Abstract
Carbon–silica composite materials (CSCMs) containing different amounts of silica and carbon components are obtained using two silica precursors (silica sol and silane) and multiwalled carbon nanotubes (MWNTs). At the initial stage of obtaining CSCMs by method 1, a fine MWNT powder is subjected to impregnation by moisture capacity with silica sol; in accordance with method 2, MWNTs are treated with tetraethoxysilane and then subjected to hydrolysis and polycondensation. The silica (SiO2) content in the composites is varied in a range of 3–60 wt %. After drying and an appropriate heat treatment at 250–350°C, the composite materials are studied by various physicochemical methods, namely, nitrogen porosimetry, electron microscopy, X-ray fluorescence analysis, and thermogravimetric analysis. It is found that the parameters, including texrural characteristics, significantly differ depending on the chemical composition of the CSCMs. Thus, with an increase in the SiO2 content, the specific surface area of the composite materials increases (by a factor of 2) and the pore diameter distribution curves exhibit maxima (at 20–40 nm). The composite materials are studied as adsorbing supports for preparing heterogeneous biocatalysts (BCs) for the low-temperature synthesis of esters, in which the active component is lipase immobilized exclusively on the carbon surface of the nanotubes. With a decrease in the MWNT content in the composite materials, the enzyme activity and operational stability of the BCs, which are measured in the esterification of heptanoic acid (С7) with butanol (С4), monotonically decrease; at the maximum SiO2 content (58 wt %), the activity decreases by a factor of 2–8.
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ACKNOWLEDGMENTS
The authors thank G.G. Ivanova for developing CSCMs of various compositions by the impregnation method (method 1) and the staff of Boreskov Institute of Catalysis of the Siberian Branch of the Russian Academy of Sciences for taking part in the physicochemical studies of carbon–silica composites, in particular, by electron microscopy, NP, XRF, and TA.
Funding
This work was supported by the Ministry of Science and Higher Education of the Russian Federation within the governmental order for Boreskov Institute of Catalysis of the Siberian Branch of the Russian Academy of Sciences (project no. AAAA-A21-121011390007-7).
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Translated by M. Timoshinina
Abbreviations and notation: CNTs, carbon nanotubes; MWNTs, multiwalled carbon nanotubes; MWNTsox, oxidized multiwalled carbon nanotubes; CSCMs, carbon–silica composite materials containing MWNTs; CoxSCMs, carbon–silica composite materials containing MWNTsox; BC, biocatalyst; FA, fatty acid; EAS, enzyme-active substance; NP, nitrogen porosimetry; TA, thermal analysis; XRF, X-ray fluorescence analysis; SEM, scanning electron microscopy; HRTEM, high-resolution transmission electron microscopy
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Kovalenko, G.A., Perminova, L.V., Goidin, V.V. et al. Development of Carbon–Silica Composite Materials and Their Studying and Testing for Preparing Heterogeneous Biocatalysts for the Low-Temperature Synthesis of Esters. Kinet Catal 64, 201–214 (2023). https://doi.org/10.1134/S0023158423020039
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DOI: https://doi.org/10.1134/S0023158423020039