Abstract The electrochemical CO 2 reduction reaction (CO 2 RR) represents a very promising future strategy for synthesizing carbon-containing chemicals in a more sustainable way. In spite of great progress in electrocatalyst design over the last decade, the critical role of wettability-controlled interfacial structures for CO 2 RR remains largely unexplored. Here, we systematically modify the structure of gas-liquid-solid interfaces over a typical Au/C gas diffusion electrode through wettability modification to reveal its contribution to interfacial CO 2 transportation and electroreduction. Based on confocal laser scanning microscopy measurements, the Cassie-Wenzel coexistence state is demonstrated to be the ideal three phase structure for continuous CO 2 supply from gas phase to Au active sites at high current densities. The pivotal role of interfacial structure for the stabilization of the interfacial CO 2 concentration during CO 2 RR is quantitatively analysed through a newly-developed in-situ fluorescence electrochemical spectroscopic method, pinpointing the necessary CO 2 mass transfer conditions for CO 2 RR operation at high current densities.

Efficient wettability-controlled electroreduction of CO2 to CO at Au/C interfaces