Superhydrophilicity and Electronic Modulation on Self‐Supported Lignin‐Derived Carbon Coupled with NiO@MoNi₄ for Enhancing Urea Electrolysis

Developing highly efficient biomass-derived carbon-based electrocatalysts remains challenging for urea electrolysis because most of these electrocatalysts show powder morphology, which can lead to Ostwald ripening during the reaction process, and its reaction mechanism should be further verified. Herein, self-supported lignin-derived carbon coupling NiO@MoNi₄ heterojunction (NiO@MoNi₄/C) possesses superhydrophilic properties and electronic modulation, boosting the performance of urea electrolysis. Electrochemical results show that an indirect oxidation step for urea oxidation reaction (UOR) and Volmer-Heyrovsky mechanism for hydrogen evolution reaction (HER) occurs on the surface of NiO@MoNi₄/C. It displays low potentials for UOR (E_10/500/1000 = 1.28/1.41/1.47 V) and for HER (E_{-10/-500/-1000} = -38/-264/-355 mV) in 1.0 M KOH + 0.5 M urea electrolyte solution. The good activity is ascribed to the self-supported lignin-derived carbon and heterojunction, which increases the number of active sites, optimizes electronic structure, and improves electron transfer. Benefiting from the self-supported lignin-derived carbon, NiO@MoNi₄/C demonstrates corrosion resistance and superhydrophilicity, which avoids Ostwald ripening and accelerates gas-liquid transfer, thus, maintaining for 100 h at ±1000/±1500 mA cm^-2 during the UOR and HER test. This work provides a good catalyst for urea electrolysis and presents a promising way for preparing lignin-derived carbon-based catalysts while expanding the application of lignin-based biomass carbon materials.