View More View Less
  • 1 Department of Physical Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, 53210, Pardubice, Czech Republic
Restricted access

Abstract

The existence of the new type of the adsorption complexes of carbon monoxide, where CO molecule interacts simultaneously with both copper and potassium cation, formed on so-called heterogeneous dual adsorption sites was detected by the FTIR spectroscopy and temperature programmed desorption technique (TPD) in the Cu, K–FER zeolite samples. The time-resolved IR spectroscopy and TPD experiments also proved their lower stability in the comparison with the classical monodentate adsorption complexes. The TPD curves of these materials exhibited low temperature desorption peak which was ascribed to these sites. The energetic parameters (i.e., energy and entropy of adsorption) as well as distribution of all present Cu+ sites were obtained by the fitting of TPD data to the phenomenological model. Obtained results suggest that the heterogeneous dual sites are special form of the adsorption sites localized on the wall of channels destabilized due to significantly higher change of the entropy of adsorption. Direct microcalorimetric measurement proved energetic equality of single and heterogeneous dual sites together with the validity of the adsorption energy values obtained from TPD.

  • 1. Vimont, A, Thibault-Starzyk, F, Daturi, M 2010 Analysing and understanding the active site by ir spectroscopy. Chem Soc Rev 36 12 45415072 .

  • 2. Lamberti, C, Zecchina, A, Groppo, E, Bordiga, S 2010 Probing the surfaces of heterogeneous catalysts by in situ IR spectroscopy. Chem Soc Rev 39 12 49515001 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 3. Auroux, A 1997 Acidity characterization by microcalorimetry and relationship with reactivity. Top Catal 4 1–2 7189 .

  • 4. Auroux, A 2002 Microcalorimetry methods to study the acidity and reactivity of zeolites, pillared clays and mesoporous materials. Top Catal 19 3–4 205213 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 5. Tsyganenko, AA, Chizhik, AM, Chizhik, AI 2010 A ftir search for linkage isomerism of CN—ions adsorbed on oxides and zeolites. Phys Chem Chem Phys 12 24 63876395 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 6. Zecchina, A, Arena, CO 1996 Diatomic molecular probes for Mid-IR studies of zeolites. Chem Soc Rev 25 3 187 .

  • 7. Xia, X, d’Alnoncourt, RN, Muhler, M 2008 Entropy of adsorption of carbon monoxide on energetically heterogeneous surfaces. J Therm Anal Calorim 91 1 167172 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 8. Salla, I, Montanari, T, Salagre, P, Cesteros, Y, Busca, G 2005 A reexamination of the adsorption of CO and nitriles on alkali-metal mordenites: characterization of multiple interactions. Phys Chem Chem Phys 7 12 25262532 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 9. Bordiga, S, Palomino, GT, Paze, C, Zecchina, A 2000 Vibrational spectroscopy of H-2, N-2, Co and No adsorbed on H, Li, Na, K-exchanged Ferrierite. Microporous Mesoporous Mat 34 1 6780 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 10. Nachtigallova, D, Bludsky, O, Arean, CO, Bulanek, R, Nachtigall, P 2006 The vibrational dynamics of carbon monoxide in a confined space—CO in zeolites. Phys Chem Chem Phys 8 42 48494852 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 11. Nachtigall, P, Delgado, MR, Frolich, K, Bulanek, R, Palomino, GT, Bauca, CL et al. 2007 Periodic density functional and FTIR spectroscopic studies on CO adsorption on the zeolite Na-Fer. Microporous Mesoporous Mat 106 1–3 162173 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 12. Garrone, E, Bulanek, R, Frolich, K, Arean, O, Delgado, Rg, Palomino, T et al. 2006 Single and dual cation sites in zeolites: theoretical calculations and FTIR spectroscopic studies on CO adsorption on K-Fer. J Phys Chem B 110:2254222550 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 13. Arean, CO, Delgado, MR, Frolich, K, Bulanek, R, Pulido, A, Bibiloni, GF et al. 2008 Computational and fourier transform infrared spectroscopic studies on carbon monoxide adsorption on the zeolites Na-ZSM-5 and K-ZSM-5: evidence of dual-cation sites. J Phys Chem C 112 12 46584666 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 14. Iwamoto M , Furukawa H, Mine Y, Uemura F, Mikuriya S, Kagawa S. Copper(II) ion-exchanged ZSM-5 zeolites as highly-active catalysts for direct and continuous decomposition of nitrogen monoxide. J Chem Soc, Chem Commun. 1986;1272.

    • Search Google Scholar
    • Export Citation
  • 15. Dedecek, J, Wichterlova, B 1994 Siting and redox behavior of Cu ions in CuH-ZSM-5 zeolites—Cu+ photoluminescence study. J Phys Chem 98 22 57215727 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 16. Dedecek, J, Sobalik, Z, Tvaruzkova, Z, Kaucky, D, Wichterlova, B 1995 Coordination of cu ions in high-silica zeolite matrices—cu+ photoluminescence, ir of no adsorbed on Cu2+, and Cu2+ ESR study. J Phys Chem 99 44 1632716337 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 17. Iwamoto, M, Hoshino, Y 1996 Assignment of nonclassical [Cu(Co)(n)](+) (n=1, 2) complex ions in zeolite cages. Inorg Chem 35 24 69186921 .

  • 18. Kuroda, Y, Yoshikawa, Y, Kumashiro, R, Nagao, M 1997 Analysis of active sites on copper ion-exchanged ZSM-5 for co adsorption through ir and adsorption-heat measurements. J Phys Chem B 101 33 64976503 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 19. Lamberti, C, Bordiga, S, Zecchina, A, Salvalaggio, M, Geobaldo, F, Arean, CO 1998 XANES, EXAFS and FTIR characterization of copper-exchanged mordenite. J Chem Soc-Faraday Trans 94 10 15191525 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 20. Lamberti, C, Salvalaggio, M, Bordiga, S, Geobaldo, F, Spoto, G, Zecchina, A et al. 1997 Cu-I sites in Cu(I)ZSM-5: a XAFS, IR and computer graphics study. J Phys IV 7 C2 905906.

    • Search Google Scholar
    • Export Citation
  • 21. Lamberti, C, Palomino, GT, Bordiga, S, Berlier, G, D’Acapito, F, Zecchina, A 2000 Structure of homoleptic Cu-I(Co)(3) cations in Cu-I-exchanged ZSM-5 zeolite: an X-ray absorption study. Angew Chem-Int Edit 39 12 2138 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 22. Kuroda, Y, Maeda, H, Yoshikawa, Y, Kumashiro, R, Nagao, M 1997 Characterization of active sites on copper ion-exchanged mordenite for dinitrogen adsorption by using co as a probe molecule. J Phys Chem B 101 8 13121316 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 23. Kumashiro, P, Kuroda, Y, Nagao, M 1999 New analysis of oxidation state and coordination environment of copper ion-exchanged in ZSM-5 zeolite. J Phys Chem B 103 1 8996 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 24. Bolis, V, Maggiorini, S, Meda, L, D’Acapito, F, Palomino, GT, Bordiga, S et al. 2000 X-ray photoelectron spectroscopy and X-ray absorption near edge structure study of copper sites hosted at the internal surface of ZSM-5 zeolite: a comparison with quantitative and energetic data on the co and NH3 adsorption. J Chem Phys 113 20 92489261 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 25. Bolis, V, Barbaglia, A, Bordiga, S, Lamberti, C, Zecchina, A 2004 Heterogeneous nonclassical carbonyls stabilized in Cu(I)- and Ag(I)-ZSM-5 zeolites: thermodynamic and spectroscopic features. J Phys Chem B 108 28 99709983 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 26. Gervasini, A, Picciau, C, Auroux, A 2000 Characterization of copper-exchanged ZSM-5 and ETS-10 catalysts with low and high degrees of exchange. Microporous Mesoporous Mat 35–6:457469 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 27. Dondur, V, Rakic, V, Damjanovic, L, Auroux, A 2005 Comparative study of the active sites in zeolites by different probe molecules. J Serb Chem Soc 70 3 457474 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 28. Nachtigall, P, Pulido, A, Frolich, K, Bulanek, R 2008 Evidence of heterogeneous dual cation sites in zeolites by combined IR and DFT investigation. Stud Surf Sci Catal 174B:10051008 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 29. Pouzar, M, Cernohorsky, T, Bulanek, R, Krejcova, A 2000 Determination of copper in zeolites by wavelenth-disperse X-ray spectrometry. Chem Listy 94 3 197201.

    • Search Google Scholar
    • Export Citation
  • 30. Kanervo, JM, Reinikainen, KM, Krause, AOI 2004 Kinetic analysis of temperature-programmed desorption. Appl Catal A-Gen 258 2 135144 .

  • 31. Bulanek, R, Cicmanec, P, Knotek, P, Nachtigallova, D, Nachtigall, P 2004 Localization of Cu+ sites and framework al positions in high-silica zeolites: combined experimental and theoretical study. PCCP Phys Chem Chem Phys 6 9 20032007.

    • Search Google Scholar
    • Export Citation
  • 32. Nachtigall, P, Bludsky, O, Nachtigallova, D, Cicmanec, P, Drobna, H, Bulanek, R 2005 Characterization of Cu+ sites in fer: combined computational and experimental TPD study. Molecular sieves: from basic research to industrial applications, pts a and b. Studies in surface science and catalysis Elsevier Science Bv Amsterdam 925932.

    • Search Google Scholar
    • Export Citation
  • 33. Bludsky, O, Nachtigall, P, Cicmamec, P, Knotek, P, Bulanek, R 2005 Characterization of the Cu+ sites in MFI zeolites: combined computational and experimental study. Catal Today 100 3–4 385389 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 34. Bludsky, O, Silhan, M, Nachtigallova, D, Nachtigall, P 2003 Calculations of site-specific co stretching frequencies for copper carbonyls with the “Near spectroscopic accuracy”: Co interaction with Cu+/MFI. J Physic Chem A 107 48 1038110388 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 35. Davidova, M, Nachtigallova, D, Bulanek, R, Nachtigall, P 2003 Characterization of the Cu+ sites in high-silica zeolites interacting with the Co molecule: combined computational and experimental study. J Physic Chem B 107 10 23272332 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 36. Bulanek, R 2004 Investigation of ir vibrational band of C–O bond of carbonyl species in Cu+-MFI zeolites. Phys Chem Chem Phys 6 16 42084214 .

  • 37. Bulanek, R, Nachtigall, P, Cicmanec, P 2008 Combined tpd and theoretical investigation of co desorption from Cu-K-Fer zeolite. Stud Surf Sci Catal 174B:893896 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 38. Bulanek, R, Drobna, H, Nachtigall, P, Rubes, M, Bludsky, O 2006 On the site-specificity of polycarbonyl complexes in Cu/zeolites: combined experimental and DFT study. Phys Chem Chem Phys 8:55355542 .

    • Crossref
    • Search Google Scholar
    • Export Citation