Electrocatalytic metal hydride generation using CPET mediators

Subal Dey, Fabio Masero, Enzo Brack, Marc Fontecave and Victor Mougel ()
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Subal Dey: ETH Zürich
Fabio Masero: ETH Zürich
Enzo Brack: ETH Zürich
Marc Fontecave: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, Collège de France, Sorbonne Université
Victor Mougel: ETH Zürich

Nature, 2022, vol. 607, issue 7919, 499-506

Abstract: Abstract Transition metal hydrides (M-H) are ubiquitous intermediates in a wide range of enzymatic processes and catalytic reactions, playing a central role in H+/H2 interconversion1, the reduction of CO2 to formic acid (HCOOH)2 and in hydrogenation reactions. The facile formation of M-H is a critical challenge to address to further improve the energy efficiency of these reactions. Specifically, the easy electrochemical generation of M-H using mild proton sources is key to enable high selectivity versus competitive CO and H2 formation in the CO2 electroreduction to HCOOH, the highest value-added CO2 reduction product3. Here we introduce a strategy for electrocatalytic M-H generation using concerted proton–electron transfer (CPET) mediators. As a proof of principle, the combination of a series of CPET mediators with the CO2 electroreduction catalyst [MnI(bpy)(CO)3Br] (bpy = 2,2′-bipyridine) was investigated, probing the reversal of the product selectivity from CO to HCOOH to evaluate the efficiency of the manganese hydride (Mn-H) generation step. We demonstrate the formation of the Mn-H species by in situ spectroscopic techniques and determine the thermodynamic boundary conditions for this mechanism to occur. A synthetic iron–sulfur cluster is identified as the best CPET mediator for the system, enabling the preparation of a benchmark catalytic system for HCOOH generation.

Date: 2022
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DOI: 10.1038/s41586-022-04874-z

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