The Importance of Cannizzaro-Type Reactions during Electrocatalytic Reduction of Carbon Dioxide

[Image: see text] A seemingly catalytically inactive electrode, boron-doped diamond (BDD), is found to be active for CO(2) and CO reduction to formaldehyde and even methane. At very cathodic potentials, formic acid and methanol are formed as well. However, these products are the result of base-catalyzed Cannizzaro-type disproportionation reactions. A local alkaline environment near the electrode surface, caused by the hydrogen evolution reaction, initiates aldehyde disproportionation promoted by hydroxide ions, which leads to the formation of the corresponding carboxylic acid and alcohol. This phenomenon is strongly influenced by the electrolyte pH and buffer capacity and not limited to BDD or formaldehyde, but can be generalized to different electrode materials and to C(2) and C(3) aldehydes as well. The importance of these reactions is emphasized as the formation of acids and alcohols is often ascribed to direct CO(2) reduction products. The results obtained here may explain the concomitant formation of acids and alcohols often observed during CO(2) reduction.