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      Size effects in Atomic-Level Epitaxial Redistribution Process of RuO 2 over TiO 2

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          Abstract

          Controls over the atomic dispersity and particle shape of noble metal catalysts are the major qualities determining their usability in industrial runs, but they are usually difficult to be simultaneously realized. Inspired from the Deacon catalyst in which RuO 2 can form epitaxial layers on the surfaces of Rutile TiO 2, here we have investigated the shape evolution process of RuO 2 nanoparticles on the surface of P25 TiO 2. It is found that size effects exist in this process and RuO 2 nanoparticles with sizes ~sub-2 nm can be transformed into epitaxial layers while nanoparticles with bigger sizes are not apt to change their shapes. Based on a thermodynamic model, we infer such transformation process is jointly driven by the surface tension and interfacial lattice match between the nanoparticles and substrates, which may be suggestive for the design of noble metal catalysts integrating both active crystal planes and high atomic exposure ratios.

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          Most cited references10

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          Reaction-driven restructuring of Rh-Pd and Pt-Pd core-shell nanoparticles.

          Heterogeneous catalysts that contain bimetallic nanoparticles may undergo segregation of the metals, driven by oxidizing and reducing environments. The structure and composition of core-shell Rh(0.5)Pd(0.5) and Pt(0.5)Pd(0.5) nanoparticle catalysts were studied in situ, during oxidizing, reducing, and catalytic reactions involving NO, O2, CO, and H2 by x-ray photoelectron spectroscopy at near-ambient pressure. The Rh(0.5)Pd(0.5) nanoparticles underwent dramatic and reversible changes in composition and chemical state in response to oxidizing or reducing conditions. In contrast, no substantial segregation of Pd or Pt atoms was found in Pt(0.5)Pd(0.5) nanoparticles. The different behaviors in restructuring and chemical response of Rh(0.5)Pd(0.5) and Pt(0.5)Pd(0.5) nanoparticle catalysts under the same reaction conditions illustrates the flexibility and tunability of the structure of bimetallic nanoparticle catalysts during catalytic reactions.
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            Onset of catalytic activity of gold clusters on titania with the appearance of nonmetallic properties

            Valden, Lai, Goodman (1998)
            Gold clusters ranging in diameter from 1 to 6 nanometers have been prepared on single crystalline surfaces of titania in ultrahigh vacuum to investigate the unusual size dependence of the low-temperature catalytic oxidation of carbon monoxide. Scanning tunneling microscopy/spectroscopy (STM/STS) and elevated pressure reaction kinetics measurements show that the structure sensitivity of this reaction on gold clusters supported on titania is related to a quantum size effect with respect to the thickness of the gold islands; islands with two layers of gold are most effective for catalyzing the oxidation of carbon monoxide. These results suggest that supported clusters, in general, may have unusual catalytic properties as one dimension of the cluster becomes smaller than three atomic spacings.
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              Shaping binary metal nanocrystals through epitaxial seeded growth.

              Morphological control of nanocrystals has become increasingly important, as many of their physical and chemical properties are highly shape dependent. Nanocrystal shape control for both single- and multiple-material systems, however, remains empirical and challenging. New methods need to be explored for the rational synthetic design of heterostructures with controlled morphology. Overgrowth of a different material on well-faceted seeds, for example, allows for the use of the defined seed morphology to control nucleation and growth of the secondary structure. Here, we have used highly faceted cubic Pt seeds to direct the epitaxial overgrowth of a secondary metal. We demonstrate this concept with lattice-matched Pd to produce conformal shape-controlled core-shell particles, and then extend it to lattice-mismatched Au to give anisotropic growth. Seeding with faceted nanocrystals may have significant potential towards the development of shape-controlled heterostructures with defined interfaces.
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                Author and article information

                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group
                2045-2322
                09 November 2012
                2012
                : 2
                : 801
                Affiliations
                [1 ]Institute of Nuclear and New Energy Technology, Tsinghua University , Beijing 100084, P. R. China
                [2 ]Department of Chemistry, Tsinghua University , Beijing 100084, P. R. China
                [3 ]Current address: Beijing Shenwu Environment & Energy Technology Corp , Beijing 102200, P. R. China
                Author notes
                Article
                srep00801
                10.1038/srep00801
                3494015
                23145318
                a9065f67-c71d-4b55-bcfb-eac8461aae4d
                Copyright © 2012, Macmillan Publishers Limited. All rights reserved

                This work is licensed under a Creative Commons Attribution-NonCommercial-ShareALike 3.0 Unported License. To view a copy of this license, visit http://creativecommons.org/licenses/by-nc-sa/3.0/

                History
                : 14 August 2012
                : 12 October 2012
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