TY - JOUR

T1 - Thermal (kinetic) stability of inclusion compounds on the basis of porous metal–organic frameworks

T2 - Dependence on the guest and framework properties

AU - Logvinenko, Vladimir A.

AU - Aliev, Sokhrab B.

AU - Bolotov, Vsevolod A.

AU - Dybtsev, Danil N.

AU - Fedin, Vladimir P.

PY - 2017/1/1

Y1 - 2017/1/1

N2 - 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.

AB - 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.

KW - Inclusion compound

KW - Kinetic diameters

KW - Kinetic stability

KW - Metal–organic frameworks

KW - Non-isothermal kinetics

KW - THERMODYNAMIC PROPERTIES

KW - APPROXIMATION

KW - DECOMPOSITION

KW - MICROPOROUS MANGANESE FORMATE

KW - ACTIVATION-ENERGY

KW - Metal-organic frameworks

UR - http://www.scopus.com/inward/record.url?scp=84961621915&partnerID=8YFLogxK

U2 - 10.1007/s10973-016-5398-6

DO - 10.1007/s10973-016-5398-6

M3 - Article

AN - SCOPUS:84961621915

VL - 127

SP - 779

EP - 787

JO - Journal of Thermal Analysis and Calorimetry

JF - Journal of Thermal Analysis and Calorimetry

SN - 1388-6150

IS - 1

ER -