Characterization and Catalytic Performance of Montmorillonites with Mixed Aluminium/Lanthanide Pillars



Pillared montmorillonites with mixed Al/lanthanide pillars were prepared. The materials present characteristics that are very different from montmorillonite pillared with only aluminium. Nuclear magnetic resonance studies indicated total absence of tetrahedral aluminium in the pillars when lanthanide cations are incorporated between the clay layers. They have a high thermal stability, high specific surface area and porosity, with pores at the limit between the microporosity and mesoporosity. The textural parameters maintained high values up to 700 °C. The number and the strength of the acid sites in these materials were also high. The increase of the conversion in dehydration of 1-butanol as in hydroisomerization of n-heptane shows their better behaviour as acid catalysts. The Al/lanthanide-pillared samples showed increased conversion and improved the selectivity towards the products of cracking. The study of 1-butanol dehydration showed that there is an increase in the acidity, thermal stability and smaller deactivation by carbonaceous deposits in the Al/lanthanide-pillared sample.


Montmorillonites Al/lanthanide Pillared clays 


  1. 1.
    Figueras F (1988) Pillared clay as catalysts. Catal Rev Sci Eng 30:457CrossRefGoogle Scholar
  2. 2.
    Tichit D, Fajula F, Figueras F, Ducouraut B, Mascherpa G, Gueguen D, Bousquet J (1988) Sintering of montmorillonites pillared by hydroxy-aluminum species. Clays Clay Miner 36:369CrossRefGoogle Scholar
  3. 3.
    Martin-Luengo MA, Martins-Carvalho H, Ladriere J, Grange P (1989) Fe(iii)-pillared montmorillonites – preparation and characterization. Clay Miner 24:495CrossRefGoogle Scholar
  4. 4.
    Figueras F, Martrod-Bashi A, Fetter G, Thrierr A, Zanchetta JV (1989) Preparation and thermal-properties of Zr-intercalated clays J Catal 119:91Google Scholar
  5. 5.
    Choudary BM, Valli VLK (1990) A novel vanadium pillared montmorillonite catalyst for molecular recognition of benzyl alcohols. J Chem Soc Chem Commun 16:1115Google Scholar
  6. 6.
    Kloprogge JT (1998) Synthesis of smectites and porous pillared clay catalysts: a review. J Porous Mater 5:5CrossRefGoogle Scholar
  7. 7.
    Gil A, Gandia LM, Vicente MA (2000) Recent advances in the synthesis and catalytic applications of pillared clays. Catal Rev Sci Eng 42:145CrossRefGoogle Scholar
  8. 8.
    Gil A, Korili SA, Vicente MA (2008) Recent advances in the control and characterization of the porous structure of pillared clay catalysts. Catal Rev Sci Eng 50(2):153CrossRefGoogle Scholar
  9. 9.
    Mitchell IV (1990) Pillared layered structures: current trends and applications. Elsevier Applied Science, LondonGoogle Scholar
  10. 10.
    Kikuchi E, Matsuda T (1988) Shape selective acid catalysis by pillared clays. Catal Today 2:297CrossRefGoogle Scholar
  11. 11.
    Mokaya R, Jones W (1995) Pillared clays and pillared acid-activated clays: a comparative study of physical, acidic, and catalytic properties. J Catal 153:76CrossRefGoogle Scholar
  12. 12.
    Hernando MJ, Pesquera C, Blanco C, González F (2002) Langmuir Increase in thermal stability of the texture in montmorillonites pillared with Al/Ce polyoxocations 18(14):5633Google Scholar
  13. 13.
    Zhu HY, Vansant EF, Xia JA, Lu GQ (1997) Porosity and thermal stability of montmorillonite pillared with mixed oxides of lanthanum, calcium and aluminium. J Porous Mater 4:17CrossRefGoogle Scholar
  14. 14.
    Cañizares P, Valverde JL, Sun Kou R, Molina CB (1999) Synthesis and characterization of PILCs with single and mixed oxide pillars prepared from two different bentonites. A comparative study. Micropor Mesopor Mater 29:267CrossRefGoogle Scholar
  15. 15.
    González F, Pesquera C, Benito I, Mendioroz S, Poncelet G (1992) High conversion and selectivity for cracking of n-heptane on cerium-aluminium-montmorillonite catalysts. J Chem Soc Chem Commun 6:491CrossRefGoogle Scholar
  16. 16.
    Hernando MJ, Pesquera C, Blanco C, Benito I, González F (1996) General, effect of Ce on catalytic properties of pillared montmorillonite wiyh Al- and GaAl-polyoxications. Appl Catal A 141:175CrossRefGoogle Scholar
  17. 17.
    López-Ortega A, Domínguez JM, Rojas-Hernández A, Benítez-Patricio A, Salmon M (1996) Synthesis and characterization of Ln/Al pillared clays. Mater Res Soc Conf Symp 431:51CrossRefGoogle Scholar
  18. 18.
    Flego C, Galasso L, Millini R, Kiricsi I (1998) General, The influence of the composition on the thermal and acid characteristics of multi-component oxide pillared montmorillonite. Appl Catal A 168:323CrossRefGoogle Scholar
  19. 19.
    Pires J, Machado M, de Carvalho MB (1998) J Mater Chem 8:1465CrossRefGoogle Scholar
  20. 20.
    Fetter G, Salas P, Velazquez LA, Bosch P (2000) Ce-Al-Pillared clays: synthesis, characterization, and catalytic performance. Ind Eng Chem Res 39:1944CrossRefGoogle Scholar
  21. 21.
    Hernando MJ (2000) Sintesis y caracterizacion de montmorillonitas apilaradas con aluminio modificadas por incorporacion de galio y cerio. Thesis, University of Cantabria, Santander, SpainGoogle Scholar
  22. 22.
    Hernando MJ, Pesquera C, Blanco C, González F (2001) Synthesis, characterization, and catalytic properties of pillared montmorillonite with aluminum/cerium polyoxycations. Chem Mater 13:2154CrossRefGoogle Scholar
  23. 23.
    Sterte J (1991) Preparation and properties of large-pore La-Al-pillared montmorillonite. Clays Clay Miner 39:167CrossRefGoogle Scholar
  24. 24.
    McCauley JR (1989) Stable intercalated clays and preparation method. US Patent 4,818,737Google Scholar
  25. 25.
    Hernando MJ, Pesquera C, Blanco C, Benito I, González F (1996) Differences in structural, textural, and catalytic properties of montmorillonite pillared with (GaAl12) and (AlAl12) polyoxycations. Chem Mater 8:76CrossRefGoogle Scholar
  26. 26.
    Pesquera C, González F, Benito I, Mendioroz S, Pajares JA (1991) Synthesis and characterization of pillared montmorillonite catalysts. Appl Catal 67:97Google Scholar
  27. 27.
    González F, Pesquera C, Blanco C, Benito I, Mendioroz S (1992) Synthesis and characterization of Al-Ga pillared clays with high thermal and hydrothermal stability. Inorg Chem 31:727CrossRefGoogle Scholar
  28. 28.
    Plee D, Borg F, Gatineau L, Fripiat JJ (1985) High-resolution solid-state 27Al and 29Si Nuclear Magnetic Resonance study of pillared clays. J Am Chem Soc 107:2362CrossRefGoogle Scholar
  29. 29.
    Fripiat JJ (1987) High resolution solid state NMR study of pillared clays. Catal Today 2:281CrossRefGoogle Scholar
  30. 30.
    Macias O, Largo J, Pesquera C, Blanco C, González F (2006) General, Characterization and catalytic properties of montmorillonites pillared with aluminum/lanthanum. Appl Catal A 314:23CrossRefGoogle Scholar
  31. 31.
    Gregg SJ, Sing KSW (1991) Adsorption surface area and porosity. Academic, LondonGoogle Scholar
  32. 32.
    Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T (1985) Reporting physisorption data for gas solid systems with special reference to the determination of surface-area and porosity. Pure Appl Chem 57:603CrossRefGoogle Scholar
  33. 33.
    Barrett EP, Joyner LG, Halenda PP (1951) The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms. J Am Chem Soc 73:373CrossRefGoogle Scholar
  34. 34.
    Olivier JP (1995) Modeling physical adsorption on porous and nonporous solids using Density Functional Theory. J Porous Mater 2:9CrossRefGoogle Scholar
  35. 35.
    Parry ER (1963) An infrared study of pyridine adsorbed on acidic solids: characterization of surface acidity. J Catal 2:371CrossRefGoogle Scholar
  36. 36.
    Wojciechowski BW, Corma A (1986) Catalytic cracking. Marcel Dekker, New YorkGoogle Scholar
  37. 37.
    Moreno S, Sun Kou R, Poncelet G (1996) Hydroconversion of heptane over Pt/Al-pillared montmorillonites and saponites. J Catal 162:198CrossRefGoogle Scholar
  38. 38.
    Wang X, Li C, Wang Y, Cai T (2004) n-Heptane isomerization over mesoporous MoOx and Ni-MoOx catalysts. Catal Today 93:135CrossRefGoogle Scholar
  39. 39.
    Roldán R, Romero FJ, Jiménez-Sanchidrián C, Marinas JM, Gómez JP (2005) General, Influence of acidity and pore geometry on the product distribution in the hydroisomerization of light paraffins on zeolites. Appl Catal A 288:104CrossRefGoogle Scholar
  40. 40.
    Berteau P, Ceckiewicz S, Delmon B (1987) Role of the acid-base properties of aluminas, modified gamma-alumina, and silica-alumina in 1-butanol dehydration. Appl Catal 31:361CrossRefGoogle Scholar
  41. 41.
    Guiu G, Grange P (1995) Acidic and catalytic properties of SiO2-Ta2O5 mixed oxides prepared by the sol-gel method. J Catal 156:132CrossRefGoogle Scholar
  42. 42.
    Bautista FM, Delmon B (1995) General, 1-Butanol dehydration on AlPO4 and modified AlPO4: catalytic behaviour and deactivation. Appl Catal A 130:47CrossRefGoogle Scholar
  43. 43.
    Gil A, Vicente MA, Korili SA (2005) Effect of the Si/Al ratio on the structure and surface properties of silica-alumina-pillared clays. J Catal 229:119CrossRefGoogle Scholar
  44. 44.
    Delsarte S, Grange P (2004) General, Butan-1-ol and butan-2-ol of dehydration on nitrided aluminophosphates: influence of nitridation on reaction pathways. Appl Catal A 259:269CrossRefGoogle Scholar
  45. 45.
    Noller H, Lercher JA, Vinek H (1988) Acidic and basic sites of maim group mixed metal oxides. Mater Chem Phys 18:577CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC 2010

Authors and Affiliations

  1. 1.Inorganic Chemistry Group, Department of Chemical Engineering and Inorganic ChemistryUniversity of CantabriaCantabriaSpain

Personalised recommendations