Shape-selected bimetallic nanoparticle electrocatalysts: evolution of their atomic-scale structure, chemical composition, and electrochemical reactivity under various chemical environments

Solid surfaces generally respond sensitively to their environment. Gas phase or liquid phase species may adsorb and react with individual surface atoms altering the solid-gas and solid-liquid electronic and chemical properties of the interface. A comprehensive understanding of chemical and electrochemical interfaces with respect to their responses to external stimuli is still missing. The evolution of the structure and composition of shape-selected octahedral PtNi nanoparticles (NPs) in response to chemical (gas-phase) and electrochemical (liquid-phase) environments was studied, and contrasted to that of pure Pt and spherical PtNi NPs. The NPs were exposed to thermal annealing in hydrogen, oxygen, and vacuum, and the resulting NP surface composition was analyzed using X-ray photoelectron spectroscopy (XPS). In gaseous environments, the presence of O2 during annealing (300 °C) lead to a strong segregation of Ni species to the NP surface, the formation of NiO, and a Pt-rich NP core, while a similar treatment in H2 lead to a more homogenous Pt-Ni alloy core, and a thinner NiO shell. Further, the initial presence of NiO species on the as-prepared samples was found to influence the atomic segregation trends upon low temperature annealing (300 °C). This is due to the fact that at this temperature nickel is only partially reduced, and NiO favors surface segregation. The effect of electrochemical cycling in acid and alkaline electrolytes on the structure and composition of the octahedral PtNi NPs was monitored using image-corrected high resolution transmission electron microscopy (TEM) and high-angle annular dark field scanning TEM (HAADF-STEM). Sample pretreatments in surface active oxygenates, such as oxygen and hydroxide anions, resulted in oxygen-enriched Ni surfaces (Ni oxides and/or hydroxides). Acid treatments were found to strongly reduce the content of Ni species on the NP surface, via its dissolution in the electrolyte, leading to a Pt-skeleton structure, with a thick Pt shell and a Pt-Ni core. The presence of Ni hydroxides on the NP surface was shown to improve the kinetics of the electrooxidation of CO and the electrocatalytic hydrogen evolution reactions. The affinity to water and the oxophilicity of Ni hydroxides are proposed as likely origin of the observed effects.