The Solvation-Induced Onsager Reaction Field Rather than the Double-Layer Field Controls CO₂ Reduction on Gold

The selectivity and activity of the carbon dioxide reduction (CO₂R) reaction are sensitive functions of the electrolyte cation. By measuring the vibrational Stark shift of in situ-generated CO on Au in the presence of alkali cations, we quantify the total electric field present at catalytic active sites and deconvolute this field into contributions from (1) the electrochemical Stern layer and (2) the Onsager (or solvation-induced) reaction field. Contrary to recent theoretical reports, the CO₂R kinetics does not depend on the Stern field but instead is closely correlated with the strength of the Onsager reaction field. These results show that in the presence of adsorbed (bent) CO₂, the Onsager field greatly exceeds the Stern field and is primarily responsible for CO₂ activation. Additional measurements of the cation-dependent water spectra using vibrational sum frequency generation spectroscopy show that interfacial solvation strongly influences the CO₂R activity. These combined results confirm that the cation-dependent interfacial water structure and its associated electric field must be explicitly considered for accurate understanding of CO₂R reaction kinetics.