Simple One-Pot Synthesis of Sulfonic-Acid-Functionalized Silica for Effective Catalytic Esterification of Levulinic Acid

Desinta Dwi Ristiana(1), Suyanta Suyanta(2), Nuryono Nuryono(3*)

(1) Department of Chemistry, Faculty Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, PO BOX BLS 21, Yogyakarta 55281, Indonesia
(2) Department of Chemistry, Faculty Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, PO BOX BLS 21, Yogyakarta 55281, Indonesia
(3) Department of Chemistry, Faculty Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, PO BOX BLS 21, Yogyakarta 55281, Indonesia
(*) Corresponding Author


Silica functionalized with sulfonic acid catalyst (SiO2−SO3H) was synthesized through a one-pot method and evaluated as the catalyst material for esterification of levulinic acid in an excess amount of ethanol. Sodium silicate solution was used as the silica source, and then a silane coupling agent, namely GPTMS, was used to incorporate the sulfonic group of 2-aminoethanesulfonic acid (AS) into the silica. Functionalization of AS using GPTMS in the slightly acidic condition has been successfully carried out based on the characterization with FTIR, SEM-EDX, and TGA measurements. Catalyst with the AS to SiO2 molar ratio of 5:6 (SiO2−SO3H(5)) showed the highest acid content (1.02 mmol g–1) and the highest conversion of levulinic acid (70%). The reaction followed pseudo-first-order with the rate constant of 0.00414 min–1. Catalyst material was regenerated by washing with alcohol and water, and the catalyst material can be reused at least for 3 cycles. From this study, the SiO2−SO3H produced from a green process is an effective catalyst to produce esters used in fuel additives.


silica acid catalyst; coupling agent; one-pot method; esterification; levulinic acid

Full Text:

Full Text PDF


[1] Malins, K., Kampars, V., Kampare, R., Prilucka, J., Brinks, J., Murnieks, R., and Apseniece, L., 2014, Properties of rapeseed oil fatty acid alkyl esters derived from different alcohols, Fuel, 137, 28–35.

[2] Liu, Y., Huo, P., Ren, J., and Wang, G., 2017, Organic–inorganic hybrid proton-conducting electrolyte membranes based on sulfonated poly(arylene ether sulfone) and SiO2–SO3H network for fuel cells, High Perform. Polym., 29 (9), 1037–1048.

[3] Diagboya, P.N.E., and Dikio, E.D., 2018, Silica-based mesoporous materials; emerging designer adsorbents for aqueous pollutants removal and water treatment, Microporous Mesoporous Mater., 266, 252–267.

[4] Berbar, Y., Hammache, Z.E., Bensaadi, S., Soukeur, R., Amara, M., and Van der Bruggen, B., 2019, Effect of functionalized silica nanoparticles on sulfonated polyethersulfone ion exchange membrane for removal of lead and cadmium ions from aqueous solutions, J. Water Process Eng., 32, 100953.

[5] Ziarani, G.M., Badiei, A., Hassanzadeh, M., and Mousavi, S., 2014, Synthesis of 1,8-dioxo-decahydroacridine derivatives using sulfonic acid functionalized silica (SiO2-Pr-SO3H) under solvent free conditions, Arabian J. Chem., 7 (3), 335–339.

[6] Xiong, Y., Zhang, Z., Wang, X., Liu, B., and Lin, J., 2014, Hydrolysis of cellulose in ionic liquids catalyzed by a magnetically-recoverable solid acid catalyst, Chem. Eng. J., 235, 349–355.

[7] Palla-Rubio, B., Araújo-Gomes, N., Fernández-Gutiérrez, M., Rojo, L., Suay, J., Gurruchaga, M., and Goñi, I., 2019, Synthesis and characterization of silica-chitosan hybrid materials as antibacterial coatings for titanium implants, Carbohydr. Polym., 203, 331–341.

[8] Rahman, I.A., and Padavettan, V., 2012, Synthesis of silica nanoparticles by sol-gel: Size-dependent properties, surface modification, and applications in silica-polymer nanocompositesa review, J. Nanomater., 2012, 132424.

[9] Nhavene, E.P.F., da Silva, W.M., Trivelato Junior, R.R., Gastelois, P.L., Venâncio, T., Nascimento, R., Batista, R.J.C., Machado, C.R., Macedo, W.A.A., and de Sousa, E.M.B., 2018, Chitosan grafted into mesoporous silica nanoparticles as benznidazol carrier for Chagas diseases treatment, Microporous Mesoporous Mater., 272, 265–275.

[10] Parale, V.G., Kim, T., Lee, K.Y., Phadtare, V.D., Dhavale, R.P., Jung, H.N.R., and Park, H.H., 2019, Hydrophobic TiO2–SiO2 composite aerogels synthesized via in situ epoxy-ring opening polymerization and sol-gel process for enhanced degradation activity, Ceram. Int., 46 (4), 4939–4946.

[11] Vueva, Y., Connell, L.S., Chayanun, S., Wang, D., McPhail, D.S., Romer, F., Hanna, J.V., and Jones, J.R., 2018, Silica/alginate hybrid biomaterials and assessment of their covalent coupling, Appl. Mater. Today, 11, 1–12.

[12] Shao, Z., Wu, G., Cheng, X., and Zhang, Y., 2012, Rapid synthesis of amine cross-linked epoxy and methyl co-modified silica aerogels by ambient pressure drying, J. Non-Cryst. Solids, 358 (18-19), 2612–2615.

[13] Vreugdenhil, A.J., Gelling, V.J., Woods, M.E., Schmelz, J.R., and Enderson, B.P., 2008, The role of crosslinkers in epoxy-amine crosslinked silicon sol-gel barrier protection coatings, Thin Solid Films, 517 (2), 538–543.

[14] de Luca, M.A., Martinelli, M., and Barbieri, C.C.T., 2009, Hybrid films synthesised from epoxidised castor oil, γ-glycidoxypropyltrimethoxysilane and tetraethoxysilane, Prog. Org. Coat., 65 (3), 375–380.

[15] Gabrielli, L., Russo, L., Poveda, A., Jones, J.R., Nicotra, F., Jiménez-Barbero, J., and Cipolla, L., 2013, Epoxide opening versus silica condensation during sol-gel hybrid biomaterial synthesis, Chem. Eur. J., 19 (24), 7856–7864.

[16] An, S., Sun, Y., Song, D., Zhang, Q., Guo, Y., and Shang, Q., 2016, Arenesulfonic acid-functionalized alkyl-bridged organosilica hollow nanospheres for selective esterification of glycerol with lauric acid to glycerol mono- and dilaurate, J. Catal., 342, 40–54.

[17] Sierra, I., and Pérez-Quintanilla, D., 2013, Heavy metal complexation on hybrid mesoporous silicas: An approach to analytical applications, Chem. Soc. Rev., 42 (9), 3792–3807.

[18] Da’na, E., 2017, Adsorption of heavy metals on functionalized-mesoporous silica: A review, Microporous Mesoporous Mater., 247, 145–157.

[19] Chen, J., Chen, J., Zhang, X., Gao, J., and Yang, Q., 2016, Efficient and stable PS-SO3H/SiO2 hollow nanospheres with tunable surface properties for acid catalyzed reactions, Appl. Catal., A, 516, 1–8.

[20] Hayes, D.J., Ross, J., Hayes, H.B., and Fitzpatrick, S., 2005, "The Biofine Process – Production of Levulinic Acid, Furfural, and Formic Acid from Lignocellulosic Feedstocks" in Biorefineries-Industrial Processes and Products: Status Quo and Future Directions, Eds. Kamm, B., Gruber, P.R., and Kamm, M., Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 139–164.

[21] Fernandes, D.R., Rocha, A.S., Mai, E.F., Mota, C.J.A., and da Silva, V.T., 2012, Levulinic acid esterification with ethanol to ethyl levulinate production over solid acid catalysts, Appl. Catal., A, 425-426, 199–204.

[22] Benak, K.R., Dominguez, L., Economy, J., and Mangun, C.L., 2002, Sulfonation of pyropolymeric fibers derived from phenol-formaldehyde resins, Carbon, 40 (13), 2323–2332.

[23] Trinh, B.M., and Mekonnen, T., 2018, Hydrophobic esterification of cellulose nanocrystals for epoxy reinforcement, Polymer, 155, 64–74.

[24] Gupta, G., Pathak, S.S., and Khanna, A.S., 2012, Anticorrosion performance of eco-friendly silane primer for coil coating applications, Prog. Org. Coat., 74 (1), 106–114.

[25] Shajesh, P., Smitha, S., Aravind, P.R., and Warrier, K.G.K., 2009, Synthesis, structure and properties of cross-linked R(SiO1.5)/SiO2 (R = 3-glycidoxypropyl) porous organic inorganic hybrid networks dried at ambient pressure, J. Colloid Interface Sci., 336 (2), 691–697.

[26] Heo, J.H., Lee, J.W., Lee, B., Cho, H.H., Lim, B., and Lee, J.H., 2017, Chemical effects of organo-silanized SiO2 nanofillers on epoxy adhesives, J. Ind. Eng. Chem., 54, 184–189.

[27] Elsayed, I., Mashaly, M., Eltaweel, F., Jackson, M.A., and Hassan, E.B., 2018, Dehydration of glucose to 5-hydroxymethylfurfural by a core-shell Fe3O4@SiO2-SO3H magnetic nanoparticle catalyst, Fuel, 221, 407–416.

[28] Ambrożewicz, D., Ciesielczyk, F., Nowacka, M., Karasiewicz, J., Piasecki, A., MacIejewski, H., and Jesionowski, T., 2013, Fluoroalkylsilane versus alkylsilane as hydrophobic agents for silica and silicates, J. Nanomater., 2013, 631938.

[29] Han, X., Zhu, G., Ding, Y., Miao, Y., Wang, K., Zhang, H., Wang, Y., and Liu, S.B., 2019, Selective catalytic synthesis of glycerol monolaurate over silica gel-based sulfonic acid functionalized ionic liquid catalysts, Chem. Eng. J., 359, 733–745.

[30] González, M.D., Salagre, P., Taboada, E., Llorca, J., Molins, E., and Cesteros, Y., 2013, Sulfonic acid-functionalized aerogels as high resistant to deactivation catalysts for the etherification of glycerol with isobutene, Appl. Catal., B, 136-137, 287–293.

[31] de Oliveira, F.M., Segatelli, M.G., and Tarley, C.R.T., 2016, Hybrid molecularly imprinted poly(methacrylic acid-TRIM)-silica chemically modified with (3-glycidyloxypropyl)trimethoxysilane for the extraction of folic acid in aqueous medium, Mater. Sci. Eng., C, 59, 643–651.

[32] Niu, S., Ning, Y., Lu, C., Han, K., Yu, H., and Zhou, Y., 2018, Esterification of oleic acid to produce biodiesel catalyzed by sulfonated activated carbon from bamboo, Energy Convers. Manage., 163, 59–65.

[33] Mahmoud, H.R., 2019, Bismuth silicate (Bi4Si3O12 and Bi2SiO5) prepared by ultrasonic-assisted hydrothermal method as novel catalysts for biodiesel production via oleic acid esterification with methanol, Fuel, 256, 115979.

[34] Cannilla, C., Bonura, G., Costa, F., and Frusteri, F., 2018, Biofuels production by esterification of oleic acid with ethanol using a membrane assisted reactor in vapour permeation configuration, Appl. Catal., A, 566, 121–129.

[35] Liu, Y., Lotero, E., and Goodwin, J.G., 2006, Effect of carbon chain length on esterification of carboxylic acids with methanol using acid catalysis, J. Catal., 243 (2), 221–228.

[36] Popova, M., Shestakova, P., Lazarova, H., Dimitrov, M., Kovacheva, D., Szegedi, A., Mali, G., Dasireddy, V., Likozar, B., Wilde, N., and Gläser, R., 2018, Efficient solid acid catalysts based on sulfated tin oxides for liquid phase esterification of levulinic acid with ethanol, Appl. Catal., A, 560, 119–131.

[37] Li, N., Wang, Q., Ullah, S., Zheng, X.C., Peng, Z.K., and Zheng, G.P., 2019, Esterification of levulinic acid in the production of fuel additives catalyzed by porous sulfonated carbon derived from pine needle, Catal. Commun., 129, 105755.

[38] Kuwahara, Y., Kaburagi, W., Nemoto, K., and Fujitani, T., 2014, Esterification of levulinic acid with ethanol over sulfated Si-doped ZrO2 solid acid catalyst: Study of the structure-activity relationships, Appl. Catal., A, 476, 186–196.

[39] Zainol, M.M., Amin, N.A.S., and Asmadi, M., 2019, Kinetics and thermodynamic analysis of levulinic acid esterification using lignin-furfural carbon cryogel catalyst, Renewable Energy, 130, 547–557.

[40] Oliveira, B.L., and da Silva, V.T., 2014, Sulfonated carbon nanotubes as catalysts for the conversion of levulinic acid into ethyl levulinate, Catal. Today, 234, 257–263.

[41] Imyen, T., Saenluang, K., Dugkhuntod, P., and Wattanakit, C., 2021, Investigation of ZSM-12 nanocrystals evolution derived from aluminosilicate nanobeads for sustainable production of ethyl levulinate from levulinic acid esterification with ethanol, Microporous Mesoporous Mater., 312, 110768.


Article Metrics

Abstract views : 3089 | views : 2239

Copyright (c) 2021 Indonesian Journal of Chemistry

Creative Commons License
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.


Indonesian Journal of Chemistry (ISSN 1411-9420 /e-ISSN 2460-1578) - Chemistry Department, Universitas Gadjah Mada, Indonesia.

Analytics View The Statistics of Indones. J. Chem.