Controlling photocatalytic activity by self-assembly – tuning perylene bisimide photocatalysts for the hydrogen evolution reaction

Daniel  McDowall; Benjamin J. Greeves; Rob Clowes; Kate McAulay; Ana M. Fuentes-Caparrós; Lisa Thomson; Nikul Khunti; Nathan  Cowieson; Michael C. Nolan; Matthew Wallace; Andrew I. Cooper; Emily R. Draper; Alexander J. Cowan; Dave J. Adams

doi:10.1002/aenm.202002469

Controlling photocatalytic activity by self-assembly – tuning perylene bisimide photocatalysts for the hydrogen evolution reaction

Daniel McDowall, Benjamin J. Greeves, Rob Clowes, Kate McAulay, Ana M. Fuentes-Caparrós, Lisa Thomson, Nikul Khunti, Nathan Cowieson, Michael C. Nolan, Matthew Wallace, Andrew I. Cooper, Emily R. Draper, Alexander J. Cowan^*, Dave J. Adams^*

^*Corresponding author for this work

Chemical Science

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

34 Citations (Scopus)

120 Downloads (Pure)

Abstract

Amino acid functionalized perylene bisimides (PBIs) form self-assembled structures in solution, the nature of which depends on the local environment. Using a high-throughput photocatalysis setup, five PBIs are studied for the hydrogen evolution reaction (HER) under a range of conditions (pH and hole scavenger concentration) across 350 experiments to explore the relationship between supramolecular structure and photocatalytic activity. Using small angle X-ray scattering (SAXS), NMR spectroscopy and ultraviolet-visible (UV-vis) absorption spectroscopy, it is shown that photocatalytic activity is determined by the nature of the self-assembled aggregate that is formed, demonstrating the potential of self-assembly to tune activity. There is a clear correlation between the presence of charged flexible cylindrical aggregates and the occurrence of photocatalytic H2 production, with UV–vis spectroscopy indicating that the most active structure type has a distinctive form of π-aggregation which is proposed to enable efficient charge separation across multiple PBI units.

Original language	English
Article number	2002469
Number of pages	10
Journal	Advanced Energy Materials
Volume	10
Issue number	46
Early online date	26 Oct 2020
DOIs	https://doi.org/10.1002/aenm.202002469
Publication status	Published - 8 Dec 2020

Keywords

hydrogen
organic photocatalysts
self‐assembly
solar fuels
self-assembly

ASJC Scopus subject areas

General Materials Science
Renewable Energy, Sustainability and the Environment

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1002/aenm.202002469

McDowall, D et al. (2020) Controlling photocatalytic activity by self-assembly – tuning perylene bisimide photocatalysts for the hydrogen evolution reaction
© 2020 The Authors. Advanced Energy Materials published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Final published version, 1.66 MBLicence: CC BY

Cite this

McDowall, D., Greeves, B. J., Clowes, R., McAulay, K., Fuentes-Caparrós, A. M., Thomson, L., Khunti, N., Cowieson, N., Nolan, M. C., Wallace, M., Cooper, A. I., Draper, E. R., Cowan, A. J., & Adams, D. J. (2020). Controlling photocatalytic activity by self-assembly – tuning perylene bisimide photocatalysts for the hydrogen evolution reaction. Advanced Energy Materials, 10(46), Article 2002469. https://doi.org/10.1002/aenm.202002469

@article{6041d0b9d8e84a75a5da974bb3ae0faa,

title = "Controlling photocatalytic activity by self-assembly – tuning perylene bisimide photocatalysts for the hydrogen evolution reaction",

abstract = "Amino acid functionalized perylene bisimides (PBIs) form self-assembled structures in solution, the nature of which depends on the local environment. Using a high-throughput photocatalysis setup, five PBIs are studied for the hydrogen evolution reaction (HER) under a range of conditions (pH and hole scavenger concentration) across 350 experiments to explore the relationship between supramolecular structure and photocatalytic activity. Using small angle X-ray scattering (SAXS), NMR spectroscopy and ultraviolet-visible (UV-vis) absorption spectroscopy, it is shown that photocatalytic activity is determined by the nature of the self-assembled aggregate that is formed, demonstrating the potential of self-assembly to tune activity. There is a clear correlation between the presence of charged flexible cylindrical aggregates and the occurrence of photocatalytic H2 production, with UV–vis spectroscopy indicating that the most active structure type has a distinctive form of π-aggregation which is proposed to enable efficient charge separation across multiple PBI units.",

keywords = "hydrogen, organic photocatalysts, self‐assembly, solar fuels, self-assembly",

author = "Daniel McDowall and Greeves, {Benjamin J.} and Rob Clowes and Kate McAulay and Fuentes-Caparr{\'o}s, {Ana M.} and Lisa Thomson and Nikul Khunti and Nathan Cowieson and Nolan, {Michael C.} and Matthew Wallace and Cooper, {Andrew I.} and Draper, {Emily R.} and Cowan, {Alexander J.} and Adams, {Dave J.}",

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doi = "10.1002/aenm.202002469",

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journal = "Advanced Energy Materials",

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McDowall, D, Greeves, BJ, Clowes, R, McAulay, K, Fuentes-Caparrós, AM, Thomson, L, Khunti, N, Cowieson, N, Nolan, MC, Wallace, M, Cooper, AI, Draper, ER, Cowan, AJ & Adams, DJ 2020, 'Controlling photocatalytic activity by self-assembly – tuning perylene bisimide photocatalysts for the hydrogen evolution reaction', Advanced Energy Materials, vol. 10, no. 46, 2002469. https://doi.org/10.1002/aenm.202002469

TY - JOUR

T1 - Controlling photocatalytic activity by self-assembly – tuning perylene bisimide photocatalysts for the hydrogen evolution reaction

AU - McDowall, Daniel

AU - Greeves, Benjamin J.

AU - Clowes, Rob

AU - McAulay, Kate

AU - Fuentes-Caparrós, Ana M.

AU - Thomson, Lisa

AU - Khunti, Nikul

AU - Cowieson, Nathan

AU - Nolan, Michael C.

AU - Wallace, Matthew

AU - Cooper, Andrew I.

AU - Draper, Emily R.

AU - Cowan, Alexander J.

AU - Adams, Dave J.

N1 - Acceptance in SAN AAM: apply 12m embargo (N/A - OA article)

PY - 2020/12/8

Y1 - 2020/12/8

N2 - Amino acid functionalized perylene bisimides (PBIs) form self-assembled structures in solution, the nature of which depends on the local environment. Using a high-throughput photocatalysis setup, five PBIs are studied for the hydrogen evolution reaction (HER) under a range of conditions (pH and hole scavenger concentration) across 350 experiments to explore the relationship between supramolecular structure and photocatalytic activity. Using small angle X-ray scattering (SAXS), NMR spectroscopy and ultraviolet-visible (UV-vis) absorption spectroscopy, it is shown that photocatalytic activity is determined by the nature of the self-assembled aggregate that is formed, demonstrating the potential of self-assembly to tune activity. There is a clear correlation between the presence of charged flexible cylindrical aggregates and the occurrence of photocatalytic H2 production, with UV–vis spectroscopy indicating that the most active structure type has a distinctive form of π-aggregation which is proposed to enable efficient charge separation across multiple PBI units.

AB - Amino acid functionalized perylene bisimides (PBIs) form self-assembled structures in solution, the nature of which depends on the local environment. Using a high-throughput photocatalysis setup, five PBIs are studied for the hydrogen evolution reaction (HER) under a range of conditions (pH and hole scavenger concentration) across 350 experiments to explore the relationship between supramolecular structure and photocatalytic activity. Using small angle X-ray scattering (SAXS), NMR spectroscopy and ultraviolet-visible (UV-vis) absorption spectroscopy, it is shown that photocatalytic activity is determined by the nature of the self-assembled aggregate that is formed, demonstrating the potential of self-assembly to tune activity. There is a clear correlation between the presence of charged flexible cylindrical aggregates and the occurrence of photocatalytic H2 production, with UV–vis spectroscopy indicating that the most active structure type has a distinctive form of π-aggregation which is proposed to enable efficient charge separation across multiple PBI units.

KW - hydrogen

KW - organic photocatalysts

KW - self‐assembly

KW - solar fuels

KW - self-assembly

U2 - 10.1002/aenm.202002469

DO - 10.1002/aenm.202002469

M3 - Article

SN - 1614-6840

VL - 10

JO - Advanced Energy Materials

JF - Advanced Energy Materials

IS - 46

M1 - 2002469

ER -

Controlling photocatalytic activity by self-assembly – tuning perylene bisimide photocatalysts for the hydrogen evolution reaction

Abstract

Keywords

ASJC Scopus subject areas

UN SDGs

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