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Investigation on the morphological and optical evolution of bimetallic Pd-Ag nanoparticles on sapphire (0001) by the systematic control of composition, annealing temperature and time.

ABSTRACT: Multi-metallic alloy nanoparticles (NPs) can offer additional opportunities for modifying the electronic, optical and catalytic properties by the control of composition, configuration and size of individual nanostructures that are consisted of more than single element. In this paper, the fabrication of bimetallic Pd-Ag NPs is systematically demonstrated via the solid state dewetting of bilayer thin films on c-plane sapphire by governing the temperature, time as well as composition. The composition of Pd-Ag bilayer remarkably affects the morphology of alloy nanostructures, in which the higher Ag composition, i.e. Pd0.25Ag0.75, leads to the enhanced dewetting of bilayers whereas the higher Pd composition (Pd0.75Ag0.25) hinders the dewetting. Depending on the annealing temperature, Pd-Ag alloy nanostructures evolve with a series of configurations, i.e. nucleation of voids, porous network, elongated nanoclusters and round alloy NPs. In addition, with the annealing time set, the gradual configuration transformation from the elongated to round alloy NPs as well as size reduction is demonstrated due to the enhanced diffusion and sublimation of Ag atoms. The evolution of various morphology of Pd-Ag nanostructures is described based on the surface diffusion and inter-diffusion of Pd and Ag adatoms along with the Ag sublimation, Rayleigh instability and energy minimization mechanism. The reflectance spectra of bimetallic Pd-Ag nanostructures exhibit various quadrupolar and dipolar resonance peaks, peak shifts and absorption dips owing to the surface plasmon resonance of nanostructures depending on the surface morphology. The intensity of reflectance spectra is gradually decreased along with the surface coverage and NP size evolution. The absorption dips are red-shifted towards the longer wavelength for the larger alloy NPs and vice-versa.

SUBMITTER: Pandey P

PROVIDER: S-EPMC5734721 | biostudies-literature | 2017

REPOSITORIES: biostudies-literature

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Investigation on the morphological and optical evolution of bimetallic Pd-Ag nanoparticles on sapphire (0001) by the systematic control of composition, annealing temperature and time.

Pandey Puran P Kunwar Sundar S Sui Mao M Bastola Sushil S Lee Jihoon J Lee Jihoon J

PloS one 20171218 12

Multi-metallic alloy nanoparticles (NPs) can offer additional opportunities for modifying the electronic, optical and catalytic properties by the control of composition, configuration and size of individual nanostructures that are consisted of more than single element. In this paper, the fabrication of bimetallic Pd-Ag NPs is systematically demonstrated via the solid state dewetting of bilayer thin films on c-plane sapphire by governing the temperature, time as well as composition. The compositi ...[more]

PMID: 29253017

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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

Investigation on the morphological and optical evolution of bimetallic Pd-Ag nanoparticles on sapphire (0001) by the systematic control of composition, annealing temperature and time.

Publications

Investigation on the morphological and optical evolution of bimetallic Pd-Ag nanoparticles on sapphire (0001) by the systematic control of composition, annealing temperature and time.

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