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Synthesis and Characterization of Mesoporous Hybrid Silica-Polyacrylamide Aerogels and Xerogels

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Abstract

We report the synthesis of highly porous hybrid silica-polyacrylamide aerogels where the inorganic network was obtained through the hydrolysis and poly-condensation of tetramethoxysilane via a two-step sol–gel process while the polyacrylamide polymer was made by photo-copolymerization of two organic monomers, the acrylamide and the bis-acrylamide. These aerogels were obtained after a carbon dioxide supercritical drying while the corresponding xerogels were dried by simple evaporation. These materials, as well as pure silica and polyacrylamide aerogels and xerogels, were characterized by FTIR spectroscopy, solid-state 29Si and 13C NMR spectroscopy, Thermogravimetric Analysis, a nitrogen adsorption-desorption technique, and Scanning Electron Microscopy. The FTIR and NMR spectra and the TGA/DTA analyses confirm the coexistence of highly branched silica and polyacrylamide networks reflecting the hybrid nature of the materials obtained. Nitrogen adsorption measurements reveal high specific surface areas and pore size distributions disclosing the mesoporous character of these hybrid materials. Hybrid silica-polyacrylamide aerogels having a specific surface area equal to 572 m2/g and a pore volume 1.92 cm3/g were successfully prepared for the first time in this study. The high porosity of these aerogels is due to a better resistance of the silica network to capillary forces during the supercritical drying when silica coexists with a polyacrylamide network.

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References

  1. Loy DA, Shea KJ (1995) Bridged polysilsesquioxanes. Highly porous hybrid organic-inorganic materials. Chem Rev 95(5):1431–1442

    Article  CAS  Google Scholar 

  2. Jeong A-Y, Koo S-M, Kim D-P (2000) Characterization of hydrophobic SiO2 powders prepared by surface modification on wet gel. J Sol-Gel Sci Technol 19(1):483–487

    Article  CAS  Google Scholar 

  3. Sun J, Akdogan EK, Klein LC, Safari A (2007) Characterization and optical properties of sol-gel processed PMMA/SiO2 hybrid monoliths. J Non-Cryst Solids 353(29):2807–2812

    Article  CAS  Google Scholar 

  4. Rubinstein MP, Sud S (1999) The use of hybrid lenses in management of the irregular cornea. Contact Lens Anterior Eye 22(3):87–90

    Article  CAS  Google Scholar 

  5. Gross S, Camozzo D, Di Noto V, Armelao L, Tondello E (2007) PMMA: a key macromolecular component for dielectric low-[kappa] hybrid inorganic-organic polymer films. Eur Polym J 43(3):673–696

    Article  CAS  Google Scholar 

  6. Lamaka SV, Montemor MF, Galio AF, Zheludkevich ML, Trindade C, Dick LF, Ferreira MGS (2008) Novel hybrid sol-gel coatings for corrosion protection of AZ31B magnesium alloy. Electrochim Acta 53(14):4773–4783

    Article  CAS  Google Scholar 

  7. Banet P, Legagneux L, Hesemann P, Moreau JJE, Nicole L, Quach A, Sanchez C, Tran-Thi TH (2008) Hybrid mesostructured thin films functionalized with DBM as new selective sensors of BF3. Sens Actuators, B 130(1):1–8

    Article  Google Scholar 

  8. Santos JC, Paula AV, Rocha CGF, Nunes GFM, de Castro HF (2008) Morphological and mechanical properties of hybrid matrices of polysiloxane-polyvinyl alcohol prepared by sol-gel technique and their potential for immobilizing enzyme. J Non-Cryst Solids 354(42–44):4823–4826

    Article  CAS  Google Scholar 

  9. Ramadan H, Ghanem A, El-Rassy H (2010) Mercury removal from aqueous solutions using silica, polyacrylamide and hybrid silica-polyacrylamide aerogels. Chem Eng J 159(1–3):107–115

    Article  CAS  Google Scholar 

  10. Brinker CJ, Scherer GW (1990) Sol-gel science. The physics and chemistry of sol-gel processing. Academic Press, New York, NY

    Google Scholar 

  11. Pierre AC, Pajonk GM (2002) Chemistry of Aerogels and Their Applications. Chem Rev Wash DC US 102(11):4243–4265

    CAS  Google Scholar 

  12. Huesing N, Schwertfeger F, Tappert W, Schubert U (1995) Influence of supercritical drying fluid on structure and properties of organically modified silica aerogels. J Non-Cryst Solids 186:37–43

    Article  CAS  Google Scholar 

  13. Novak Z, Habulin M, Krmelj V, Knez Z (2003) Silica aerogels as supports for lipase catalyzed esterifications at sub- and supercritical conditions. J Supercrit Fluids 27(2):169–178

    Article  CAS  Google Scholar 

  14. Yoldas BE, Annen MJ, Bostaph J (2000) Chemical engineering of aerogel morphology formed under nonsupercritical conditions for thermal insulation. Chem Mater 12(8):2475–2484

    Article  CAS  Google Scholar 

  15. Forest L, Gibiat V, Woignier T (1998) Biot’s theory of acoustic propagation in porous media applied to aerogels and alcogels. J Non-Cryst Solids 225(1):287–292

    Article  CAS  Google Scholar 

  16. Cantin M, Casse M, Koch L, Jouan R, Mestran P, Roussel D, Bonnin F, Moutel J, Teichner S (1974) Nucl Instrum Methods 118:177

    Article  CAS  Google Scholar 

  17. Zhou B, Wang J, Zhao L, Shen J, Deng Z, Li Y (2000) Preparation of C60-doped silica aerogels and the study of photoluminescence properties. J Vacuum Sci Technol B Microelectron Nanometer Struct 18(4):2001–2004

    Article  CAS  Google Scholar 

  18. Reed ST, Ashley CS, Brinker CJ, Walko RJ, Ellefson R, Gill J (1990) Porous optical composites. SPIE 1328:220–229

    Article  CAS  Google Scholar 

  19. Eid J, Pierre AC, Baret G (2005) Preparation and characterization of transparent Eu doped Y2O3 aerogel monoliths, for application in luminescence. J Non-Cryst Solids 351(3):218–227

    Article  CAS  Google Scholar 

  20. Tsou P (1995) Silica aerogel captures cosmic dust intact. J Non-Cryst Solids 186:415–427

    Article  CAS  Google Scholar 

  21. Guise MT, Hosticka B, Earp BC, Norris PM (2001) An experimental investigation of aerosol collection utilizing packed beds of silica aerogel microspheres. J Non-Cryst Solids 285(1–3):317–322

    Article  CAS  Google Scholar 

  22. Abramian L, El-Rassy H (2009) Adsorption kinetics and thermodynamics of azo-dye Orange II onto highly porous titania aerogel. Chem Eng J 150(2–3):403–410

    Article  CAS  Google Scholar 

  23. Akl J, Ghaddar T, Ghanem A, El-Rassy H (2009) Cobalt ferrite aerogels by epoxide sol-gel addition: efficient catalysts for the hydrolysis of 4-nitrophenyl phosphate. J Mol Catal A: Chem 312(1–2):18–22

    Article  CAS  Google Scholar 

  24. Pajonk GM (1991) Aerogel catalysts. Appl Catal 72(2):217–266

    Article  CAS  Google Scholar 

  25. El Rassy H, Perrard A, Pierre AC (2004) Application of lipase encapsulated in silica aerogels to a transesterification reaction in hydrophobic and hydrophilic solvents: Bi-Bi Ping-Pong kinetics. J Mol Catal B Enzym 30(3–4):137–150

    Article  CAS  Google Scholar 

  26. Buisson P, Pierre AC (2006) Immobilization in quartz fiber felt reinforced silica aerogel improves the activity of Candida rugosa lipase in organic solvents. J Mol Catal B Enzym 39(1–4):77–82

    Article  CAS  Google Scholar 

  27. Nassreddine S, Karout A, Lorraine Christ M, Pierre AC (2008) Transesterification of a vegetal oil with methanol catalyzed by a silica fibre reinforced aerogel encapsulated lipase. Appl Catal, A 344(1–2):70–77

    CAS  Google Scholar 

  28. Karout A, Chopard C, Pierre AC (2007) Immobilization of a lipoxygenase in silica gels for application in aqueous media. J Mol Catal B Enzym 44(3–4):117–127

    Article  CAS  Google Scholar 

  29. Al-Oweini R, El-Rassy H (2009) Synthesis and characterization by FTIR spectroscopy of silica aerogels prepared using several Si(OR)4 and R''Si(OR')3 precursors. J Mol Struct 919(1–3):140–145

    Article  CAS  Google Scholar 

  30. Nadargi DY, Rao AV (2009) Methyltriethoxysilane: new precursor for synthesizing silica aerogels. J Alloy Comp 467(1–2):397–404

    Article  CAS  Google Scholar 

  31. Husing N, Schubert U, Mezei R, Fratzl P, Riegel B, Kiefer W, Kohler D, Mader W (1999) Formation and Structure of Gel Networks from Si(OEt)4/(MeO)3Si(CH2)3NR'2 Mixtures (NR'2 = NH2 or NHCH2CH2NH2). Chem Mater 11(2):451–457

    Article  Google Scholar 

  32. El Rassy H, Buisson P, Bouali B, Perrard A, Pierre AC (2003) Surface characterization of silica aerogels with different proportions of hydrophobic groups, dried by the CO2 supercritical method. Langmuir 19(2):358–363

    Article  CAS  Google Scholar 

  33. Rama Rao GV, Krug ME, Balamurugan S, Xu H, Xu Q, Lopez GP (2002) Synthesis and characterization of silica-poly(N-isopropylacrylamide) hybrid membranes: switchable molecular filters. Chem Mater 14(12):5075–5080

    Article  Google Scholar 

  34. Fu Q, Rama Rao GV, Ward TL, Lu Y, Lopez GP (2007) Thermoresponsive transport through ordered mesoporous Silica/PNIPAAm copolymer membranes and microspheres. Langmuir 23(1):170–174

    Article  Google Scholar 

  35. Zareba-Grodz I, Mista W, Strek W, Bukowska E, Hermanowicz K, Maruszewski K (2004) Synthesis and properties of an inorganic-organic hybrid prepared by the sol-gel method. Opt Mater 26(2):207–211

    Article  CAS  Google Scholar 

  36. Durme KV, Van Mele B, Loos W, Du Prez FE (2005) Introduction of silica into thermo-responsive poly(N-isopropyl acrylamide) hydrogels: a novel approach to improve response rates. Polymer 46(23):9851–9862

    Article  Google Scholar 

  37. Brunauer S, Emmett PH, Teller E (1938) Adsorption of gases in multimolecular layers. J Am Chem Soc 60(2):309–319

    Article  CAS  Google Scholar 

  38. Barrett EP, Joyner LG, Halenda PP (1951) The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms. J Am Chem Soc 73(1):373–380

    Article  CAS  Google Scholar 

  39. Lowell S, Shields JE, Thomas MA, Thommes M (2004) Characterization of porous solids and powders: surface area, pore size, and density. Kluwer Academic, Dordrecht

    Google Scholar 

  40. Song Y, Nan C-W (2007) Preparation of Ca3Co4O9 by polyacrylamide gel processing and its thermoelectric properties. J Sol-Gel Sci Technol 44(2):139–144

    Article  CAS  Google Scholar 

  41. Suzuki A, Yamazaki M, Kobiki Y (1996) Direct observation of polymer gel surfaces by atomic force microscopy. J Chem Phys 104(4):1751–1757

    Article  CAS  Google Scholar 

  42. Socrates G (2001) Infrared and Raman characteristic group frequencies: Tables and Charts. 3 edn. John Wiley & Sons

  43. Gopal NO, Narasimhulu KV, Rao JL (2004) EPR, optical, infrared and Raman spectral studies of Actinolite mineral. Spectrochim Acta A Mol Biomol Spectrosc 60(11):2441–2448

    Article  CAS  Google Scholar 

  44. Duran A, Fernandez Navarro JM, Casariego P, Joglar A (1986) Optical properties of glass coatings containing Fe and Co. J Non-Cryst Solids 82(1–3):391–399

    Article  CAS  Google Scholar 

  45. Bertoluzza A, Fagnano C, Antonietta Morelli M, Gottardi V, Guglielmi M (1982) Raman and infrared spectra on silica gel evolving toward glass. J Non-Cryst Solids 48(1):117–128

    Article  CAS  Google Scholar 

  46. Gunzler H, Gremlich H-U (2002) IR Spectroscopy: an introduction. Wiley-VCH

  47. Fan Y, Zhang M, Feng Y-Q (2005) Poly(acrylamide-vinylpyridine-N, N'-methylene bisacrylamide) monolithic capillary for in-tube solid-phase microextraction coupled to high performance liquid chromatography. J Chromatogr A 1099(1–2):84–91

    Article  CAS  Google Scholar 

  48. Peng Liu LZ, Zhixing Su (2006) Core/shell SiOx@PAM nanospheres from UV-assisted surface-initiated free radical polymerization. J Appl Polym Sci 100(5):3433–3438

    Article  Google Scholar 

  49. Pomonis PJ, Petrakis DE, Ladavos AK, Kolonia KM, Armatas GS, Sklari SD, Dragani PC, Zarlaha A, Stathopoulos VN, Sdoukos AT (2004) A novel method for estimating the C-values of the BET equation in the whole range 0 < P/P0 < 1 using a Scatchard-type treatment of it. Microporous Mesoporous Mater 69(1–2):97–107

    Article  CAS  Google Scholar 

  50. Buisson P, Hernandez C, Pierre M, Pierre AC (2001) Encapsulation of lipases in aerogels. J Non-Cryst Solids 285(1–3):295–302

    Article  CAS  Google Scholar 

  51. Tanaka T (1992) Phase transitions of gels. In: Polyelectrolyte gels, vol 480. ACS Symposium Series, pp 1-21

  52. Sindorf DW, Maciel GE (1983) Silicon-29 NMR study of dehydrated/rehydrated silica gel using cross polarization and magic-angle spinning. J Am Chem Soc 105(6):1487–1493

    Article  CAS  Google Scholar 

  53. Zhu Z, Jian O, Paillet S, Desbrières J, Grassl B (2007) Hydrophobically modified associating polyacrylamide (HAPAM) synthesized by micellar copolymerization at high monomer concentration. Eur Polym J 43(3):824–834

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, American University of Beirut, P.O. Box 11-0236, Riad El-Solh, 1107 2020, Beirut, Lebanon

    Hiba Ramadan & Houssam El-Rassy

  2. UPMC Université Paris 06, UMR 7574, Chimie de la Matière Condensée de Paris, Paris, F-75005, France

    Thibaud Coradin & Sylvie Masse

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  1. Hiba Ramadan
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  2. Thibaud Coradin
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Correspondence to Houssam El-Rassy.

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Ramadan, H., Coradin, T., Masse, S. et al. Synthesis and Characterization of Mesoporous Hybrid Silica-Polyacrylamide Aerogels and Xerogels. Silicon 3, 63–75 (2011). https://doi.org/10.1007/s12633-010-9064-5

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