Abstract
In this paper, the calcination of SBA-15 in vacuum is followed by in situ and ex situ small angle X-ray scattering (SAXS) measurements at different temperatures and the material properties are compared with the conventional calcination process in nitrogen and air. The whole process of template decomposition and by-products elimination is investigated as a function of temperature, showing early stages of polymer decomposition at 200 °C. The textural properties of the vacuum-calcined material, analyzed by nitrogen adsorption isotherm data at the end of the calcination process at 540 °C, revealed a smaller surface area and no detectable volume of micropores. A sharp monomodal pore size distribution with a mean value around 108 Å is obtained, larger than the material calcined via the usual procedure, which gives values around 98 Å. The results indicate that the vacuum heat treatment is an alternative calcination strategy for applications which require a well-ordered mesoporous structure, rigid pore walls, and large pore diameters.
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C.T. Kresge, M.E. Leonowicz, J.W. Roth, J.C. Vartuli, J.S. Beck, Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature 359, 710–712 (1992)
M.E. Davis, Ordered porous materials for emerging applications. Nature 417, 813–821 (2002)
B.J. Melde, B.J. Johnson, P.T. Charles, Mesoporous silicate materials in sensing. Sensors 8, 5202–5228 (2008)
M. Vallet-Regí, International scholarly research network materials science, ID 608548, 20 pages (2012)
A. Popat, S. Jambhrunkar, J. Zhang, J. Yang, H. Zhang, A. Meka, C. Yu, Programmable drug release using bioresponsive mesoporous silica nanoparticles for site-specific oral drug delivery. Chem. Commun. 50(42), 5547–5550 (2014)
K. Scaramuzzi, G.D. Tanaka, F.M. Neto, P.R.A.F. Garcia, J.J.M. Gabrili, D.C.A. Oliveira, D.V. Tambourgi, J.S. Mussalem, D. Paixão-Cavalcante, M.T. D’Azeredo Orlando, V.F. Botosso, C.L.P. Oliveira, M.C.A. Fantini, O.A. Sant’Anna, Nanostructured SBA-15 silica: an effective protective vehicle to oral hepatitis B vaccine immunization. Nanomedicine 12, 2241–2250 (2016)
D. Zhao, Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 Angstrom pores. Science 279, 548–552 (1998)
T. Benamor, L. Michelin, B. Lebeau, C. Marichal, Flash induction calcination: a powerful tool for total template removal and fine tuning of the hydrophobic/hydrophilic balance in SBA-15 type silica mesoporous materials. Microporous Mesoporous Mater. 147, 334–342 (2012)
F. Kleitz, W. Schmidt, F. Schüth, Calcination behavior of different surfactant-templated mesostructured silica materials. Microporous Mesoporous Mater. 65, 1–29 (2003)
S.A. Bagshaw, I.J. Bruce, Rapid calcination of high quality mesostructured MCM-41, MSU-X, and SBA-15 silicate materials: a step towards continuous processing? Microporous Mesoporous Mater. 109, 199–209 (2008)
F. Bérubé, S. Kaliaguine, Calcination and thermal degradation mechanisms of triblock copolymer template in SBA-15 materials. Microporous Mesoporous Mater. 115, 469–479 (2008)
V. Cauda, C. Argyo, D.G. Piercey, T. Bein, “Liquid-phase calcination” of colloidal mesoporous silica nanoparticles in high-boiling solvents. J. Am. Chem. Soc. 133(17), 6484–6486 (2011)
T.L. Lai, Y.Y. Shu, Y.C. Lin, W.N. Chen, C.B. Wang, Rapid removal of organic template from SBA-15 with microwave assisted extraction. Mater. Lett. 63, 1693–1695 (2009)
Z. Zhang, J. Yin, H.J. Heeres, I. Melián-Cabrera, Thermal detemplation of SBA-15 mesophases. Effect of the activation protocol on the framework contraction. Microporous Mesoporous Mater. 176, 103–111 (2013)
S.G. Avila, L.C.C. Silva, J.R. Matos, Optimisation of SBA-15 properties using Soxhlet solvent extraction for template removal. Microporous Mesoporous Mater. 234, 277–286 (2016)
S. Brunauer, P.H. Emmett, E. Teller, Adsorption of gases in multimolecular layers. J. Am. Chem. Soc. 60, 309–319 (1938)
E.P. Barrett, L.G. Joyner, P.P. Halenda, The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms. J. Am. Chem. Soc. 73(1), 373–380 (1951)
M. Jaroniec, L.A. Solovyov, Improvement of the Kruk−Jaroniec−Sayari method for pore size analysis of ordered silicas with cylindrical mesopores. Langmuir 22, 6757–6760 (2006)
A. Sundblom, C.L.P. Oliveira, A.E.C. Palmqvist, J.S. Pedersen, Modeling in situ small-angle X-ray scattering measurements following the formation of mesostructured silica. J. Phys. Chem. C 113, 7706–7713 (2009)
A. Sundblom, C.L.P. Oliveira, J.S. Pedersen, A.E.C. Palmqvist, Decoupling particle formation from intraparticle ordering in mesostructured silica colloids. Microporous Mesoporous Mater. 145, 59–64 (2011)
S. Förster et al., Scattering Curves of Ordered Mesoscopic Materials. J. Phys. Chem. B 109, 1347–1360 (2005)
J.K. Pedersen, Analysis of small-angle scattering data from colloids and polymer solutions: modeling and least-squares fitting. Adv. Colloid Interface Sci. 70, 171–210 (1997)
J.S. Pedersen, Analysis of small-angle scattering data from colloids and polymer solutions: modeling and least-squares fitting. Adv. Colloid Interf. Sci. 70, 171–210 (1997)
K.S.W. Sing et al., Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (recommendations 1984). Pure Appl. Chem. 57, 603–619 (1985)
J.R. Matos, L.P. Mercuri, M. Kruk, M. Jaroniec, Toward the synthesis of extra-large-pore MCM-41 analogues. Chem. Mater. 13, 1726–1731 (2001)
G. Socrates, Infrared and Raman characteristic group frequencies (Wiley, Chichester, 2001)
R. Ojeda-Lopez, I.J. Perez-Hermosillo, J.M. Esparza-Schulz, A. Cervantes-Uribe, A. Dominguez-Ortiz, SBA-15 materials: calcination temperature influence on textural properties and total silanol ratio. Adsorption 21, 659–669 (2015)
V. Escax, E. Delahaye, M. Imperor-Clerc, P. Beaunier, M.D. Appay, A. Davidson, Modifying the porosity of SBA-15 silicas by post-synthesis basic treatments. Microporous Mesoporous Mater. 102, 234–241 (2007)
C.M. Yang, B. Zibrowius, W. Schmidt, F. Schuth, Stepwise removal of the copolymer template from mesopores and micropores in SBA-15. Chem. Mater. 16, 2918–2925 (2004)
Funding
This work has been supported by the Brazilian Synchrotron Light Laboratory (LNLS) under proposal D11A - SAXS1 5820. Thanks are due to CNPq and FAPESP for supporting this research. M.C.A. Fantini and C.L.P. Oliveira are CNPq fellows.
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Mariano-Neto, F., Cides da Silva, L.C., Oliveira, C.L.P. et al. Vacuum Calcination Behavior of SBA-15 Ordered Mesoporous Silica. Braz J Phys 48, 442–450 (2018). https://doi.org/10.1007/s13538-018-0579-3
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DOI: https://doi.org/10.1007/s13538-018-0579-3