Abstract
The functionalization of the carbon fiber based on polyacrylonitrile with sulfur-containing groups of high acidity was carried out in order to obtain the acid-base processes catalysts. Fibers were treated with sulfur vapors in the temperature range of 400-800°C, followed by surface oxidation with 30% hydrogen peroxide solution. Modified samples were investigated by chemical analysis, thermo-programmed desorption with mass spectrometric registration of products, IR spectroscopy and thermogravimetry. It is shown that the obtained materials contain SO3H-functional groups and oxygen-containing groups (carboxyl, lactone, phenolic, etc.) formed in the surface layer during the oxidation of the fiber surface. The chemical analysis showed that the concentration of sulfur in the samples of the modified fiber is 1.6-6.5 mmol/g. The synthesized samples have a satisfactory thermal stability.
The synthesized catalysts were investigated in the model reaction - gas phase dehydration of isopropyl alcohol. It was found that obtained SO3H-containing carbon fibers were catalytically active and had high propylene selectivity. For all the samples obtained there is a complete conversion of alcohol into propylene. The activity of modified carbon fiber samples in the reaction indicated is a fairly high, temperatures of the total conversion of alcohol into propylene are in the range of 160-190°C. During the study of synthesized catalysts in several cycles of catalysis it have been shown that within repeated use (3 cycles) of all modified fiber samples, the yield of propylene does not decrease, the activity remains stable - the temperature of the dehydration reaction remains unchanged or increases insignificantly (by 5-10ºС). The temperatures of complete conversion of isopropyl alcohol in propylene for synthesized catalysts are lower than the temperatures of destruction maxima of surface sulfogroups. Thus, modified carbon fibers can be used as low-temperature catalysts of acid-base processes, in particular dehydration of alcohols.
Publisher
V.I. Vernadsky Institute of General and Inorganic Chemistry
Reference28 articles.
1. . Knaggs E.A., Nepras M.J., Othmer K. Encyclopedia of Chemical Technology. (Hoboken: Wiley, 2014).
2. Rodriguez-Reinoso F. The role of carbon materials in heterogeneous catalysis. Carbon. 1998. 36: 159–175.
3. Carrasco-Marin F., Mueden A., Moreno-Castilla C. Surface-treated activated carbons as catalysts for the dehydration and dehydrogenation reactions of ethanol. J. Phys. Chem. B. 1998. 102: 9239–9244.
4. Kang S., Ye J., Chang J. Recent advances in carbon-based sulfonated catalyst: preparation and application. Int. Rev. Chem. Eng. 2013. 5: 133–143.
5. Georgakilas V., Otyepka M., Bourlinos A.B., Chandra B., Kim N., Kemp K.C., Hobza P., Zboril R., Kim K.S. Functionalization of graphene: covalent and non-covalent approaches, derivatives and applications. Chem. Rev. 2011. 112(11): 6156–6214.