Triphenylphosphine-Assisted Transformation of NiS to Ni2P through a Solvent-Less Pyrolysis Route: Synthesis and Electrocatalytic Performance

Straightforward synthetic routes to the preparation of transition metal phosphides or their chalcogenide analogues are highly desired due to their widespread applications, including catalysis. We report a facile and simple route for the preparation of a pure phase nickel phosphide (Ni2P) and phase transformations in the nickel sulfide (NiS) system through a solvent-less synthetic protocol. Decomposition of different sulfur-based complexes (dithiocarbamate, xanthate, and dithiophosphonate) of nickel(II) was investigated in the presence and absence of triphenylphosphine (TPP). The optimization of reaction parameters (nature of precursor, ratio of TPP, temperature, and time) indicated that phosphorus- and sulfur-containing inorganic dithiophosphonate complexes and TPP (1:1 mole ratio) produced pure nickel phosphide, whereas different phases of nickel sulfide were obtained from dithiocarbamate and xanthate precursors in the presence or absence of TPP. A plausible explanation of the sulfide or phosphide phase formation is suggested, and the performance of Ni2P was investigated as an electrocatalyst for supercapacitance and overall water-splitting reactions. The performance of Ni2P with the surface free of any capping agents is not well explored, as common synthetic methods are solution-based routes; therefore, the electrocatalytic performance was also compared with metal phosphides, prepared by other routes. The highest specific capacitance of 367 F/g was observed at 1 A/g, and the maximum energy and power density of Ni2P were calculated to be 17.9 Wh/kg and 6951 W/kg, respectively. The prepared nickel phosphide required overpotentials of 174 and 316 mV along with Tafel slopes of 115 and 95 mV/dec to achieve a current density of 10 mA/cm2 for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), respectively.