Electrochemical Reduction of Carbon Dioxide at a Platinum Electrode in Acetonitrile‐Water Mixtures

Electrochemical reduction of CO 2 yields (COO - ) 2 as a main product in water free electrolyte. The current efficiency of CO and HCOO - initially increases and then decreases with increase of water concentration in the electrolyte. CO, reduced from CO 2 , is strongly adsorbed on Pt electrode, and prevents further reduction of CO 2 in aqueous media. Adsorbed CO is present on Pt in nonaqueous media as well, but reduction of CO 2 still proceeds. Since the supply of H 2 O is severely limited in nonaqueous media, H 2 evolution is suppressed. CO 2 , diffusing to the electrode, may be readily reduced to CO 2 · - CO 2 · - will react with CO 2 , eventually forming (COO - ) 2 (oxalate). (COO - ) 2 may also be formed by coupling of CO 2 · - With increase of H 2 O concentration, H 2 evolution is enhanced. HCOO - and CO may be produced in the reaction of CO 2 · - and H 2 O.

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