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Crystal size: Versus paddle wheel deformability: Selective gated adsorption transitions of the switchable metal-organic frameworks DUT-8(Co) and DUT-8(Ni) / S. Ehrling [et al.] // J. Mater. Chem. A. - 2019. - Vol. 7, Is. 37. - P. 21459-21475, DOI 10.1039/c9ta06781g. - Cited References: 106. - The authors thank DFG (FOR 2433) for financial support. We thank HZB for the allocation of synchrotron radiation beam-time and financial support. PP, TW and TH used high performance facilities of ZIH Dresden. TW thanks the European Social Funds for Germany for a PhD fellowship.
. - ISSN 2050-7488
Кл.слова (ненормированные):
Cobalt -- Crystallite size -- Density functional theory -- Dichloromethane -- Inclusions -- Nickel -- Organometallics -- Particle size -- Physisorption -- Single crystals -- Wheels -- X ray powder diffraction
Аннотация: 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.
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Держатели документа:
Department of Inorganic Chemistry, Technische Universitat Dresden, Bergstrasse 66, Dresden, 01069, Germany
University of Sofia, Faculty of Chemistry and Pharmacy, Sofia, 1126, Bulgaria
Leibniz Institute for Solid State and Materials Research, IFW Dresden, Helmholtz-strasse 20, Dresden, 01069, Germany
Wilhelm-Ostwald-Institute of Physical and Theoretical Chemistry, Faculty for Chemistry and Mineralogy, Leipzig University, Leipzig, 04103, Germany
Helmholtz-Zentrum Dresden-Rossendorf, Institute of Resource Ecology, Research Site Leipzig, Permoserstr. 15, Leipzig, 04318, Germany
Kirensky Institute of Physics, Federal Research Center KSC SB RAS, Krasnoyarsk, 660036, Russian Federation
Siberian Federal University, Svobodny Prospect 79, Krasnoyarsk, 660041, Russian Federation
Institute of Automation and Electrometry of the SB RAS, Novosibirsk, 630090, Russian Federation
Research Group Macromolecular Crystallography, Helmholtz-Zentrum Berlin fur Materialien und Energie, Albert-Einstein-Stra?e 15, Berlin, 12489, Germany
Department of Theoretical Chemistry, Technische Universitat Dresden, Berg-strasse 66, Dresden, 01069, Germany
Доп.точки доступа:
Ehrling, S.; Senkovska, I.; Bon, V.; Evans, J. D.; Petkov, P.; Krupskaya, Y.; Kataev, V.; Wulf, T.; Krylov, A. S.; Крылов, Александр Сергеевич; Vtyurin, A. N.; Втюрин, Александр Николаевич; Krylova, S. N.; Крылова, Светлана Николаевна; Adichtchev, S.; Slyusareva, E.; Weiss, M. S.; Buchner, B.; Heine, T.; Kaskel, S.
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