Highly alkaline electrolytes have been shown to improve the formation rate of C2+ products in the electrochemical reduction of carbon dioxide (CO2) and carbon monoxide (CO) on copper surfaces, with the assumption that higher OH− concentrations promote the C−C coupling chemistry. Herein, by systematically varying the concentration of Na+ and OH− at the same absolute electrode potential, we demonstrate that higher concentrations of cations (Na+), rather than OH−, exert the main promotional effect on the production of C2+ products. The impact of the nature and the concentration of cations on the electrochemical reduction of CO is supported by experiments in which a fraction or all of Na+ is chelated by a crown ether. Chelation of Na+ leads to drastic decrease in the formation rate of C2+ products. The promotional effect of OH− determined at the same potential on the reversible hydrogen electrode scale is likely caused by larger overpotentials at higher electrolyte pH.
All Science Journal Classification (ASJC) codes