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Understanding structure-activity relationships in linear polymer photocatalysts for hydrogen evolution

Michael Sachs, Reiner Sebastian Sprick, Drew Pearce, Sam A. J. Hillman, Adriano Monti, Anne A. Y. Guilbert, Nick J. Brownbill, Stoichko Dimitrov Orcid Logo, Xingyuan Shi, Frédéric Blanc, Martijn A. Zwijnenburg, Jenny Nelson Orcid Logo, James Durrant Orcid Logo, Andrew I. Cooper

Nature Communications, Volume: 9, Issue: 1

Swansea University Authors: Stoichko Dimitrov Orcid Logo, Jenny Nelson Orcid Logo, James Durrant Orcid Logo

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DOI (Published version): 10.1038/s41467-018-07420-6

Abstract

Conjugated polymers have sparked much interest as photocatalysts for hydrogen production. However, beyond basic considerations such as spectral absorption, the factors that dictate their photocatalytic activity are poorly understood. Here we investigate a series of linear conjugated polymers with ex...

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Published in: Nature Communications
ISSN: 2041-1723
Published: 2018
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URI: https://cronfa.swan.ac.uk/Record/cronfa46234
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spelling 2020-09-17T15:40:48.3495282 v2 46234 2018-12-05 Understanding structure-activity relationships in linear polymer photocatalysts for hydrogen evolution 9fc26ec1b8655cd0d66f7196a924fe14 0000-0002-1564-7080 Stoichko Dimitrov Stoichko Dimitrov true false e0e41c0bb2b9cae677f7fbbf88abe590 0000-0003-1048-1330 Jenny Nelson Jenny Nelson true false f3dd64bc260e5c07adfa916c27dbd58a 0000-0001-8353-7345 James Durrant James Durrant true false 2018-12-05 EEN Conjugated polymers have sparked much interest as photocatalysts for hydrogen production. However, beyond basic considerations such as spectral absorption, the factors that dictate their photocatalytic activity are poorly understood. Here we investigate a series of linear conjugated polymers with external quantum efficiencies for hydrogen production between 0.4 and 11.6%. We monitor the generation of the photoactive species from femtoseconds to seconds after light absorption using transient spectroscopy and correlate their yield with the measured photocatalytic activity. Experiments coupled with modeling suggest that the localization of water around the polymer chain due to the incorporation of sulfone groups into an otherwise hydrophobic backbone is crucial for charge generation. Calculations of solution redox potentials and charge transfer free energies demonstrate that electron transfer from the sacrificial donor becomes thermodynamically favored as a result of the more polar local environment, leading to the production of long-lived electrons in these amphiphilic polymers. Journal Article Nature Communications 9 1 2041-1723 31 12 2018 2018-12-31 10.1038/s41467-018-07420-6 COLLEGE NANME Engineering COLLEGE CODE EEN Swansea University 2020-09-17T15:40:48.3495282 2018-12-05T09:57:12.4926121 Faculty of Science and Engineering School of Engineering and Applied Sciences - Materials Science and Engineering Michael Sachs 1 Reiner Sebastian Sprick 2 Drew Pearce 3 Sam A. J. Hillman 4 Adriano Monti 5 Anne A. Y. Guilbert 6 Nick J. Brownbill 7 Stoichko Dimitrov 0000-0002-1564-7080 8 Xingyuan Shi 9 Frédéric Blanc 10 Martijn A. Zwijnenburg 11 Jenny Nelson 0000-0003-1048-1330 12 James Durrant 0000-0001-8353-7345 13 Andrew I. Cooper 14 0046234-05122018095947.pdf sachs2018.pdf 2018-12-05T09:59:47.9300000 Output 6741013 application/pdf Version of Record true 2018-12-05T00:00:00.0000000 true eng
title Understanding structure-activity relationships in linear polymer photocatalysts for hydrogen evolution
spellingShingle Understanding structure-activity relationships in linear polymer photocatalysts for hydrogen evolution
Stoichko Dimitrov
Jenny Nelson
James Durrant
title_short Understanding structure-activity relationships in linear polymer photocatalysts for hydrogen evolution
title_full Understanding structure-activity relationships in linear polymer photocatalysts for hydrogen evolution
title_fullStr Understanding structure-activity relationships in linear polymer photocatalysts for hydrogen evolution
title_full_unstemmed Understanding structure-activity relationships in linear polymer photocatalysts for hydrogen evolution
title_sort Understanding structure-activity relationships in linear polymer photocatalysts for hydrogen evolution
author_id_str_mv 9fc26ec1b8655cd0d66f7196a924fe14
e0e41c0bb2b9cae677f7fbbf88abe590
f3dd64bc260e5c07adfa916c27dbd58a
author_id_fullname_str_mv 9fc26ec1b8655cd0d66f7196a924fe14_***_Stoichko Dimitrov
e0e41c0bb2b9cae677f7fbbf88abe590_***_Jenny Nelson
f3dd64bc260e5c07adfa916c27dbd58a_***_James Durrant
author Stoichko Dimitrov
Jenny Nelson
James Durrant
author2 Michael Sachs
Reiner Sebastian Sprick
Drew Pearce
Sam A. J. Hillman
Adriano Monti
Anne A. Y. Guilbert
Nick J. Brownbill
Stoichko Dimitrov
Xingyuan Shi
Frédéric Blanc
Martijn A. Zwijnenburg
Jenny Nelson
James Durrant
Andrew I. Cooper
format Journal article
container_title Nature Communications
container_volume 9
container_issue 1
publishDate 2018
institution Swansea University
issn 2041-1723
doi_str_mv 10.1038/s41467-018-07420-6
college_str Faculty of Science and Engineering
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hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Materials Science and Engineering{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Materials Science and Engineering
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description Conjugated polymers have sparked much interest as photocatalysts for hydrogen production. However, beyond basic considerations such as spectral absorption, the factors that dictate their photocatalytic activity are poorly understood. Here we investigate a series of linear conjugated polymers with external quantum efficiencies for hydrogen production between 0.4 and 11.6%. We monitor the generation of the photoactive species from femtoseconds to seconds after light absorption using transient spectroscopy and correlate their yield with the measured photocatalytic activity. Experiments coupled with modeling suggest that the localization of water around the polymer chain due to the incorporation of sulfone groups into an otherwise hydrophobic backbone is crucial for charge generation. Calculations of solution redox potentials and charge transfer free energies demonstrate that electron transfer from the sacrificial donor becomes thermodynamically favored as a result of the more polar local environment, leading to the production of long-lived electrons in these amphiphilic polymers.
published_date 2018-12-31T03:57:59Z
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