Thermal (kinetic) stability of inclusion compounds on the basis of porous metal–organic frameworks: Dependence on the guest and framework properties

Vladimir A. Logvinenko, Sokhrab B. Aliev, Vsevolod A. Bolotov, Danil N. Dybtsev, Vladimir P. Fedin

Research output: Contribution to journalArticlepeer-review

3 Citations (Scopus)

Abstract

Metal–organic frameworks (MOFs) have promising practical applications in gas storage, in separation and purification of substances, and in catalysis. The standard process of the MOF production begins from the synthesis of the inclusion compound; the molecules of the used organic solvent are caught in the channels and caves of the MOF structure. These primary included guest molecules are excluded further by the evacuation or by the heating. We studied the correlation between the thermal (kinetic) stability of the inclusion compounds and the framework and guest molecules properties. The thermogravimetric curves were used for the kinetic studies; kinetic parameters of decomposition were estimated within the approaches of the non-isothermal kinetics (“model-free” kinetics and nonlinear regression methods). Studied compounds series: [Zn2(bdc)2(dabco)]·4DMF and [Zn4(DMF)(ur)2(ndc)4]·5DMF, [Zn4(DMF)(ur)2(ndc)4]·6benzene and [Zn4(DMF)(ur)2(ndc)4]·5toluene (bdc = bdc2− = terephthalate, dabco = 1,4-diazabicyclo[2.2.2]octane, DMF = dimethylformamide; ur = hexamethylenetetramine, ndc2− = 2,6-naphthalenedicarboxylate); [Mn(HCOO)2]·0.33dioxane and [Li2(H2btc)]·dioxane (H4btc = 1,2,4,5-benzenetetracarboxylic acid). The values of commonly used molecular kinetic diameters do not take into consideration the real molecular form and the size (e.g. benzene and toluene molecules have the same kinetic diameters 5.85 Å). Therefore, the ease of removal of guest molecules does not correlate with them directly.

Original languageEnglish
Pages (from-to)779-787
Number of pages9
JournalJournal of Thermal Analysis and Calorimetry
Volume127
Issue number1
DOIs
Publication statusPublished - 1 Jan 2017

Keywords

  • Inclusion compound
  • Kinetic diameters
  • Kinetic stability
  • Metal–organic frameworks
  • Non-isothermal kinetics
  • THERMODYNAMIC PROPERTIES
  • APPROXIMATION
  • DECOMPOSITION
  • MICROPOROUS MANGANESE FORMATE
  • ACTIVATION-ENERGY
  • Metal-organic frameworks

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