Abstract
Electrochemical CO(2) reduction is a topic of major interest in contemporary research as an approach to use renewably-derived electricity to synthesise useful hydrocarbons from waste CO(2). Various strategies have been developed to optimise this challenging reaction at electrode interfaces, but to-date, decoupled electrolysis has not been demonstrated for the reduction of CO(2). Decoupled electrolysis aims to use electrochemically-derived charged redox mediators - electrical charge and potential vectors - to separate catalytic product formation from the electrode surface. Utilising an electrochemically generated highly reducing redox mediator; chromium propanediamine tetraacetate, we report the first successful application of decoupled electrolysis to electrochemical CO(2) reduction. A study of metals and metal composites found formate to be the most accessible product, with bismuth metal giving the highest selectivity. Copper, tin, gold, nickel and molybdenum carbide heterogeneous catalysts were also investigated, in which cases H(2) was found to be the major product, with minor yields of two-electron CO(2) reduction products. Subsequent optimisation of the bismuth catalyst achieved a high formate selectivity of 85%. This method represents a radical new approach to CO(2) electrolysis, which may be coupled directly with renewable energy storage technology and green electricity.