Modulating O-H Activation of Methanol Oxidation on Nickel-Organic Frameworks for Overall CO₂ Electrolysis

Advanced anodic electrocatalysis is essential for boosting overall carbon dioxide (CO₂) electrolysis. In this work, we demonstrate partially pyrolyzed nickel-organic frameworks for efficient methanol oxidation at the anode. Experimental validation and theoretical calculation results demonstrate that the partial deligandation could maintain the porous skeleton and ensure more accessible nickel sites for in situ transformation to the Ni-OOH active phase, modulating the O-H activation pathway of methanol upgradation for selective and efficient formate electrosynthesis. An overall electrolysis system driving methanol and CO₂ covalorization reduces the energy consumption of 23% at 200 mA cm^-2 in a flow cell and is further implemented in a zero-gap membrane electrode assembly device with an improved processing capacity of ca. 500 mA cm^-2 at 2.4 V. This work provides significant concepts for designing advanced electrocatalysts and electrolyzer configurations to realize decarbonization and valuables coproduction with high energy efficiency.