Crystal size: Versus paddle wheel deformability: Selective gated adsorption transitions of the switchable metal-organic frameworks DUT-8(Co) and DUT-8(Ni)

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Sebastian Ehrling - , Chair of Inorganic Chemistry I (Author)
  • Irena Senkovska - , Chair of Inorganic Chemistry I (Author)
  • Volodymyr Bon - , Chair of Inorganic Chemistry I (Author)
  • Jack D. Evans - , Chair of Inorganic Chemistry I (Author)
  • Petko Petkov - , Sofia University St. Kliment Ohridski (Author)
  • Yulia Krupskaya - , Leibniz Institute for Solid State and Materials Research Dresden (Author)
  • Vladislav Kataev - , Leibniz Institute for Solid State and Materials Research Dresden (Author)
  • Toshiki Wulf - , Leipzig University, Helmholtz-Zentrum Dresden-Rossendorf (Author)
  • Alexander Krylov - , RAS - Kirensky Institute of Physics, Siberian Branch (Author)
  • Alexander Vtyurin - , RAS - Kirensky Institute of Physics, Siberian Branch, Siberian Federal University (Author)
  • Svetlana Krylova - , RAS - Kirensky Institute of Physics, Siberian Branch (Author)
  • Sergey Adichtchev - , RAS - Institute of Automation and Electrometry, Siberian Branch (Author)
  • Evgenia Slyusareva - , Siberian Federal University (Author)
  • Manfred S. Weiss - , Helmholtz Centre Berlin for Materials and Energy (Author)
  • Bernd Büchner - , Leibniz Institute for Solid State and Materials Research Dresden (Author)
  • Thomas Heine - , Chair of Theoretical Chemistry, Helmholtz-Zentrum Dresden-Rossendorf (Author)
  • Stefan Kaskel - , Chair of Inorganic Chemistry I (Author)

Abstract

Switchable pillared layer metal-organic frameworks M2(2,6-ndc)2(dabco) (DUT-8(M), M = Ni, Co, 2,6-ndc = 2,6-naphthalenedicarboxylate, dabco = 1,4-diazabicyclo-[2.2.2]octane, DUT-Dresden University of Technology) were synthesised in two different crystallite size regimes to produce particles up to 300 μm and smaller particles around 0.1 μm, respectively. The textural properties and adsorption-induced switchability of the materials, obtained from both syntheses, were studied by physisorption of N2 at 77 K, CO2 at 195 K and n-butane at 273 K, revealing pronounced differences in adsorption behavior for Ni and Co analogues. While the smaller nano-sized particles (50-200 nm) are rigid and show no gating transitions confirming the importance of crystallite size, the large particles show pronounced switchability with characteristic differences for the two metals resulting in distinct recognition effects for various gases and vapours. Adsorption of various vapours demonstrates consistently a higher energetic barrier for the "gate opening" of DUT-8(Co) in contrast to DUT-8(Ni), as the "gate opening" pressure for Co based material is shifted to a higher value for adsorption of dichloromethane at 298 K. Evaluation of crystallographic data, obtained from single crystal and powder X-ray diffraction analysis, showed distinct geometric differences in the paddle wheel units of the respective MOFs. These differences are further disclosed by solid-state UV-vis, FT-IR and Raman spectroscopy. Magnetic properties of DUT-8(Co) and DUT-8(Ni) were investigated, indicating a high-spin state for both materials at room temperature. Density functional theory (DFT) simulations confirmed distinct energetic differences for Ni and Co analogues with a higher energetic penalty for the structural "gate opening" transformation for DUT-8(Co) compared to DUT-8(Ni) explaining the different flexibility behaviour of these isomorphous MOFs.

Details

Original languageEnglish
Pages (from-to)21459-21475
Number of pages17
JournalJournal of Materials Chemistry. A, Materials for energy and sustainability
Volume7
Issue number37
Publication statusPublished - 2019
Peer-reviewedYes