Heat‐Induced Alterations in the Surface Population of Metal Sites in Bimetallic Nanoparticles

The ability to alter the surface population of metal sites in bimetallic nanoparticles (NPs) is of great interest in the context of heterogeneous catalysis. Here, we report findings of surface alterations of Pt and Ru metallic sites in bimetallic carbon‐supported (PtRu/C) NPs that were induced by employing a controlled thermal‐treatment strategy. The thermal‐treatment procedure was designed in such a way that the particle size of the initial NPs was not altered and only the surface population of Pt and Ru was changed, thus allowing us to deduce structural information independent of particle‐size effects. X‐ray absorption spectroscopy (XAS) was utilized to deduce the structural parameters that can provide information on atomic distribution and/or extent of alloying as well as the surface population of Pt and Ru in PtRu/C NPs. The PtRu/C catalyst sample was obtained from Johnson Matthey, and first the as‐received catalyst was reduced in 2 % H 2 and 98 % Ar gas mixture at 300 °C for 4 h (PtRu/C as‐reduced). Later this sample was subjected to thermal treatment in either oxygen (PtRu/C‐O 2 ‐300) or hydrogen (PtRu/C‐H 2 ‐350). The XAS results reveal that when the as‐reduced PtRu/C catalyst was exposed to the O 2 thermal‐treatment strategy, a considerable amount of Ru was moved to the catalyst surface. In contrast, the H 2 thermal‐treatment strategy led to a higher population of Pt on the PtRu/C surface. Characterization of the heat‐treated PtRu/C samples by X‐ray diffraction and transmission electron microscopy reveals that there is no significant change in the particle size of thermally treated samples when compared to the as‐received PtRu/C sample. The electrochemical properties of the as‐reduced and heat‐treated PtRu/C catalyst samples were confirmed by cyclic voltammetry, CO‐adsorption stripping voltammetry, and linear sweep voltammetry. Both XAS and electrochemical investigations concluded that the PtRu/C‐H 2 ‐350 sample exhibits significant enhancement in reactivity toward methanol oxidation as a result of the increased surface population of the Pt when compared to the PtRu/C‐O 2 ‐300 and PtRu/C as‐reduced samples.