Electrocatalytic layers for hydrogen evolution reaction based on nickel phosphides: cost-effective fabrication and XPS characterization

The development of efficient electrocatalysts based on Pt-free materials is a crucial step for the maturation of competitive water splitting technologies able to sustain the upcoming hydrogen-based economy. In this context, the present work optimizes a codeposition/annealing methodology to produce electrocatalytic layers for the hydrogen evolution reaction (HER) based on one of the most promising alternatives to Pt-based catalysts: nickel phosphides. A nickel–phosphorus solid solution is codeposited with red phosphorus microparticles and the obtained composites are annealed to promote interdiffusion and reaction between nickel and phosphorus. The experimentation carried out demonstrates that the properties of the final phosphide layers depend on the conditions employed in both the codeposition step and the annealing step. It is fundamental to evaluate and optimize the NiP/P codeposition process, and it is also important to understand the influence of annealing time and temperature on the microstructure and HER performance of the layers obtained. X-ray photoelectron spectroscopy (XPS) is employed to evaluate the phase composition at the surface, highlighting the presence of a top layer characterized by a Ni2P/Ni12P5 ratio significantly lower than the value found in the bulk of the coating. Annealed NiP/P layers are tested for HER in 0.5 M sulphuric acid solution. The tests demonstrate a clear correlation between the Ni2P/Ni12P5 ratio on the surface and the overpotential for HER. Coherently, when the outer Ni12P5-rich layer is mechanically removed, lower overpotentials are observed (169.5 mV vs. RHE for 10 mA cm−2).