Electrochemical CO2 reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products

In the future, industrial CO 2 electroreduction using renewable energy sources could be a sustainable means to convert CO 2 and water into commodity chemicals at room temperature and atmospheric pressure. This study focuses on the electrocatalytic reduction of CO 2 on polycrystalline Au surfaces, which have high activity and selectivity for CO evolution. We explore the catalytic behavior of polycrystalline Au surfaces by coupling potentiostatic CO 2 electrolysis experiments in an aqueous bicarbonate solution with high sensitivity product detection methods. We observed the production of methanol, in addition to detecting the known products of CO 2 electroreduction on Au: CO, H 2 and formate. We suggest a mechanism that explains Au's evolution of methanol. Specifically, the Au surface does not favor C-O scission, and thus is more selective towards methanol than methane. These insights could aid in the design of electrocatalysts that are selective for CO 2 electroreduction to oxygenates over hydrocarbons.