Authors: Song, Jianbo
Pallach, Roman
Frentzel-Beyme, Louis
Kolodzeiski, Pascal
Kieslich, Gregor
Vervoorts, Pia
Hobday, Claire L.
Henke, Sebastian
Title: Tuning the high-pressure phase behaviour of highly compressible zeolitic imidazolate frameworks: from discontinuous to continuous pore closure by linker substitution
Language (ISO): en
Abstract: The high-pressure behaviour of flexible zeolitic imidazolate frameworks (ZIFs) of the ZIF-62 family with the chemical composition M(im)2−x(bim)x is presented (M2+=Zn2+, Co2+; im−=imidazolate; bim−=benzimidazolate, 0.02≤x≤0.37). High-pressure powder X-ray diffraction shows that the materials contract reversibly from an open pore (op) to a closed pore (cp) phase under a hydrostatic pressure of up to 4000 bar. Sequentially increasing the bim− fraction (x) reinforces the framework, leading to an increased threshold pressure for the op-to-cp phase transition, while the total volume contraction across the transition decreases. Most importantly, the typical discontinuous op-to-cp transition (first order) changes to an unusual continuous transition (second order) for x≥0.35. This allows finetuning of the void volume and the pore size of the material continuously by adjusting the pressure, thus opening new possibilities for MOFs in pressure-switchable devices, membranes, and actuators.
Subject Headings: High-pressure crystallography
Mechanical properties
Metal-organic frameworks
Phase transition
Responsive materials
Issue Date: 2022-02-04
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Appears in Collections:Lehrstühle für Anorganische Chemie

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