Heterogeneous Co–Ni phosphide with active sites for water dissociation and efficient hydrogen evolution reaction

Abstract

The construction of highly active and stable transition phosphide-based materials is widely regarded as an alternative approach to the use of Pt-based catalysts in the field of electrocatalytic hydrogen evolution. Herein, self-supported heterostructure Co–Ni phosphides (denoted as Co_xNi_1−x-P) were synthesized with different metal ratios by a low temperature electrodeposition strategy. Impressively, the optimized heterogeneous Co_0.5Ni_0.5-P nanocomposites displayed outstanding hydrogen evolution performance, with low overpotentials of 67 mV and 181 mV to deliver current densities of 10 mA cm⁻² and 100 mA cm⁻² in alkaline electrolyte. X-ray photoelectron spectroscopy revealed the optimized electronic structure of Co_0.5Ni_0.5-P, which led to an improvement in the conductivity. Density functional theory calculations demonstrated that the Co_0.5Ni_0.5-P heterostructure could provide a more optimal water-dissociation-related Volmer process for hydrogen evolution reaction (HER), in which water molecules could be easily activated on Co_0.5Ni_0.5-P with a low energy barrier. Moreover, the downshift of the d-band center confirmed the optimized H adsorption, further accelerating the HER kinetics.