Effect of Surface Sulfonation on the Ordered and Textural Properties of Vanadium and Iron Containing SBA-15

Year 2017, Volume: 4 Issue: 4, 85 - 92, 27.12.2017

Suna Balcı Sultan Yüksel

Abstract

Sulfanation of
SBA-15 by use of H₂SO₄ as the synthesis acid and post
surface sulfanation of hydrothermally synthesized V-, Fe-SBA-15 samples with
different M/Si mole ratios were carried out by use of dilute sulfuric acid. The
doubling of hydrogen ions’ amount in case H₂SO₄ usage led
to partial deterioration of the ordered structure. X-ray diffraction patterns
showed that the metal loading to SBA-15 matrix caused increases in (100) plane
reflections up to four-five times supporting the formation of longer hexagonal
arrays. The improved ordered structure of metal-SBA-15 was not destroyed by post-sulfanation.
Micro-mesoporus structure of the samples resembled type IV nitrogen isotherm
with a H4 hysteresis loop of IUPAC classification. Increase of BET surface area accompanied
with around 20% increase in micropore volume took place by metal contribution.
Increases both in Saito–Foley (SF) mean micropore and Barrett–Joyner–Halenda
(BJH) mean mesopore sizes were designated by
the increase of M/Si ratio in the synthesis solution. Around 150-200 m².g^-1
decreases in BET surface area were accompanied by the decreases in the mesopore
volume and mean mesopore dimensions, and partly increases in the micropore
volume and mean micropore diameters were observed with sulfanation.

Keywords

sulfonation, crystalline structure, pore structure, textural properties

References

• Zhao, D., Feng, J., Huo, Q., Melosh, N., Fredrickson, G.H., Chmelka, B.F., Stucky, G.D., “Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 Angstrom pores”, Science, 279, 548-552, 1998 Meynen, V., Cool, P., Vansant, E.F., “Verified syntheses of mesoporous materials”, Micropor. Mesopor. Mater., 125, 170–223, 2009 Taguchi, A., Schüth, F., Ordered mesoporous materials in catalysis, Micropor. Mesopor. Mater., 77, 1–45, 2005 Chmielarz, L., Kus´trowski, P., Dziembaj, R., Cool, P., Vansant, E.F., SBA-15 mesoporous silica modified with metal oxides by MDD method in the role of DeNOx catalysts. Micropor. Mesopor. Mater., 127, 133–141, 2010 Zhang, H., Tang, C., Lv, Y., Sun, C., Gao, F., Dong, L., Chen, Y., “Synthesis, characterization, and catalytic performance of copper-containing SBA-15 in the phenol hydroxylation” J. Colloid Inter. Sci., 380, 16–24, 2012 Hea, S., Hea, S., Zhang, L., Li, X., Wang, J., He, D., Lu, J., Luo, Y., Hydrogen production by ethanol steam reforming over Ni/SBA-15 mesoporous catalysts: Effect of Au addition Cataly. Today, 258, 162–168, 2015 Karthikeyan, S., Pachamuthu, M.P., Isaacs, M.A., Kumar, S., Lee, A.F., Sekaran, G., Cu and Fe oxides dispersed on SBA-15: A Fenton type bimetallic catalyst for N,N-diethyl-p-phenyl diamine degradation, Appl. Catal. B: Environ., 199, 323–330, 2016 Chirieac, A., Dragoi, B., Ungureanu, A., Ciotonea, C., Mazilu, I., Royer, S., Mamede, A.S., Rombi, E., Ferino, I., Dumitriu, E., Facile synthesis of highly dispersed and thermally stable copper-based nanoparticles supported on SBA-15 occluded with P123 surfactant for catalytic applications, J. Catal., 339, 270–283,2016 Popova, M., Szegedi, A., Zheleva, C., Mitov, I., Kostova, N., Tsoncheva, T., “Toluene oxidation on titanium- and iron-modified MCM-41 materials”, J. Hazard. Mater., 168, 226–232, 2009 Hess, C., Drake, I.J., Hoefelmeyer, J.D., Tilley, T.D. , Bell, A.T., “Partial oxidation of methanol over highly dispersed vanadia supported on silica SBA-15”, Catal. Lett., 5, 1-8, 2005 Capek, L., Adam, J., Bulanek, L., Kosova, G., Cicmanec, P., Knotek, P., “Oxidative dehydrogenation of ethane over vanadium supported on mesoporous materials of M41S family”, Appl. Catal. A: Gen., 342, 99-106, 2008 Moreno, S., Sanabria, N., Alvarez, A., “Synthesis of pillared bentonite starting from the Al-Fe polymeric precursor in solid state, and its catalytic evaluation in the phenol oxidation reaction”, Catal. Today, 133-135, 530-533, 2008 Tsoncheva, T., Ivanova, L., Dimitrova, R., Rosenholm, J., “Physicochemical and catalytic properties of grafted vanadium species on different mesoporous silicas”, J. Colloid Inter. Sci., 321, 342-349, 2008 Gracia, M.D., Balu, A.M., Campelo, J.M., Luque, R., Marinas, J.M., Romero, A.A., “Evidences of the in situ generation of highly active Lewis acid species on Zr-SBA-15”, Appl. Catal. A: Gen., 371, 85-91, 2009 Zhang, Q., Li, Y., An, D., Wang, Y., “Catalytic behavior and kinetic features of FeOx/SBA-15 catalyst for selective oxidation of methane by oxygen”, Appl. Catal. A: Gen., 356, 103–111, 2009 Hua, W., Yue, Y., Gao, Z., “Acidity enhancement of SBA mesoporous molecular sieve by modification with SO4 2−/ZrO2”, J. Molecular Catal. A: Chemical, 170, 195-202, 2001 Kilos, B., Nowak, I., Ziolek, M., Tuel, A., Volta, J.C., “Transition metal containing (Nb, V, Mo) SBA-15 molecular sieves- synthesis, characteristic and catalytic activity in gas and liquid phase oxidation”, Studies in Surf. Sci. Catal., 158, 1461-1468, 2005 Hess, C., Drake, I.J., Hoefelmeyer, J.D., Tilley, T.D. , Bell, A.T., “Partial oxidation of methanol over highly dispersed vanadia supported on silica SBA-15”, Catal. Letters, 5, 1-8, 2005 Chen, C.L., Li, T., Cheng, S., Lin, H.P., Bhongale, C.J., Mou, C.Y., Direct impregnation method for preparing sulfated zirconia supported on mesoporous silica Micropor. Mesopor. Mater. 50, 201-208, 2001 Mishra, T., Parida, K.M., Effect of sulfate on the surface and catalytic properties of iron–chromium mixed oxide pillared clay, Journal of Colloid and Interface Science 301, 554–559, 2006 Fuxiang, L., Feng, Y., Yongli, L.., Ruifeng, L., Kechang, X., Direct synthesis of Zr-SBA-15 mesoporous molecular sieves with high zirconium loading: Characterization and catalytic performance after sulfated, Micropor. Mesopor. Mater. 101, 250–255, 2007 Zhao, J., Yue, Y., Hua, W., He, H., Gao, Z., Catalytic activities and properties of sulfated zirconia supported on mesostructured g-Al2O3, Appl. Catal. A: Gen. 336 (1–2), 133-139, 2008. Garg, S., Soni, K., Kumaran, G.M., Bal, R., Gora-Marek, K., Gupta, J.K., Sharma, L.D., Dhar, G.M., Acidity and catalytic activities of sulfated zirconia inside SBA-15, Catal. Today 141, 125–129, 2009 Yüksel, S, Vanadyum ve demir içerikli SBA-15 sentezi ve yüzey sülfatlamasının yapısal özellikler üzerine etkisi, Gazi Üniversitesi, Fen Bilimleri Enstitüsü, Kimya Mühendisliği Bölümü, Yüksek Lisans, 2012 S. Lowell, J.E. Shields, M.A. Thomas, M.M. Thommes, Characterization of porous solids and powders: surface area and pore size and density, Kluwer Academic Publishers, NewYork, 2006, pp. 12, 23, 132. Kilos, B., Nowak, I., Ziolek, M., Tuel, A., Volta, J.C., “Transition metal containing (Nb, V, Mo) SBA-15 molecular sieves- synthesis, characteristic and catalytic activity in gas and liquid phase oxidation”, Stud. Surf. Sci. Catal., 158, 1461-1468, 2005 Zhang, Q., Li, Y., An, D., Wang, Y., “Catalytic behavior and kinetic features of FeOx/SBA-15 catalyst for selective oxidation of methane by oxygen”, Appl. Catal. A: General, 356, 103–111, 2009 Qiang, L., Wen-Zhi, L., Dong, Z., Xi-Feng, Z., “Analytical pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) of sawdust with Al/SBA-15 catalysts”, J. Anal. Appl. Pyroly., 84, 131–138, 2009 O. Aktas, S. Yasyerli, G. Dogu, T. Dogu, Structural variations of MCF and SBA-15-like mesoporous materials as a result of differences in synthesis solution pH, Mat. Chem. Phys. 131, 151–159, 2011 Balcı, S., Gökçay, E., “Effects of drying methods and calcination temperature on the physicochemical properties of iron intercalated clays”, Mater. Chem. Phys., 76, 46-51, 2002 Moronta, A., Oberto, T., Carruyo, G., Solano, R., Sanchez, J., Gonzalez, E., Huerta, L., “Isomerization of 1-butene catalyzed by ion-exchanged, pillared and ion exchanged/pillared clays”, App. Catal. A. General, 334, 173-178, 2008 Yuan, P., Bergaya, F.A., Tao, Q., “A combined study by XRD, FTIR, TG and HRTEM on the structure of delaminated Fe-intercalated/pillared clay”, J. Colloid Inter. Sci., 324, 142-149, 2008 Balcı, S., Gökçay, E., “Pore structure and surface acidity evaluation of Fe-PILCs”, Turk J. Chem., 33, 843-856, 2009