Formation Characteristics of Pt‐Ni Alloy Nanoparticles Fabricated by Nanolamination of Atomic Layer Deposition in Hydrogen

Forced-flow atomic layer deposition nanolamination is employed to fabricate Pt-Ni nanoparticles on XC-72, with the compositions ranging from Pt₉₄Ni₆ to Pt₆₇Ni₃₃. Hydrogen is used as a co-reactant for depositing Pt and Ni. The growth rate of Pt is slower than that using oxygen reactant, and the growth exhibits preferred orientation along the (111) plane. Ni shows much slower growth rate than Pt, and it is only selectively deposited on Pt, not on the substrate. Higher ratios of Ni would hinder subsequent stacking of Pt atoms, resulting in lower overall growth rate and smaller particles (1.3-2.1 nm). Alloying of Pt with Ni causes shifted lattice that leads to larger lattice parameter and d-spacing as Ni fraction increases. From the electronic state analysis, Pt 4f peaks are shifted to lower binding energies with increasing the Ni content, suggesting charge transfer from Ni to Pt. Schematic of the growth behavior is proposed. Most of the alloy nanoparticles exhibit higher electrochemical surface area and oxygen reduction reaction activity than those of commercial Pt. Especially, Pt₈₃Ni₁₇ and Pt₈₇Ni₁₃ show excellent mass activities of 0.76 and 0.59 A mg_Pt ^-1, respectively, higher than the DOE target of 2025, 0.44 A mg_Pt ^-1.