Killing Two Birds with One Stone: Selective Oxidation of Small Organic Molecule as Anodic Reaction to Boost CO₂ Electrolysis

Replacing anodic oxygen evolution reaction (OER) with the oxidation of small organic molecules in CO₂ electrolysis is an ingenious strategy to reduce the energy consumption while produce valuable anodic products instead of low‐value O₂. Herein, an advanced CO₂ electrolysis system constructed by replacing OER with selective methanol oxidation reaction (MOR) is reported as a proof‐of‐concept, which achieves the yielding of value‐added products in both cathode and anode. Notably, the MOR over a self‐supported NiCo‐based metal–organic framework‐derived anode (NiCo‐NF‐ET) only needs 1.291 V to reach a high current density of 100 mA cm⁻², which is about 346 mV lower than that of OER. Simultaneously, formate can also be produced with the Faradaic efficiencies approaching to 100%. Consequently, in comparison with the conventional CO₂ electrolysis system, integrating cathodic CO₂ reduction reaction (CO₂RR) with anodic MOR can lead to the reduction of about 880 mV to deliver the current density of 30 mA cm⁻², while without compromising the selectivity of the products in both electrodes. Herein, the great potential to increase the economic benefits of CO₂ electrolysis via the rational design of nonprecious electrocatalysts and participated anodic oxidation reactions is shown.