Photocatalytic polymers of intrinsic microporosity for hydrogen production from water

Bai, Yang; Gao, Hui; Clowes, Rob; Yang, Haofan; Zwijnenburg, Martijn A.; Cooper, Andrew I.; Sprick, Reiner Sebastian

doi:10.1039/d1ta03098a

Cited by 42 publications

(33 citation statements)

References 70 publications

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“…Out of these series, P38 (16) showed the highest H 2 evolution performance up to 5226 μmol g À 1 h À 1 with an external quantum efficiency of 18.1 % under visible light irradiation (420 nm) . [70] The comparison of linear conjugated polymers exhibited that the A proposed visible-light-induced H 2 evolution mechanism on g-C 3 N 4 À P3HT polymer composite photocatalysts [65] . Copyright © Royal Society of Chemistry, 2011.…”

Section: Linear Conjugated Polymersmentioning

confidence: 98%

“…also reported a breakthrough work using a series of linear‐conjugated polymers with intrinsic microporosity for H 2 evolution from water in the presence of hole‐scavenger (Scheme 5). Out of these series, P38 ( 16 ) showed the highest H 2 evolution performance up to 5226 μmol g −1 h −1 with an external quantum efficiency of 18.1 % under visible light irradiation (420 nm) [70] . The comparison of linear conjugated polymers exhibited that the hydrogen evolution reaction gained success with proper tuning in molecular structures, doping with other materials, engaging the donor‐acceptor characteristics in the backbone (Table 1).…”

Section: Conjugated Polymers For Photocatalytic H2o Splittingmentioning

confidence: 98%

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Photocatalytic Water‐Splitting by Organic Conjugated Polymers: Opportunities and Challenges

Mansha

Ahmad

Khan

et al. 2022

The Chemical Record

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The future challenges associated with the shortage of fossil fuels and their current environmental impacts intrigued the researchers to look for alternative ways of generating green energy. Solar‐driven water splitting into oxygen and hydrogen is one of those advanced strategies. Researchers have studied various semiconductor materials to achieve potential results. However, it encountered multiple challenges such as high cost, low photostability and efficiency, and required multistep modifications. The conjugated polymers (CPs) have emerged as promising alternatives for conventional inorganic semiconductors. The CPs offer low cost, sufficient light absorption efficiency, excellent photo and chemical stability, and molecular optoelectronic tunable characteristics. Furthermore, organic CPs also present higher flexibility to tune the basic framework of the backbone of the polymers, amendments in the sidechain to incorporate desired functionalities, and much‐needed porosity to serve better for photocatalytic applications. This review article summarizes the recent advancements made in visible‐light‐driven water splitting covering the aspects of synthetic strategies and experimental parameters employed for water splitting reactions with special emphasis on conjugated polymers such as linear CPs, planarized CPs, graphitic carbon nitride (g‐C3N4), conjugated microporous polymers (CMPs), covalent organic frameworks (COFs), and conjugated polymer‐based nanocomposites (CPNCs). The current challenges and future prospects have also been described briefly.

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Section: Linear Conjugated Polymersmentioning

confidence: 98%

Section: Conjugated Polymers For Photocatalytic H2o Splittingmentioning

confidence: 98%

Photocatalytic Water‐Splitting by Organic Conjugated Polymers: Opportunities and Challenges

Mansha

Ahmad

Khan

et al. 2022

The Chemical Record

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“…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.…”

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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“…Polymers of intrinsic microporosity (PIMs) with extended π-planes, large specific surface area, structural diversity, and good chemical stability are used to develop porous photocatalysts for H 2 evolution . A triptycene unit with abundant reaction sites is easy to polymerize to form triptycene-based polymers, indicating the superior electronic transfer property. , Different from metal–organic frameworks (MOFs), triptycene-based polymers with strong covalent bonds (TCP) emerge as a novel class of photocatalysts for solar H 2 generation, and the significantly enhanced photocatalytic performance can be achieved through rational design and construction of the polymer heterostructures .…”

Section: Introductionmentioning

confidence: 99%

Triptycene-Based Polymer Embedded in ZnIn₂S₄ to Construct a Hierarchical Heterostructure for Efficient Photocatalytic Hydrogen Evolution

Zhu

Liang

Zhou

et al. 2021

ACS Appl. Energy Mater.

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Development of promising photocatalysts with a synergistic effect for hydrogen generation holds paramount significance for solving the global energy problem. Herein, we rationally design a hierarchical heterostructure in which a triptycene covalent polymer (TCP) is grown in situ on ZnIn 2 S 4 through a Suzuki coupling reaction. Assorted experimental results demonstrate that amorphous TCP with a high BET surface area (903 m 2 g −1 ) is embedded on 2D ZnIn 2 S 4 nanoflakes by a self-assembly process, thus indicating the unique hierarchical architecture, high surface area, and large interface contact area. Based on the favorable heterojunction structure, ZnIn 2 S 4 /TCP-2 yields the highest visible-light-derived hydrogen production rate of 1432.8 μmol h −1 g −1 , which is more than 9 times that of bare ZnIn 2 S 4 . The enhanced hydrogen evolution of ZnIn 2 S 4 /TCP comes from the enhanced absorption of visible light, a well-matched band structure, and effective electron transfer. This work provides a promising approach to enhance the solar hydrogen production performance of metal sulfide by using a triptycene covalent polymer.

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Photocatalytic polymers of intrinsic microporosity for hydrogen production from water

Abstract: The most common strategy for introducing porosity into organic polymer photocatalysts has been the synthesis of cross-linked conjugated networks or frameworks. Here, we study the photocatalytic performance of a series...

Cited by 42 publications

References 70 publications

Photocatalytic Water‐Splitting by Organic Conjugated Polymers: Opportunities and Challenges

Photocatalytic Water‐Splitting by Organic Conjugated Polymers: Opportunities and Challenges

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

Triptycene-Based Polymer Embedded in ZnIn₂S₄ to Construct a Hierarchical Heterostructure for Efficient Photocatalytic Hydrogen Evolution

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Photocatalytic polymers of intrinsic microporosity for hydrogen production from water

Abstract: The most common strategy for introducing porosity into organic polymer photocatalysts has been the synthesis of cross-linked conjugated networks or frameworks. Here, we study the photocatalytic performance of a series...

Cited by 42 publications

References 70 publications

Photocatalytic Water‐Splitting by Organic Conjugated Polymers: Opportunities and Challenges

Photocatalytic Water‐Splitting by Organic Conjugated Polymers: Opportunities and Challenges

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

Triptycene-Based Polymer Embedded in ZnIn2S4 to Construct a Hierarchical Heterostructure for Efficient Photocatalytic Hydrogen Evolution

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Triptycene-Based Polymer Embedded in ZnIn₂S₄ to Construct a Hierarchical Heterostructure for Efficient Photocatalytic Hydrogen Evolution