Efficient Electrolysis of Biomass-Derived Carbonyl Compounds to Alcohols via Lanthanide-Modulated Hydrogenation Pathways

Electrocatalytic hydrogenation of biomass-derived carbonyl compounds offers a sustainable alternative to thermochemical routes, yet its selectivity is often constrained by unavoidable competition with hydrogen evolution through surface-bound H* intermediates. Here we demonstrate that electrocatalytic hydrogenation pathways can be reprogrammed via lanthanide assisted adsorption configuration engineering strategy, enabling direct control over reaction mechanisms at the electrode–electrolyte interface. Using levulinic acid (LA) as a representative biomass-derived carbonyl compound, cobalt nanoparticles modified with lanthanum oxide (La 2 O 3 ) selectively catalyze its conversion to γ-valerolactone (GVL) with a Faradaic efficiency of up to 95.8% under mild aqueous conditions. Mechanistic investigations reveal that La 2 O 3 introduces dual-site adsorption configurations that strengthen carbonyl coordination while suppressing interfacial water activation. This adsorption configuration inhibits the Volmer step, eliminates H*-mediated hydrogen atom transfer and redirects the reaction toward a proton-coupled electron transfer pathway. By translating pathway-level control into high selectivity and energy efficiency, this lanthanide assisted adsorption-controlled strategy enables electrocatalytic hydrogenation that is both mechanistically distinct and techno-economically viable for an industrially relevant biomass transformation. These findings establish lanthanide mediated proton-coupled electron transfer pathway as an effective approach and general strategy toward electrolysis of challenging biomass-derived carbonyl compounds to alcohols.