Platinum-Nickel Nanowires with Improved Hydrogen Evolution Performance in Anion Exchange Membrane-Based Electrolysis

Platinum-nickel (Pt-Ni) nanowires were developed as hydrogen evolving catalysts for anion exchange membrane electrolyzers. Following synthesis by galvanic displacement, the nanowires had Pt surface areas of 90 m² g_Pt^-1. The nanowire specific exchange current densities were 2-3 times greater than commercial nanoparticles and may benefit from the extended nanostructure morphology that avoids fringe facets and produces higher quantities of Pt{100}. Hydrogen annealing was used to alloy Pt and Ni zones and compress the Pt lattice. Following annealing, the nanowire activity improved to 4 times greater than the as-synthesized wires and 10 times greater than Pt nanoparticles. Density functional theory calculations were performed to investigate the influence of lattice compression and exposed facet on the water-splitting reaction; it was found that at a lattice of 3.77 Å, the (100) facet of a Pt-skin grown on Ni₃Pt weakens hydrogen binding and lowers the barrier to water-splitting as compared to pure Pt(100). Moreover, the activation energy of water-splitting on the (100) facet of a Pt-skin grown on Ni₃Pt is particularly advantageous at 0.66 eV as compared to the considerably higher 0.90 eV required on (111) surfaces of pure Pt or Pt-skin grown on Ni₃Pt. This favorable effect may be slightly mitigated during further optimization procedures such as acid leaching near-surface Ni, necessary to incorporate the nanowires into electrolyzer membrane electrode assemblies. Exposure to acid resulted in slight dealloying and Pt lattice expansion, which reduced half-cell activity, but exposed Pt surfaces and improved single-cell performance. Membrane electrode assembly performance was kinetically 1-2 orders of magnitude greater than Ni and slightly better than Pt nanoparticles while at one tenth the Pt loading. These electrocatalysts potentially exploit the highly active {100} facets and provide an ultralow Pt group metal option that can enable anion exchange membrane electrolysis, bridging the gap to proton exchange membrane-based systems.