Electrocatalysts based on metal/semiconductor heterostructures are promising for integrated biomass conversion and hydrogen evolution, yet often suffer from inefficient interfacial charge transfer. Herein, a hierarchical NiMo@NiCuP heterostructure with built-in ohmic contact is fabricated on nickel foam. The intimate interface between the conductive NiMo and semiconducting NiCuP domains enables barrier-free electron transfer and optimized intermediate adsorption. The catalyst exhibits exceptional bifunctional performance, achieving a HER overpotential of only 13 mV and furfural oxidation reaction potential of 1.33 V at 10 mA cm–2. In the membrane electrode system, it delivers 100 mA cm–2 at 1.64 V, which is 270 mV more efficient than overall water splitting technologies. Operando Raman and XPS analyses reveal that the NiMo alloy ensures structural integrity and electron modulation, while Cu and P sites dynamically reconfigure under reaction conditions: reduced Cu(I) and electron-enriched P promote HER, whereas oxidized Cu(II) and metal-phosphide bonds facilitate FOR. This study demonstrates a design strategy based on interfacial ohmic contact and dynamic active-site evolution, advancing efficient coupled electrosynthesis of chemicals and green hydrogen.
Feng et al. (Mon,) studied this question.