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      Coreduction methodology for immiscible alloys of CuRu solid-solution nanoparticles with high thermal stability and versatile exhaust purification ability†

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          Abstract

          This study provides a coreduction methodology for solid solution formation in immiscible systems, with an example of a whole-region immiscible Cu–Ru system. Although the binary Cu–Ru alloy system is very unstable in the bulk state, the atomic-level well-mixed CuRu solid solution nanoparticles were found to have high thermal stability up to at least 773 K in a vacuum. The exhaust purification activity of the CuRu solid solution was comparable to that of face-centred cubic Ru nanoparticles. According to in situ infrared measurements, stronger NO adsorption and higher intrinsic reactivity of the Ru site on the CuRu surface than that of a pure Ru surface were found, affected by atomic-level Cu substitution. Furthermore, CuRu solid solution was a versatile catalyst for purification of all exhaust gases at a stoichiometric oxygen concentration.

          Abstract

          This study provides a coreduction methodology for solid solution formation in immiscible systems, with an example of a whole-region immiscible Cu–Ru system.

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          One-Pot Synthesis of Highly Anisotropic Five-Fold-Twinned PtCu Nanoframes Used as a Bifunctional Electrocatalyst for Oxygen Reduction and Methanol Oxidation.

          Five-fold-twinned PtCu nanoframes (NFs) with nanothorns protruding from their edges are synthesized by a facile one-pot method. Compared to commercial Pt/C catalyst, the obtained highly anisotropic five-fold-twinned PtCu NFs show enhanced electrocatalytic performance toward the oxygen reduction reaction and methanol oxidation reaction under alkaline conditions.
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            Solid solution alloy nanoparticles of immiscible Pd and Ru elements neighboring on Rh: changeover of the thermodynamic behavior for hydrogen storage and enhanced CO-oxidizing ability.

            Pd(x)Ru(1-x) solid solution alloy nanoparticles were successfully synthesized over the whole composition range through a chemical reduction method, although Ru and Pd are immiscible at the atomic level in the bulk state. From the XRD measurement, it was found that the dominant structure of Pd(x)Ru(1-x) changes from fcc to hcp with increasing Ru content. The structures of Pd(x)Ru(1-x) nanoparticles in the Pd composition range of 30-70% consisted of both solid solution fcc and hcp structures, and both phases coexist in a single particle. In addition, the reaction of hydrogen with the Pd(x)Ru(1-x) nanoparticles changed from exothermic to endothermic as the Ru content increased. Furthermore, the prepared Pd(x)Ru(1-x) nanoparticles demonstrated enhanced CO-oxidizing catalytic activity; Pd0.5Ru0.5 nanoparticles exhibit the highest catalytic activity. This activity is much higher than that of the practically used CO-oxidizing catalyst Ru and that of the neighboring Rh, between Ru and Pd.
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              The Structure of Metals and Alloys

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                Author and article information

                Journal
                Chem Sci
                Chem Sci
                SC
                CSHCBM
                Chemical Science
                The Royal Society of Chemistry
                2041-6520
                2041-6539
                18 September 2020
                14 November 2020
                18 September 2020
                : 11
                : 42
                : 11413-11418
                Affiliations
                [a] Division of Chemistry, Graduate School of Science, Kyoto University Kitashirakawa-Oiwakecho, Sakyo-ku Kyoto 606-8502 Japan kitagawa@ 123456kuchem.kyoto-u.ac.jp bohuang@ 123456xjtu.edu.cn
                [b] JST, PRESTO 4-1-8 Honcho Kawaguchi Saitama 332-0012 Japan
                [c] Department of Applied Quantum Physics and Nuclear Engineering, Kyushu University Motooka 744, Nishi-ku Fukuoka 819-0395 Japan
                [d] The Ultramicroscopy Research Centre, Kyushu University Motooka 744, Nishi-ku Fukuoka 819-0395 Japan
                [e] INAMORI Frontier Research Centre, Kyushu University Motooka 744, Nishi-ku Fukuoka 819-0395 Japan
                [f] Department of Chemical Systems Engineering, Graduate School of Engineering, Nagoya University Furo-cho, Chikusa-ku Nagoya 464-8603 Japan
                [g] Elements Strategy Initiative for Catalysts and Batteries, Kyoto University 1-30 Goryo-Ohara, Nishikyo-ku Kyoto 615-8245 Japan
                [h] Advanced Ceramics Research Centre, Nagoya Institute of Technology 10-6-29 Asahigaoka, Tajimi Gifu 507-0071 Japan
                [i] Frontier Research Institute for Materials Science, Nagoya Institute of Technology Gokiso-cho, Showa-ku Nagoya 465-8555 Japan
                [j] Japan Synchrotron Radiation Research Institute (JASRI) SPring-8, 1-1-1 Kouto, Sayo-cho, Sayo-gun Hyogo 679-5198 Japan
                [k] Department of Physical Science, Graduate School of Science, Osaka Prefecture University Sakai Osaka 599-8531 Japan
                [l] Institute for Integrated Cell-Material Sciences (iCeMS), Kyoto University Yoshida, Sakyo-ku Kyoto 606-8501 Japan
                Author notes
                [‡]

                Current addresses: School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an 710049, P. R. China.

                Author information
                https://orcid.org/0000-0002-7429-8765
                https://orcid.org/0000-0002-3998-7012
                https://orcid.org/0000-0003-1774-1537
                https://orcid.org/0000-0001-6955-3015
                Article
                d0sc03373a
                10.1039/d0sc03373a
                8162931
                34094383
                a4817002-0105-4f34-8f76-35a168825b6f
                This journal is © The Royal Society of Chemistry
                History
                : 18 June 2020
                : 18 September 2020
                Page count
                Pages: 6
                Funding
                Funded by: Japan Science and Technology Agency, doi 10.13039/501100002241;
                Award ID: JPMJAC1501
                Funded by: Xi’an Jiaotong University, doi 10.13039/501100002412;
                Award ID: xxj032019005
                Categories
                Chemistry
                Custom metadata
                Paginated Article

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