MSA  Vol.9 No.2 , February 2018
Using Swellable Polymers as Structure Directing Scaffolds in Mesoporous Titania Synthesis
Abstract: This paper presents a novel synthesis of well characterized nanoporous materials. The development of mesoporous TiO2 with the use of crosslinked polymer network as structure and surface texture directing agent is reported in this study. Randomly cross-linked DMAEMA-50-PEGMA-50-EGDMA1 was synthesized by radical polymerisation to be used as removable scaffold. The resulting materials were characterized by powder X-ray diffraction (pXRD), nitrogen adsorption, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The synthesized oxides morphology was strongly influenced by the polymer network used as removable scaffold. The modified materials exhibited a narrower pore size distribution and marginally higher specific surface area compared to the unmodified samples. The scaffold cross-linking ratio was also found to have a significant effect on the synthesized materials polymorph. The modification has a strong effect on the titania polymorph as the anatase-rutile transformation was observed only for the modified titania samples.
Cite this paper: Papatryfonos, C. and Theocharis, C. (2018) Using Swellable Polymers as Structure Directing Scaffolds in Mesoporous Titania Synthesis. Materials Sciences and Applications, 9, 211-227. doi: 10.4236/msa.2018.92014.

[1]   Benjwal, P. and Kar, K.K. (2015) Simultaneous Photocatalysis and Adsorption Based Removal of Inorganic and Organic Impurities from Water by Titania/Activated Carbon/Carbonized Epoxy Nanocomposite. Journal of Environmental Chemical Engineering, 3, 2076-2083.

[2]   Borges, M.E., Sierra, M., Cuevas, E., et al. (2016) Photocatalysis with Solar Energy: Sunlight-Responsive Photocatalyst Based on TiO2 Loaded on a Natural Material for Wastewater Treatment. Solar Energy, 135, 527-535.

[3]   Fujishima, A., Rao, T.N. and Tryk, D.A. (2000) Titanium Dioxide Photocatalysis. Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 1, 1-21.

[4]   Wang, H., Lin, T., Zhu, G., et al. (2015) Colored Titania Nanocrystals and Excellent Photocatalysis for Water Cleaning. Catalysis Communications, 60, 55-59.

[5]   Zhang, R., Elzatahry, A., Al-Deyab, S.S., et al. (2012) Mesoporous Titania: From Synthesis to Application. Nano Today, 7, 344-366.

[6]   Bahar, M., Gholami, M. and Azim-Araghi, M.E. (2014) Sol-Gel Synthesized Titania Nanoparticles Deposited on Porous Polycrystalline Silicon: Improved Carbon Dioxide Sensor Properties. Materials Science in Semiconductor Processing, 26, 491-500.

[7]   Tantis, I., Dozzi, M.V., Bettini, L.G., et al. (2016) Highly Functional Titania Nanoparticles Produced by Flame Spray Pyrolysis. Photoelectrochemical and Solar Cell Applications. Applied Catalysis B: Environmental, 182, 369-374.

[8]   Attipa, C. and Theocharis, C.R. (2009) Investigation of the Synthesis and Properties of Ternary V-Cu-Ce Oxides of Composition VxCuxCe1-2xO2. Adsorption Science and Technology, 9, 811-820.

[9]   Attipa, C. and Theocharis, C.R. (2007) Preparation and Characterization of Nanoporous Ternary Mixed Cerium Oxides. Studies in Surface Science and Catalysis, 160, 600-615.

[10]   Theocharis, C., Attipa, C., Hapeshi, E., et al. (2008) Study of the Crystallization of Nanoporous Mixed Metal Oxide Phases. Adsorption Science & Technology, 26, 643-650.

[11]   Tillirou, A. and Theo-charis, C.R. (2006) Preparation of Mesoporous Ceria in the Presence of Non-Aqueous Phases. Studies in Surface Science and Catalysis, 160, 639-644.

[12]   Theocharis, C.R., Kyriacou, G. and Christophidou, M. (2005) Preparation and Characterization of Nanoporous Ceria Containing Heteroatoms, with and without a Matrix. Adsorption, 11, 763-767.

[13]   Tillirou, A. and Theocharis, C. (2008) Synthesis and Characterization of Mesoporous Cerium Oxide Prepared Using an Organic Base and a Templating Agent. Adsorption Science & Technology, 26, 687-692.

[14]   Pal, N. and Bhaumik, A. (2013) Soft Templating Strategies for the Synthesis of Mesoporous Materials: Inorganic, Organic-Inorganic Hybrid and Purely Organic Solids. Advances in Colloid and Interface Science, 189-190, 21-41.

[15]   Yuan, R., Fu, X., Liu, P., et al. (2006) Influence of Solvents on Morphology of TiO2 Fibers Prepared by Template Synthesis. Scripta Materialia, 55, 1003-1006.

[16]   Suk, Y.H., Miyazawa, K., Honma, I., et al. (2003) Synthesis of Semicrystallized Mesoporous TiO2 Thin Films using Triblock Copolymer Templates. Materials Science and Engineering C, 23, 487-494.

[17]   Loryuenyong, V., Buasri, A., Srilachai, C., et al. (2012) The Synthesis of Microporous and Mesoporous Titania with High Specific Surface Area using Sol-Gel Method and Activated Carbon Templates. Materials Letters, 87, 47-50.

[18]   Tang, G., Liu, S., Tang, H., et al. (2013) Template-Assisted Hydrothermal Synthesis and Photocatalytic Activity of Novel TiO2 Hollow Nanostructures. Ceramics International, 39, 4969-4974.

[19]   Miao, Y., Zhai, Z., He, J., et al. (2010) Synthesis, Characterizations and Photocatalytic Studies of Mesoporous Titania Prepared by Using Four Plant Skins as Templates. Materials Science and Engineering C, 30, 839-846.

[20]   Shin, Y. and Exarhos, G.J. (2007) Template Synthesis of Porous Titania using Cellulose Nanocrystals. Materials Letters, 61, 2594-2597.

[21]   Shamaila, S., Leghari Sajjad, A.K., Chen, F., et al. (2011) Mesoporous Titania with High Crystallinity during Synthesis by Dual Template System as an Efficient Photocatalyst. Catalysis Today, 175, 568-575.

[22]   Ji, L., Wang, Z., Li, Z., et al. (2008) Preparation of Aligned Titania Nanowires with an Aligned Carbon Nanotube Composite Template. Materials Letters, 62, 1979-1982.

[23]   Hanaor, D.A.H. and Sorrell, C.C. (2011) Review of the Anatase to Rutile Phase Transformation. Journal of Materials Science, 46, 855-874.

[24]   Rouquerol, F., Rouquerol, J., Sing, K.S.W., et al. (2014) Index. In: Adsorption by Powders and Porous Solids, Academic Press, London, 611-626.

[25]   Li, Z., Yang, X., Wu, L., et al. (2009) Synthesis, Characterization and Biocompatibility of Biodegradable Elastomeric Poly(ether-ester urethane)s Based on Poly(3-hydroxybutyr-ate-co-3-hydroxyhexanoate) and Poly(ethylene glycol) via Melting Polymerization. Journal of Biomaterials Science, Polymer Edition, 20, 1179-1202.

[26]   Li, Z., Yuan, D., Fan, X., et al. (2015) Poly(ethylene glycol) Conjugated Poly(lactide)-Based Polyelectrolytes: Synthesis and Formation of Stable Self-Assemblies Induced by Stereocomplexation. Langmuir, 31, 2321-2333.

[27]   Mondal, S., Madhuri, R. and Sharma, P.K. (2015) PVA Assisted Low Temperature Anatase to Rutile Phase Transformation (ART) and Properties of Titania Nanoparticles. Journal of Alloys and Compounds, 646, 565-572.

[28]   Shin, H.S., Jo, C., Ko, S.H., et al. (2015) Mesoporous Titania with Anatase Framework Synthesized using Polyphenolic Structure-Directing Agent: Synthesis Domain and Catalytic Metal Loading. Microporous and Mesoporous Materials, 212, 117-124.

[29]   Papatryfonos, C. and Theocharis, C.R. (2016) On the Use of Swellable Polymers as Structure Directing Scaffolds in Porous Solids Design. 7th Panhellenic Symposium on Porous Materials, Ioannina, 2-4 June 2016, 169-170.