Tuning and mechanistic insights of metal chalcogenide molecular catalysts for the hydrogen-evolution reaction

McAllister, J., Bandeira, N. A.G., McGlynn, J. C., Ganin, A. Y. , Song, Y.-F., Bo, C. and Miras, H. N. (2019) Tuning and mechanistic insights of metal chalcogenide molecular catalysts for the hydrogen-evolution reaction. Nature Communications, 10, 370. (doi: 10.1038/s41467-018-08208-4) (PMID:30670694)

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Abstract

The production of hydrogen through water splitting using earth-abundant metal catalysts is a promising pathway for converting solar energy into chemical fuels. However, existing approaches for fine stoichiometric control, structural and catalytic modification of materials by appropriate choice of earth abundant elements are either limited or challenging. Here we explore the tuning of redox active immobilised molecular metal-chalcoxide electrocatalysts by controlling the chalcogen or metal stoichiometry and explore critical aspects of the hydrogen evolution reaction (HER). Linear sweep voltammetry (LSV) shows that stoichiometric and structural control leads to the evolution of hydrogen at low overpotential with no catalyst degradation over 1000 cycles. Density functional calculations reveal the effect of the electronic and structural features and confer plausibility to the existence of a unimolecular mechanism in the HER process based on the tested hypotheses. We anticipate these findings to be a starting point for further exploration of molecular catalytic systems.

Item Type:Articles
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Ganin, Dr Alexey and Moiras, Dr Haralampos and McGlynn, Miss Jessica and McAllister, Mr James
Authors: McAllister, J., Bandeira, N. A.G., McGlynn, J. C., Ganin, A. Y., Song, Y.-F., Bo, C., and Miras, H. N.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Nature Communications
Publisher:Nature Research
ISSN:2041-1723
ISSN (Online):2041-1723
Copyright Holders:Copyright © 2019 The Authors
First Published:First published in Nature Communications
Publisher Policy:Reproduced under a Creative Commons License
Data DOI:10.19061/iochem-bd-1-99

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
727411Modular assembly of high temperature superconductors from dimensionally reduced iron-based chalcogenide blocksAlexey GaninEngineering and Physical Sciences Research Council (EPSRC)EP/P001653/1SCHOOL OF CHEMISTRY
3005910Programmable Molecular Metal Oxides (PMMOs) - From Fundamentals to ApplicationLeroy CroninEngineering and Physical Sciences Research Council (EPSRC)EP/R01308X/1Chemistry