Selective Adsorption–Oxidation of Glycerol to Formate at Ni–O–Ce Nanoheterointerfaces

Electrocatalytic glycerol oxidation converts biomass to high-value formate but suffers from low Faradaic efficiency (FE) and selectivity due to the random hydroxyl group adsorption of glycerol. Precise control of the adsorption configuration for glycerol to direct the reaction along a single pathway is crucial for achieving highly selective formate production. Herein, Mg-doped NiOOH/CeO2 heterojunction aerogels were prepared via the sol–gel method. Mg doping induced the formation of oxygen vacancies and optimized the adsorption energy of intermediates (*OH, *OOH). The differential adsorption of hydroxyl groups in glycerol at the NiOOH/CeO2 nanoheterojunction interface enabled selective C–C bond cleavage, which achieved an FEformate of 95.7%, representing a significant enhancement compared to Mg-CeO2 (61.3%). Density functional theory calculations confirmed that Ni–O–Ce 3d–2p–4f orbital hybridization at the NiOOH/CeO2 interface promoted cross-interface electron transfer. This work optimizes the glycerol oxidation pathway, offering new insights into the high-value conversion of biomass and green hydrogen production.