Correlating CO Coverage and CO Electroreduction on Cu via High-Pressure in Situ Spectroscopic and Reactivity Investigations.

The absolute coverage of CO has been a missing piece in the mechanistic puzzle of the CO reduction reaction (CORR) on Cu. For the first time, we revealed the upper bound of the CO coverage under electrocatalytic conditions to be 0.05 monolayer at atmospheric pressure and the saturation CO coverage to be ∼0.25 monolayer by conducting surface enhanced infrared spectroscopy at CO pressures up to 60 barg in a custom-designed spectroelectrochemical cell. CORR activities on Cu were also determined in the same pressure range. Calculated reaction orders of C ₂₊ products with respect to adsorbed CO are substantially less than unity, clearly indicating that the coupling of adsorbed CO is not the rate-determining step leading to multicarbon products. The increase in CO coverage can reduce the C affinity on the Cu surface and favor the selectivity towards oxygenates, especially acetate, over ethylene. Uncommon products, including ethane, glycolaldehyde, and ethylene glycol, were detected in appreciable amounts, likely due to a new C-C coupling mechanism taking place at elevated CO pressures.