Abstract
Here, we have examined the nanoporous activated carbon fibers (ACFs) sulfonated using the direct sulfonation and the staged method that included bromination, followed by sulfidation and oxidation. TEM confirmed the nanoporous structure of the prepared sulfonated ACFs. Nitrogen porometry and 2D nonlocal DFT simulations showed the nanoporosity reduction and variations of the pore size distribution because of the functionalization. Comparison of parameters of the SO3H groups confined in nanopores, e.g., the thermal stability and catalytic potential, showed that the most efficient acid sites, in the catalytic 2-propanol dehydration to propylene, are the SO3H groups grafted by the staged Houben–Weil methods. From the productivity of reactions used at the preparation stage, and in contrast to the one-staged aromatic substitution, the bromine addition to π sites of the edges of carbon matrix supplies enough active sites and is a reason for further high yields of the grafted thermostable SO3H groups. Hydrolysis of the grafted bromine and the surface oxidation of nanopores walls are parallel reactions that lowered the SO3H-related acidity, increasing the total acidity to 1.5 mmol g−1. The reported nanoporous sulfonated ACFs are effective to be used in the dehydration reactions catalyzed by solid acids.
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Acknowledgements
This work was supported in a part by an educational program of the Cabinet of Ministers of Ukraine “100 + 100 + 100”, according to the Cabinet of Ministers of Ukraine regulations No 411 of 13.04.2011 and No 546 of 16.05.2011, which is gratefully acknowledged by L.M.G. The authors (L.M.G., V.E.D., A.V.V., and V.V.L.) thank the Ministry of Education and Science of Ukraine for the financial support under the State budget programs [0111U006260] and [0114U003554]. One of the authors, V.V.L. acknowledges a partial financial support from the National Scholarship Program of Slovak Republic, Slovak Academic International Agency scholarships, ID numbers: [14511] and [20917], and the International Visegrad Fund for the scholarship, ID number [51810574] in 2018. V.V.L. and R.T.M. thankful for a partial support from the European Regional Development Fund (ERDF), the project “University Science Park TECHNICOM for innovation applications supported by knowledge technology”, ITMS: 26220220182, Operational Programme ‘Research and Development’.
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Grishchenko, L.M., Diyuk, V.E., Mariychuk, R.T. et al. Surface reactivity of nanoporous carbons: preparation and physicochemical characterization of sulfonated activated carbon fibers. Appl Nanosci 10, 2923–2939 (2020). https://doi.org/10.1007/s13204-019-01069-3
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DOI: https://doi.org/10.1007/s13204-019-01069-3