Continuous structure modification of metal-organic framework glasses via halide salts

Abstract Melting and glass formation of metal-organic frameworks (MOFs) allow them to be processed into bulk materials. However, two major challenges remain: only a small fraction of MOF crystals undergo melting and glass-formation, and no well-established strategies exist for tuning MOF glass struc...

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Main Authors: Fengming Cao, Søren S. Sørensen, Anders K. R. Christensen, Samraj Mollick, Xuan Ge, Daming Sun, Anders B. Nielsen, Niels Chr. Nielsen, Nina Lock, Ronghui Lu, Rebekka Klemmt, Peter K. Kristensen, Lars R. Jensen, Francesco Dallari, Jacopo Baglioni, Giulio Monaco, Martin A. Karlsen, Volodymyr Baran, Morten M. Smedskjaer
Format: Article
Language:English
Published: Nature Portfolio 2025-07-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-62143-9
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Summary:Abstract Melting and glass formation of metal-organic frameworks (MOFs) allow them to be processed into bulk materials. However, two major challenges remain: only a small fraction of MOF crystals undergo melting and glass-formation, and no well-established strategies exist for tuning MOF glass structures and properties. Here, we address both challenges through co-melting of zeolitic imidazole frameworks (ZIFs), a subset of MOFs, with heterocycle-based halide salts. The salt acts as a chemical “modifier”, akin to the role of alkali modifiers in traditional silicate glasses, e.g., allowing the melting of ZIF-8 that otherwise decomposes prior to melting. Through experimental and computational analyses, we show that the salts depolymerize the ZIFs, enabling continuous tuning of the fraction of bridging to non-bridging imidazolate linkers and, thereby, the thermal and mechanical properties. The proposed strategy enables diversification of MOF glass chemistry, tunable structures and properties, and ultimately an increased number of glass-forming MOFs with improved functionalities.
ISSN:2041-1723