Structure and Properties of Functionalized Porous Silica Hybrid Materials

Elena V. Todorova, Georgi E. Chernev, Stoqn P. Djambazov

Department “Silicate technology”, University of Chemical Technology and Metallurgy, Sofia, Bulgaria.

DOI: 10.4236/ojinm.2014.43006                

Abstract

Functionalized silica hybrid materials are extensively studied and applied materials in the field of science and technology. Functionalization is an approach, which allows for the application of organic components in the improvement of the design, properties and potential application of silicate materials. Silica hybrid materials, functionalized via incorporation of organic components (chitosan and methacrylic acid) were synthesized by the sol-gel method. The base silica structure of the hybrids was obtained via hydrolysis and condensation of the silicate precursor, tetraethyl orthosilicate. The investigations of synthesized hybrids are focused on the influence of the nature and quantity of functional organic components on their final structures and properties. The structural characteristics of obtained hybrid materials were investigated using XRD, FTIR, SEM and DTA/TG analysis. The obtained results presented the formation of amorphous porous structure and the organic components are evenly distributed into the silica network. The functional radicals of chitosan and methacrylic acid (amine, hydroxyl groups) exist in the hybrid structure as free reactive centers, as their quantity increases with increasing the organic amount. The swelling behavior in acidic and neutral solutions of the synthesized materials is investigated and the results presented, that the silicate materials exhibit hydrophilic character.

Keywords

Sol-Gel, Silica Hybrids, Functionalization, Porosity, Biomaterials

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	Lee, K., Morad, N., Teng, T. and Poh, B. (2012) Development, Characterization and the Application of Hybrid Materials in Coagulation/Flocculation of Wastewater: A Review. Chemical Engineering Journal, 203, 370-386. http://dx.doi.org/10.1016/j.cej.2012.06.109
[2]	Xia, K., Ferguson, R., Losier, M., Tchoukanova, N., Brüning, R. and Djaoueda, R. (2010) Synthesis of Hybrid Silica materials with Tunable Pore Structures and Morphology and Their Application for Heavy Metal Removal from Drinking Water. Journal of Hazardous Materials, 183, 554-564. http://dx.doi.org/10.1016/j.jhazmat.2010.07.060
[3]	Wang, T., Chen, Y., Ma, Y., Chen, M., Nie, C., Hu, M., Li, Y., Jia, Z., Fang, J. and Gao, H. (2013) Ampholine-Functionalized Hybrid Organic-Inorganic Silica Material as Sorbent for Solid-Phase Extraction of Acidic and Basic Compounds. Journal of Chromatography A, 1308, 63-72. http://dx.doi.org/10.1016/j.chroma.2013.08.025
[4]	Miao, T. and Wang, L. (2007) Immobilization of Copper in Organic-Inorganic Hybrid Materials: A Highly Efficient and Reusable Catalyst for the Ullmann Diaryl Etherification. Tetrahedron Letters, 48, 95-99. http://dx.doi.org/10.1016/j.tetlet.2006.11.001
[5]	Hu, Y., Tang, S., Jiang L., Zou, B., Yang, J. and Huang, H. (2012) Immobilization of Burkholderia Cepacia Lipase on Functionalized Ionic Liquids Modified Mesoporous Silica SBA-15. Process Biochemistry, 47, 2291-2299. http://dx.doi.org/10.1016/j.procbio.2012.09.007
[6]	Crippa, M., Callone, E., D’Arienzo, M., Müller, K., Polizzi, S., Wahba, L., Morazzoni, F. and Scotti, R. (2011) TiO2 Nanocrystals Grafted on Macroporous Silica: A Novel Hybrid Organic-Inorganic Sol-Gel Approach for the Synthesis of Highly Photoactive Composite Material. Applied Catalysis B: Environmental, 104, 282-290. http://dx.doi.org/10.1016/j.apcatb.2011.03.018
[7]	Tang, H., Guo, J., Sun, Y., Chang, B., Ren, Q. and Yang, W. (2011) Facile Synthesis of pH Sensitive Polymer-Coated Mesoporous Silica Nanoparticles and Their Application in Drug Delivery. International Journal of Pharmaceutics, 421, 388-396. http://dx.doi.org/10.1016/j.ijpharm.2011.10.013
[8]	O’Brien, S., Copuroglu, M. and Crean, G.M. (2007) Effects of Refractive Index Modifiers and UV Light on an Epoxyfunctional Inorganic-Organic Hybrid Sol-Gel Derived Thin Film System. Applied Surface Science, 253, 7969-7972. http://dx.doi.org/10.1016/j.apsusc.2007.02.202
[9]	Liu, J., Xu, S. and Yan, B. (2011) Photoactive Hybrids with the Functionalized Schiff-Base Derivatives Covalently Bonded Inorganic Silica Network: Sol-Gel Synthesis, Characterization and Photoluminescence. Colloids and Surfaces A: Physicochemical Enineering Aspects, 373, 116-123. http://dx.doi.org/10.1016/j.colsurfa.2010.10.036
[10]	Yen, M. and Kuo, M. (2012) Sol-Gel Synthesis of Organiceinorganic Hybrid Materials Comprising Boehmite, Silica, and Thiazole Dye. Dyes and Pigments, 94, 349-354.
[11]	Hasanzadeh, M., Shadjou, N., Eskandani, M. and Guardia, M. (2012) Mesoporous Silica-Based Materials for Use in Electrochemical Enzyme Nanobiosensors. Trends in Analytical Chemistry, 40, 106-118. http://dx.doi.org/10.1016/j.trac.2012.06.007
[12]	Hao, J., Han, M., Wang, C. and Meng, X., Enhanced Removal of Arsenite from Water by a Mesoporous Hybrid Material-Thiol-Functionalized Silica Coated Activated Alumina. Microporous and Mesoporous Materials, 124, 1-7.
[13]	Wang, D., Zhang, J., Tian, X., Liu, D. and Sumathy, K. (2014) Progress in Silica Gel-Water Adsorption Refrigeration Technology. Renewable and Sustainable Energy Reviews, 30, 85-104. http://dx.doi.org/10.1016/j.rser.2013.09.023
[14]	Yuan, Y., Liu, R., Wang, C., Luo, J. and Liu, X. (2014) Synthesis of UV-Curable Acrylate Polymer Containing Sulfonic Groups for Anti-Fog Coatings. Progress in Organic Coatings, in press. http://dx.doi.org/10.1016/j.porgcoat.2014.01.001
[15]	Nollenberger, K. and Albers, J. (2013) Poly(meth)acrylate-Based Coatings. International Journal of Pharmaceutics, 457, 461-469. http://dx.doi.org/10.1016/j.ijpharm.2013.09.029
[16]	Liao, W., Qu, J., Li, Z. and Chen H. (2010) Preparation of Organic/Inorganic Hybrid Polymer Emulsions with High Silicon Content and Sol-Gel-Derived Thin Films. Chinese Journal of Chemical Engineering, 18, 156-163. http://dx.doi.org/10.1016/S1004-9541(08)60337-7
[17]	Liu, J., Ma, J., Bao, Y., Zhu, Z., Zhang, J. and Ma, J. (2011) Effect of Long-Chain Acrylate on the Properties of Polyacrylate/Nano-SiO2 Composite Leather Finishing Agent. Polymer-Plastics Technology and Engineering, 50, 1546-1551. http://dx.doi.org/10.1080/03602559.2011.603782
[18]	Mitchell, J.S. (2011) Spin-Coated Methacrylic Acid Copolymer Thin Films for Covalent Immobilization of Small Molecules on Surface Plasmon Resonance Substrates. European Polymer Journal, 47, 16-23. http://dx.doi.org/10.1016/j.eurpolymj.2010.10.028
[19]	Sevsek, U. and Krajnc, P. (2012) Methacrylic Acid Microcellular Highly Porous Monoliths: Preparation and Functionalisation. Reactive & Functional Polymers, 72, 221-226. http://dx.doi.org/10.1016/j.reactfunctpolym.2012.02.007
[20]	An, F., Feng, X. and Gao, B. (2010) Adsorption Property and Mechanism of Composite Adsorbent PMAA/SiO2 for Aniline. Journal of Hazardous Materials, 178, 499-504. http://dx.doi.org/10.1016/j.jhazmat.2010.01.109
[21]	Panic, V.V., Madzarevic, Z.P., Volkov-Husovic, T. and Velickovic, S.J. (2013) Poly(Methacrylic Acid) Based Hydrogels as Sorbents for Removal of Cationic Dye Basic Yellow 28: Kinetics, Equilibrium Study and Image Analysis. Chemical Engineering Journal, 217, 192-204. http://dx.doi.org/10.1016/j.cej.2012.11.081
[22]	Anirudhan, T.S. and Rijith, S. (2012) Synthesis and Characterization of Carboxyl Terminated Poly(Methacrylic Acid) Grafted Chitosan/Bentonite Composite and Its Application for the Recovery of Uranium(VI) from Aqueous Media. Journal of Environmental Radioactivity, 106, 8-19. http://dx.doi.org/10.1016/j.jenvrad.2011.10.013
[23]	Kwok, K.S., Koong, L.F., Chen, G. and McKay, G. (2014) Mechanism of Arsenic Removal Using Chitosan and Nanochitosan. Journal of Colloid and Interface Science, 416, 1-10. http://dx.doi.org/10.1016/j.jcis.2013.10.031
[24]	Khalek, M.D., Mahmoud, G.A. and El-Kelesh, N.A. (2012) Synthesis and Characterization of Poly-Methacrylic Acid Grafted Chitosan-Bentonite Composite and Its Application for Heavy Metals Recovery. Chemistry and Materials Research, 2, 1-12.
[25]	Song, R., Xue, R., He, L., Liu, Y. and Xiao, Q. (2008) The Structure and Properties of Chitosan/Polyethyleneglycol/Silica Ternary Hybrid Organic-Inorganic Films. Chinese Journal of Polymer Science, 26, 621-630. http://dx.doi.org/10.1142/S0256767908003357
[26]	Lee, E., Jun, S., Kim, H., Kim, H., Koh, Y. and Jang, J. (2010) Silica Xerogel-Chitosan Nano-Hybrids for Use as Drug Eluting Bone Replacement. Journal of Material Science: Material Medicine, 21, 207-214. http://dx.doi.org/10.1007/s10856-009-3835-9
[27]	Sivakami, M.S., Gomathi, T., Venkatesan, J., Jeong, H., Kim, S. and Sudha, P.N. (2013) Preparation and Characterization of Nano Chitosan for Treatment Wastewaters. International Journal of Biological Macromolecules, 57, 204-212. http://dx.doi.org/10.1016/j.ijbiomac.2013.03.005
[28]	Abdel-Raouf, M.E., Abdul-Raheim, A.M., El-Kafrawy, A.F., Maysour, N.E., Ibraheim, A.K. and Abdel-Azim, A.A. (2013) PHEMA Magnetic Nanogels for Removal of Cu(II) Ions from Aqueous Solution. International Journal of Chemistry and Material Science, 1, 36-44.
[29]	Kyzas, G.Z. and Lazaridis, N.K. (2009) Reactive and Basic Dyes Removal by Sorption onto Chitosan Derivatives. Journal of Colloid and Interface Science, 331, 32-39. http://dx.doi.org/10.1016/j.jcis.2008.11.003
[30]	Mahmoodian, H., Moradi, O. and Shariatzadeh, B. (2014) Grafting Chitosan and PolyHEMA on Carbon Nanotubes Surfaces: “Grafting to” and “Grafting from” Methods. International Journal of Biological Macromolecules, 63, 92-97. http://dx.doi.org/10.1016/j.ijbiomac.2013.10.030
[31]	Deng, W., Li, R., Zhang, M., Gong, L. and Kan, C. (2010) Influences of MAA on the Porous Morphology of P(St- MAA) Latex Particles Produced by Batch Soap-Free Emulsion Polymerization Followed by Stepwise Alkali/Acid Post-Treatment. Journal of Colloid and Interface Science, 349, 122-126. http://dx.doi.org/10.1016/j.jcis.2010.05.033
[32]	Purcar, V., Stamatin, I., Cinteza, O., Petcu, C., Raditoiu, V., Ghiurea, M., Miclaus, T. and Andronie, A. (2012) Fabrication of Hydrophobic and Antireflective Coatings Based on Hybrid Silica Films by Sol-Gel Process. Surface and Coatings Technology, 206, 4449-4454. http://dx.doi.org/10.1016/j.surfcoat.2012.04.094
[33]	Zhang, J., Wang, L. and Wang, A. (2007) Preparation and Properties of Chitosan-g-Poly(Acrylic Acid)/Montmorillonite Superabsorbent Nanocomposite via in Situ Intercalative Polymerization. Industrial and Engineering Chemistry Research, 46, 2497-2502. http://dx.doi.org/10.1021/ie061385i
[34]	Liu, Y., Liu, W., Chen, W., Sun, L. and Zhang, G. (2007) Investigation of Swelling and Controlled-Release Behaviors of Hydrophobically Modified Poly(Methacrylic Acid) Hydrogels. Polymer, 48, 2665-2671. http://dx.doi.org/10.1016/j.polymer.2007.03.010
[35]	de Moura, M., Aouada, F. and Mattoso, L. (2008) Preparation of Chitosan Nanoparticles Using Methacrylic Acid. Journal of Colloid and Interface Science, 321, 477-483. http://dx.doi.org/10.1016/j.jcis.2008.02.006
[36]	Neto, B., Mata, A., Lopes, M., Rossi-Bergmannd, B. and Ré, M. (2014) Preparation and Evaluation of Chitosan-Hydrophobic Silica Composite Microspheres: Role of Hydrophobic Silica in Modifying Their Properties. Power Technology, 225, 109-126. http://dx.doi.org/10.1016/j.powtec.2013.10.046
[37]	Zou, H., Wu, S. and Shen, J. (2008) Polymer/Silica Nanocomposites: Preparation, Characterization, Properties, and Applications. Chemical Reviews, 108, 3893-3957. http://dx.doi.org/10.1021/cr068035q
[38]	Treccani, L., Klein, T., Meder, F., Pardun, K. and Rezwan, K. (2013) Functionalized Ceramics for Biomedical, Biotechnological and Environmental Applications. Acta Biomaterialia, 9, 7115-7150. http://dx.doi.org/10.1016/j.actbio.2013.03.036
[39]	Copello, G., Mebert, A., Raineri, M., Pesenti, M. and Diaz, L. (2011) Removal of Dyes from Water Using Chitosan Hydrogel/ SiO2 and Chitin Hydrogel/SiO2 Hybrid Materials Obtained by the Sol-Gel Method. Journal of Hazardous Materials, 186, 932-939. http://dx.doi.org/10.1016/j.jhazmat.2010.11.097
[40]	Zou, H., Wu, S. and Shen, J. (2008) Polymer/Silica Nanocomposites: Preparation, Characterization, Properties, and Applications. Chemical Reviews, 108, 3893-3957.