Photocatalytically active ladder polymers

Anastasia Vogel; Mark Forster; Liam Wilbraham; Charlotte L. Smith; Alexander J. Cowan; Martijn A. Zwijnenburg; Reiner Sebastian Sprick; Andrew I. Cooper

doi:10.1039/c8fd00197a

Photocatalytically active ladder polymers

Anastasia Vogel
, Mark Forster
, Liam Wilbraham
, Charlotte L. Smith
, Alexander J. Cowan
, Martijn A. Zwijnenburg
, Reiner Sebastian Sprick
, Andrew I. Cooper^*

^*Corresponding author for this work

Pure And Applied Chemistry

Research output: Contribution to journal › Article › peer-review

23 Citations (Scopus)

7 Downloads (Pure)

Abstract

Conjugated ladder polymers (cLaPs) are introduced as organic semiconductors for photocatalytic hydrogen evolution from water under sacrificial conditions. Starting from a linear conjugated polymer (cLiP1), two ladder polymers are synthesized via post-polymerization annulation and oxidation techniques to generate rigidified, planarized materials bearing dibenzo[b,d]thiophene (cLaP1) and dibenzo[b,d]thiophene sulfone subunits (cLaP2). The high photocatalytic activity of cLaP1 (1307 μmol h^-1 g^-1) in comparison to that of cLaP2 (18 μmol h^-1 g^-1) under broadband illumination (λ > 295 nm) in the presence of a hole-scavenger is attributed to a higher yield of long-lived charges (μs to ms timescale), as evidenced by transient absorption spectroscopy. Additionally, cLaP1 has a larger overpotential for proton reduction and thus an increased driving force for the evolution of hydrogen under sacrificial conditions.

Original language	English
Pages (from-to)	84-97
Number of pages	14
Journal	Faraday Discussions
Volume	215
Early online date	22 Jan 2019
DOIs	https://doi.org/10.1039/c8fd00197a
Publication status	Published - 1 Jul 2019

Funding

This project has received funding from the European Union’s Horizon 2020 research and innovation programme (Marie-Skłodowska-Curie Individual Fellowship to AV) under grant agreement No. 796322. The UK Engineering and Physical Sciences Research Council (EPSRC) is acknowledged for funding through grants EP/N004884/1 and EP/P034497/1. We thank Catherine M. Aitchison for help with SEM imaging.

Keywords

conjugated ladder polymers (cLaPs)
organic semiconductors
photocatalytic hydrogen evolution

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title = "Photocatalytically active ladder polymers",

abstract = "Conjugated ladder polymers (cLaPs) are introduced as organic semiconductors for photocatalytic hydrogen evolution from water under sacrificial conditions. Starting from a linear conjugated polymer (cLiP1), two ladder polymers are synthesized via post-polymerization annulation and oxidation techniques to generate rigidified, planarized materials bearing dibenzo[b,d]thiophene (cLaP1) and dibenzo[b,d]thiophene sulfone subunits (cLaP2). The high photocatalytic activity of cLaP1 (1307 μmol h-1 g-1) in comparison to that of cLaP2 (18 μmol h-1 g-1) under broadband illumination (λ > 295 nm) in the presence of a hole-scavenger is attributed to a higher yield of long-lived charges (μs to ms timescale), as evidenced by transient absorption spectroscopy. Additionally, cLaP1 has a larger overpotential for proton reduction and thus an increased driving force for the evolution of hydrogen under sacrificial conditions.",

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AU - Vogel, Anastasia

AU - Forster, Mark

AU - Wilbraham, Liam

AU - Smith, Charlotte L.

AU - Cowan, Alexander J.

AU - Zwijnenburg, Martijn A.

AU - Sprick, Reiner Sebastian

AU - Cooper, Andrew I.

PY - 2019/7/1

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N2 - Conjugated ladder polymers (cLaPs) are introduced as organic semiconductors for photocatalytic hydrogen evolution from water under sacrificial conditions. Starting from a linear conjugated polymer (cLiP1), two ladder polymers are synthesized via post-polymerization annulation and oxidation techniques to generate rigidified, planarized materials bearing dibenzo[b,d]thiophene (cLaP1) and dibenzo[b,d]thiophene sulfone subunits (cLaP2). The high photocatalytic activity of cLaP1 (1307 μmol h-1 g-1) in comparison to that of cLaP2 (18 μmol h-1 g-1) under broadband illumination (λ > 295 nm) in the presence of a hole-scavenger is attributed to a higher yield of long-lived charges (μs to ms timescale), as evidenced by transient absorption spectroscopy. Additionally, cLaP1 has a larger overpotential for proton reduction and thus an increased driving force for the evolution of hydrogen under sacrificial conditions.

AB - Conjugated ladder polymers (cLaPs) are introduced as organic semiconductors for photocatalytic hydrogen evolution from water under sacrificial conditions. Starting from a linear conjugated polymer (cLiP1), two ladder polymers are synthesized via post-polymerization annulation and oxidation techniques to generate rigidified, planarized materials bearing dibenzo[b,d]thiophene (cLaP1) and dibenzo[b,d]thiophene sulfone subunits (cLaP2). The high photocatalytic activity of cLaP1 (1307 μmol h-1 g-1) in comparison to that of cLaP2 (18 μmol h-1 g-1) under broadband illumination (λ > 295 nm) in the presence of a hole-scavenger is attributed to a higher yield of long-lived charges (μs to ms timescale), as evidenced by transient absorption spectroscopy. Additionally, cLaP1 has a larger overpotential for proton reduction and thus an increased driving force for the evolution of hydrogen under sacrificial conditions.

KW - conjugated ladder polymers (cLaPs)

KW - organic semiconductors

KW - photocatalytic hydrogen evolution

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VL - 215

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JO - Faraday Discussions

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ER -

Photocatalytically active ladder polymers

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Keywords

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