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Modulating the Primary and Secondary Coordination Spheres of Single Ni(II) Sites in Metal–Organic Frameworks for Boosting Photocatalysis

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    Modulating the Primary and Secondary Coordination Spheres of Single Ni(II) Sites in Metal–Organic Frameworks for Boosting Photocatalysis
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    • Ge Yang
      Ge Yang
      Hefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China
      More by Ge Yang
    • Denan Wang
      Denan Wang
      Department of Chemistry and Schiller Institute for Integrated Science and Society, Boston College, Chestnut Hill, Massachusetts 02467, United States
      More by Denan Wang
      Orcidhttps://orcid.org/0000-0003-3603-6788
    • Yang Wang
      Yang Wang
      Key Laboratory of Precision and Intelligent Chemistry, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China
      More by Yang Wang
    • Wenhui Hu
      Wenhui Hu
      Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201, United States
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    • Shuaishuai Hu
      Shuaishuai Hu
      Hefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China
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    • Jun Jiang
      Jun Jiang
      Key Laboratory of Precision and Intelligent Chemistry, School of Chemistry and Materials Science, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China
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      Orcidhttps://orcid.org/0000-0002-6116-5605
    • Jier Huang*
      Jier Huang
      Department of Chemistry and Schiller Institute for Integrated Science and Society, Boston College, Chestnut Hill, Massachusetts 02467, United States
      *Email: [email protected]
      More by Jier Huang
      Orcidhttps://orcid.org/0000-0002-2885-5786
    • Hai-Long Jiang*
      Hai-Long Jiang
      Hefei National Research Center for Physical Sciences at the Microscale, Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China
      *Email: [email protected]
      More by Hai-Long Jiang
      Orcidhttps://orcid.org/0000-0002-2975-7977
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2024, 146, 15, 10798–10805
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    https://doi.org/10.1021/jacs.4c00972
    Published April 5, 2024
    Copyright © 2024 American Chemical Society
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    Abstract

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    Though the coordination environment of single metal sites has been recognized to be of great importance in promoting catalysis, the influence of simultaneous precise modulation of primary and secondary coordination spheres on catalysis remains largely unknown. Herein, a series of single Ni(II) sites with altered primary and secondary coordination spheres have been installed onto metal–organic frameworks (MOFs) with UiO-67 skeleton, affording UiO–Ni–X–Y (X = S, O; Y = H, Cl, CF3) with X and Y on the primary and secondary coordination spheres, respectively. Upon deposition with CdS nanoparticles, the resulting composites present high photocatalytic H2 production rates, in which the optimized CdS/UiO–Ni–S–CF3 exhibits an excellent activity of 13.44 mmol g–1, ∼500 folds of the pristine catalyst (29.6 μmol g–1 for CdS/UiO), in 8 h, highlighting the key role of microenvironment modulation around Ni sites. Charge kinetic analysis and theoretical calculation results demonstrate that the charge transfer dynamics and reaction energy barrier are closely correlated with their coordination spheres. This work manifests the advantages of MOFs in the fabrication of structurally precise catalysts and the elucidation of particular influences of microenvironment modulation around single metal sites on the catalytic performance.

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2024, 146, 15, 10798–10805
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.4c00972
    Published April 5, 2024
    Copyright © 2024 American Chemical Society
    Request reuse permissions

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