Electrolytic CO(2) Reduction in Tandem with Oxidative Organic Chemistry

[Image: see text] Electrochemical reduction of CO(2) into carbon-based products using excess clean electricity is a compelling method for producing sustainable fuels while lowering CO(2) emissions. Previous electrolytic CO(2) 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 CO(2) 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 CO(2) 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.