Thermal (kinetic) stability of inclusion compounds on the basis of porous metal–organic frameworks

详细信息    查看全文

• 作者：Vladimir A. Logvinenko ; Sokhrab B. Aliev…
• 关键词：Inclusion compound ; Kinetic diameters ; Kinetic stability ; Metal–organic frameworks ; Non ; isothermal kinetics
• 刊名：Journal of Thermal Analysis and Calorimetry
• 出版年：2017
• 出版时间：January 2017
• 年：2017
• 卷：127
• 期：1
• 页码：779-787
• 全文大小：
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Physical Chemistry; Analytical Chemistry; Polymer Sciences; Inorganic Chemistry; Measurement Science and Instrumentation;
• 出版者：Springer Netherlands
• ISSN：1588-2926
• 卷排序：127

文摘

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.