Adsorption properties of a surface-layer adsorbent based on wide-pore SiO2 and metal-organic framework polymer MIL-100(Cr) in relation to volatile organic compounds of different classes
Abstract
The study of the adsorption and selective properties of the composite surface-layer adsorbent SiO2/MIL-100(Cr) was performed using the inverse gas chromatography method. The composite was prepared on the basis of silicon dioxide and MIL-100(Cr) – benzene-1,3,5-tricarboxylate Cr(III), which is a mesoporous metal-organic coordination polymer (MOCP). The textural characteristics of the original MIL-100(Cr) and the composite with it were determined using the method of low-temperature nitrogen adsorption/desorption. A sharp decrease in the specific surface area of the composite compared to the synthesized MOCP was established, which is explained by the low mass content of the latter (15 %) relative to the silica support. Based on experimental data, the thermodynamic characteristics of the adsorption of various hydrocarbons and chlorinated methane derivatives on a surface-layer adsorbent were calculated. An analysis of the specific retention volumes and thermodynamic characteristics of adsorption demonstrated that the composite adsorbent exhibits a mixed adsorption mechanism. Depending on the nature of the adsorbate and the shape and size of its molecule, various types of intermolecular interactions appear, and a sieve effect was also observed. Using cyclohexane as an example, the possibility of the passage of its molecules only into the pores of one type of framework due to the discrepancy between the dimensions of the pore window was demonstrated. It is proposed to consider the interaction of adsorbate molecules with the porous structure of MIL-100(Cr) in the framework of “guest-host” complex formation by analogy with macrocyclic compounds. Surface layer adsorbent SiO2/MIL-100(Cr) exhibited selective properties towards isomeric alkanes and arenes. Separation factor for isomeric octanes at 160 ℃ was 1.4 for the 2,3,4-trimethylpentane/2,2,4-trimethylpentane pair and 1.5 for the 2,3-dimethylhexane/2,2,4-trimethylpentane pair. In the case of xylene isomers, the highest separation factor was observed for o- and m-xylenes (αo/m = 1.2).
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