Functionalization of silica surfaces using organo-silanes is highly sensitive to reaction conditions. Silica-coated nanoparticles were functionalized with propyl-sulfonic acid groups (PS) under different synthesis conditions including, various solvents (Ethanol, methanol, acetonitrile, and toluene), water content in the reaction media (0% to 50%), 3-mercaptopropyl-trimethoxysilane concentration (MPTMS) (0.5% to 10%), and reaction time (6 to 16 h). Size of the PS-nanoparticles was determined by TEM and varied from 3.5 to 20.3 nm with sulfur load. Elemental analysis revealed sulfur contents from 0.8% to 22%. FTIR analysis showed increased C-H band intensities with increasing sulfur content of PS-nanoparticles. Although PS-nanoparticles with sulfur loads under 3% did not improve the hydrolysis of cellobiose, PS acid-functionalized nanoparticles with about 6% S achieved 96.0% cellobiose conversion. The control experiment, without catalyst, converted 32.8% of the initial cellobiose. PS-nanoparticles with (6% - 8% S) were obtained using (0.5%) silane concentration and 15 - 16 h reaction time in ethanol.
KeywordsSurfaceNanoparticlesCellobioseHydrolysis
Chang, M.M., Chou, T.Y.C. and Tsao, G.T. (1981) Structure, Pretreatment and Hydrolysis of Cellulose. In: Bioenergy, Springer, Berlin, Heidelberg, 15-42.
Fleming, K., Gray, D. and Matthews, S. (2001) Cellulose Crystallites. Chemistry, 7, 1831-1835. http://dx.doi.org/10.1002/1521-3765(20010504)7:9 3.0.CO;2-S
Gardner, K.H. and Blackwell, J. (1974) Structure of Native Cellulose. Biopolymers, 13, 1975-2001. http://dx.doi.org/10.1002/bip.1974.360131005
Okamura, K. (1991) Structure of Cellulose. In: Hon, D.N. and Shiraishi, N., Eds., Wood and Cellulosic Chemistry, Marcel Dekker, New York, 89-111.
Bobleter, O. (1994) Hydrothermal Degradation of Polymers Derived from Plants. Progress in Polymer Science, 19, 797-841. http://dx.doi.org/10.1016/0079-6700(94)90033-7
McMillan, J.D. (1994) Pretreatment of Lignocellulosic Biomass. In: Himmel, M.E., Baker, J.O. and Overend, R.P., Eds., Enzymatic Conversion of Biomass for Fuels Production, American Chemical Society, 292-294. http://dx.doi.org/10.1021/bk-1994-0566.ch015
Wooley, R., Ruth, M., Glassner, D. and Sheehan, J. (1999) Process Design and Costing of Bioethanol Technology: A Tool for Determining the Status and Direction of Research and Development. Biotechnology Progress, 15, 794-803. http://dx.doi.org/10.1021/bp990107u
Klein Marcuschamer, D., Oleskowicz Popiel, P., Simmons, B. and Blanch, H. (2012) The Challenge of Enzyme Cost in the Production of Lignocellulosic Biofuels. Biotechnology and Bioengineering, 109, 1083-1087.http://dx.doi.org/10.1002/bit.24370
De Vries, R. and Visser, J. (2001) Aspergillus Enzymes Involved in Degradation of Plant Cell Wall Polysaccharides. Microbiology and Molecular Biology Reviews, 65, 497-522. http://dx.doi.org/10.1128/MMBR.65.4.497-522.2001
Xiros, C., Katapodis, P. and Christakopoulos, P. (2011) Factors Affecting Cellulose and Hemicellulose Hydrolysis of Alkali Treated Brewers Spent Grain by Fusarium oxysporum Enzyme Extract. Bioresource Technology, 102, 1688-1696. http://dx.doi.org/10.1016/j.biortech.2010.09.108
Yadav, G.D. (2005) Synergism of Clay and Heteropoly Acids as Nano-Catalysts for the Development of Green Processes with Potential Industrial Applications. Catalysis Surveys from Asia, 9, 117-137.
Chafin, S., Pennybaker, K., Fahey, D., Subramaniam, B. and Gong, K. (2008) Economic and Environmental Impact Analyses of Solid Acid Catalyzed Isoparaffin/Olefin Alkylation in Supercritical Carbon Dioxide. Industrial & Engineering Chemistry Research, 47, 9072-9080. http://dx.doi.org/10.1021/ie800399s
Harmer, M.A., Junk, C., Rostovtsev, V., Carcani, L.G., Vickery, J. and Schnepp, Z. (2007) Synthesis and Applications of Superacids. 1,1,2,2-Tetrafluoroethanesulfonic Acid, Supported on Silica. Green Chemistry, 9, 30-37. http://dx.doi.org/10.1039/b607428f
Harmer, M.A., Farneth, W.E. and Sun, Q. (1998) Towards the Sulfuric Acid of Solids. Advanced Materials, 10, 1255-1255-1257. http://dx.doi.org/10.1002/(SICI)1521-4095(199810)10:15 3.0.CO;2-T
Dhepe, P. and Sahu, R. (2010) A Solid-Acid-Based Process for the Conversion of Hemicellulose. Green Chemistry, 12, 2153-2156. http://dx.doi.org/10.1039/c004128a
Shimizu, K., Furukawa, H., Kobayashi, N., Itaya, Y. and Satsuma, A. (2009) Effects of Bronsted and Lewis Acidities on Activity and Selectivity of Heteropolyacid-Based Catalysts for Hydrolysis of Cellobiose and Cellulose. Green Chemistry, 11, 1627-1632. http://dx.doi.org/10.1039/b913737h
Bootsma, J.A. and Shanks, B.H. (2007) Cellobiose Hydrolysis Using Organic-Inorganic Hybrid Mesoporous Silica Catalysts. Applied Catalysis A: General, 327, 44-51. http://dx.doi.org/10.1016/j.apcata.2007.03.039
Vigier, K.D.O. and Jerome, F. (2010) Heterogeneously-Catalyzed Conversion of Carbohydrates. In: Rauter, A.P., Vogel, P. and Queneau, Y., Eds., Topics in Current Chemistry, Springer Berlin Heidelberg, Berlin, 63-92.
Glass, N., Tjeung, R., Chan, P., Yeo, L. and Friend, J. (2011) Organosilane Deposition for Microfluidic Applications. Biomicrofluidics, 5, Article ID: 036501. http://dx.doi.org/10.1063/1.3625605
Ulman, A. (1996) Formation and Structure of Self-Assembled Monolayers. Chemical Reviews, 96, 1533-1554. http://dx.doi.org/10.1021/cr9502357
Norton, F.J. (1944) Organo-Silicon Films. General Electric Review, 47, 6-16.
Hunter, M., Gordon, M., Barry, A., Hyde, J. and Heidenreich, R. (1947) Properties of Polyorganosiloxane Surfaces on Glass. Industrial & Engineering Chemistry, 39, 1389-1395. http://dx.doi.org/10.1021/ie50455a605
Corma, A. and Garcia, H. (2006) Silica-Bound Homogeneous Catalysts as Recoverable and Reusable Catalysts in Organic Synthesis. Advanced Synthesis & Catalysis, 348, 1391-1412. http://dx.doi.org/10.1002/adsc.200606192
Lai, D., Deng, L., Guo, Q. and Fu, Y. (2011) Hydrolysis of Biomass by Magnetic Solid Acid. Energy & Environmental Science, 4, 3552-3557. http://dx.doi.org/10.1039/c1ee01526e
Boveri, M., Agundez, J., Diaz, I., Perez Pariente, J. and Sastre, E. (2003) Synthesis and Characterisation of Ordered Mesoporous Acid Catalysts for Synthesis of Biodegradable Surfactants. Collection of Czechoslovak Chemical Communications, 68, 1914-1926. http://dx.doi.org/10.1135/cccc20031914
Gao, Y. (2007) Nano-Reagents with Cooperative Catalysis and Their Uses in Multiple Phase Reactions. US Patent Publication No. US 20070184970 A1.
Fan, J. and Gao, Y. (2006) Nanoparticle-Supported Catalysts and Catalytic Reactions: A Mini-Review. Journal of Experimental Nanoscience, 1, 457-475. http://dx.doi.org/10.1080/17458080601067708
Phan, N.T.S. and Jones, C.W. (2006) Highly Accessible Catalytic Sites on Recyclable Organosilane-Functionalized Magnetic Nanoparticles: An Alternative to Functionalized Porous Silica Catalysts. Journal of Molecular Catalysis A: Chemical, 253, 123-131. http://dx.doi.org/10.1016/j.molcata.2006.03.019
Raja, R. and Thomas, J.M. (2003) The Expanding World of Nanoparticle and Nanoporous Catalysts. In: The Chemistry of Nanostructured Materials, World Scientific Publishing Co. Pte. Ltd., Singapur, 329-357.
Hayashi, K., Moriya, M., Sakamoto, W. and Yogo, T. (2009) Chemoselective Synthesis of Folic Acid-Functionalized Magnetite Nanoparticles via Click Chemistry for Magnetic Hyperthermia. Chemistry of Materials, 21, 1318-1325. http://dx.doi.org/10.1021/cm803113e
Shylesh, S., Wagner, A., Seifert, A., Ernst, S. and Thiel, W. (2009) Cooperative Acid-Base Effects with Functionalized Mesoporous Silica Nanoparticles: Applications in Carbon-Carbon Bond-Formation Reactions. Chemistry: A European Journal, 15, 7052-7062. http://dx.doi.org/10.1002/chem.200900851
Fiurasek, P. and Reven, L. (2007) Phosphonic and Sulfonic Acid-Functionalized Gold Nanoparticles: A Solid-State NMR Study. Langmuir, 23, 2857-2866. http://dx.doi.org/10.1021/la0629781
Peña, L., Ikenberry, M., Hohn, K.L. and Wang, D. (2012) Acid-Functionalized Nanoparticles for Pretreatment of Wheat Straw. Journal of Biomaterials and Nanobiotechnology, 3, 342-352. http://dx.doi.org/10.4236/jbnb.2012.33032
Gill, C.S., Price, B.A. and Jones, C.W. (2007) Sulfonic Acid-Functionalized Silica-Coated Magnetic Nanoparticle Catalysts. Journal of Catalysis, 251, 145-152. http://dx.doi.org/10.1016/j.jcat.2007.07.007
Siril, P.F., Davison, A.D., Randhawa, J.K. and Brown, D.R. (2007) Acid Strengths and Catalytic Activities of Sulfonic Acid on Polymeric and Silica Supports. Journal of Molecular Catalysis A: Chemical, 267, 72-78. http://dx.doi.org/10.1016/j.molcata.2006.11.022
Tripp, C. and Hair, M. (1995) Reaction of Methylsilanols with Hydrated Silica Surfaces: The Hydrolysis of Trichloro-, Dichloro-, and Monochloromethylsilanes and the Effects of Curing. Langmuir, 11, 149-155. http://dx.doi.org/10.1021/la00001a027
Dubois, L. and Zegarski, B. (1993) Bonding of Alkoxysilanes to Dehydroxylated Silica Surfaces: A New Adhesion Mechanism. Journal of Chemical Physics, 97, 1665-1670. http://dx.doi.org/10.1021/j100110a032
Lee, L. (1968) Wettability and Conformation of Reactive Polysiloxanes. Journal of Colloid and Interface Science, 27, 751-760. http://dx.doi.org/10.1016/0021-9797(68)90109-4
Mealey, S.K. and Thomas, B. (2005) Past, Present and Future of Organosilane Treatments for Fillers. Rubber World, 12, 32-34.
Ishida, H. and Koenig, J. (1978) Fourier-Transform Infrared Spectroscopic Study of Silane Coupling Agent-Porous Silica Interface. Journal of Colloid and Interface Science, 64, 555-564. http://dx.doi.org/10.1016/0021-9797(78)90398-3
Chirachanchai, S., Chungchamroenkit, R. and Ishida, H. (1999) Adsorption of Tetrasulfide-Functional Silane on High Surface Area Silica Treated with Aqueous and Non-Aqueous Solutions. Composite Interfaces, 6, 155-167. http://dx.doi.org/10.1163/156855499X00369
Rondinone, A.J., Samia, A.C.S. and Zhang, Z.J. (1999) Superparamagnetic Relaxation and Magnetic Anisotropy Energy Distribution in CoFe2O4 Spinel Ferrite Nanocrystallites. Journal of Physical Chemistry B, 103, 6876-6880. http://dx.doi.org/10.1021/jp9912307
Moumen, N., Bonville, P. and Pileni, M. (1996) Control of the Size of Cobalt Ferrite Magnetic Fluids: Mossbauer Spectroscopy. Journal of Chemical Physics, 100, 14410-14416. http://dx.doi.org/10.1021/jp953324w
Shen, X., Fang, X., Zhou, Y. and Liang, H. (2004) Synthesis and Characterization of 3-Aminopropyltriethoxysilane-modified Superparamagnetic Magnetite Nanoparticles. Chemistry Letters, 33, 1468-1469. http://dx.doi.org/10.1246/cl.2004.1468
Peña, L., Ikenberry, M., Ware, B., Hohn, K.L., Boyle, D. and Wang, D. (2011) Cellobiose Hydrolysis Using Acid-Functionalized Nanoparticles. Biotechnology and Bioprocess Engineering, 16, 1214-1222. http://dx.doi.org/10.1007/s12257-011-0166-8
Rac, B., Molnar, A., Forgo, P., Mohai, M. and Bertoti, I. (2006) A Comparative Study of Solid Sulfonic Acid Catalysts Based on Various Ordered Mesoporous Silica Materials. Journal of Molecular Catalysis A: Chemical, 244, 46-57. http://dx.doi.org/10.1016/j.molcata.2005.08.043
Badley, R. and Ford, W. (1989) Silica-Bound Sulfonic-Acid Catalysts. Journal of Organic Chemistry, 54, 5437-5443. http://dx.doi.org/10.1021/jo00284a014
Brunel, D., Cauvel, A., Di Renzo, F., Fajula, F. and Fubini, B. (2000) Preferential Grafting of Alkoxysilane Coupling Agents on the Hydrophobic Portion of the Surface of Micelle-Templated Silica. New Journal of Chemistry, 24, 807-813. http://dx.doi.org/10.1039/b002945i
Melero, J.A., Stucky, G.D., van Grieken, R. and Morales, G. (2002) Direct Syntheses of Ordered SBA-15 Mesoporous Materials Containing Arenesulfonic Acid Groups. Journal of Materials Chemistry, 12, 1664-1670. http://dx.doi.org/10.1039/b110598c
Kitano, M., Yamaguchi, D., Suganuma, S., Nakajima, K., Kato, H., Hayashi, S. and Hara, M. (2009) Adsorption-Enhanced Hydrolysis of Beta-1,4-Glucan on Graphene-Based Amorphous Carbon Bearing SO3H, COOH, and OH Groups. Langmuir, 25, 5068-5075. http://dx.doi.org/10.1021/la8040506
Zeng, M., Ximenes, E., Ladisch, M., Mosier, N., Vermerris, W., Huang, C. and Sherman, D. (2012) Tissue-Specific Biomass Recalcitrance in Corn Stover Pretreated with Liquid Hot-Water: Enzymatic Hydrolysis (Part 1). Biotechnology and Bioengineering, 109, 390-397. http://dx.doi.org/10.1002/bit.23337
Sluiter, A., Hames, B., Ruiz, R., Scarlata, C., Sluiter, J. and Templeton, D. (2008) Determination of Sugars, Byproducts and Degradation Products in Liquid Fraction Process Samples. NREL/TP-510-42623.
Cano Serrano, E., Campos Martin, J. and Fierro, J. (2003) Sulfonic Acid-Functionalized Silica through Quantitative Oxidation of Thiol Groups. Chemical Communications, 2, 246-247. http://dx.doi.org/10.1039/b210766j
Melero, J., Fernando Bautista, L., Morales, G., Iglesias, J. and Sanchez Vazquez, R. (2010) Biodiesel Production from Crude Palm Oil Using Sulfonic Acid-Modified Mesostructured Catalysts. Chemical Engineering Journal, 161, 323-331. http://dx.doi.org/10.1016/j.cej.2009.12.037
Lim, M., Blanford, C. and Stein, A. (1998) Synthesis of Ordered Microporous Silicates with Organosulfur Surface Groups and Their Applications as Solid Acid Catalysts. Chemistry of Materials, 10, 467-470. http://dx.doi.org/10.1021/cm970713p
Diaz, I., Marquez-Alvarez, C., Mohino, F., Perez-Pariente, J. and Sastre, E. (2000) Combined Alkyl and Sulfonic Acid Functionalization of MCM-41-Type Silica: Part 1. Synthesis and Characterization. Journal of Catalysis, 193, 283-294. http://dx.doi.org/10.1006/jcat.2000.2898
Sterman, S. and Bradley, H. (1961) A New Interpretation of the Glass-Coupling Agent Surface through Use of Electron Microscopy. Polymer Engineering & Science, 1, 224-233.
Hair, M. (1975) Hydroxyl-Groups on Silica Surface. Journal of Non-Crystalline Solids, 19, 299-309. http://dx.doi.org/10.1016/0022-3093(75)90095-2
Colilla, M., Izquierdo-Barba, I., Sanchez-Salcedo, S., Fierro, J., Hueso, J. and Vallet-Regi, M. (2010) Synthesis and Characterization of Zwitterionic SBA-15 Nanostructured Materials. Chemistry of Materials, 22, 6459-6466. http://dx.doi.org/10.1021/cm102827y
Alvaro, M., Corma, A., Das, D., Fornes, V. and Garcia, H. (2005) “Nafion”-Functionalized Mesoporous MCM-41 Silica Shows High Activity and Selectivity for Carboxylic Acid Esterification and Friedel-Crafts Acylation Reactions. Journal of Catalysis, 231, 48-55. http://dx.doi.org/10.1016/j.jcat.2005.01.007
Buzzoni, R., Bordiga, S., Ricchiardi, G., Spoto, G. and Zecchina, A. (1995) Interaction of H2O, CH3OH, (CH3)2O, CH3CN and Pyridine with the Superacid Perfluorosulfonic Membrane Nafion: An IR and Raman Study. Journal of Chemical Physics, 99, 11937-11951. http://dx.doi.org/10.1021/j100031a023
Bossaert, W., De Vos, D., Van Rhijn, W., Bullen, J. and Grobet, P. (1999) Mesoporous Sulfonic Acids as Selective Heterogeneous Catalysts for the Synthesis of Monoglycerides. Journal of Catalysis, 182, 156-164. http://dx.doi.org/10.1006/jcat.1998.2353
Macquarrie, D., Jackson, D., Mdoe, J. and Clark, J. (1999) Organomodified Hexagonal Mesoporous Silicates. New Journal of Chemistry, 23, 539-544. http://dx.doi.org/10.1039/a900839j