Strongly Coupled Heterostructured CoP/MoO₂ as an Advanced Electrocatalyst for Urea-Assisted Water Electrolysis

Developing low-cost electrocatalysts with excellent activity and durability in urea-assisted water splitting is urgently needed in order to achieve sustainable hydrogen production. Herein, we in situ synthesized a robust coupled heterostructured electrocatalyst (CoP/MoO₂) on a nickel foam (NF) substrate and explored its electrocatalytic performances in the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and urea oxidation reaction (UOR). The overpotential of CoP/MoO₂/NF is found to be only 11 mV at 10 mA cm^-2 during the HER process, which is significantly lower than that of commercial Pt/C. Meanwhile, the UOR catalytic performance of CoP/MoO₂/NF indicates fast reaction kinetics, along with a considerable low driving potential (1.26 V) compared to that of the OER (1.51 V). In situ and ex situ techniques demonstrate that these excellent electrocatalytic properties are mainly ascribed to the effective synergistic coupled effect and strong electronic interactions between single-component CoP and MoO₂, which can tune electronic states of Co and Mo, expose more active sites, enhance intrinsic catalytic activity, and accelerate charge transfer. Moreover, when used in electrochemical overall water splitting and urea-assisted water electrolysis, CoP/MoO₂/NF can reach a current density of 10 mA cm^-2 at only 1.46 and 1.32 V. This outperforms Pt/C||RuO₂ and numerous nonprecious metal electrocatalysts and maintains a stable long-term electrolytic operation for 84 h. This work provides a promising pathway for the development of efficient catalysts during urea-assisted water electrolysis for hydrogen production.