Hydroxyl Radical Modulation on MoNi3/MoO2+x Heterostructure via Synergistic Vacancy and Interfacial Engineering for Highly Selective Imine Synthesis Coupled with Hydrogen Evolution

The production of high-value chemicals from renewable biomass carbon resources represents a critical pathway toward sustainable development. However, this process is often constrained by harsh reaction conditions and low selectivity. Herein, we design an oxygen vacancy (OV)-rich MoNi3/MoO2+x heterostructure catalyst, which exhibited superior performance in a neutral phosphate buffer (pH = 7), with an anodic reaction selectivity of 95% for the biomass derived benzylamine oxidation to N-benzylidene benzylamine and a low overpotential of 64 mV at 10 mA cm–2 for cathode H2 evolution. The high selectivity was achieved by tuning •OH coverage through the precise construction of a unique interface between OV-rich amorphous MoO2+x and metallic MoNi3. Moreover, the dual electrode system operated stably for 150 h at 10 mA cm–2 under an applied voltage of only 1.53 V. This work provides an effective approach for the green production of high-value imines and H2 by synergistic vacancy and interfacial engineering.