Mo-doped NiO@TiO₂ electrocatalyst for highly selective and durable hydrogenolysis of furfural to 2-methylfuran

The electrocatalytic hydrogenolysis of biomass-derived furfurals to 2-methylfuran (MF) is a vital pathway for sustainable energy development, yet it is hindered by the complex parallel reaction networks and competitive hydrogen evolution reaction. Herein, we rationally designed and synthesized a core-shell-like heterostructure consisting of a structurally stable TiO₂ core encapsulated by an open interface-rich Mo-NiO shell electrocatalyst (denoted as Mo-NiO@TiO₂). Experimental characterization reveals that the heterojunction reconstructs the local electronic microenvironment and promotes oxygen vacancy generation. Simultaneously, the Mo dopants improved the stability of NiO in acidic electrolytes. Consequently, the Mo-NiO@TiO₂ catalyst demonstrates efficient electrocatalytic performance for the hydrogenolysis of furfural to MF, achieving a selectivity of 97% and a faradaic efficiency of 82%, alongside stable cycling performance over 130 hours. Kinetic and mechanistic investigations elucidate that the hydrogenation proceeds via a proton-coupled electron transfer pathway dictated by local proton availability, which profoundly mitigates the kinetic energy barrier and suppresses the parasitic HER. This work delivers deep mechanistic insights into atomic-level electronic engineering and provides a robust paradigm for designing advanced electrocatalysts for sustainable biomass valorization.