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Tuning and Mechanistic Insights of Metal Chalcogenide Molecular Catalysts for the Hydrogen-Evolution Reaction

preprint
submitted on 14.12.2018, 08:28 and posted on 14.12.2018, 16:28 by James McAllister, Nuno Bandeira, Jessica McGlynn, Alexey Ganin, Yu-Fei Song, Carles Bo, Haralampos Miras
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 immobilized 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

History

Email Address of Submitting Author

charalampos.moiras@glasgow.ac.uk

Institution

University of Glasgow

Country

United Kingdom

ORCID For Submitting Author

0000-0002-0086-5173

Declaration of Conflict of Interest

N/A

Exports