TY - JOUR

T1 - Some basic correlations in the thermal (kinetic) stability of inclusion compounds on the basis of microporous metal–organic frameworks

AU - Logvinenko, Vladimir

AU - Zavakhina, Marina

AU - Bolotov, Vsevolod

AU - Pishchur, Denis

AU - Dybtsev, Danil

PY - 2017/10/1

Y1 - 2017/10/1

N2 - Metal–organic frameworks (MOFs) have promising practical applications in gas storage, separation and purification, and catalysis. The standard process for MOF production begins with the synthesis of the inclusion compound. The molecules of the organic solvent used are caught in the channels and caves of the MOF structure. These primary inclusion guest molecules are excluded further by the evacuation or by the heating. We investigate a series of inclusion compounds and study the correlation between their thermal (kinetic) stability and the framework and guest molecule properties. Thermogravimetric curves are used for the kinetic studies. Kinetic parameters of decomposition are estimated within the approaches of non-isothermal kinetics (“model-free” kinetics and nonlinear regression methods). We discuss guest molecular kinetic diameters, guest molecule sizes, shape and polarity, the guest phase state (fluid or solid) within the framework pores, the flexibility of the framework structures, the enthalpy and entropy contributions to the kinetic stability and the inclusion compound properties with very similar frameworks (channel walls with similar chemical constitutions), but with different channels length.

AB - Metal–organic frameworks (MOFs) have promising practical applications in gas storage, separation and purification, and catalysis. The standard process for MOF production begins with the synthesis of the inclusion compound. The molecules of the organic solvent used are caught in the channels and caves of the MOF structure. These primary inclusion guest molecules are excluded further by the evacuation or by the heating. We investigate a series of inclusion compounds and study the correlation between their thermal (kinetic) stability and the framework and guest molecule properties. Thermogravimetric curves are used for the kinetic studies. Kinetic parameters of decomposition are estimated within the approaches of non-isothermal kinetics (“model-free” kinetics and nonlinear regression methods). We discuss guest molecular kinetic diameters, guest molecule sizes, shape and polarity, the guest phase state (fluid or solid) within the framework pores, the flexibility of the framework structures, the enthalpy and entropy contributions to the kinetic stability and the inclusion compound properties with very similar frameworks (channel walls with similar chemical constitutions), but with different channels length.

KW - Inclusion compounds

KW - Kinetic stability

KW - Metal–organic frameworks

KW - Molecular kinetic diameters

KW - Non-isothermal kinetics

UR - http://www.scopus.com/inward/record.url?scp=85016941287&partnerID=8YFLogxK

U2 - 10.1007/s10973-017-6317-1

DO - 10.1007/s10973-017-6317-1

M3 - Article

AN - SCOPUS:85016941287

VL - 130

SP - 335

EP - 342

JO - Journal of Thermal Analysis and Calorimetry

JF - Journal of Thermal Analysis and Calorimetry

SN - 1388-6150

IS - 1

ER -