Pre-Equilibrium Reaction Mechanism as a Strategy to Enhance Rate and Lower Overpotential in Electrocatalysis.

ABSTRACT: Pre-equilibrium reaction kinetics enable the overall rate of a catalytic reaction to be orders of magnitude faster than the rate-determining step. Herein, we demonstrate how pre-equilibrium kinetics can be applied to breaking the linear free-energy relationship (LFER) for electrocatalysis, leading to rate enhancement 5 orders of magnitude and lowering of overpotential to approximately thermoneutral. This approach is applied to pre-equilibrium formation of a metal-hydride intermediate to achieve fast formate formation rates from CO₂ reduction without loss of selectivity (i.e., H₂ evolution). Fast pre-equilibrium metal-hydride formation, at 10⁸ M^-1 s^-1, boosts the CO₂ electroreduction to formate rate up to 296 s^-1.

SUBMITTER: Pattanayak S 

PROVIDER: S-EPMC9936576 | biostudies-literature | 2023 Feb

REPOSITORIES: biostudies-literature