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Striking effects are expected in solid-solution alloying, which offers enormous possibilities for various applications, especially in industrial catalysis. However, phase diagrams have revealed that a wide range of metallic elements are immiscible with each other even above their melting points. Achieving such unknown alloying between different immiscible metallic elements is highly desirable but challenging. Here, for the first time, by using an innovative solid ligand-assisted approach, we achieve the solid-solution alloying between the bulk-immiscible Au and Rh in plenty of clean, ultrafine (~ 1.6 nm) and highly dispersed nanoclusters. The solid-solution alloying of immiscible Au and Rh significantly enhances their catalytic performance toward the hydrogen evolution from formic acid in contrast to the monometallic Au and Rh nanoclusters. Moreover, the resultant binary solid-solution nanoclusters are stable without any segregation during catalytic reactions. The approach demonstrated here for homogeneously mixing the immiscible metals at the atomic scale will benefit the creation of advanced alloys and their catalytic applications in future.


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Solid-solution alloy nanoclusters of the immiscible gold-rhodium system achieved by a solid ligand-assisted approach for highly efficient catalysis

Show Author's information Xinchun Yang1,2Zhangpeng Li1Mitsunori Kitta1Nobuko Tsumori3Wenhan Guo4Zitao Zhang4Jianbo Zhang5Ruqiang Zou4( )Qiang Xu1,2,6( )
Institute of Electrochemical Energy, National Institute of Advanced Industrial Science and Technology (AIST), Ikeda, Osaka 563-8577, Japan
Graduate School of Engineering, Kobe University, Nada Ku, Kobe, Hyogo 657-8501, Japan
Department of Applied Chemistry and Chemical Engineering, Toyama National College of Technology, Toyama 939-8630, Japan
Department of Materials Science and Engineering, Peking University, Beijing 100871, China
Centre for High-Pressure Science and Technology Advanced Research, Beijing 100094, China
AIST-Kyoto University Chemical Energy Materials Open Innovation Laboratory, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan

Abstract

Striking effects are expected in solid-solution alloying, which offers enormous possibilities for various applications, especially in industrial catalysis. However, phase diagrams have revealed that a wide range of metallic elements are immiscible with each other even above their melting points. Achieving such unknown alloying between different immiscible metallic elements is highly desirable but challenging. Here, for the first time, by using an innovative solid ligand-assisted approach, we achieve the solid-solution alloying between the bulk-immiscible Au and Rh in plenty of clean, ultrafine (~ 1.6 nm) and highly dispersed nanoclusters. The solid-solution alloying of immiscible Au and Rh significantly enhances their catalytic performance toward the hydrogen evolution from formic acid in contrast to the monometallic Au and Rh nanoclusters. Moreover, the resultant binary solid-solution nanoclusters are stable without any segregation during catalytic reactions. The approach demonstrated here for homogeneously mixing the immiscible metals at the atomic scale will benefit the creation of advanced alloys and their catalytic applications in future.

Keywords: heterogeneous catalysis, metal nanoclusters, solid-solution alloys, formic acid dehydrogenation

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Publication history
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Acknowledgements

Publication history

Received: 30 October 2019
Revised: 21 November 2019
Accepted: 22 November 2019
Published: 06 December 2019
Issue date: January 2020

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Acknowledgements

The authors thank METI, AIST and Kobe University for financial support, and Dr. Takeyuki Uchida for TEM measurements. X. C. Y. is grateful to the MEXT and CSC for a PhD scholarship.

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