title: Carbon Monoxide-Induced Stability and Atomic Segregation Phenomena in Shape-Selected Octahedral PtNi Nanoparticles.
abstract: The chemical and morphological stability of size- and shape-selected octahedral PtNi nanoparticles (NP) were investigated after different annealing treatments up to a maximum temperature of 700 °C in a vacuum and under 1 bar of CO. Atomic force microscopy was used to examine the mobility of the NPs and their stability against coarsening, and X-ray photoelectron spectroscopy to study the surface composition, chemical state of Pt and Ni in the NPs, and thermally and CO-induced atomic segregation trends. Exposing the samples to 1 bar of CO at room temperature before annealing in a vacuum was found to be effective at enhancing the stability of the NPs against coarsening. In contrast, significant coarsening was observed when the sample was annealed in 1 bar of CO, most likely as a result of Ni(CO)4 formation and their enhanced mobility on the support surface. Sample exposure to CO at room temperature prior to annealing led to the segregation of Pt to the NP surface. Nevertheless, oxidic PtOx and NiOx species still remained at the NP surface, and, irrespective of the initial sample pretreatment, Ni surface segregation was observed upon annealing in a vacuum at moderate temperature (T < 300 °C). Interestingly, a distinct atomic segregation trend was detected between 300 and 500 °C for the sample pre-exposed to CO; namely, Ni surface segregation was partially hindered. This might be attributed to the higher bonding energy of CO to Pt as compared to Ni. Annealing in the presence of 1 bar CO also resulted in the initial surface segregation of Ni (T < 400 °C) as long as PtOx and NiOx species were available on the surface as a result of the higher affinity of Ni for oxygen. Above 500 °C, and regardless of the sample pretreatment, the diffusion of Pt atoms to the NP surface and the formation of a Ni-Pt alloy are observed.
authors.affiliation: Department of Physics, University of Central Florida , Orlando, Florida 32816, United States.
authors.forename: Mahdi
authors.initials: M
authors.lastname: Ahmadi
authors.affiliation: Department of Chemistry, Chemical Engineering Division, Technical University Berlin , Berlin, Germany.
authors.forename: Chunhua
authors.initials: C
authors.lastname: Cui
authors.affiliation: Department of Physics, University of Central Florida , Orlando, Florida 32816, United States.|Department of Physics, Ruhr-University Bochum , 44780 Bochum, 10623 Berlin, Germany.
authors.forename: Hemma
authors.initials: H
authors.lastname: Mistry
authors.affiliation: Department of Chemistry, Chemical Engineering Division, Technical University Berlin , Berlin, Germany.
authors.forename: Peter
authors.initials: P
authors.lastname: Strasser
authors.affiliation: Department of Physics, Ruhr-University Bochum , 44780 Bochum, 10623 Berlin, Germany.
authors.forename: Beatriz Roldan
authors.initials: BR
authors.lastname: Cuenya
keywords: AFM; CO; Ni; Pt; XPS; atomic segregation; nanoparticles