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Tuning the high-pressure phase behaviour of highly compressible zeolitic imidazolate frameworks: from discontinuous to continuous pore closure by linker substitution

DOI: 10.1002/anie.202117565 DOI Help

Authors: Jianbo Song (TU Dortmund) , Roman Pallach (TU Dortmund) , Louis Frentzel-Beyme (TU Dortmund) , Pascal Kolodzeiski (TU Dortmund) , Gregor Kieslich (TU Munchen) , Pia Vervoorts (TU Munchen) , Claire L. Hobday (The University of Edinburgh) , Sebastian Henke (TU Dortmund University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Angewandte Chemie International Edition

State: Published (Approved)
Published: February 2022
Diamond Proposal Number(s): 21603

Open Access Open Access

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 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.

Journal Keywords: metal-organic frameworks; phase transition; responsive materials; high-pressure crystallography; mechanical properties

Subject Areas: Chemistry, Materials

Instruments: I15-Extreme Conditions

Other Facilities: P02.1 at PETRA III

Added On: 07/02/2022 09:04

Angewandte Chemie Intl Edit - 2022 - Song - Tuning the High%E2%80%90Pressure Phase Behaviour of Highly Compressible Zeolitic.pdf

Discipline Tags:

Chemistry Materials Science Metal-Organic Frameworks Metallurgy Organometallic Chemistry

Technical Tags:

Diffraction X-ray Powder Diffraction