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Volume 62, Issue 3
  • ISSN: 2056-5135


The understanding of location and accessibility of zeolite acid sites is a key issue in heterogeneous catalysis. This paper provides a brief overview of Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) characterisation of acidity in zeolites based on the application of test molecules with a diverse range of basicity and kinetic diameters. Many zeolites, including ZSM-5 and BEA, have been characterised by monitoring the interaction between the zeolite acid sites and test molecules, such as 1,3,5-triisopropylbenzene, pyridine and alkylpyridines, to probe the location, accessibility and strength of the Brønsted acid sites. 1,3,5-triisopropylbenzene can be used to distinguish Brønsted acid sites located on the external and internal surface in most medium and large pore channel zeolites. Brønsted acid sites on the external surface of medium pore zeolites can also be quantified using 2,6-di--butyl-pyridine and 2,4,6-trimethylpyridine. It is concluded that using a combination of probe molecules, including co-adsorption experiments, affords differentiation between acid sites located in channels and cavities of different sizes and on the external and internal surfaces of various zeolitic structures.


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  1. Weitkamp J. Solid State Ionics, 2000, 131, (1–2), 175 LINK [Google Scholar]
  2. Corma A. J. Catal., 2003, 216, (1–2), 298 LINK [Google Scholar]
  3. Čejka J., Centi G., Perez-Pariente J., and Roth W. J. Catal. Today, 2012, 179, (1), 2LINK [Google Scholar]
  4. Xu R., Pang W., Yu J., Huo Q., and Chen J. “Chemistry of Zeolites and Related Porous Material: Synthesis and Structure”, John Wiley & Sons (Asia) Pte Ltd, Singapore, 2007, 616 pp [Google Scholar]
  5. Corma A. Chem. Rev., 1997, 97, (6), 2373 LINK [Google Scholar]
  6. van Donk S., Janssen A. H., Bitter J. H., and de Jong K. P. Catal. Rev. Sci. Eng., 2003, 45, (2), 297 LINK [Google Scholar]
  7. Pérez-Ramírez J., Christensen C. H., Egeblad K., Christensen C. H., and Groen J. C. Chem. Soc. Rev., 2008, 37, (11), 2530 LINK [Google Scholar]
  8. Wei Y., Parmentier T. E., de Jong K. P., and Zečević J. Chem. Soc. Rev., 2015, 44, (20), 7234 LINK [Google Scholar]
  9. Milina M., Mitchell S., Crivelli P., Cooke D., and Pérez-Ramírez J. Nat. Commun., 2014, 5, 3922 LINK [Google Scholar]
  10. “Mesoporous Zeolites: Preparation, Characterization and Applications”, eds. García-Martínez J., and Li K. Wiley-VCH Verlag GmbH & Co, Weinheim, Germany, 2015, 608 pp [Google Scholar]
  11. Hadjiivanov K. Adv. Catal., 2014, 57, 99 LINK [Google Scholar]
  12. Zhai D., Li Y., Zheng H., Zhao L., Gao J., Xu C., and Shen B. J. Catal., 2017, 352, 627 LINK [Google Scholar]
  13. Lamberti C., Zecchina A., Groppo E., and Bordiga S. Chem. Soc. Rev., 2010, 39, (12), 4951 LINK [Google Scholar]
  14. Bordiga S., Lamberti C., Bonino F., Travert A., and Thibault-Starzyk F. Chem. Soc. Rev., 2015, 44, (20), 7262 LINK [Google Scholar]
  15. Vimont A., Thibault-Starzyk F., and Daturi M. Chem. Soc. Rev., 2010, 39, (12), 4928 LINK [Google Scholar]
  16. Niwa M., Katada N., and Okumura K. “Characterisation and Design of Zeolite Catalysts: Solid Acidity, Shape Selectivity and Loading Properties”, Springer-Verlag, Berlin, Germany, 2010, 184 pp [Google Scholar]
  17. Busca G. Micro. Meso. Mater., 2017, 254, 3 LINK [Google Scholar]
  18. Sandoval-Díaz L.-E., González-Amaya J.-A., and Trujillo C.-A. Micro. Meso. Mater., 2015, 215, 229 LINK [Google Scholar]
  19. Trombetta M., Busca G., Lenarda M., Storaro L., and Pavan M. Appl. Catal. A: Gen., 1999, 182, (2), 225 LINK [Google Scholar]
  20. Armaroli T., Bevilacqua M., Trombetta M., Milella F., Alejandre A. G., Ramírez J., Notari B., Willey R. J., and Busca G. Appl. Catal. A: Gen., 2001, 216, (1–2), 59 LINK [Google Scholar]
  21. Trombetta M., Armaroli T., Alejandre A. G., Solis J. R., and Busca G. Appl. Catal. A: Gen., 2000, 192, (1), 125 LINK [Google Scholar]
  22. Bevilacqua M., and Busca G. Catal. Commum., 2002, 3, (11), 497 LINK [Google Scholar]
  23. Montanari T., Bevilacqua M., and Busca G. Appl. Catal. A: Gen., 2006, 307, (1), 21 LINK [Google Scholar]
  24. Tzoulaki D., Jentys A., Pérez-Ramírez J., Egeblad K., and Lercher J. A. Catal. Today, 2012, 198, (1), 3 LINK [Google Scholar]
  25. Marie O., Massiani P., and Thibault-Starzyk F. J. Phys. Chem. B, 2004, 108(16), 5073 LINK [Google Scholar]
  26. Maache M., Janin A., Lavalley J. C., and Benazzi E. Zeolites, 1995, 15, (6), 507 LINK [Google Scholar]
  27. Baerlocher C., McCusker L. B., and Olson D. H. ‘MOR: Cmcm’, in “Atlas of Zeolite Framework Types”, 6th Edn., Elsevier Science BV, Amsterdam, The Netherlands, 2007, pp. 218–219 LINK [Google Scholar]
  28. Chua L. M., Hitchcock I., Fletcher R. S., Holt E. M., Lowe J., and Rigby S. P. J. Catal., 2012, 286, 260 LINK [Google Scholar]
  29. Nesterenko N. S., Thibault-Starzyk F., Montouillout V., Yuschenko V. V., Fernandez C., Gilson J.-P., Fajula F., and Ivanova I. I. Micro. Meso. Mater., 2004, 71, (1–3), 157 LINK [Google Scholar]
  30. Nesterenko N. S., Thibault-Starzyk F., Montouilliout V., Yushchenko V. V., Fernandez C., Gilson J.-P., Fajula F., and Ivanova I. I. Kinet. Katal., 2006, 47, (1), 45; translated into English in Kinet. Catal., 2006, 47, (1), 40 LINK [Google Scholar]
  31. Bleken F. L., Barbera K., Bonino F., Olsbye U., Lillerud K. P., Bordiga S., Beato P., Janssens T. V. W., and Svelle S. J. Catal., 2013, 307, 62 LINK [Google Scholar]
  32. Jacobs P. A., and Heylen C. F. J. Catal., 1974, 34, (2), 267 LINK [Google Scholar]
  33. Ordomsky V. V., Murzin V. Y., Monakhova Yu. V., Zubavichus Y. V., Knyazeva E. E., Nesterenko N. S., and Ivanova I. I. Micro. Meso. Mater., 2007, 105, (1–2), 101 LINK [Google Scholar]
  34. Corma A., Fornés V., Forni L., Márquez F., Martínez-Triguero J., and Moscotti D. J. Catal., 1998, 179, (2), 451 LINK [Google Scholar]
  35. Góra-Marek K., Tarach K., and Choi M. J. Phys. Chem. C, 2014, 118, (23), 12266 LINK [Google Scholar]
  36. Oliviero L., Vimont A., Lavalley J.-C., Sarria F. R., Gaillard M., and Maugé F. Phys. Chem. Chem. Phys., 2005, 7, (8), 1861 LINK [Google Scholar]
  37. Onfroy T., Clet G., and Houalla M. Micro. Meso. Mater., 2005, 82, (1–2), 99 LINK [Google Scholar]
  38. Corma A., Rodellas C., and Fornes V. J. Catal., 1984, 88, (2), 374 LINK [Google Scholar]
  39. Armaroli T., Bevilacqua M., Trombetta M., Alejandre A. G., Ramirez J., and Busca G. Appl. Catal. A: Gen., 2001, 220, (1–2), 181 LINK [Google Scholar]
  40. Barbera K., Bonino F., Bordiga S., Janssens T. V. W., and Beato P. J. Catal., 2011, 280, (2), 196 LINK [Google Scholar]
  41. Almutairi S. M. T., Mezari B., Pidko E. A., Magusin P. C. M. M., and Hensen E. J. M. J. Catal., 2013, 307, 194 LINK [Google Scholar]
  42. Holm M. S., Svelle S., Joensen F., Beato P., Christensen C. H., Bordiga S., and Bjørgen M. Appl. Catal. A: Gen., 2009, 356, (1), 23 LINK [Google Scholar]
  43. Thibault-Starzyk F., Vimont A., and Gilson J.-P. Catal. Today, 2001, 70, (1–3), 227 LINK [Google Scholar]
  44. Thibault-Starzyk F., Stan I., Abelló S., Bonilla A., Thomas K., Fernandez C., Gilson J.-P., and Pérez-Ramírez J. J. Catal., 2009, 264, (1), 11 LINK [Google Scholar]
  45. Mlekodaj K., Tarach K., Datka J., Góra-Marek K., and Makowski W. Micro. Meso. Mater., 2014, 183, 54 LINK [Google Scholar]
  46. Sadowska K., Góra-Marek K., and Datka J. J. Phys. Chem. C, 2013, 117, (18), 9237 LINK [Google Scholar]
  47. Zecchina A., Bordiga S., Spoto G., Scarano D., Spanò G., and Geobaldo F. J. Chem. Soc., Faraday Trans., 1996, 92, (23), 4863 LINK [Google Scholar]
  48. Crépeau G., Montouillout V., Vimont A., Mariey L., Cseri T., and Maugé F. J. Phys. Chem. B, 2006, 110, (31), 15172 LINK [Google Scholar]
  49. Daniell W., Topsøe N.-Y., and Knözinger H. Langmuir, 2001, 17, (20), 6233 LINK [Google Scholar]
  50. Traa Y., Sealy S., Weitkamp J., ‘Characterization of the Pore Size of Molecular Sieves Using Molecular Probes’, in “Molecular Sieves: Characterization II”, eds. Karge H. G., and Weitkamp J. 5, Springer-Verlag, Berlin, Germany, 2007, pp. 103–154 LINK [Google Scholar]
  51. Müller M., Harvey G., and Prins R. Micro. Meso. Mater., 2000, 34, (3), 281 LINK [Google Scholar]
  52. Jiang Y., Huang J,, Dai W., and Hunger M. Solid State Nucl. Magn. Reson., 2011, 39, (3–4), 116 LINK [Google Scholar]
  53. Sandoval-Díaz L.-E., González-Amaya J.-A., and Trujillo C.-A. Micro. Meso. Mater., 2015, 215, 229 LINK [Google Scholar]
  54. Lunsford J. H., Rothwell W. P., and Shen W. J. Am. Chem. Soc., 1985, 107, (6), 1540 LINK [Google Scholar]
  55. Rakiewicz E. F., Peters A. W., Wormsbecher R. F., Sutovich K. J., and Mueller K. T. J. Phys. Chem. B, 1998, 102, (16), 2890 LINK [Google Scholar]
  56. Kao H.-M., Yu C.-Y., and Yeh M.-C. Micro. Meso. Mater., 2002, 53, (1–2), 1 LINK [Google Scholar]
  57. Guan J., Li X., Yang G., Zhang W., Liu X., Han X., and Bao X. J. Mol. Catal. A: Chem., 2009, 310, (1–2), 113 LINK [Google Scholar]
  58. Seo Y., Cho K., Jung Y., and Ryoo R. ACS Catal., 2013, 3, (4), 713 LINK [Google Scholar]
  59. Zheng A., Huang S.-J., Wang Q., Zhang H., Deng F., and Liu S.-B. J. Catal., 2013, 34, (3), 436 LINK [Google Scholar]
  60. Zheng A., Liu S.-B., and Deng F. Solid State Nucl. Magn. Reson., 2013, 55–56, 12 LINK [Google Scholar]
  61. Zheng A., Deng F., and Liu S.-B. Ann. Rep. NMR Spectrosc., 2014, 81, 47 LINK [Google Scholar]
  62. Hernandez-Tamargo C. E., Roldan A., and de Leeuw N. H. J. Phys. Chem. C, 2016, 120, (34), 19097 LINK [Google Scholar]
  63. Zheng A., Li S., Liu S.-B., and Deng F. Acc. Chem. Res., 2016, 49, (4), 655 LINK [Google Scholar]
  64. Zhao R., Zhao Z., Li S., and Zhang W. J. Phys. Chem. Lett., 2017, 8, (10), 2323 LINK [Google Scholar]
  65. Zheng A., Huang S.-J., Liu S.-B., and Deng F. Phys. Chem. Chem. Phys., 2011, 13, (33), 14889 LINK [Google Scholar]
  66. Hayashi S., Jimura K., and Kojima N. Micro. Meso. Mater., 2014, 186, 101 LINK [Google Scholar]
  67. Zheng A., Liu S.-B., and Deng F. Chem. Rev., 2017, 117, (19), 12475 LINK [Google Scholar]
  68. Zhao Q., Chen W.-H., Huang S.-J., Wu Y.-C., Lee H.-K., and Liu S.-B. J. Phys. Chem. B, 2002, 106, (17), 4462 LINK [Google Scholar]
  69. Webster C. E., Drago R. S., and Zerner M. C. J. Phys. Chem. B, 1999, 103, (8), 1242 LINK [Google Scholar]
  70. Wiper P. V., Amelse J., and Mafra L. J. Catal., 2014, 316, 240 LINK [Google Scholar]
  71. Zheng A., Chen L., Yang J., Zhang M., Su Y., Yue Y., Ye C., and Deng F. J. Phys. Chem. B, 2005, 109, (51), 24273 LINK [Google Scholar]
  72. Leydier F., Chizallet C., Chaumonnot A., Digne M., Soyer E., Quoineaud A.-A., Costa D., and Raybaud P. J. Catal., 2011, 284, (2), 215 LINK [Google Scholar]

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