Electronic Structure Engineering of CuNi Alloys: Enabling Dual‐Path Synergy and Enhanced Performance in Furfural Electrohydrogenation

ABSTRACT The development of efficient electrocatalysts for biomass‐derived furfural hydrogenation is crucial for sustainable chemical production. Herein, we report a systematic study of transition metal catalysts for electrocatalytic furfural reduction to furfuryl alcohol (FA) synthesized by precisely controlled magnetron sputtering. Monometallic thin films (Cu, Ni, Co, Ag, Cr, Mo and W) on Ti substrates reveal a volcano‐shaped correlation between the d‐band center position and catalytic activity, establishing fundamental binding energy‐activity relationships. Building on these insights, we designed bimetallic CuNi alloys with tunable compositions, where the Cu 40 Ni 60 variant demonstrated exceptional performance, achieving twice the FA formation rate of pure Ni while maintaining 100% selectivity. Mechanistic studies reveal that the Cu 40 Ni 60 catalyst exhibits intermediate behavior between Cu (preferring the Langmuir–Hinshelwood pathway) and Ni (favoring the proton‐coupled electron transfer pathway), with enhanced contributions from both pathways synergistically boosting the overall reaction rate. Alloying induces synergistic electronic effects that optimize furfural and H adsorption energy to regulate surface coverage and balance the reaction pathways. This work establishes a standardized platform for evaluating composition‐activity relationships in furfural hydrogenation and provides fundamental design principles for non‐precious metal alloy catalysts, highlighting electronic structure engineering as a key strategy for optimizing hydrogenation performance.