Sulfide oxidation tuning in 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-<i>b</i>:4,5-<i>b′</i>]dithiophene based dual acceptor copolymers for highly efficient photocatalytic hydrogen evolution

Lin, Wei-Hsiu; Jayakumar, Jayachandran; Chang, Chih‐Li; Ting, Li‐Yu; Huang, Tse-Fu; Elsayed, Mohamed Hammad; Elewa, Ahmed M.; Lin, Yu-Tung; Liu, Jia‐Jen; Tseng, Yuan-Ting; Chou, Ho‐Hsiu

doi:10.1039/d2ta00241h

Cited by 27 publications

(27 citation statements)

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“…This high HER value of 126.81 mmol h –1 g –1 is comparable with that of the reported polymer photocatalysts with high photocatalytic activity (Table S1, Supporting Information). For example, the linear polymer TP‐BTDO‐2 comprising of multi‐thiophene and BTDO units showed a HER of 161.28 mmol h –1 g –1 with 1 wt% Pt under UV–Vis light, [ 17 ] the linear polymer PBDTTS‐1SO exhibited a HER of 97.1 mmol h –1 g –1 under the assistance of 3 wt% Pt and irradiation of 380–780 nm light, [ 33 ] the copolymer Py‐T‐BTDO‐3 consisting of pyrene, BTDO and thiophene showed a HER of 127.9 mmol h –1 g –1 under UV–Vis light by loading 1 wt% Pt cocatalyst, [ 29 ] the thiophene and pyrene based CP‐St polymer demonstrated a high HER of 303.7 mmol h –1 g –1 under the assistance of 0.5 wt% Pt and visible light, [ 34 ] and the ionothermal‐synthesized polymeric carbon nitride of CN‐NaK showed a HER of 5.56 mmol h –1 with the assistance of 3 wt% Pt under visible light irradiation. [ 35 ] In sharp contrast, the polymer TPE‐BTDO with TPE donor shows pretty low photocatalytic activity at various photocatalytic reaction conditions (Figure 4a–c).…”

Section: Resultsmentioning

confidence: 99%

An Efficient Electron Donor for Conjugated Microporous Polymer Photocatalysts with High Photocatalytic Hydrogen Evolution Activity

Han

Xiang

et al. 2022

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electronic structure. [3][4][5] Nevertheless, most inorganic photocatalysts suffer from low activity under visible light, complexity in the preparation, and the limited natural resources. Recent studies demonstrated that organic semiconductors could be a promising class of photocatalysts for hydrogen evolution because of their diverse structures, various synthetic strategies, and tunable electronic properties. [6][7][8] To date, various organic polymers with conjugated skeletons have been developed as photocatalysts for hydrogen evolution. [9][10][11] In particular, significant advances in the preparation of conjugated microporous polymer (CMP) photocatalysts with high photocatalytic activity have been achieved. [12][13][14] Many studies revealed that designing a donor-acceptor (D-A) molecular structure is an efficient strategy to boost the photocatalytic activity of conjugated polymer photocatalysts, [15][16][17][18] since the intrinsic electron push-pull effect in a D-A conjugated polymer could promote the separation of light-induced hole/ electron. The nature of electron donor and acceptor units plays a key point in the charges transfer and separation, which affect significantly the photocatalytic activity. Therefore, the selection of electron donor and acceptor is of great importance for constructing organic polymer photocatalysts with high photocatalytic activity. In general, aromatic heterocyclic compounds with narrow band gap are commonly used as electron acceptors, and aromatic hydrocarbons with delocalized π-electron are employed as electron donors to build D-A type polymer photocatalysts. Based on the developed D-A polymer photo catalysts to date, [15,[19][20][21][22] dibenzo[b,d]thiophene-S,S-dioxide (BTDO) might be the most effective acceptor unit due to its strong electronwithdrawing capability and high hydrophilicity, [23][24][25] and pyrene with planar molecular structure and large delocalized π-electron system is the most effective electron donor to prepare high performance polymer photocatalysts. [26,27] Although there have been significant advances in the photo catalytic activity of polymer photocatalysts by structure optimization, [28,29] the limited scope of high efficient electron donors and acceptors hinders the further development of organic polymer photo catalysts. To further improve the photocatalytic activity and enrich the D-A) molecular structure show high photocatalytic activity for hydrogen evolution due to the efficient light-induced electron/hole separation, which is mostly determined by the nature of electron donor and acceptor units. Therefore, the selection of electron donor and acceptor holds the key point to construct high performance polymer photocatalysts. Herein, two dibenzo[b,d]thiophene-S,Sdioxide (BTDO) containing CMP photocatalysts using tetraphenylethylene (TPE) or dibenzo[g,p]chrysene (DBC) as the electron donor to investigate the influence of the geometry of electron donor on the photocatalytic activity are design and synthesized. Compared with the twisted TPE donor,...

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Section: Resultsmentioning

confidence: 99%

An Efficient Electron Donor for Conjugated Microporous Polymer Photocatalysts with High Photocatalytic Hydrogen Evolution Activity

Han

Xiang

et al. 2022

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“…However, the sulfone unit does clearly also improve the kinetics of electron transfer to the palladium co-catalyst, and the high performance of sulfone-rich materials is not solely tied to TEA oxidation: recent studies has demonstrated that sulfone-containing materials can be used without TEA either by loading them with IrO2 57 or FeOOH 65 , or by combining it in a Z-scheme with BiVO4 24 . Sulfone-containing polymers have also been shown to evolve hydrogen when using ascorbic acid as a scavenger 39,40,43,44 .…”

Section: Discussionmentioning

confidence: 99%

“…Since then, numerous research groups have synthesised series of photocatalysts in which sulfone-containing materials have outperformed sulfone-free materials [30][31][32][33][34][35][36][37][38][39][40][41][42] . Sulfone-containing photocatalysts have rapidly reached impressive apparent quantum efficiencies of 29.3% at 420 nm 43 , 18% at 500 nm 44 and 13.6% at 550 nm 40 when paired with hole scavengers. Despite the popularity of the sulfone monomer building block, few studies have shed further light on precisely why the sulfone unit improves performance in such a wide range of different materials.…”

Section: Introductionmentioning

confidence: 99%

Why do sulfone-containing polymer photocatalysts work so well for sacrificial hydrogen evolution from water?

Hillman

Sprick

Pearce

et al. 2022

Preprint

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In recent years, many of the highest performing polymer photocatalysts for hydrogen evolution from water have contained dibenzo[b,d]thiophene sulfone units in their polymer backbones. However, the reasons behind the dominance of this building block are not well understood. We use a new set of processable materials, in which the sulfone content is systematically controlled, to understand how the sulfone unit affects the three key processes involved in photocatalytic hydrogen generation in this system: light absorption; transfer of the photogenerated hole to the hole scavenger triethylamine (TEA); and transfer of the photogenerated electron to the palladium metal co-catalyst that remains in the polymer from synthesis. Using transient absorption spectroscopy and electrochemical measurements, and combined with molecular dynamics and density functional theory simulations, we find that the sulfone unit has two primary effects. On the picosecond timescale, it dictates the thermodynamics of hole transfer out of the polymer. The sulfone unit attracts water molecules such that the average permittivity experienced by the solvated polymer is increased, and we demonstrate here that TEA oxidation is only thermodynamically favourable above a certain permittivity threshold. On the microsecond timescale, we present experimental evidence that the sulfone unit acts as the electron transfer site out of the polymer, with the kinetics of electron extraction to palladium dictated by the ratio of photogenerated electrons to the number of sulfone units. For the highest performing, sulfone-rich material, hydrogen evolution appears to be limited by the photogeneration rate of electrons rather than their extraction from the polymer.

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“…4,5 Recently, 2D COFs have been revealed as a potential type of excellent photocatalyst for H 2 generation under visible light due to their unique properties, such as prominent visible light absorbance, large surface areas, tunable bandgaps, and long-range ordered structures beside pp stacked architectures, which can improve their charge-carrier mobilities, charge separation, and optical properties. [6][7][8][9] A number of conjugated organic photocatalysts, including linear polymers, [10][11][12][13] polymer dots, 14,15 hydrophilic polymers, and conjugated microporous polymers (CMPs), [16][17][18][19][20][21] have been used for photocatalytic hydrogen generation from water under visible light. However, COF materials are distinguished from polymer photocatalysts by (a) an ideally one-step reaction, (b) limited solvent wastage, (c) high reaction yields, (d) a cheap and available co-catalyst, (e) high crystallinity, and (f) efficient charge transfer.…”

Section: Introductionmentioning

confidence: 99%

Solvent polarity tuning to enhance the crystallinity of 2D-covalent organic frameworks for visible-light-driven hydrogen generation

et al. 2022

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Sulfide oxidation tuning in 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene based dual acceptor copolymers for highly efficient photocatalytic hydrogen evolution

Abstract: Polymeric photocatalysts for hydrogen evolution by water splitting have drawn tremendous research interest in recent years. However, the relatively low photocatalytic hydrogen evolution efficiency still needs to be overcome for...

Cited by 27 publications

References 44 publications

An Efficient Electron Donor for Conjugated Microporous Polymer Photocatalysts with High Photocatalytic Hydrogen Evolution Activity

An Efficient Electron Donor for Conjugated Microporous Polymer Photocatalysts with High Photocatalytic Hydrogen Evolution Activity

Why do sulfone-containing polymer photocatalysts work so well for sacrificial hydrogen evolution from water?

Solvent polarity tuning to enhance the crystallinity of 2D-covalent organic frameworks for visible-light-driven hydrogen generation

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