The reactivity of water and OH on Pt-Ni(111) films

Bimetallic Pt catalysts are of interest as water redox catalysts in low temperature fuel cells. Here we compare water and hydroxyl adsorption on Pt-Ni(111) films and a PtNi(111) alloy surface with the behaviour on the pure metals. Whereas water adsorbs and desorbs intact from close packed Pt and Ni, it dissociates on PtNi surfaces to form adsorbed hydroxyl and hydrogen. Reactivity to water increases in the order Pt(111) < monolayer Pt-Ni(111) < multilayer (2-6 ML) Pt-Ni(111) ∼ PtNi(111) surface alloy and does not scale directly with the Pt strain. Hydroxyl can also be formed by reaction with pre-adsorbed O and is less stable than on pure Pt, decomposing to water and O in a broad peak near 180 K, 20 K lower than on Pt(111). The reduced stability of OH on Pt-Ni(111) films is common to all the PtNi surfaces and consistent with bimetallic PtNi surfaces showing less blocking by OH during the oxygen reduction reaction. Highly strained Pt-Ni(111) films display quite different reactivity to their parent surfaces, dissociating water efficiently but not being passivated by oxygen or hydroxyl.