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Stellated Ag-Pt bimetallic nanoparticles: an effective platform for catalytic activity tuning.

ABSTRACT: The usefulness of Pt-based nanomaterials for catalysis can be greatly enhanced by coupling morphology engineering to the strategic presence of a second or even third metal. Here we demonstrate the design and preparation of stellated Ag-Pt bimetallic nanoparticles where significant activity difference between the methanol oxidation reaction (MOR) and the oxygen reduction reaction (ORR) may be realized by relegating Ag to the core or by hollowing out the core. In particular the stellated Pt surface, with an abundance of steps, edges, corner atoms, and {111} facets, is highly effective for the ORR but is ineffective for MOR. MOR activity is only observed in the presence of a Ag core through electronic coupling to the stellated Pt shell. The bimetallic Ag-Pt stellates therefore demonstrate the feasibility of tuning a Pt surface for two very different structure sensitive catalytic reactions. Stellated bimetallics may therefore be an effective platform for highly tunable catalyst designs.

SUBMITTER: Liu H

PROVIDER: S-EPMC3913913 | biostudies-literature | 2014 Feb

REPOSITORIES: biostudies-literature

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Stellated Ag-Pt bimetallic nanoparticles: an effective platform for catalytic activity tuning.

Liu Hui H Ye Feng F Yao Qiaofeng Q Cao Hongbin H Xie Jianping J Lee Jim Yang JY Yang Jun J

Scientific reports 20140205

The usefulness of Pt-based nanomaterials for catalysis can be greatly enhanced by coupling morphology engineering to the strategic presence of a second or even third metal. Here we demonstrate the design and preparation of stellated Ag-Pt bimetallic nanoparticles where significant activity difference between the methanol oxidation reaction (MOR) and the oxygen reduction reaction (ORR) may be realized by relegating Ag to the core or by hollowing out the core. In particular the stellated Pt surfac ...[more]

PMID: 24495979

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Project description:Fly ash (FA)-supported bimetallic nanoparticles (PdxAgy/FA) with varying Pd:Ag ratios were prepared by coprecipitation of Pd and Ag involving in situ reduction of Pd(II) and Ag(I) salts in aqueous medium. All the supported nanoparticles were thoroughly characterized with the aid of powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), electron microscopy (field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM)), and elemental analyses, which include inductively coupled plasma-optical emission spectroscopy (ICP-OES) and energy-dispersive X-ray spectroscopy (EDS). A gradual broadening and shifting of PXRD peaks, ascribable to Ag, to higher angles with an increase in the Pd:Ag ratio affirms the alloying of interface between Pd and Ag nanoparticles. The coexistence of Pd and Ag was further confirmed by EDS elemental mapping as well as by the presence of bimetallic lattices on the FA surface, as evident from the high-resolution TEM analysis. The dependency of crystallite size and average size of bimetallic nanoparticles on Ag loading (mol %) was elucidated with the help of a combination of PXRD and TEM studies. Based on XPS analysis, the charge transfer phenomenon between contacting Pd-Ag sites could be evident from the shifting of 3d core electron binding energy for both Pd and Ag compared with monometallic Pd and Ag nanoparticles. Following a pseudo-first-order reaction kinetics, all the nanocatalysts were able to efficiently reduce 4-nitrophenol into 4-aminophenol in aqueous NaBH4. The superior catalytic performance of the bimetallic nanocatalysts (PdxAgy/FA) over their monometallic (Pd100/FA and Ag100/FA) analogues has been demonstrated. Moreover, the tunable synergistic effect of the bimetallic systems has been explored in detail by varying the Pd:Ag mol ratio in a systematic manner which in turn allowed us to achieve an optimum reaction rate (k = 1.050 min-1) for the nitrophenol reduction using a Pd25Ag75/FA system. Most importantly, all the bimetallic nanocatalysts explored here exhibited excellent normalized rate constants (K ≈ 6000-15,000 min-1 mmol-1) compared with other supported bimetallic Pd-Ag nanocatalysts reported in the literature.

Dataset Information

Stellated Ag-Pt bimetallic nanoparticles: an effective platform for catalytic activity tuning.

Publications

Stellated Ag-Pt bimetallic nanoparticles: an effective platform for catalytic activity tuning.

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