Nanoneedles of Mixed Transition Metal Phosphides as Bifunctional Catalysts for Electrocatalytic Water Splitting in Alkaline Media.

In this work, mixed Ni/Co and Ni/Fe metal phosphides with different metal ratios were synthesized through the phosphidization of high-surface-area hydroxides grown hydrothermally on carbon cloth. The materials were characterized by means of X-ray photoemission spectroscopy, X-ray diffraction, energy dispersive X-ray analysis, and electron microscopies. The electrocatalytic performance in the electrochemical water splitting was tested in alkaline media. With the aim of determining the chemical stability of the mixed phosphides and the possible changes undergone under catalytic conditions, the materials were characterized before and after the electrochemical tests. The best performances in the hydrogen evolution reaction were achieved when synergic interactions are established among the metal centers, as suggested by the outstanding performances (50 mV to achieve 10 mA/cm 2 ) of materials containing the highest amount of ternary compounds, i.e., NiCoP and NiFeP. The best performances in the oxygen evolution reaction were reached by the Ni-Fe materials. Under these conditions, it was demonstrated that a strong oxidation of the surface and the dissolution of the phosphide/phosphate component takes place, with the consequent formation of the corresponding metal oxides and hydroxides.