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

Abstract

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 % H2 and 98 % Ar gas mixture at 300 degrees C for 4 h (PtRu/C as-reduced). Later this sample was subjected to thermal treatment in either oxygen (PtRu/C-O2-300) or hydrogen (PtRu/C-H2-350). The XAS results reveal that when the as-reduced PtRu/C catalyst was exposed to the O2 thermal-treatment strategy, a considerable amount of Ru was moved to the catalyst surface. In contrast, the H2 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-H2-350 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-O2-300 and PtRu/C as-reduced samples.

Chemical Dealloying Mechanism of Bimetallic Pt–Co Nanoparticles and Enhancement of Catalytic Activity toward Oxygen Reduction

“…Proper annealing enables the modification of the imperfect Pt skin, which may improve the catalytic activity and stability. [22,40] These findings demonstrate the importance of appropriate treatment and could apply to other Pt bimetallic alloys associated with transition metals.…”

Effect of heat treatment on PtRu/C catalyst for methanol electro-oxidation

“…Li et al [23] and Takasu et al [24] also reported that heat treatment can increase specific activity of the PtRu catalyst. This behavior can be explained by Pt rich surface formation during the heat treatments under reducing atmosphere due to Pt-H interactions [25][26][27]. Figure 4 shows the CV results of the PtRu/C catalysts measured for 30 cycles.…”

Promotion of Pt–Ru/C catalysts driven by heat treated induced surface segregation for methanol oxidation reaction

“…66%) may assist the CO oxidation through a bifunctional mechanism [53]. Herein, we can summarize that the H570 has high I f /I b value, high EASA, and low onset potential for anodic CO stripping is probably assigned to the metallic Pt and Ru or PtO x species on the surface [42,58]. Nevertheless, the H570 cannot exhibit a comparative catalytic activity toward methanol decomposition at I 07 , suggesting that the surface amount of active sites for MOR is not sufficient.…”

“…5 shows the CO stripping scans recorded on the glassy carbon electrode of various PtRu/C catalysts in 0.1 M HClO 4 . It is generally accepted the fact that the activity for electrochemically [58]. For the O570 sample, the dramatically decreased EASA is observed due to a large amount of RuO 2 species occupied on the surface and a decrease in the number of Pt active sites accordingly.…”