Flexible Molecular Precursors for Selective Decomposition to Nickel Sulfide or Nickel Phosphide for Water Splitting and Supercapacitance

Herein, the synthesis of three nickel(II) dithiophosphonate complexes of the type [Ni{S2P(OR)(4‐C6H4OMe)}2] [R=H (1), C3H7 (2)] and [Ni{S2P(OR)(4‐C6H4OEt}2] [R=(C6H5)2CH (3)] is described; their structures were confirmed by single‐crystal X‐ray studies. These complexes were subjected to surfactant/solvent reactions at 300 °C for one hour as flexible molecular precursors to prepare either nickel sulfide or nickel phosphide particles. The decomposition of complex 2 in tri‐octylphosphine oxide/1‐octadecene (TOPO/ODE), TOPO/tri‐n‐octylphosphine (TOP), hexadecylamine (HDA)/TOP, and HDA/ODE yielded hexagonal NiS, Ni2P, Ni5P4, and rhombohedral NiS, respectively. Similarly, the decomposition of complex 1 in TOPO/TOP and HDA/TOP yielded hexagonal Ni2P and Ni5P4, respectively, and that of complex 3 in similar solvents led to hexagonal Ni5P4, with TOP as the likely phosphorus provider. Hexagonal NiS was prepared from the solvent‐less decomposition of complexes 1 and 2 at 400 °C. NiS (rhom) had the best specific supercapacitance of 2304 F g−1 at a scan rate of 2 mV s−1 followed by 1672 F g−1 of Ni2P (hex). Similarly, NiS (rhom) and Ni2P (hex) showed the highest power and energy densities of 7.4 kW kg−1 and 54.16 W kg−1 as well as 6.3 kW kg−1 and 44.7 W kg−1, respectively. Ni5P4 (hex) had the lowest recorded overpotential of 350 mV at a current density of 50 mA cm−2 among the samples tested for the oxygen evolution reaction (OER). NiS (hex) and Ni5P4 (hex) had the lowest overpotentials of 231 and 235 mV to achieve a current density of 50 mA cm−2, respectively, in hydrogen evolution reaction (HER) examinations. Just as good or better: Molecular precursors were used to prepare selectively nickel phosphide or nickel sulfide nanoparticles. Different phosphide and sulfide phases were prepared by controlling the reaction parameters and the performance of the different phases was investigated for energy storage and energy generation applications.