Continuous structure modification of metal- organic framework glasses via halide salts
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, 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 new functionalities.
Authors
- G. Monaco (ORCID: https://orcid.org/0000-0003-2497-6422)
- Niels Chr. Nielsen (ORCID: https://orcid.org/0000-0003-2978-4366)
- Morten M. Smedskjær (ORCID: https://orcid.org/0000-0003-0476-2021)
- Peter Kjær Kristensen (ORCID: https://orcid.org/0000-0001-7260-0548)
- Samraj Mollick (ORCID: https://orcid.org/0000-0002-8617-6343)
- Francesco Dallari (ORCID: https://orcid.org/0000-0003-0171-8084)
- Volodymyr Baran (ORCID: https://orcid.org/0000-0003-2379-3632)
- Martin A. Karlsen (ORCID: https://orcid.org/0000-0003-1262-8965)
- Søren S. Sørensen (ORCID: https://orcid.org/0000-0003-2230-7823)
- Ronghui Lu (ORCID: https://orcid.org/0000-0001-6837-2562)
- Nina Lock (ORCID: https://orcid.org/0000-0003-1874-8773)
- Daming Sun (ORCID: https://orcid.org/0000-0002-4469-1187)
- Anders B. Nielsen (ORCID: https://orcid.org/0000-0002-3937-1170)
- Lars R. Jensen (ORCID: https://orcid.org/0000-0003-1617-0306)
- Xuan Ge (ORCID: https://orcid.org/0000-0002-5184-9499)
- Jacopo Baglioni (ORCID: https://orcid.org/0000-0003-0322-0941)
- Anders K. R. Christensen (ORCID: https://orcid.org/0009-0005-8613-9808)
- Fengming Cao
- Rebekka Klemmt (ORCID: https://orcid.org/0009-0006-4912-2043)
Institutions
- University of Padua (IT)
- Aarhus University (DK)
- Deutsches Elektronen-Synchrotron DESY (DE)
- Aalborg University (DK)
Publication Details
- Journal
- ChemRxiv
- Published
- 2025-04-06
- DOI
- https://doi.org/10.26434/chemrxiv-2024-bgf8b-v2
- Citations
- 1
- Primary Topic
- Pigment Synthesis and Properties
- Type
- article
- Field-Weighted Citation Impact
- 0.54
Funders
- Aarhus Universitet
- European Commission
- Aalborg Universitet
- Carlsbergfondet
- Università degli Studi di Padova
- Novo Nordisk
- China Scholarship Council
- Danish e-Infrastructure Cooperation
- Novo Nordisk Fonden
- European Research Council
- Deutsches Elektronen-Synchrotron
- Danish Agency for Science and Higher Education