Surface Modification With Phosphoric Acid Of Sio2/nb 2o5 Prepared By The Sol-gel Method: Structural-textural And Acid Sites Studies And An Ion Exchange Model

In this work, the structural and textural properties of the SiO 2/Nb2O5 system prepared by the sol-gel method and then modified by phosphoric acid were studied. The different materials were prepared, with three different mol % Nb2O5 (2.5, 5.0, and 7.5 mol %), and calcined in the temperature range of 423-1273 K. BET specific surface area determinations, scanning electron microscopy connected to a X-ray emission analyzer, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS) were used for the investigation. For the lowest temperature of calcination (423 K), the mesopores and micropores of the modified material were blocked, resulting in a decrease of the specific surface area compared to the SBET values obtained for the SiNb matrix. Under intermediate temperatures of calcination (423-873 K), the modified material acquired textural stability. By XPS analysis, the presence of the dihydrogenphosphate species was identified, the P/Nb atomic ratios being independent of the thermal treatment. 31P magic angle spinning NMR confirmed the XPS data and also showed that the chemical shift of the (H 2PO4 ions strongly depended on the crystallization degree of the Mb2O5. Structural thermal stability was also shown by the presence of Brønsted acid sites in the modified material calcined at high temperature (1273 K). The thermal stability is directly associated with obtainment of the same value for K+ exchange capacity (0.74 mmol g-1, average value) for the modified materials calcined at 423 and 1273 K. The chemical analyses of phosphorus for the modified materials were made by using the inductively coupled plasma. The value was 0.36 mmol g -1, corroborating the presence of (H2PO4 - ions. The ion exchange isotherms presented an S-shaped form characteristic of energetically heterogeneous ion exchangers, permitting application of a model of fixed polydentate centers, in which ion exchange took place.202087078714Alfaya, A.A.S., Gushikem, Y., Decastro, S.C., (1998) Chem. Mater., 10, p. 909Gonçalves, J.E., Gushikem, Y., Decastro, S.C., (1999) J. Non-cryst. Solids, 260, p. 125Alfaya, A.A.S., Gushikem, Y., Decastro, S.C., (2000) Microporous Mesoporous Mater., 39, p. 57Zaitseva, G., Gushikem, Y., (2002) J. Braz. Chem. Soc., 13, p. 611Tanabe, K., (2003) Catal. Today, 78, p. 65Tanabe, K., Okazaki, S., (1995) Appl. Catal. A, 133, p. 191Ziolek, M., (2003) Catal. Today, 78, p. 47Kishor, N., Fujiwara, M., (2002) Chem. Commun., p. 2702Wang, X., Liu, L., Jacobson, A.J., (2002) J. Mater. Chem., 12, p. 1824Wang, X., Liu, L., Jacobson, A.J., (2000) J. Mater. Chem., 10, p. 2774Wang, X., Liu, L., Cheng, H., Jacobson, A.J., (1999) Chem. Commun., p. 2531Okazaki, S., Kurosaki, A., (1990) Catal. Today, 8, p. 113Jones, D.J., Aptel, G., Brandhorst, M., Jacquin, M., Jimenezjiménez, J., Jiménez-López, A., Maireles-Torres, P., Roziere, J., (2000) J. Mater. Chem., 10, p. 1957Quartararo, J., Guelton, M., Rigole, M., Amoureux, J.-P., Fernandez, C., Grimblot, J., (1999) J. Mater. Chem., 9, p. 2637Farias, A.M.D., Gonzalez, W.A., Oliveira, P.G.P., Eon, J.-G., Herrmann, J.-M., Aouine, M., Loridant, S., Volta, J.-C., (2002) J. Catal., 208, p. 238Armaroli, T., Busca, G., Carlini, C., Giuttari, M., Galletti, A.M.R., Sbrana, G., (2000) J. Mol. Catal. A, 151, p. 233Kurosaki, A., Okuyama, T., Okazaki, K., (1987) Bull. Chem. Soc. Jpn., 60, p. 37Francisco, M.S.P., Gushikem, Y., (2002) J. Mater. Chem., 12, p. 2552Francisco, M.S.P., Landers, R., Gushikem, Y., (2004) J. Solid State Chem., 177, p. 2432Morselli, S., Moggi, P., Cauzzi, D., Predieri, G., (1998) Preparation of Catalysts, 7, pp. 763-772. , Delmon B., Ed.Elsevier: AmsterdamScofield, J.H., (1976) J. Electron Spectrosc., 89, p. 129Wagray, A., Ko, E.I., (1996) Catal. Today, 28, p. 41Okazaki, S., Kurusaki, A., (1990) Catal. Today, 8, p. 113(1992) Handbook of Photoelectron Spectroscopy, , Perkin-Elmer: Eden PrairieJehng, J.-M., Turek, A.M., Wachs, I.E., (1992) Appl. Catal. A, 83, p. 179Takahashi, H., Oi, T., Hosoe, M., (2002) J. Mater. Chem., p. 2513Da Suva, J.C.G., Folgueras-Dominguez, S., Dos Santos, A.C.B., (1999) J. Mater. Sci. Lett., 18, p. 197McGuire, G.E., Schweitzer, G.K., Carlson, T.A., (1973) Inorg. Chem., 12, p. 2450Wagner, C.D., Passoja, D.E., Hillery, H.F., Kinisky, T.G., Sic, H.A., Jansen, W.T., Taylor, J.A., (1982) J. Vac. Sci. Technol., 21, p. 933Nefedov, V.I., Gati, D., Dzhurinskii, B.F., Sergushin, N.P., Salyn, Y.V., (1975) Russ. J. Inorg. Chem., 20, p. 1279Pârvulescu, V., Pârvulescu, V.I., Grange, P., (2000) Catal. Today, 57, p. 193Reddy, B.M., Ganesh, I., Reddy, E.P., (1997) J. Phya. Chem. B, 101, p. 1769Clayden, N.J., Esposito, S., Pirnioe, P., Aronne, A., (2001) J. Mater. Chem., p. 936Takahashi, H., Oi, T., Hosoe, M., (2002) J. Mater. Chem., 12, p. 2513Nakayama, H., Eguohi, T., Nakamura, N., Yamagushi, S., Danjyo, M., Tasuhako, M., (1997) J. Mater. Chem., 7, p. 1063Clayden, N.J., (1987) J. Chem. Soc., Dalton Trans., p. 1877Bortun, A.I., Jaimez, E., Llavona, R., García, J.R., Rodrguez, J., (1995) Mater. Res. Bull., 30, p. 413Bortun, A.I., Khainakov, S.A., Bortun, L.N., Poojary, D.M., Rodriguez, J., García, J.R., Clearfield, A., (1997) Chem. Mater., 9, p. 18Okazaki, S., Wada, N., (1992) Catal. Today, 16, p. 349Benvenutti, E.V., Gushikem, Y., Davanzo, C.U., De Castro, S.C., Torriani, I.L., (1992) J. Chem. Soc., Faraday Trans., 88, p. 3193Lefrancois, M., Malbois, G., (1975) J. Catal., 20, p. 350Inoue, Y., Yamazaki, H., Kimura, Y., (1985) Bull, Chem. Soc. Jpn., 58, p. 2481Zahedi-Niaki, M.H., Kaliaguine, Z.S.M.J., (1999) S. Microporous Mesoporous Mater., 32, p. 251Busca, G., (1986) Langmuir, 2, p. 577Draper, N.R., Smith, H., (1981) Applied. Regression Analysis, 2nd Ed., p. 2. , John Wiley & Sons: New YorkBugaevsky, A.A., Kholin, Yu.V., (1991) Anal. Chim. Acta, 241, p. 353Merny, S.A., Konyaev, D.S., Kholin, Yu.V., (1998) Kharkov University Bull., 420, p. 112Sachs, L., (1972) Statistische Auswertungsmethoden, , Springer-Verlag: BerlinBelinskaya, F.A., Ion-exchangers and ion exchange (1987) Physical Chemistry. Theoretical and Practical Guide, 2nd Ed., pp. 666-705. , Nikolsky, B. P., Ed.Khimiya: Leningrad, Chapter 11Kokotov, Yu.A., Zolotarev, P.P., Elkin, G.E., (1986) Theoretical Foundations of Ion Exchange: Complicated Ion Exchange Systems, , Nikolsky, A. B. P., Ed.Khimiya: LeningradKudryavtsev, G.V., Milchenko, D.V., Yagov, V.V., Lopatkin, A.A., (1990) J. Colloid Interface Sci., 140, p. 114Lazarin, A.M., Borgo, C.A., Gushikem, Y., Kholin, Y.V., (2003) Anal. Chim. Acta, 477, p. 305Borgo, C.A., Lazarin, A.M., Kholin, Y.V., Landers, R., Gushikem, Y., (2004) J. Braz. Chem. Soc., 15, p. 5