Constructing Heteronuclear Bridging Atoms toward Bifunctional Electrocatalysis

Superseding the oxygen evolution reaction with the thermodynamically favorable and economically attractive organic oxidation reaction is crucial to acquiring eco-friendly hydrogen production via an electrochemical process coupled with renewable energy. A bifunctional electrocatalyst, Ru@NixCo1–x(OH)2, featuring a dandelion-liked structure and assembled into a two-electrode configuration, requires a voltage of 1.35 V for cathode H2 and anode 2,5-furandicarboxylic acid. The heteronuclear bridging atoms at the Ru–Ni sites accelerate water splitting through the Volmer–Tafel mechanism and enhance the *H coverage, as demonstrated by in situ spectroscopy and electrochemical analysis. Simultaneously, the Ru–Co sites serve as adsorption sites for 5-hydroxymethylfurfural, achieving 100% Faradic efficiency and selectivity. Upon upscaling the configuration to a 2 × 2 cm2 membrane electrode assembly reactor, an FDCA production rate of 243 mg/h was achieved, with electricity savings of approximately 0.67 kWh/m3 (H2). This work offers a promising avenue for concurrent hydrogen production and biomass upgrading with industrial practicability.