Synergistic interfacial electronic modulation of topotactically developed bimetallic CoNiP on NiS nanorods for...

Designing hybrid transition metal phosphosulfide electrocatalysts is critical for the hydrogen evolution reaction (HER). We propose a novel approach by designing a hierarchical structure of cobalt phosphide (CoP) and nickel phosphide (Ni₈P₃) nanoparticles topotactically developed on nickel sulfide (Ni₃S₂) nanorods (CoNiP/NiS) via a sulfuration-phosphorization strategy using conductive 3D nickel foam. Hierarchical heterostructured nanorods were achieved without the need for template removal steps or the assistance of surfactants. This not only simplifies the process but also improves the exposure of active sites for catalytic purposes. Furthermore, the theoretical calculation results revealed that the high H* adsorption-free energy for CoP and Ni₈P₃ phases significantly decreases upon coupling with Ni₃S₂, which indicates that the interfacial electronic interaction synergistically modulates both CoP and Ni₈P₃ (CoNiP) at the coupled interfaces and facilitates the adsorption and desorption of H* intermediates during the HER process. The resulting electrode exhibits excellent performance in the HER catalytic process and shows great performance for further exploration in the urea oxidation reaction (UOR). Our work provides a stepping stone toward rational topotactic transformation of active materials on porous substrates, using electronic structure regulation and heterointerfaces to produce promising electrocatalysts for sustainable, large-scale hydrogen production from water electrolysis.