Electrolytic CO₂ Reduction in Tandem with Oxidative Organic Chemistry

Electrochemical reduction of CO₂ into carbon-based products using excess clean electricity is a compelling method for producing sustainable fuels while lowering CO₂ emissions. Previous electrolytic CO₂ reduction studies all involve dioxygen production at the anode, yet this anodic reaction requires a large overpotential and yields a product bearing no economic value. We report here that the cathodic reduction of CO₂ to CO can occur in tandem with the anodic oxidation of organic substrates that bear higher economic value than dioxygen. This claim is demonstrated by 3 h of sustained electrolytic conversion of CO₂ into CO at a copper–indium cathode with a current density of 3.7 mA cm^–2 and Faradaic efficiency of >70%, and the concomitant oxidation of an alcohol at a platinum anode with >75% yield. These results were tested for four alcohols representing different classes of alcohols and demonstrate electrolytic reduction and oxidative chemistry that form higher-valued carbon-based products at both electrodes