Synergistic design of hierarchical and heterostructural P-NiMoO4@Net-like Ni2P for enhanced hydrogen evolution electrocatalysis

Hierarchical structure design and heterostructure engineering are effective strategies for enhancing hydrogen evolution reaction (HER) performance, yet their synergistic integration remains underexplored. In this work, a novel hierarchical P-NiMoO 4 @Net-like Ni 2 P heterostructure HER electrocatalyst was prepared via a two-step hydrothermal method followed by low-temperature phosphorization. The three-dimensional net like Ni 2 P was closely integrated with one-dimensional phosphorus-doped NiMoO 4 micro/nanorod arrays, enabling hierarchical structural assembly and the formation of synergistic heterointerfaces. The hierarchical structure significantly increased active site exposure, with a double-layer capacitance of 254.4 mF cm −2 , more than five times that of single-component Ni 2 P (48.4 mF cm −2 ). Density functional theory calculations revealed that the heterostructure lowered the d-band center of active Ni 3 sites and optimized the hydrogen adsorption energy, thereby enhancing HER activity. The P-NiMoO 4 @Net-like Ni 2 P catalyst exhibited an alkaline HER overpotential of 49 mV at a current density of 10 mA cm −2 . It also maintained stable operation for 100 h at 10mA cm −2 and 120 h at 100mA cm −2 . This study demonstrates the potential of integrating hierarchical and heterostructural strategies, providing a reference for advanced nanostructured catalyst development.