Time-Resolved Infrared Spectroscopic Evidence for Interfacial pH-Dependent Kinetics of Formate Evolution on Cu Electrodes

By deployment of rapid-scan (second time scale) electrochemical FT-IR reflection-absorption spectroscopy, we studied the reduction of CO₂ in 0.1 M Na₂SO₄ in deuterated water at a pD of 3.7. We report on the impact of dynamic changes in the bicarbonate equilibrium concentration in the vicinity of a polycrystalline Cu electrode, induced by step changes in applied electrode potential. We correlate these changes in interfacial composition and concentrations of dissolved species to the formation rate of formate, and provide evidence for the following conclusions: (i) the kinetics for the conversion of dissolved CO₂ to formate (formic acid) are fast, (ii) bicarbonate is also converted to formate, but with less favorable kinetics, and (iii) carbonate does not yield any formate. These results reveal that formate formation requires (mildly) acidic conditions at the interface for CO₂ to undergo a proton-coupled conversion step, and we postulate that bicarbonate reduction to formate is driven by catalytic hydrogenation via in situ formed H₂. Interestingly CO was not observed, suggesting that the kinetics of the CO₂ to CO reaction are significantly less favorable than formate formation under the experimental conditions (pH and applied potential). We also analyzed the feasibility of pulsed electrolysis to enhance the (average) rate of formation of formate. While a short positive potential pulse enhances the CO₂ concentration, this also leads to the formation of basic copper carbonates, resulting in electrode deactivation. These observations demonstrate the potential of rapid-scan EC-IRRAS to elucidate the mechanisms and kinetics of electrochemical reactions, offering valuable insights for optimizing catalyst and electrolyte performance and advancing CO₂ reduction technologies.