Interfacial electronic polarization–induced bifurcated CO2 electroreduction pathways to 2-propanol on Ce(OH)x/Ni2P

Abstract

Electrochemical CO2 reduction reaction to produce selective C3 alcohols, particularly 2-propanol (2-PrOH), remains challenging due to sluggish kinetics of *C2–*C1 coupling through direct CO2 conversion under mild conditions. Conventional electrochemical routes to C3+ alcohols often require sacrificing operational simplicity and energy efficiency to overcome intrinsic kinetic barriers. Consequently, the selective formation of C3+ alcohols under ambient aqueous conditions remains a central challenge in electrochemical CO2 reduction. Herein, we demonstrate synergistic dual-pathway CO2 reduction arising from spatially engineered electronic heterogeneity in Ce(OH)x-doped Ni2P (Ce(OH)x/Ni2P). Low-valent Niδ+ sites induced by Ce(OH)x doping uniquely stabilize bidentate *OCHO intermediates, while pristine Ni2P regions maintain conventional *COOH pathways. This distinctive coexistence of dual pathways facilitates *C2–*C1 coupling through aldol condensation with *CHx insertion from Fischer-Tropsch-like process, resulting in highly efficient 2-PrOH production. At an ultralow overpotential of −0.02 V vs. RHE under ambient atmospheric conditions, Ce(OH)x/Ni2P achieves 21.0% of Faradaic efficiency and 17.3% of energy efficiency for 2-PrOH, with excellent stability over 48 h. This work reveals that engineered nanoscale heterogeneity leads to the coexistence of reaction pathways rather than their competition, yielding superior product selectivity for sustainable CO2 valorization.