Journal article 945 views 121 downloads
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
,
Xingyuan Shi,
Frédéric Blanc,
Martijn A. Zwijnenburg,
Jenny Nelson
,
James Durrant
,
Andrew I. Cooper
Nature Communications, Volume: 9, Issue: 1
Swansea University Authors:
Stoichko Dimitrov , Jenny Nelson
, James Durrant
-
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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...
Published in: | Nature Communications |
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ISSN: | 2041-1723 |
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2018
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URI: | https://cronfa.swan.ac.uk/Record/cronfa46234 |
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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 |
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Nature Communications |
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2041-1723 |
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10.1038/s41467-018-07420-6 |
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Faculty of 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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1763752940166709248 |
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11.021648 |