Directing Selectivity of Electrochemical Carbon Dioxide Reduction Using Plasmonics

Catalysts for electrochemical carbon dioxide reduction in aqueous electrolytes suffer from high energy input requirements, competition with hydrogen evolution from water reduction, and low product selectivity. Theory suggests that plasmonic catalysts can be tuned to selectively lower the energy barrier for a specific reaction in a set of competitive reactions, but there has been little experimental evidence demonstrating plasmon-driven selectivity in complicated multielectron electrochemical processes. Here, the photoactivity at a plasmonically active silver thin film electrode at small cathodic potentials selectively generates carbon monoxide while simultaneously suppressing hydrogen production. At larger cathodic potentials, the photoactivity promotes production of methanol and formate. Methanol production is observed only under illumination, not in dark conditions. The preference of the plasmonic activity for carbon dioxide reduction over hydrogen evolution and the ability to tune plasmonic activity with voltage demonstrates that plasmonics provide a promising approach to promote complex electrochemical reactions over other competing reactions.