Highly defective ultra-small tetravalent MOF nanocrystals

Shan Dai, Charlotte Simms, Gilles Patriarche, Marco Daturi, Antoine Tissot (), Tatjana N. Parac-Vogt () and Christian Serre ()
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Shan Dai: PSL University
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

Nature Communications, 2024, vol. 15, issue 1, 1-9

Abstract: 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.

Date: 2024
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DOI: 10.1038/s41467-024-47426-x

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