Microgravity - Science and Technology

, Volume 19, Issue 2, pp 5–11 | Cite as

The catalytic activity of space versus terrestrial synthesized zeolite Beta catalysts in the Meerwein Ponndorf Verley Reactions: Support for PFAL as the Lewis active site for cis-alcohol selectivity

  • Burcu Akata
  • Trevor L. Goodrich
  • Katherine S. Ziemer
  • Albert Sacco


The Lewis activity of the Meerwein-Ponndorf-Verley (MPV) reactions is hypothesized to be due to partial framework aluminum (PFAl) that is either octahedrally or tri-coordinated. Crystals grown in the free-fall environment of low earth orbit (LEO) are more uniform; that is, have fewer lattice “defects” compared to those grown in a gravity field (i.e., on earth). Therefore, crystals grown in orbit should be less catalytically active relative to their earth grown counterparts. The catalytic activity towards the MPV reaction, and the associated IR and XPS spectrum for zeolite Beta that was synthesized on earth (1g) and aboard the International Space Station (10−3–10−5g) were compared in their as-synthesized forms, and after applying heat treatment protocols designed to stress the crystal structure to generate Lewis acid sites (i.e., tri and octahedrally coordinated PFAl). The activity of the MPV reaction and cis-alcohol selectivity over the heat-treated flight samples was observed to be lower than the identically heat-treated terrestrial zeolite Beta samples. Higher MPV activity as well as cis-alcohol selectivity is related to both a higher number of partial framework Al atoms (PFAl), and a constrained pore volume. As PFAl are created by the destruction of the framework upon heat treatment, flight samples were shown to be thermally more stable with fewer lattice defects and less associated stress in zeolite Beta crystals. The changes observed in the IR spectra, as well as the XPS Al Auger and 2p peaks, of the terrestrial samples support this conclusion. Additionally, the flight samples showed higher tr-alcohol selectivity, which implies more pore volume and less channel blockage. This is consistent with the fact that crystals grown in space have less stress, fewer lattice defects, and thus there are fewer channel obstructions.


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  1. [1]
    Creyghton, E.J., Ganeshie, S.D., Downing, R.S., van Bekkum, H.: Stereoselective reduction of 4-tert-butylcyclohexanone tocis-4-tert-butyl-cyclohexanol catalysed by zeolite BEA. J. Chem. Soc. Chem. Commun. p. 1859 (1995)Google Scholar
  2. [2]
    Jansen, J.C., Creyghton, E.J., Njo, S.L., van Koningsveld, H., van Bekkum, H.: On the remarkable behaviour of zeolite Beta in acid catalysis. Catal. Today, vol. 38, p. 205 (1997)CrossRefGoogle Scholar
  3. [3]
    van der Waal, J.C., Creyghton, E.J., Kunkeler, P.J., Tan, K. van Bekkum, H.: Beta-type zeolites as selective and regenerable catalysis in the Meerwein-Ponndorf-Verley reduction of carbonyl compounds. Topics Catal, vol. 4, p. 261 (1997)CrossRefGoogle Scholar
  4. [4]
    Creyghton, E.J., Ganeshie, S.D., Downing, R.S., van Bekkum, H.: Stereoselective Meerwein-Ponndorf-Verley and Oppenauer reactions catalysed by zeolite BEA. J. Mol. Catal. A. vol. 115, p. 457 (1997)CrossRefGoogle Scholar
  5. [5]
    Satterfield C.N.: Heterogeneous Catalysis in Industrial Practice, Krieger Publishing Company, Malabar, Florida, New York (1991)Google Scholar
  6. [6]
    Kunkeler, P.J., Zuurdeeg, B.J., van der Waal, J.C., van Bokhoven, J.A., Koningsberger, D.C., van Bekkum, H.: Zeolite Beta: The relationship between calcination procedure, aluminum configuration, and Lewis acidity. J. Catal. v. 180, p. 234 (1998)CrossRefGoogle Scholar
  7. [7]
    Bortnovsky, O., Sobalik, Z., Wichterlova, B., Bastl, Z.: Structure of Al-Lewos Site in Beta Zeolite Active in the Meerwein-Ponndorf-Verley Reduction of Ketone to Alcohol. J. Catal. v. 210, p. 171 (2002)CrossRefGoogle Scholar
  8. [8]
    Sand, L.B., Sacco, A., Thompson, R.W., Dixon, A.G.: Large zeolite crystals: their potential growth in space. Zeolites vol. 7, p. 387 (1987)CrossRefGoogle Scholar
  9. [9]
    Sacco Jr.,A.: Proc. Soc. Photo-opt. Instrum. Eng.: Large zeolites: why and how to grow in space. v. 1557, p. 6 (1991)Google Scholar
  10. [10]
    Akata, B., Yilmaz, B., Jirapongphan, S.S., Warywoda, J., Sacco Jr,A.: Characterization of zeolite Beta grown in microgravity. Micropor. Mesopor. Mater. v. 71, p. 1 (2004)CrossRefGoogle Scholar
  11. [11]
    Kiricsi, I., Flego, C., Pazzuconi, G., Parker Jr.W.O., Millini, R., Perego, C., Bellussi, G.: Progress toward Understanding Zeolite Beta Acidity: An IR and 27AI NMR Spectroscopic Study. J. Phys. Chem. v. 98, p. 4627 (1994)CrossRefGoogle Scholar
  12. [12]
    Perez-Pariente, J., Martens, J.A., Jacobs, P.A.: Crystallization Mechanism of Zeolite Beta From (TEA)//2O, NA//2O and K//2O Containing Aluminosilicate Gels. Applied Catal. v. 31, p. 35 (1987)CrossRefGoogle Scholar
  13. [13]
    Kaushik, V.K., Bhat, S.G.T., Corbin, D.R.: Surface composition and electronic structure of zeolites using X-ray photoelectron spectroscopy. Zeolites v. 13, p. 671 (1993)CrossRefGoogle Scholar
  14. [14]
    Collignon, F., Jacobs, P.A., Gorbet, P., Poncelet, G.: Investigation of the coordination state of aluminum in β zeolites by X-ray photoelectron spectroscopy. J. Phys. Chem. B v. 105, p. 6812 (2001)CrossRefGoogle Scholar
  15. [15]
    Borade, R., Sayari, A., Adnot, A., Kaliaguine, S.: XPS study of acid sites in dehydroxylated Y zeolites. J. Phys. Chem. v. 94, p. 5989 (1990)CrossRefGoogle Scholar
  16. [16]
    Akata, B., Warzywoda, J., Sacco Jr,A.: Gas Phase Meerwein-Ponndorf-Verley Reaction: Correlation of the 3665 cm-1 IR Band with theCis-Alcohol Selectivity. J. Catal. v. 222, p. 397 (2004)CrossRefGoogle Scholar
  17. [17]
    Bourgeat-Lami, E., Massiani, P., Di Renzo, F., Espiau, P., Fajula, F., des Courieres, T.: Study of the state of aluminum in zeolite-Beta. Appl. Catal. v. 72, p. 139 (1991)CrossRefGoogle Scholar
  18. [18]
    Kunkeler, P.J., Zuurdeeg, B.J., van der Waal, J.C., van Bokhoven, J.A., Koningsberger, D.C., van Bekkum, H.: Zeolite Beta: The relationship between Calcination Procedure, Aluminum Configuration, and Lewis Acidity. J. Catal. v. 180, p. 234 (1998)CrossRefGoogle Scholar
  19. [19]
    van Bokhoven, J.A., Koningsberger, D.C., Kunkeler, P., van Bekkum, H.: Influence of Steam Activation on Pore Structure and Acidity of Zeolite Beta: An Al K Edge XANES Study of Aluminum Coordination. J. Catal. v. 211, p. 540 (2002)CrossRefGoogle Scholar
  20. [20]
    Yang, C. Xu, Q.: States of aluminum in zeolite Beta and influence of acidic or basic medium. Zeolites v. 19, p. 404 (1997)CrossRefGoogle Scholar
  21. [21]
    Vimont, A., Thibault-Starzyk, F., Lavalley, J.C.: Infrared Spectroscopic Study of the Acidobasic Properties of Beta Zeolite. J. Phys. Chem. B. v. 104, p. 286 (2000)CrossRefGoogle Scholar
  22. [22]
    Jia, C., Massiani, C.P., Barthomeuf, D.: Characterization by infrared and nuclear magnetic resonance spectroscopies of calcined beta zeolite. J. Chem Soc. Faraday Trans. v. 89, p. 3659 (1993)CrossRefGoogle Scholar
  23. [23]
    Loeffler, E., Lohse, U., Peuker, C., Oehlmann, G., Kustov, L.M., Zholobenko, V.L., Kazansky, V.B.: Study of different states of nonframework aluminum in hydrothermally dealuminated HZSM-5 zeolites using diffuse reflectance i.r. spectroscopy. Zeolites v. 10, p. 266 (1990)CrossRefGoogle Scholar

Copyright information

© Z-Tec Publishing 2007

Authors and Affiliations

  • Burcu Akata
    • 2
  • Trevor L. Goodrich
    • 3
  • Katherine S. Ziemer
    • 1
  • Albert Sacco
    • 1
  1. 1.Center for Advanced Microgravity Materials Processing, Department of Chemical EngineeringNortheastern UniversityBostonUSA
  2. 2.Central LaboratoryMiddle East Technical UniversityAnkaraTurkey
  3. 3.Department of Chemical EngineeringNortheastern UniversityBostonUSA

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