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Acid-Promoter-Free Ethylene Methoxycarbonylation over Ru-Clusters/Ceria: The Catalysis of Interfacial Lewis Acid–Base Pair

  • Jinghua An
    Jinghua An
    State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China
    University of Chinese Academy of Sciences, Beijing 100049, China
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  • Yehong Wang
    Yehong Wang
    State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China
    More by Yehong Wang
  • Jianmin Lu
    Jianmin Lu
    State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China
    More by Jianmin Lu
  • Jian Zhang
    Jian Zhang
    State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China
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  • Zhixin Zhang
    Zhixin Zhang
    State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China
    More by Zhixin Zhang
  • Shutao Xu
    Shutao Xu
    State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China
    More by Shutao Xu
  • Xiaoyan Liu
    Xiaoyan Liu
    State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China
    More by Xiaoyan Liu
  • Tao Zhang
    Tao Zhang
    State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China
    More by Tao Zhang
  • Martin Gocyla
    Martin Gocyla
    Ernst Ruska Centre for Microscopy and Spectroscopy with Electrons and Peter Grünberg Institute, Forschungszentrum Juelich GmbH, Juelich 52425, Germany
  • Marc Heggen
    Marc Heggen
    Ernst Ruska Centre for Microscopy and Spectroscopy with Electrons and Peter Grünberg Institute, Forschungszentrum Juelich GmbH, Juelich 52425, Germany
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  • Rafal E. Dunin-Borkowski
    Rafal E. Dunin-Borkowski
    Ernst Ruska Centre for Microscopy and Spectroscopy with Electrons and Peter Grünberg Institute, Forschungszentrum Juelich GmbH, Juelich 52425, Germany
  • Paolo Fornasiero
    Paolo Fornasiero
    Department of Chemical and Pharmaceutical Sciences, INSTM, Center of Excellence for Nanostructured Materials (CENMAT), University of Trieste, Via L. Giorgieri 1, Trieste 34127, Italy
  • , and 
  • Feng Wang*
    Feng Wang
    State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China
    *[email protected]
    More by Feng Wang
Cite this: J. Am. Chem. Soc. 2018, 140, 11, 4172–4181
Publication Date (Web):February 26, 2018
https://doi.org/10.1021/jacs.8b01742
Copyright © 2018 American Chemical Society

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    Abstract

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    The interface of metal-oxide plays pivotal roles in catalytic reactions, but its catalytic function is still not clear. In this study, we report the high activity of nanostructured Ru/ceria (Ru-clusters/ceria) in the ethylene methoxycarbonylation (EMC) reaction in the absence of acid promoter. The catalyst offers 92% yield of MP with TOF of 8666 h–1, which is about 2.5 times of homogeneous Pd catalyst (∼3500 h–1). The interfacial Lewis acid–base pair [Ru-O-Ce-], which consists of acidic Ce- (oxygen vacancy) site and basic interfacial oxygen of Ru-O-Ce linkage, acts as active site for the dissociation of methanol and the subsequent transfer of hydrogen to the activated ethylene, which is the key step in acid-promoter-free EMC reaction. The combination of 1H MAS NMR, pyridine-IR and DFT calculations reveals the hydrogen species derived from methanol contains Brönsted acidity. The EMC reaction mechanism under acid-promoter-free condition over Ru-clusters/ceria catalyst is discussed.

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