Pressure dependence in aqueous-based electrochemical CO(2) reduction

Electrochemical CO(2) reduction (CO(2)R) is an approach to closing the carbon cycle for chemical synthesis. To date, the field has focused on the electrolysis of ambient pressure CO(2). However, industrial CO(2) is pressurized—in capture, transport and storage—and is often in dissolved form. Here, we find that pressurization to 50 bar steers CO(2)R pathways toward formate, something seen across widely-employed CO(2)R catalysts. By developing operando methods compatible with high pressures, including quantitative operando Raman spectroscopy, we link the high formate selectivity to increased CO(2) coverage on the cathode surface. The interplay of theory and experiments validates the mechanism, and guides us to functionalize the surface of a Cu cathode with a proton-resistant layer to further the pressure-mediated selectivity effect. This work illustrates the value of industrial CO(2) sources as the starting feedstock for sustainable chemical synthesis.