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

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Title: Understanding structure-activity relationships in linear polymer photocatalysts for hydrogen evolution
Authors: Sachs, M
Sprick, RS
Pearce, D
Hillman, SAJ
Monti, A
Guilbert, AAY
Brownbill, NJ
Dimitrov, S
Shi, X
Blanc, F
Zwijnenburg, MA
Nelson, J
Durrant, JR
Cooper, AI
Item Type: Journal Article
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 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.
Issue Date: 23-Nov-2018
Date of Acceptance: 31-Oct-2018
URI: http://hdl.handle.net/10044/1/66649
DOI: https://dx.doi.org/10.1038/s41467-018-07420-6
ISSN: 2041-1723
Publisher: Nature Research (part of Springer Nature)
Journal / Book Title: Nature Communications
Volume: 9
Copyright Statement: © 2018 The Author(s). This article is licensed under a Creative CommonsAttribution 4.0 International License, which permits use, sharing,adaptation, distribution and reproduction in any medium or format, as long as you giveappropriate credit to the original author(s) and the source, provide a link to the CreativeCommons license, and indicate if changes were made. The images or other third partymaterial in this article are included in the article’s Creative Commons license, unlessindicated otherwise in a credit line to the material. If material is not included in thearticle’s Creative Commons license and your intended use is not permitted by statutoryregulation or exceeds the permitted use, you will need to obtain permission directly fromthe copyright holder. To view a copy of this license, visithttp://creativecommons.org/licenses/by/4.0/
Sponsor/Funder: Commission of the European Communities
Engineering and Physical Sciences Research Council
Funder's Grant Number: 291482
Keywords: Science & Technology
Multidisciplinary Sciences
Science & Technology - Other Topics
POROUS CONJUGATED POLYMERS
COVALENT ORGANIC FRAMEWORK
TRIAZINE-BASED FRAMEWORKS
EXCITON DIFFUSION LENGTH
GAUSSIAN-BASIS SETS
VISIBLE-LIGHT
CARBON NITRIDE
TRANSIENT ABSORPTION
RATIONAL DESIGN
CHARGE-TRANSFER
Science & Technology
Multidisciplinary Sciences
Science & Technology - Other Topics
POROUS CONJUGATED POLYMERS
COVALENT ORGANIC FRAMEWORK
TRIAZINE-BASED FRAMEWORKS
EXCITON DIFFUSION LENGTH
GAUSSIAN-BASIS SETS
VISIBLE-LIGHT
CARBON NITRIDE
TRANSIENT ABSORPTION
RATIONAL DESIGN
CHARGE-TRANSFER
MD Multidisciplinary
Publication Status: Published
Open Access location: https://www.nature.com/articles/s41467-018-07420-6.pdf
Article Number: ARTN 4968
Appears in Collections:Physics
Chemistry
Experimental Solid State
Centre for Environmental Policy



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