Year: 2026
Type: article
Abstract: Modifying glass compositions is key to creating silicate-based glasses for technologies including optical fibres, catalytic supports, protective coatings and separation membranes. Here we extend this concept to metal–organic framework (MOF) glasses by modifying the MOF glass former ZIF-62 with Li(bim) and Na(bim) as compatible glass modifiers (benzimidazolate, bim − ). Melt-quenching of physical mixtures with increasing Na(bim) content yields modified MOF glasses that exhibit a systematic decrease in the glass transition temperature ( T g ), accompanied by increased liquid fragility, configurational heat capacity at T g and density: paralleling silicate glass chemistry through partial network depolymerization. Structural and spectroscopic analysis, coupled with density-functional theory calculations, confirm that Na(bim) is incorporated homogeneously into the MOF glass framework rather than the pores and reveal the presence of undercoordinated sodium ion environments. Finally, extraction of the modifier by water treatment increases glass porosity, akin to established borosilicate glass processes. This work introduces a transferable approach for tailoring the structure and properties of MOF glasses.
Source: Nature Chemistry
Language: English
Subfield: Ceramics and Composites
Field: Materials Science
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $12,690
Funders: UK Research and Innovation, Fonds der Chemischen Industrie, University of Warwick, Deutsche Forschungsgemeinschaft, Boehringer Ingelheim Stiftung, Technische Universität Dortmund, HORIZON EUROPE Framework Programme, Engineering and Physical Sciences Research Council, Deutsches Elektronen-Synchrotron, Leibniz-Gemeinschaft, Leibniz-Rechenzentrum
Awards: G1032415807, CCP9: Computational Electronic Structure of Condensed Matter, G2044512954, G2158296250, G340479512, Sulis: An EPSRC platform for ensemble computing delivered by HPC Midlands+, The UK Car-Parrinello HEC Consortium, G4197476736, G563088842, The UK High-Field Solid-State NMR National Research Facility, G6407092752, Collaborative Computational Project in NMR Crystallography, G6831956292, G7912415199, Solid-State NMR at 1.0 GHz: A World-Leading UK Facility to Deliver Advances in Chemistry, Biology and Materials Science, MetallImidazolatGläser aus schmelzbaren Zeolitischen ImidazolatGerüsten – Fundamentales Verständnis, Porosität, Funktionalisierung & Modifizierung
OpenAlex ID: W4416398426