Article, 2024

Structural Origin of the Deformation Propensity of Zeolitic Imidazolate Framework Glasses

Chemistry of Materials, ISSN 1520-5002, 0897-4756, Volume 36, 12, Pages 6167-6179, 10.1021/acs.chemmater.4c00921

Contributors

Du, Tao 0000-0003-2402-6320 [1] Ge, Xuan 0000-0002-5184-9499 [1] Cao, Fengming 0000-0003-0761-5019 [1] Liu, Han 0000-0002-4899-9998 [2] Shi, Caijuan [3] Ding, Junwei 0000-0003-3474-9127 [1] Sun, Da-Ming 0000-0002-4469-1187 [1] Zhang, Qiangqiang 0009-0008-7041-0642 [4] Yue, Yuan-Zheng 0000-0002-6048-5236 [1] Smedskjaer, Morten Mattrup 0000-0003-0476-2021 (Corresponding author) [1]

Affiliations

  1. [1] Aalborg University
    2. [NORA names: AAU Aalborg University; University; Denmark; Europe, EU; Nordic; OECD];
  2. [2] Sichuan University
    3. [NORA names: China; Asia, East];
  3. [3] Institute of High Energy Physics
    4. [NORA names: China; Asia, East];
  4. [4] Lanzhou University
    5. [NORA names: China; Asia, East]

Abstract

Zeolitic imidazolate framework (ZIF) glasses featuring nanoscale porosity have attracted significant attention due to their potential applications in catalysis, energy storage, gas sorption, and separation. However, their mechanical properties may limit some of these applications. In this work, we investigate the structural origins of the variation of mechanical properties of zinc-based ZIF-62 (ZnIm2–x bIm x ) glasses with different benzimidazolate (bIm) to imidazolate (Im) ratios. This is achieved using large-scale molecular dynamics simulations with a recent machine learning force field. We find that the simulated ZIF glass structures match those determined using X-ray total scattering. The relatively large bIm group is found to hinder the reconstruction of the coordination network during quenching of the ZIF melts, leading to more disordered Zn tetrahedra. Both Young’s modulus and fracture toughness decrease with an increase in bIm content. Upon fracturing, all of the organic linkers remain intact, while Zn–N bond switching dissipates the strain energy. By correlating the atomic dynamics with the static structure, we find that the deformation propensity of ZIF glass is correlated with Zn mobility, which is in turn determined by the initial atomic volume before deformation across a variety of glass compositions and strain values. These findings could be helpful for designing more fracture-resistant metal–organic framework glasses in the future.

Keywords

BIM, BIM content, Bim group, X-ray, X-ray total scattering, Young's modulus, ZIF-62, Zn mobility, Zn tetrahedra, applications, atomic dynamics, atomic volume, attention, benzimidazole, bond switching, bonds, catalysis, composition, content, coordination, coordination networks, decrease, deformation, dynamics, dynamics simulations, energy, energy storage, field, findings, force field, fracture, fracture toughness decrease, framework, future, gas, gas sorption, glass, glass composition, glass structure, group, imidazolate frameworks, imidazole, increase, large-scale molecular dynamics simulations, linker, machine, machine learning force fields, mechanical properties, melting, metal-organic framework glasses, mobility, modulus, molecular dynamics simulations, nanoscale, nanoscale porosity, network, organic linkers, origin, porosity, properties, quenching, ratio, reconstruction, scattering, separation, simulation, sorption, static structure, storage, strain, strain energy, strain values, structural origin, structure, switching, tetrahedra, total scattering, toughness decrease, values, variation, volume, zeolitic imidazolate framework, zeolitic imidazolate framework glasses

Funders

  • Carlsberg Foundation
  • Institute of High Energy Physics
  • European Commission

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