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Highly defective ultra-small tetravalent MOF nanocrystals

Author

Listed:
  • Shan Dai

    (PSL University
    Laboratoire Catalyse et Spectrochimie)

  • Charlotte Simms

    (KU Leuven)

  • Gilles Patriarche

    (Centre de Nanosciences et de Nanotechnologies)

  • Marco Daturi

    (Laboratoire Catalyse et Spectrochimie)

  • Antoine Tissot

    (PSL University)

  • Tatjana N. Parac-Vogt

    (KU Leuven)

  • Christian Serre

    (PSL University)

Abstract

The size and defects in crystalline inorganic materials are of importance in many applications, particularly catalysis, as it often results in enhanced/emerging properties. So far, applying the strategy of modulation chemistry has been unable to afford high-quality functional Metal–Organic Frameworks (MOFs) nanocrystals with minimized size while exhibiting maximized defects. We report here a general sustainable strategy for the design of highly defective and ultra-small tetravalent MOFs (Zr, Hf) crystals (ca. 35% missing linker, 4–6 nm). Advanced characterizations have been performed to shed light on the main factors governing the crystallization mechanism and to identify the nature of the defects. The ultra-small nanoMOFs showed exceptional performance in peptide hydrolysis reaction, including high reactivity, selectivity, diffusion, stability, and show emerging tailorable reactivity and selectivity towards peptide bond formation simply by changing the reaction solvent. Therefore, these highly defective ultra-small M(IV)-MOFs particles open new perspectives for the development of heterogeneous MOF catalysts with dual functions.

Suggested Citation

  • Shan Dai & Charlotte Simms & Gilles Patriarche & Marco Daturi & Antoine Tissot & Tatjana N. Parac-Vogt & Christian Serre, 2024. "Highly defective ultra-small tetravalent MOF nanocrystals," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-47426-x
    DOI: 10.1038/s41467-024-47426-x
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    References listed on IDEAS

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    1. Xueling Wang & Qiang Lyu & Tiezheng Tong & Kuo Sun & Li-Chiang Lin & Chuyang Y. Tang & Fenglin Yang & Michael D. Guiver & Xie Quan & Yingchao Dong, 2022. "Robust ultrathin nanoporous MOF membrane with intra-crystalline defects for fast water transport," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    2. Pengpeng Zhang & Emma Tevaarwerk & Byoung-Nam Park & Donald E. Savage & George K. Celler & Irena Knezevic & Paul G. Evans & Mark A. Eriksson & Max G. Lagally, 2006. "Electronic transport in nanometre-scale silicon-on-insulator membranes," Nature, Nature, vol. 439(7077), pages 703-706, February.
    3. Simon Krause & Volodymyr Bon & Irena Senkovska & Daniel M. Többens & Dirk Wallacher & Renjith S. Pillai & Guillaume Maurin & Stefan Kaskel, 2018. "The effect of crystallite size on pressure amplification in switchable porous solids," Nature Communications, Nature, vol. 9(1), pages 1-8, December.
    4. Sujing Wang & Hong Giang T. Ly & Mohammad Wahiduzzaman & Charlotte Simms & Iurii Dovgaliuk & Antoine Tissot & Guillaume Maurin & Tatjana N. Parac-Vogt & Christian Serre, 2022. "A zirconium metal-organic framework with SOC topological net for catalytic peptide bond hydrolysis," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
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