Hostname: page-component-76fb5796d-2lccl Total loading time: 0 Render date: 2024-04-27T07:41:31.229Z Has data issue: false hasContentIssue false
  • English
  • Français

Evaluation of the Acidity of Pillared Montmorillonites by Pyridine Adsorption

Published online by Cambridge University Press:  28 February 2024

M. R. Sun Kou ,
S. Mendioroz  and
V. Muñoz
M. R. Sun Kou
Affiliation:
Instituto de Catálisis y Petroleoquímica, Campus UAM, Cantoblanco, 28049 Madrid, Spain
S. Mendioroz*
Affiliation:
Instituto de Catálisis y Petroleoquímica, Campus UAM, Cantoblanco, 28049 Madrid, Spain
V. Muñoz
Affiliation:
Departamento de Química Inorgánica y Química Técnica U.N.E.D., Senda del Rey s/n, 28040 Madrid, Spain
*
E-mail of corresponding author: smendioroz@icp.csic.es
Get access Rights & Permissions [Opens in a new window]

Abstract

Two series of pillared clays were prepared from a purified montmorillonite (95%) from La Serrata of Nijar, Spain, and polycations of Al and Zr using various methods. The effect of both the pillaring cation and the procedure of preparation on the physicochemical characteristics of the resulting materials was studied. Changes in texture were determined by X-ray diffraction (XRD) and N2 adsorption at 76 K and changes in acidity were determined by thermogravimetry following pyridine adsorption at room temperature and further desorption at a constant heating rate of 10 K min−1 in the range of 298–623 K. The relation between the size and charge (n/q) of the pillaring cation, which is dependent on the degree of cation hydrolysis, is the main factor affecting pore size and acidity of the synthesized materials. The pH of the pillaring solution affects the stability of the parent clay and the properties of the pillared clay. Below a pH of 3 and depending on contact time, the montmorillonite may delaminate and partially dissolve to produce products that affect the properties of the resulting materials. Microporosity increases for both Al or Zr-pillared clays. For Zr-pillared clays, microporosity is accompanied by changes in the mesoporosity and macroporosity as a result of clay delamination. Acidity dramatically increases by pillaring, especially strong acidity, and the acid strength distribution depends on starting salt concentration, aging time, and temperature.

Keywords

AcidityAl-Pillared MontmorilloniteMesoporous MaterialsPyridine AdsorptionZr-Pillared Montmorillonite
Type
Research Article
Information
Clays and Clay Minerals , Volume 48 , Issue 5 , October 2000 , pp. 528 - 536
Copyright
Copyright © 2000, The Clay Minerals Society

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Aharoni, C., (1984) Kinetics of adsorption: the S-Shaped z-t plot Adsorption Science and Technology 1 1–29 10.1177/026361748400100101.CrossRefGoogle Scholar
Auer, H. and Hofmann, H., (1993) Pillared clays. Characterization of acidity and catalytic properties and comparison with some zeolites Applied Catalysis A 97 23–28 10.1016/0926-860X(93)80064-W.CrossRefGoogle Scholar
Barrer, R.M., (1984) Sorption and molecular sieve properties of clays and their importance as catalysts Philadelphia Transactions. Royal Society London 311 333–352 10.1098/rsta.1984.0032.Google Scholar
Barrer, R.M., (1989) Shape selective sorbents based on clay minerals: A review Clays and Clay Minerals 37 385–395 10.1346/CCMN.1989.0370501.CrossRefGoogle Scholar
Barrer, R.M. and McLeod, D.M., (1954) Intercalation and sorption by montmorillonite Transactions of the Faraday-Society 50 980–989 10.1039/tf9545000980.CrossRefGoogle Scholar
Barrer, R.M. and McLeod, D.M., (1955) Activation of montmorillonite by ion exchange and sorption complexes of tetra-alkylammonium montmorillonites Transactions of the Faraday Society 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 distribution in porous substances. A computation from N2 isotherms Journal of the American Chemical Society 73 373–380 10.1021/ja01145a126.CrossRefGoogle Scholar
Bartley, G.J. and Burch, R., (1985) Zr-containing pillared interlayer clays. Influence of method of preparation on the thermal and hydrothermal stability Applied Catalysis 19 175–185 10.1016/S0166-9834(00)82679-2.CrossRefGoogle Scholar
Bartley, J., (1988) Zirconium pillared clays Catalysis Today 2 233–241 10.1016/0920-5861(88)85006-5.CrossRefGoogle Scholar
Brunauer, S. Emmett, P.H. and Teller, E., (1938) Adsorption of gases in multimolecular layers Journal of the American Chemical Society 62 1723–1732 10.1021/ja01864a025.CrossRefGoogle Scholar
Bodoardo, S F E and Garrone, E., (1994) IR study of Brönsted acidity of Al-pillared montmorillonite Journal of Catalysis 147 223–230 10.1006/jcat.1994.1133.CrossRefGoogle Scholar
Bodoardo, S. Chiappetta, R Onida B F E and Garrone, E., (1998) Ammonia interaction and reaction with Al-pillared montmorillonite: An IR study Microporous and Mesoporous Materials 20 187–196 10.1016/S1387-1811(97)00034-6.CrossRefGoogle Scholar
Carrado, K.A. Hayatsu, R. Botto, R.E. and Winans, R.E., (1990) Reactivity of anisoles on clay and pillared clay surfaces Clays and Clay Minerals 38 250–256 10.1346/CCMN.1990.0380303.CrossRefGoogle Scholar
Cornet, I., (1943) Sorption of NH3 on montmorillonitic clay Journal of Chemical Physics 11 217–226 10.1063/1.1723832.CrossRefGoogle Scholar
Defay, R. Prigogine, I. Bellemans, A. and Everett, D.H., (1966) Surface Tension and Adsorption London Longmans.Google Scholar
Fripiat, J.J., (1988) High resolution solid state NMR study of pillared clays Catalysis Today 2 281–295 10.1016/0920-5861(88)85010-7.CrossRefGoogle Scholar
Gregg, S.J. and Sing, K.S.W., (1982) Adsorption, Surface Area and Porosity London Academic Press.Google Scholar
Gutierrez Rios, E., (1949) Bentonitas Espaholas Madrid Consejo Superior de Investigaciones Científicas 32–33.Google Scholar
Hashimoto, K. Hanada, Y. Minami, Y. and Kera, Y., (1996) Conversion of methanol to dimethyl ether and formaldehyde over alumina intercalated in a montmorillonite Applied Catalysis A 141 57–69 10.1016/0926-860X(96)00058-0.CrossRefGoogle Scholar
Harkins, W.D. and Jura, G., (1944) Surface of solids. X. Extension of the attractive energy of a solid into an adjacent liquid or film, the decrease of energy with distance, and the thickness of films Journal of the American Chemical Society 66 919–927 10.1021/ja01234a024.CrossRefGoogle Scholar
IUPAC, International PureApplied Chemistry, (1985) Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity Pure and Applied Chemistry 57 609–617.Google Scholar
Jones, S.L., (1988) The preparation and solution chemistry of Al(III) and Zr(IV) pillaring species Catalysis Today 2 209–216 10.1016/0920-5861(88)85004-1.CrossRefGoogle Scholar
Lahav, N. Shani, U. and Shabtai, J., (1978) Cross linked smectites I. Synthesis and properties of hydroxy-aluminium montmorillonite Clays and Clay Minerals 26 107–115 10.1346/CCMN.1978.0260205.CrossRefGoogle Scholar
Lippens, B.C. and de Boer, J.W., (1965) Studies on pore systems in catalysis. V. The t method Journal of Catalysis 4 319–323 10.1016/0021-9517(65)90307-6.CrossRefGoogle Scholar
McLellan, A.L. and Harnsberger, H.F., (1967) Cross-sectional areas of molecules adsorbed on solids surface Journal of Colloid Interface Science 23 577–599 10.1016/0021-9797(67)90204-4.CrossRefGoogle Scholar
Mendioroz, S. Pajares, J.A. Benito, I. Pesquera, C G E and Blanco, C., (1987) Texture evolution of montmorillonite under progressive acid treatment: Change from H3 to H2 type of hysteresis Langmuir 3 676–681 10.1021/la00077a017.CrossRefGoogle Scholar
Miehé-Brendlé, J. Khouchaf, L. Baron, J. Le Dred, R. and Tuilier, M.H., (1997) Zr-exchanged and pillared beidellite: Preparation and characterization by chemical analysis, XRD and Zr K EXAFS Microporous Materials 11 171–183 10.1016/S0927-6513(97)00041-2.CrossRefGoogle Scholar
Ming Yuan, H. Liu, Z. and Enze, M., (1988) Acidic and hydrocarbon catalytic properties of pillared clays Catalysis Today 2 321–338 10.1016/0920-5861(88)85013-2.CrossRefGoogle Scholar
Occelli, M.L., (1986) New routes to the preparation of pillared montmorillonite catalysis Journal of Molecular Catalysis 35 377–389 10.1016/0304-5102(86)87085-7.CrossRefGoogle Scholar
Occelli, M.L. and Tindwa, R.M., (1983) Physicochemical properties of montmorillonite interlayered with cationic ox-yaluminum pillars Clays and Clay Minerals 31 22–28 10.1346/CCMN.1983.0310104.CrossRefGoogle Scholar
Pesquera, C. Gonzalez, F. Benito, I. Mendioroz, S. and Pajares, J. A., (1991) Synthesis and characterization of pillared montmorillonite catalysis Applied Catalysis 69 97–104 10.1016/S0166-9834(00)83294-7.CrossRefGoogle Scholar
Ross, C.S. and Hendricks, S.B., (1945) Minerals of the Montmorillonite Group Washington, D.C. U.S. Geological Survey Professional Paper 205-B.Google Scholar
Schönherr, S. Gotz, H. Bertram, R. Muller, D. and Gessner, W., (1983) Basic aluminum salt and its solutions Zeitschrift für Anorganische und Allgemeine Chemie 502 113–118 10.1002/zaac.19835020715.CrossRefGoogle Scholar
Serratosa, J.M. Rausell-Colom, J.A. and Sanz, J., (1984) Charge density and its distribution in phillosilicates: Effect of the arrangement and reactivity of the adsorbed species Journal of Molecular Catalysis 27 225–234 10.1016/0304-5102(84)85082-8.CrossRefGoogle Scholar
Sterte, J., (1986) Synthesis and properties of titanium oxide cross-linked montmorillonite Clays and Clay Minerals 34 658–664 10.1346/CCMN.1986.0340606.CrossRefGoogle Scholar
Sterte, J., (1988) Hydrothermal treatment of hydroxycation precursor solutions Catalysis Today 2 219–230 10.1016/0920-5861(88)85005-3.CrossRefGoogle Scholar
Sun Kou, M.R. Mendioroz, S. and Guijarro, I., (1998) A thermal study of Zr-pillared montmorillonite Thermochim-ica Acta 323 145–157 10.1016/S0040-6031(98)00540-1.CrossRefGoogle Scholar
Tichit, D. Mountassir, Z. Figueras, F. Auroux, A., Poncelet, G. Jacobs, P.A. Grange, P. and Delmon, B., (1991) Control of the acidity of montmorillonites pillared by Al-hydroxy cationic species Preparation of Catalysts V Amsterdam Elsevier Science Publishers 345–353.Google Scholar
Tokarz, M. and Shabtai, J., (1985) Cross-linked smectites. IV. Preparation and properties of hydroxyaluminum-pillared Ce- and La-montmorillonites and fluorinated NH4 +-mont-morillonites Clays and Clay Minerals 33 89–98 10.1346/CCMN.1985.0330202.CrossRefGoogle Scholar
Vaugham, D.E.W. Lussier, R.J. and Magee, J.S., (1981) Stabilized pillared clays .Google Scholar
Yamanaka, S. and Brindley, G.W., (1978) Hydroxy-nickel in-terlayering in montmorillonite by titration method Clays and Clay Minerals 26 21–28 10.1346/CCMN.1978.0260102.CrossRefGoogle Scholar
Yamanaka, S. and Brindley, G.W., (1979) High surface area solids obtained by reaction of montmorillonite with zyr-conyl chloride Clays and Clay Minerals 27 119–124 10.1346/CCMN.1979.0270207.CrossRefGoogle Scholar