The Central Role of Bicarbonate in the Electrochemical Reduction of Carbon Dioxide on Gold.

Much effort has been devoted in the development of efficient catalysts for electrochemical reduction of CO. Molecular level understanding of electrode-mediated process, particularly the role of bicarbonate in increasing CO reduction rates, is still lacking due to the difficulty of directly probing the electrochemical interface. We developed a protocol to observe normally invisible reaction intermediates with a surface enhanced spectroscopy by applying square-wave potential profiles. Further, we demonstrate that bicarbonate, through equilibrium exchange with dissolved CO, rather than the supplied CO, is the primary source of carbon in the CO formed at the Au electrode by a combination of in situ spectroscopic, isotopic labeling, and mass spectroscopic investigations. We propose that bicarbonate enhances the rate of CO production on Au by increasing the effective concentration of dissolved CO near the electrode surface through rapid equilibrium between bicarbonate and dissolved CO.