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.
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