Abstract
Functionalization of a novel nanoporous monolithic alumina synthesized from amalgam is investigated. The structure is studied by X-ray diffraction, BET, MEB and IR spectroscopy, before and after chemical functionalization by trimethylethoxy silane adsorption and annealing at high temperature. These treatments retain both monolith microstructure and nanostructure while strongly improving material mechanical properties. Allyldimethoxysilane and alcohol adsorption on the annealed samples, proves that highly reactive sites are available for further polymer grafting, as demonstrated by a significant shift of allyldimethoxysilane νSiH to 2,215 cm−1 and adsorbed acetate formation. Simple quantum computations on model systems support this conclusion. Chemical processes reported in this paper, allow a nanostructured alumina monoliths functionalization to optimize ceramics-polymer bonds, and to tune new hybrid biomaterial properties.
Similar content being viewed by others
References
Kirchner A, MacKenzie KJD, Brown IWM, Kemmitt T, Bowden ME. Structural characterisation of heat-treated anodic alumina membranes prepared using a simplified fabrication process. J Membr Sci. 2007;287:264–70.
Vansant EF, Cool P. Chemical modifications of oxide surfaces. Colloid Surf A. 2001;179:145–50.
Tilley TD. Molecular design and synthesis of heterogeneous and single-site supported catalysts. J Mol Cat A Chem. 2002;182–183:17–24.
Shin E-J, Miser DE, Chan WG, Hajaligol MR. Catalytic cracking of catechols and hydroquinones in the presence of nano-particle iron oxide. Appl Cat B Environ. 2005;61:79–89.
Zhang Z, Hicks RW, Pauly TR, Pinnavaia TJ. Mesostructured forms of gamma alumina. J Am Chem Soc. 2002;124:1592–3.
Shi Q, Liang H, Feng D, Wang J, Stucky GD. Porous carbon and carbon/metal oxide microbers with well-controlled pore structure and interface. J Am Chem Soc. 2008;130:5034–5.
Flammea KEL, Popatb KC, Leonic L, Markiewiczc E, Tempad TJL, Romanc BB, Grimesd CA, Desaia TA. Biocompatibility of nanoporous alumina membranes for immunoisolation. Biomaterials. 2007;28:2638–45.
Popat KC, Swana EE, Mukhatyara V, Chatvanichkul K-I, Mor GK, Grimes CA, Desai TA. Influence of nanoporous alumina membranes on long-term osteoblast response. Biomaterials. 2005;26:4516–22.
Castner DG, Ratner BD. Biomedical surface science: foundations to frontiers. Surf Sci. 2002;500:28–60.
Jones FH. Teeth and bones: applications of surface science to dental materials and related biomaterials. Surf Sci Rep. 2001;42:75–205.
Greil PJ. Biomorphous ceramics from lignocellulosics. Eur Ceram Soc. 2001;21:105–18.
Ignjatovic N, Uskokovic D, Mihailova K.Synthesis and application of hydroxyapatite/polylactide composite biomaterial. Appl Surf Sci. 2004;238:314–19.
Advinculaa MC, Rahemtullaa FG, Advinculac RC, Adae ET, Lemonsa JE, Bellisa SL. Osteoblast adhesion and matrix mineralization on solgel-derived titanium oxide. Biomaterials. 2006;27:2201–12.
Qi X, Osterloh FE. Chemical sensing with LiMo3Se3 nanowire films. J Am Chem Soc. 2005;127:7666–7.
Dillon A, Mahan A, Deshpande R, Alleman J, Blackburn J, Parillia P, Heben M, Engtrakul C, Gilbert K, Jones K, To R, Lee S-H, Lehman J. Hot-wire chemical vapor synthesis for a variety of nano-materials with novel applications. Thin Solid Films. 2006;501:216–20.
Ionescu R, Espinosa E, Leghrib R, Felten A, Pireaux J, Erni R, Tendeloo GV, Bittencourt C, Canellas N, Llobet E. Novel hybrid materials for gas sensing applications made of metal-decorated MWCNTs dispersed on nano-particle metal oxides. Sens Actuators B Chem. 2008;131:174–82.
Gole JL, Lewis SE. Porous silicon and sensors and future applications. Nanosilicon 2008;4:149–75.
Long JW, Logan MS, Rhodes CP, Carpenter EE, Stroud RM, Rolison DR. Nanocrystalline iron oxide aerogels as mesoporous magnetic architectures. J Am Chem Soc. 2004;126:16879–89.
Schultz FS, Anderson MA. Effects of surface adsorption and confinement on the photochemical selectivity of previtamin D3 adsorbed within porous sol-gel derived alumina. J Am Chem Soc. 1999;121:4933–40.
Vignes JL, Mazerolles L, Michel D. A novel method for preparing porous alumina objects. Key Eng Mater. 1997;132:432–5.
Pluedemann EP. Silane coupling agents. New York: Plenum Press; 1991.
Hair ML. Infrared spectroscopy in surface chemistry. London: Edward Arnold Publishers Ltd.; 1967.
Peri JB. A model for the surface of gamma alumina. J Phys Chem. 1965;69:220–30.
Knozinger H, Ratnasamy P. Catalytic aluminas: surface models and characterization of surface sites. Catal Rev. Sci Eng. 1978;17:31–70.
Tsyganenko AA, Mardilovich PP. Structure of alumina surfaces. J Chem Soc Faraday Trans. 1996;92:4843–52.
Morterra C. Proceedings of the 6th international Congress on catalysis, London 1976; 194.
Busca G, Lorenzelli V, Sanchez-Escribano V, Guidetti R. FT-IR study of the surface properties of the spinels NiAl2O4 and CoAl2O4 in relation to those of transitional aluminas. J Catal. 1991;131:167–77.
Morterra C, Magnacca G. A case study: surface chemistry and surface structure of catalytic aluminas, as studied by vibrational spectroscopy of adsorbed species. Catal Today. 1996;27:497–532.
Wislicenus H. Versuche zur Gerbstoffbestimmung ohne Hautpulver. Z Angew Chem. 1904;25:801–10.
Bennett J, Pinnel MJ. Reactions between mercury-wetted aluminium and liquid water. Mater Sci. 1973;8:1189–93.
Zhou RS, Snyder RL. Structures and transformation mechanisms of transition aluminas. Acta Crystallogr B Struct Sci. 1991;47:617–30.
Van Santen RA. Theoretical heterogeneous catalysis. Singapore: World Scientific Publishing; 1991.
Flanigen EM, Khatami H, Syzmanski HA. Molecular sieve zeolites. Adv Chem Ser. 1971;16:201–28.
Aronne A, Esposito S, Pernice P. FTIR and DTA study of lanthanum aluminosilicate glasses. Mater Chem Phys. 1997;51:163–8.
Aronne A, Esposito S, Ferone C, Pansini M, Pernice P. FTIR study of the thermal transformation of barium-exchanged zeolite A to celsian. J Mater Chem. 2002;12:3039–45.
Sitarz M, Mozgawa W, Handke M. Rings in the structure of silicate glasses. J Mol Struct. 1999;511:281–5.
Lutz W, Ruscher C, Heidemann, D. Determination of the framework and non-framework SiO2 and AlO2 species of steamed and leached faujasite type zeolites: calibration of IR, NMR, and XRD data by chemical methods. Microporous Mesoporous Mater. 2002;55:193–202.
Wang S, Dou T, Li Y, Zhang Y, Li X, Yan Z. Synthesis, characterization, and catalytic properties of stable mesoporous molecular sieve MCM-41 prepared from zeolite mordenite. J Solid State Chem. 2004;177:4800–5.
Davydov AA. Infrared spectroscopy of adsorbed species on the surface of transition metal oxides. Chichester: Wiley; 1990.
Lamotte J, Moravek V, Bensitel M, Lavalley J. FT-IR study of the structure and reactivity of methoxy species on ThO2 and CeO2. React Kinet Catal Lett. 1988;36:113–18.
Jayasooriya UA, Anson C, Al-Joder O, dAlfonso G, Stanghellini P, Rossetti R. Vibrational assignments for methoxy ligands on metal clusters: interpretation of RAIRS data from methoxy groups on single crystal copper surfaces. Surf Sci. 1993;294:131–40.
Dastoor H, Gardner P, King D. Identification of two tilted adsorbed methoxy species on Ni(110) using RAIRS. Chem Phys Lett. 1993;209:493–8.
Montagne X, Lynch J, Freund E, Lamotte J, Lavalley J. A study of the adsorption sites on thoria by scanning transmission electron microscopy and Fourier-transform infrared spectroscopy. Adsorption and desorption of water and methanol. J Chem Soc Faraday Trans I. 1987;83:1417–25.
Nakamoto K. Infrared spectra of inorganic and coordination compounds. New York: Wiley; 1970.
Dyan A, Cenedese P, Dubot P. Physical properties of gamma alumina surface hydroxyls revisited through a large scale periodic quantum-chemistry approach. J Phys Chem B. 2006;20:10041–50.
Dubot P, Cndse P. Modeling of molecular hydrogen and lithium adsorption on single-wall carbon nanotubes. Phys Rev B. 2001;63:241402(1)–(4).
Hoffmann R. Solids and surfaces. A chemists view of bonding in extended structures. New York: VHC Publishers, Inc.; 1988.
Little L. Infrared spectra of adsorbed species. London: Academic Press Inc.; 1966.
Barr TL. Recent advances in x-ray photoelectron spectroscopy studies of oxides. J Vac Sci Technol A. 1991;9:1793–806.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Azevedo, C., Cenedese, P. & Dubot, P. Two steps bulk-surface functionalization of nanoporous alumina by methyl and vinyl-silane adsorption. Evidence for oxide surface highly reactive sites creation. J Mater Sci: Mater Med 22, 1161–1169 (2011). https://doi.org/10.1007/s10856-011-4286-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10856-011-4286-7