Mesoporous Hybrid Organosilica Materials Functionalized with Biphenyl Moiety
Eduardo R. Magdaluyo, Jr.1, Raymond V. Rivera Virtudazo2,
Leonard P. dela Cruz3, Emily V. Castriciones3,4 , and Herman D. Mendoza1
1Department of Mining, Metallurgical and Materials Engineering
University of the Philippines, 1101 Diliman, Quezon City, Philippines
2Department of Ceramic Engineering
Mariano Marcos State University, Batac, Ilocos Norte, Philippines
3Natural Science Research Institute, University of the Philippines,
1101 Diliman, Quezon City, Philippines
4Inorganic Synthesis and Computational Research Laboratory,
Institute of Chemistry University of the Philippines, 1101 Diliman, Quezon City, Philippines
*Corresponding author: This email address is being protected from spambots. You need JavaScript enabled to view it.
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ABSTRACT
The synthesis of well-defined structures of inorganic silica framework systems functionalized with organic moiety renders these systems versatile in designing new materials. We have obtained in our laboratories a mesoporous hybrid organosilica material incorporating a biphenyl moiety from the condensation of 4,4’-bis(triethoxysilyl) biphenyl monomer with tetraethoxysilane and 1,2-bis(triethoxysilyl)ethane in basic medium. The polymerization was carried out via surfactant–templated method. Infrared spectroscopic analyses showed that the biphenyl moiety was covalently integrated in the polymeric organosilica structure, and X-ray diffraction investigation confirmed the reflection of two-dimensional hexagonal symmetry lattice. The incorporation of this organic moiety is limited by the proportion of 1,2-bis(triethoxysilyl)ethane. The interplanar spacing was decreased with increasing amount of organosilane incorporation. Morphology of the hybrid xerogel material was in the form of agglomerated particles composed of rope-like orientation. Our results indicated that by manipulating the synthesis conditions, it is possible to tailor and tune the structural and textural properties of the obtained mesoporous hybrid material, allowing some possible flexibility in their design for specific application.
INTRODUCTION
The new developments in the field of hybrid materials include the synthesis of well-ordered structures of inorganic silica incorporating an organic moiety in the framework. The mesoporous organosilica with pore diameters from 20 to 500 Å have a distinct advantage over other mesoporous silica materials (Inagaki 2003; Yamamoto et al. 2003; Hatton et al. 2005). The integration of organic functionality within the inorganic porous hosts expanded their applications. The functionalization represents a useful tool to fine-tune hybrid materials for specific physical, chemical, and surface properties as well as better thermal and hydrothermal stabilities for a wider range of applications in catalysis, adsorption, separation science, sensing technology, and nanoelectronics (Asefa et al. 1999; Davis 2000; Burleigh et al. 2001; 2003; Baleizao et al. 2003).
REFERENCES
ASEFA T, KRUK M, MACHLACHLAN M, COOMBS N, GRONDEY H, JARONIEC M, OZIN G. 2001. Novel Bifunctional Periodic Mesoporous Organosilicas, BPMOs: Synthesis, Characterization, Properties and In situ Selective Hydroboration-Alcoholysis Reactions of Functional Groups. J Am Chem Soc 123: 8520-30.
ASEFA T, MACHLACHLAN M, COOMBS N, OZIN G. 1999. Periodic Mesoporous Organosilica with Organic Group Inside the Channel Walls. Nat 402: 867-871.
BALEIZAO C, GIGANTE B, DAS D, ALVARO M, GARCIA H, CORMA C. 2003. Synthesis and Catalytic Activity of a Chiral Periodic Mesoporous Organosilica. Chem Commun 15: 1860-61.
BANEY R, ITOH M, SAKAKIBARA A, SUZUKI T. 1995. Silsesquioxanes. Chem Rev 95(5): 1409-30.
BAO X, ZHAO X, LI X, CHIA P, LI J. 2004. A Novel Route toward the Synthesis of High-Quality Large Pore Periodic Mesoporous Organosilicas. J Phys Chem B 108: 4684-89.
BURLEIGH M, DAI S, HAGAMAN E, LIN J. 2001. Imprinted Polysilsesquioxanes for the Enhanced recognition of Metals. Chem Mater 13: 2537-46.
BURLEIGH M, MARKOWITZ M, JAYASUNDERA S, SPECTOR S, THOMAS C, GABER B. 2003. Mechanical and Hydrothermal Stabilities of Aged periodic Mesoporous orgaosilicas. J Phys Chem B 107: 12628-34.
DAVIS M. 2000. Ordered Porous Materials for Emerging Applications. Nat 417: 813-821.
FUKUOKA A, SAKAMOTO Y, GUAN S, INAGAKI S, SUGIMOTO N, FUKUSHIMA Y, HIRAHARA K, IIJIMA S, ICHIKAWA M. 2001. Novel Templating Synthesis of Necklace-shaped Mono- and Bimetallic Nanowires in Hybrid Organic-inorganic Mesoporous Material. J Am Chem Soc 123: 3373-74.
GRIN S, KOVALENKO A, ALEKSEEV S, IL’IN V. 2004. Organosilica Materials with 1,5-Bis-(2’ethyl)- 2,4-dimethyl Benzene Bridging Groups. Theor Exp Chem 40(6): 389-395.
HAMPSEY J, DE CASTRO C, MCCAUGHEY B, WANG D, MITCHELL B, LU Y. 2004. Preparation of Micrometer- to Sub-micrometer-sized Nanostructured Silica Particles Using High-energy Ball Milling. J Am Ceramic Soc 87(7): 1280-86.
HATTON B, LANDSKRON K, WHITNALL W, PEROVIC D, OZIN G. 2005. Past, Present, and Future of Periodic Mesoporous Organosilicas-The PMOs. Acc Chem Res 38: 305-312.
INAGAKI S. 2003. A New Family of Organic-bridged Mesoporous Materials. Studies in Surface Science and Catalysis 146: 1-8.
INAGAKI S, GUAN S, FUKUSHIMA Y, OHSUNA T, TERASAKI O.1999. Novel Mesoporous Materials with a Uniform Distribution of Organic Groups and Inorganic Oxide in their Frameworks. J Am Chem Soc 121: 9611-14.
INAGAKI S, GUAN S, OHSUNA T, TERASAKI O. 2002. An Ordered Mesoporous Organosilica Hybrid Material with a Crystal-like Wall Structure. Nat 416: 304-307.
ISHII C, ASEFA T, COOMBS N, MACLACHLAN M, OZIN G. 1999. Periodic Mesoporous Organosilica: Fusion of Organic and Inorganic Chemistry Inside the Channel Walls of Hexagonal Mesoporous Silica. Chem Commun 24: 2539-40.
ISHIZAKI K, KOMARNENI S, NANKO M. 1998. Porous Materials Process Technology and Applications, Chapter 2. The Netherlands: Kluwer Academic Publishers. p. 12-35.
JEONG H, KWAK C, KIM I, HA C. 2004. Preparation of Periodic Mesoporous Organosilica using Congo Red Precursor for Potential Optical Applications. Molecular Crystals and Liquid Crystals Science and Technology 425: 173-180.
KUROKI M, ASEFA T, WHITNALL W, KRUK M, YOSHINA-ISHII C, JARONIEC M, OZIN G. 2002. Synthesis and Properties of 1,3,5-Benzene Periodic Mesoporus Organosilica: Novel Aromatic PMO with Three Point Attachments and Unique Thermal Transformations. J Am Chem Soc 124: 13886-95.
LLUSAR M, MONROS G, ROUX C, POZZO J, SANCHEZ C. 2003. One-pot Synthesis of Phenyl- and Amine-functionalized Silica Fibers through the use of Anthracenic and Phenazinic Organogelators. J Mater Chem 13: 2505-14.
MELDE B, HOLLAND B, BLANFORD C, STEIN A. 1999. Mesoporous Sieves with Unified Hybrid Inorganic/ Organic Frameworks. Chem Mater 11: 3302-08.
PARK S, LEE C, CHEON J, JOON S, PAR D. 2001. Morphological Control of Periodic Mesoporous Organosilica with Agitation. Bull Korean Chem Soc 22: 948-952.
SHEA K, LOY D, WEBSTER O.1992. Arylsilsesquioxane Gels and Related Materials, New Hybrids of Organic and Inorganic Networks. J Am Chem Soc 114: 6700-10.
TEMTSIN G, ASEFA T, BITTNER S, OZIN G. 2001. Aromatic PMOs: Tolyl, xylyl and Dimethoxyphenyl Groups Integrated within the Channel Walls of Hexagonal Mesoporous Silica. J Mater Chem 11: 3202-06.
WAHAB M, IMAE I, KAWAKAMI Y, HA C. 2005. Periodic Mesoporous Organosilica Materials Incorporating Various Organic Functional Groups: Synthesis, Structural Characterization and Morphology. Chem Mater 17: 2165-74.
XIAO Y, ZHAO X. 2005. Morphologies of Large-pore Periodic Mesoporous Organosilica. J Phys Chem B 109: 10727-36.
YAMAMOTO K, SAKATA Y, NOHARA Y, TAKAHASHI Y, TATSUMI T. 2003. Organic-inorganic Hybrid Zeolites Containing Organic Frameworks. Sci 300: 470-472.
ZHANG L, YANG Q, ZHANG W, LI Y, YANG J, JIANG D, ZHUA G, LI C. 2005. Highly Ordered Periodic Mesoporous Ethane Silica Synthesized under Neutral Conditions. J Mater Chem 15: 2562-68.