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Properties and Characterization of Al2O3 and SiO2-TiO2 Pillared Saponite

Published online by Cambridge University Press:  28 February 2024

P. B. Malla  and
S. Komarneni
P. B. Malla
Affiliation:
Research and Development, Thiele Kaolin Company, P.O. Box 1056, Sandersville, Georgia 31082
S. Komarneni*
Affiliation:
Materials Research Laboratory, The Pennsylvania State University, University Park, Pennsylvania 16802
*
*Department of Agronomy, USA
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Abstract

A saponite pillared with a single (Al2O3) or a mixed (SiO2-TiO2) oxide exhibited basal spacings of 16–19 and 30–40Å, respectively. The pillared structures were found to be stable up to 700°C. Water, nitrogen, and high resolution argon adsorption were used to study the effect of thermal treatments on surface chemistry, pore structure, and surface area of these pillared clays. The pillared saponites exhibited a hydrophobic behavior at temperatures > 500°C, whereas such behavior was observed at ≥300°C for montmorillonite. Most of the micropores in the Al2O3 pillared clays were < 10 Å, whereas the SiO2-TiO2 pillared clays showed a broad distribution of pores in both micropore and mesopore regions. The SiO2-TiO2 pillared samples possessed higher surface area compared with Al2O3 pillared clays. The percent decrease in surface area was smaller for pillared saponites compared with pillared montmorillonites when calcined from 300° to 700°C, indicating a higher thermal stability of the former. The pillared clays were also characterized by solid state 27Al and 29Si magic-angle spinning nuclear magnetic resonance (MAS/NMR) spectroscopy. There was no direct evidence of cross-linking (covalent bonding between the clay layer and pillar) in montmorillonite irrespective of the types of pillars. In saponite, however, a significant structural modification took place. 27Al spectra of Al2O3 pillared saponite heated at ≥300°C appear to indicate an increase in AlVI as a result, at least in part, of initiation of hydrolytic splitting of Si-O-Al bonds. The actual release of Al from the tetrahedral sheet probably occurred at a temperature > 500°C and completed around 700°C with the formation of Si-O-Si linkages. The decreased intensity of peak due to Si(1Al) in 29Si spectra of the sample heated at 700°C corroborates the 27Al MAS/NMR results. Additionally, the 29Si spectra indicated a cross-linking between SiO4 (clay sheet) with Al2O3 pillars, which could be achieved by inverting some silica tetrahedra into the interlayer. 27Al and 29Si spectra of SiO2TiO2 pillared saponite also showed the trend similar to that exhibited by Al2O3 pillared saponite, indicating that the crystal chemistry of the host may be more important than the nature of pillars in the structural modification and cross-linking behavior of thermally treated pillared clays.

Keywords

AdsorptionClaysCross-linkingMASNMRMontmorillonitePillared claySaponiteSmectite
Type
Research Article
Information
Clays and Clay Minerals , Volume 41 , Issue 4 , August 1993 , pp. 472 - 483
Copyright
Copyright © 1993, The Clay Minerals Society

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References

Barrer, M. and MacLoed, D. M., 1955 Activation of mont-morillonite by ion exchange and sorption complexes of tet-ra-alkylammoniummontmorillonites Trans. Faraday Soc. 51 1290 – 1300 10.1039/tf9555101290.CrossRefGoogle Scholar
Barrett, E. P., Joyner, L. G. and Halenda, P. P., 1951 The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms J. Am. Chem. Soc. 73 373 – 380 10.1021/ja01145a126.CrossRefGoogle Scholar
Bellaoui, A., Plee, D. and Meriaudeau, P., 1990 Gallium containing pillared interlayer clays. Preparation, characterization and catalytic properties Appl. Catal. 63 L7 – L10 10.1016/S0166-9834(00)81701-7.CrossRefGoogle Scholar
Brindley, G. W. and Sempels, R. E., 1977 Preparation and properties of some hydroxy-aluminum beidellites Clays & Clay Minerals 12 229 – 236 10.1180/claymin.1977.012.3.05.CrossRefGoogle Scholar
Cariati, F., Erre, L., Micera, G., Piu, P. and Gessa, C., 1983 Effect of layer charge on the near-infrared spectra of water molecules in smectites and vermiculites Clays & Clay Minerals 31 447 – 449 10.1346/CCMN.1983.0310606.CrossRefGoogle Scholar
Chen, Y., 1976 Hydrophobic properties of zeolites J. Phys. Chem. 80 60 – 64 10.1021/j100542a013.CrossRefGoogle Scholar
Gonzalez, F., Pesquera, C., Blanco, C., Benito, I. and Men-dioroz, S., 1992 Synthesis and characterization of Al-Ga pillared clays with high thermal and hydrothermal stability Inorg. Chem. 31 727 – 731 10.1021/ic00031a007.CrossRefGoogle Scholar
Gregg, S. J. and Sing, K. S. W., 1982 Adsorption, Surface Area and Porosity 2 New York Academic Press.Google Scholar
Harward, M. E. and Brindley, G. W., 1965 Swelling properties of synthetic smectites in relation to lattice substitutions Clays & Clay Minerals 3 209 – 222.Google Scholar
Harward, M. E., Carstea, D. D. and Sayegh, A. H., 1969 Properties of vermiculites and smectites: Expansion and collapse Clays & Clay Minerals 16 437 – 447 10.1346/CCMN.1969.0160605.CrossRefGoogle Scholar
Horvath, G. and Kawazoe, K., 1983 Methods for the calculation of effective pore size distribution in molecular sieve carbon J. Chem. Eng. Jpn. 16 470 – 475 10.1252/jcej.16.470.CrossRefGoogle Scholar
Ingamells, C. O., 1970 Lithium metaborate flux in silicate analysis Anal. Chemica Acta 52 323 – 334 10.1016/S0003-2670(01)80963-6.CrossRefGoogle Scholar
Jackson, M. L., 1969 Soil Chemical Analysis—Advanced Course 2 Madison, Wisconsin Department Soil Science, University of Wisconsin.Google Scholar
LaCourse, W. C., Kim, S., Hench, L. L. and Ulrich, D. R., 1986 Use of mixed titanium alkoxides for sol-gel processing Science of Ceramic Chemical Processing New York John Wiley & Sons 304 – 310.Google Scholar
McDaniel, C. V., Maher, P. K. and Rabo, J. A., 1976 Zeolite stability and ultrastable zeolites Zeolite Chemistry and Catalysis, 1976, ACS Monograph Washington D.C. American Chemical Society 285 – 331.Google Scholar
Malla, P. B. and Douglas, L. A., 1987 Layer charge properties of smectites and vermiculites: tetrahedral vs. octahedral Soil Sci. Soc. Am. J. 51 1362 – 1366 10.2136/sssaj1987.03615995005100050048x.CrossRefGoogle Scholar
Malla, P. B., Yamanaka, S. and Komarneni, S., 1989 Unusual water vapor adsorption behavior of montmorillonite pillared with ceramic oxides Solid State Ionics 32/33 354 – 362 10.1016/0167-2738(89)90241-5.CrossRefGoogle Scholar
Malla, P. B. and Komarneni, S., 1990a Synthesis of highly microporous and hydrophilic alumina-pillared montmorillonite: Water-sorption study Clays & Clay Minerals 38 363 – 372 10.1346/CCMN.1990.0380405.CrossRefGoogle Scholar
Malla, P. B. and Komarneni, S., 1990b Effect of crystal chemistry on pore structure and hydrophilicity of alumina-pillared smectites: Water sorption study Sci. Geol., Mem. 86 59 – 68.Google Scholar
Medlin, J. H., Suhr, N. H. and Bodkin, J. B., 1969 Atomic absorption analysis of silicate employing LiB02 fusion Atomic Abs. News Lett. 8 25 – 29.Google Scholar
Michot, L. J. and Pinnavaia, T. J., 1992 Improved synthesis of alumina-pillared montmorillonite by surfactant modification Chem. Mater. 4 1433 – 1437 10.1021/cm00024a054.CrossRefGoogle Scholar
Mortland, M. M. and Raman, K. V., 1968 Surface acidity of smectites in relation to hydration, exchangeable cation, and structure Clays & Clay Minerals 16 393 – 398 10.1346/CCMN.1968.0160508.CrossRefGoogle Scholar
Occelli, M. L., Schultz, L. G., van Olphen, H. and Mumpton, F. A., 1987 Surface and catalytic properties of some pillared clays Proc. Int. Clay Conf., Denver, 1985 Bloomington, Indiana The Clay Minerals Society 319 – 323.Google Scholar
Pinnavaia, T. J., Tzou, M., Landau, S. D. and Raythatha, H., 1984 On the pillaring and delamination of smectite clay catalysts by polyoxo cations of aluminum J. Mol. Catal. 27 195 – 212 10.1016/0304-5102(84)85080-4.CrossRefGoogle Scholar
Pinnavaia, T. J., Tzou, M. and Landau, S. D., 1985a New chromia pillared clay catalysts J. Amer. Chem. Soc. 107 4783 – 4785 10.1021/ja00302a033.CrossRefGoogle Scholar
Pinnavaia, T. J., Landau, S. D., Tzou, M. and Johnson, I. D., 1985b Layer cross-linking in pillared clays J. Amer. Chem. Soc. 107 7222 – 7224 10.1021/ja00310a102.CrossRefGoogle Scholar
Plee, D., Borg, F., Gatineau, L. and Fripiat, J. J., 1985 High resolution solid state 27Al and 29Si nuclear magnetic resonance study of pillared clays J. Amer. Chem. Soc. 107 2362 – 2369 10.1021/ja00294a028.CrossRefGoogle Scholar
Plee, D., Borg, F., Gatineau, L. and Fripiat, J. J., 1987 Pillaring processes of smectites with and without tetrahe-dral substitution Clays & Clay Minerals 35 81 – 88 10.1346/CCMN.1987.0350201.CrossRefGoogle Scholar
Robert, M., 1973 The experimental transformation of mica toward smectite. Relative importance of total charge and tetrahedral substitution Clays & Clay Minerals 21 167 – 174 10.1346/CCMN.1973.0210305.CrossRefGoogle Scholar
Schutz, A., Stone, W E E Poncelet, G. and Fripiat, J. J., 1987 Preparation and characterization of bidimensional zeolitic and hydroxy-aluminum solutions Clays & Clay Minerals 35 251 – 261 10.1346/CCMN.1987.0350402.CrossRefGoogle Scholar
Sing, K. S. W., 1985 Reporting physisorption data for gas/solid systems Pure Appl. Chem. 57 603 – 619 10.1351/pac198557040603.CrossRefGoogle Scholar
Sterte, J., 1986 Synthesis and properties of titanium oxide cross-linked montmorillonite Clays & Clay Minerals 35 658 – 664 10.1346/CCMN.1986.0340606.CrossRefGoogle Scholar
Sterte, J. and Shabtai, J., 1987 Cross-linked smectites. V. Synthesis and properties of hydroxy-silicoaluminum mont-morillonites and fluorohectorites Clays & Clay Minerals 35 429 – 439 10.1346/CCMN.1987.0350603.CrossRefGoogle Scholar
Tennakoon, D T B Jones, W. and Thomas, J. M., 1986 Structural aspects of metal-oxide-pillared sheet silicates J. Chem. Soc., Farad. Trans. 182 3081 – 3095 10.1039/f19868203081.CrossRefGoogle Scholar
Tennakoon, D T B Jones, W., Thomas, J. M., Ballantine, J. H. and Purnell, J. H., 1987 Characterization of clay and pillared clay catalysts Solid State Ionics 24 205 – 212 10.1016/0167-2738(87)90161-5.CrossRefGoogle Scholar
Van Olphen, H., 1966 Collapse of potassium montmorillonite clays upon heating—”Potassium fixation” Clays & Clay Minerals 14 393 – 405 10.1346/CCMN.1966.0140134.CrossRefGoogle Scholar
Vaughan, D. E. W., 1988 Pillared clays—A historical perspective Catal. Today 2 187 – 198 10.1016/0920-5861(88)85002-8.CrossRefGoogle Scholar
Weir, J. I. and White, J. L., 1951 Potassium fixation in clay minerals as related to crystal structure Soil Sci. 71 1 – 14 10.1097/00010694-195101000-00001.CrossRefGoogle Scholar
Yamanaka, S. and Brindley, G. W., 1979 High surface area solids obtained by reaction in montmorillonite with zir-conyl chloride Clays & Clay Minerals 27 119 – 124 10.1346/CCMN.1979.0270207.CrossRefGoogle Scholar
Yamanaka, S., Nishihara, T. and Hattori, M., 1987 Preparation and properties of titania pillared clays Materials Chemistry Physics 17 87 – 101 10.1016/0254-0584(87)90050-2.CrossRefGoogle Scholar
Yamanaka, S., Nishihara, T., Hattori, M., Treacy, M M J Thomas, J. M. and White, J. M., 1988 Adsorption and acidic properties of clays pillared with oxide sols Microstructure and Properties of Catalysts, Proc. Materials Research Society, Boston, Massachusetts, 1987 Pittsburgh, Pennsylvania Materials Research Society 283 – 288.Google Scholar
Yamanaka, S., Malla, P. B. and Komarneni, S., 1990 Water adsorption properties of alumina-pillared clays J. Colloid Interface Sci. 134 51 – 58 10.1016/0021-9797(90)90250-R.CrossRefGoogle Scholar
Yamanaka, S., and Komarneni, S., (1991) Apparatus for measuring liquid vapor adsorption and desorption characteristics of a sample: U.S. Patent 5,058,442, October 22, 1991.Google Scholar