Tunable Synthesis of Metal-Rich and Phosphorus-Rich Nickel Phosphides and Their Comparative Evaluation as Hydrogen Evolution Electrocatalysts.

Flexible synthetic routes to crystalline metal-rich to phosphorus-rich nickel phosphides are highly desired for comparable electrocatalytic HER studies. This report details solvent-free, direct, and tin-flux-assisted synthesis of five different nickel phosphides from NiCl2 and phosphorus at moderate temperatures (500 °C). Direct reactions are thermodynamically driven via PCl3 formation and tuned through reaction stoichiometry to produce crystalline Ni-P materials from metal-rich (Ni2P, Ni5P4) to phosphorus-rich (cubic NiP2) compositions. A tin flux in NiCl2/P reactions allows access to monoclinic NiP2 and NiP3. Intermediates in tin flux reactions were isolated to help identify phosphorus-rich Ni-P formation mechanisms. These crystalline micrometer-sized nickel phosphide powders were affixed to carbon-wax electrodes and investigated as HER electrocatalysts in acidic electrolyte. All nickel phosphides show moderate HER activity in a potential range of -160 to -260 mV to achieve current densities of 10 mA/cm2 ordered as c-NiP2 ≥ Ni5P4 > NiP3 > m-NiP2 > Ni2P, with NiP3 activity showing some particle size influence. Phosphorus-rich c/m-NiP2 appears most stable under acidic conditions during extended reactions. The HER activity of these different nickel phosphides appears influenced by a combination of factors such as particle size, phosphorus content, polyphosphide anions, and surface charge.