The electrochemical generation of metal hydride (M-H) species remains one of the major hurdles for a wide range of catalytic reactions to be carried out electrochemically. We present here a new strategy for electrocatalytic M-H generation using coupled proton-electron transfer (CPET) mediators. We investigate the combination of a series of CPET mediators with the CO2 electroreduction catalyst [MnI(bpy)(CO)3Br] (bpy = 2,2’-bipyridine), probing the reversal of product selectivity from CO to HCOOH to evaluate the efficiency of the M-H generation step. We demonstrate the formation of the manganese-hydride 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 that system, enabling the preparation of a benchmark catalytic system for HCOOH generation.

Electrocatalytic metal hydride generation using coupled proton-electron transfer mediators

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ACS Fall 2022

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