton reduction reaction.22
employed to investigate the charge separation and migration of Hence, we studied the effect of the introduction of
as-prepared samples. Traditional three-electrode system was peryleno[1,12-bcd] thiophene sulfone unit on the hydrophilicity
used in these tests, and the preparation process of working and interfacial reaction kinetics of polymers. In general, the
electrode was shown in experimental details. As shown in Fig. better the hydrophilicity of the polymer obtains, the smaller the
6a, all I–t curves of samples showed well correlation of on–off particle size of the semiconductor has, which may contribute to
visible-light illuminate, implying the photocatalytic activity of shorter charge transfer path from internal to surface of
polymers. Among samples, PS-1 obtained the lowest semiconductor, higher external surface and better activity for
photocurrent density of
peryleno[1,12-bcd] thiophene sulfone unit,
photocurrent density was reached for PS-2 at
0.6 µA cm-2. In particle size of polymer related to its hydrophilicity was
addition, the photocurrent densities of PS-3 PS-7 were 0.8 µA characterized by the dynamic light scattering (DLS)
cm-2, 0.9 µA cm-2, 1.0 µA cm-2, 1.2 µA cm-2 and 1.3 µA cm- measurement, the corresponding calculated particle sizes are
2, respectively, and the PS-8 obtained the highest photocurrent listed in Table 1. And the particle size distribution of all polymers
densities at
1.4 µA cm-2. Obviously, there was a positive from DLS was between hundreds and thousands of nanometers.
~
0.3 µA cm-2. After introducing further participating in the interface proton reduction reaction
higher to promote hydrogen evolution.58 As shown in Fig. 7a, the
a
~
~
~
~
~
~
~
~
correlation between photocurrent density and the
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statistical co-polymerization and investigated for efficient
View Article Online
hydrogen evolution. The experimentDalOI:r1e0s.1u0l3t9s/Da0TnAd072D8F6AT
calculation clearly indicated that, the material’s band gap,
charge separation ability, driving force for proton reduction, the
wettability and the photocatalytic activity were finely turned by
the ratio of monomers. Based on the basic calculation formula
of photocatalytic efficiency (Efficiency (ŋ) = ŋSolar light adsorption
×
ŋCharge separation × ŋConversion reaction),45 the photocatalytic activity of
polymers is not only affected by light absorption, but also
influenced by the charge separation ability of semiconductors
and interfacial reactions. Firstly, the visible-light capability of
semiconductor is widely believed to be one of the important
factors affecting photocatalytic activity. After replacing the
dibenzo[b,d]thiophene sulfone unit with peryleno[1,12-bcd]
thiophene sulfone in the skeleton of polymer, PS-2 exhibited
the wider visible-light absorption range, resulting in the higher
HERs than PS-1. For series-2, with the increasing peryleno[1,12-
bcd] thiophene sulfone content, the visible-light capture
capability of polymers was hugely enhanced and hence more
photons were absorbed, indicating that the more excitons were
generated for the photocatalytic redox reaction. As a results,
Fig. 7. (a) Dynamic light scattering measurements of as-prepared samples; (b)
Water contact angle of as-prepared samples.
Compare to PS-1 (4053 nm), the surface area mean diameter of
PS-2 increased to 5017 nm, suggesting that PS-2 had the bigger
the HERs of PS-3, PS-4 and PS-5 showed a trend of increasing
particle
size.
For
series-2,
homopolymer
of
performance, and PS-5 reached the highest HERs.
dibenzo[b,d]thiophene sulfone PS-3 by replacing benzene with
hydrophilic sulfone behaved a sharply reduced particle size, and
the surface area mean diameter of PS-3 was 830 nm. However,
with the gradually increasing the peryleno[1,12-bcd] thiophene
sulfone content, the surface area means diameter of samples
Secondly, the internal charge separation ability was
discussed in photoelectrochemical experiments and DFT
calculation. After introducing the peryleno[1,12-bcd] thiophene
sulfone, the polymers behaved the higher degree of LUMO-
HOMO separation and faster charge transfer, which was
benefited for hydrogen evolution. In addition, compared to
inorganic semiconductor, most organic materials with strong
binding energies typically have the trend to undergo charge
recombination and exciton dissociation cannot be carried out
easily and spontaneously. With the further increasing of the
peryleno[1,12-bcd] thiophene sulfone in the skeleton of
polymer, the LUMO lied lower in energy level, resulting in the
decreasing of thermodynamic driving force for electron-holes
separation and proton reduction. So at the beginning of series-
2 (PS-3 to PS-5), we supposed that the driving force was enough,
the broaden visible-light absorption and the improved internal
charge separation ability were the main factors accelerate the
hydrogen generation. However, with the further lowering
LUMO of polymers, the decreased thermodynamic driving force
might dominate the HERs, and the PS-8 with the lowest
thermodynamic driving force (0.25 eV) even showed the
negligible HER at 0.025 mmol h-1 g-1, although it behaved the
narrowest band gap among all as-prepared samples.
(
PS-3~PS-8) increased. It was obviously found that with the
increasing of the peryleno[1,12-bcd] thiophene sulfone content
in the hybrid polymer, the particle size of polymers increased
and the hydrophilicity of the samples decreased, which was not
conducive to photocatalytic processes.
The same phenomenon was also observed in the water
contact angle experiment (Fig. 7b). Compare to the PS-1 (68.81
o
o), the water contact angle of PS-2 increased to 71.75
,
indicated the that PS-2 had worse hydrophilicity. And for series-
2, with the increasing of the peryleno[1,12-bcd] thiophene
sulfone content, the water contact angle of samples (PS-3 to PS-
o
o
8
) gradually increased from 58.18 to 66.37 . The larger the
water contact angle of the semiconductor has, the worse the
hydrophilicity of the polymer obtains. It was found that the
hydrophilicity of the sulfone group is critical to the high catalytic
activity of the polymers, and the peryleno[1,12-bcd] thiophene
sulfone with extending π–conjugation has less sulfone group
content in the polymer backbone, resulting in the relatively
worse hydrophilicity compared to dibenzo-[b,d]thiophene
sulfone. In conclusion, with the increasing of the peryleno[1,12-
bcd] thiophene sulfone content, hydrophilicity of the co-
polymer deceased, leading to the reduced interface proton
reduction reaction and further lower HERs of the polymer from
Finally, the correlation between HERs and wettability of
the samples was discussed, which was regarded as a parameter
of reaction kinetics. Sulfone group-containing monomer such as
dibenzo[b,d]thiophene sulfone unit was widely employed as
acceptor for constructing the polymers for photocatalytic
hydrogen production, due to its strong charge separation ability
and excellent hydrophilicity. Compared to samples in series-1,
PS-6 to PS-8
.
4. Summary
In this work, a novel peryleno[1,12-bcd] thiophene sulfone
monomer was firstly developed and then a series of the sulfone-
based hybrid conjugated co-polymers were designed by
sulfone polymers (PS-3
better wettability characterized by DLS analysis and contact
angle experiment, and the polymers (PS-3 PS-6) exhibited the
~PS-8) in series-2 obtained the much
~
higher HERs than those of series-1. Unfortunately, with the
8 | J. Name., 2012, 00, 1-3
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further increasing the peryleno[1,12-bcd] thiophene sulfone in 14 I. K. Konstantinou and T. A. Albanis, Appl. Catal. B, 2V0ie0w4,Ar4ti9cl,e1On1lin4e.
the skeleton of polymer in series-2, the thermodynamic driving 15 F. Zhang, A. Yamakata, K. Maeda, Y. MoriDyOa,I:T1.0T.1a0k3a9t/aD,0JT. AK0u7b2o8t6aA,
force for proton reduction of PS-7 to PS-8 got lower, which
might partially lead to reduction of HERs.
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transfer, sufficient driving force and wettability of the PS-5 48, 54545487.
contributes the strong ability for water spitting into hydrogen. 17 X. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J. M. Carlsson,
The polymer PS-5 achieved HERs of 7.5 mmol h -1 g -1 with a AQY
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of 15.3 % under λ = 420 nm monochromatic illumination 18 X. Sun, L. Shi, H. Huang, X. Song and T. Ma, Chem. Commun., 2020,
without co-catalyst, to the best of our knowledge, which was DOI: 10.1039/d0cc04790b.
the highest value among liner conjugated polymers. This work 19 X. Sun, H. Huang, Q. Zhao, T. Ma and L. Wang, Adv. Funct. Mater.
highlights that rationally balancing the multifarious factors on 2020, 30, 1910005
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organic semiconductor and provides new ideas for the rational
design of efficient and stable photocatalysts.
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21 R. S. Sprick, B. Bonillo, R. Clowes, P. Guiglion, N. J. Brownbill, B. J.
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Conflicts of interest
There are no conflicts to declare.
23 Z. A. Lan, G. Zhang, X. Chen, Y. Zhang, K. A. I. Zhang and X. Wang,
Angew. Chem. Int. Ed., 2019, 58, 1023610240.
Acknowledgements
24 R. S. Sprick, Catherine M. Aitchison, E. Berardo, L. Turcani, L.
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For financial support of this research, we thank the project
supported by the National Natural Science Foundation of China
(21971064, 21825301 and 21772040), Shanghai Science and
Technology Committee (17520750100), Shanghai Municipal
Science and Technology Major Project (Grant No.
2018SHZDZX03), the Fundamental Research Funds for the
Central Universities (222201717003 and 50321101918001) and
the Programme of Introducing Talents of Discipline to
Universities (B16017). The authors thank the Research Center of
Analysis and Test of East China University of Science and
Technology for the help on the characterization.
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Page 11 of 11
Journal of Materials Chemistry A
View Article Online
DOI: 10.1039/D0TA07286A
Graphical abstract
Bandgap engineering of a novel peryleno[1,12-bcd] thiophene sulfone based
conjugated co-polymers for significantly enhanced hydrogen evolution without co-
catalyst
Haonan Ye, Zhiqiang Wang, Zhicheng Yang, Shicong Zhang, Xueqing Gong* Jianli Hua*
A peryleno[1,12-bcd] thiophene sulfone based conjugated co-polymer PS-5
achieved so far highest HERs of 7.5 mmol h-1 g-1 without Pt-loading.