Electric Field Redistribution Triggered Surface Adsorption and Mass Transfer to Boost Electrocatalytic Glycerol Upgrading Coupled with Hydrogen Evolution

Electrocatalytic glycerol oxidation reaction (GOR) stands out as an economical and prospective technology to replace oxygen evolution reaction for co‐producing high‐valued chemicals and hydrogen (H2). Regulating the adsorption of glycerol (GLY) and hydroxyl (OH) species is of great significance for improving the GOR performance. Herein, a hierarchical p–n heterojunction by combining Co‐metal organic framework (MOF) nanosheets with CuO nanorod arrays (CuO@Co‐MOF) is developed to realize the optimization on GOR. Specifically, CuO@Co‐MOF electrode exhibits superior performance with a conversion of 98.4%, formic acid (FA) selectivity of 87.3%, and Faradaic efficiency (FE) of 98.9%. The flow‐cell system with the bifunctional CuO@Co‐MOF electrode for pairing GOR with the hydrogen evolution reaction (HER) reveals better energy conversion efficiency. Experimental results and theoretical calculations unravel the redistributed electric field by introducing Co‐containing species that contribute to the improved performance, which not only enhances the OH adsorption but also modulates the excessive GLY adsorption of CuO, thus reducing reaction energy barriers of FA desorption. Simultaneously, finite element analysis reveals that the novelty hierarchical structure can increase the concentration of OH− and facilitate the mass transfer of OH− in the solution. A hierarchical CuO@Co‐MOF heterojunction is developed to realize the optimization of electrocatalytic glycerol oxidation reaction. The redistributed electric field by introducing Co‐MOF enhances the OH adsorption, modulates the excessive glycerol adsorption of CuO, and reduces reaction energy barriers of formic acid desorption. The hierarchical structure also facilitates the mass transfer of OH− in the solution.