Abstract
The suitability of cluster models and combined quantum mechanics/interatomic potential function models for the description of properties of Cu/zeolite systems is discussed. The latter are able to discriminate between different types of sites in a given framework and between different frameworks. Two types of Cu+ sites are identified. Type I sites are found at the channel walls with Cu+ coordinated to 3 – 4 oxygen atoms of a five- or six-membered (TO)n ring. Type II sites occur at the channel intersections with Cu+ coordinated to two O atoms of the A1O4 tetrahedron only. Bands observed in photoluminescence spectra are assigned to these types of sites. Cu+ ions on the channel intersection (type I) bind NO stronger than naked Cu+ ions and it is suggested that these sites are catalytically active. A possible explanation of the higher catalytic activity of Cu/ZSM-5 compared to Cu/FER is proposed.
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References
See other contributions to this volume and references therein.
Iwamoto, M., Furukawa, H., Mine, Y., Uemura, F., Mikuriya, S., and Kagawa, S. (1986) Copper(ii) ionexchanged ZSM-5 zeolites as highly-active catalysts for direct and continuous decomposition of nitrogen monoxide J. Chem. Soc., Chem. Commun., 1272–1273.
Hass, K.C. and Schneider, W. F. (1999) Density functional studies of adsorbates in Cu-exchanged zeolites: model comparisons and SOX binding, Phys. Chem. Chem. Phys. 1, 639–648.
Blint, R.J. (1996) Copper coordination in zeolite-supported lean NOX Catalysts, J. Phys. Chem. 100, 19518–19524.
Trout, B. L., Chakraborty, A.K., and Bell, A. T. (1996) Local spin density functional theory study of copper ion-exchanged ZSM-5, J. Phys. Chem. 100, 4173–4179.
Teraishi, K., Ishida, M., Irisawa, J., Kume, M., Takahashi, Y., Nakano, T., Nakamura, H., and Miyamoto, A. (1997) Active site structure of Cu/ZSM-5: computational study, J. Phys. Chem. B, 101, 8079–8089.
Zhanpeisov, N. U., Nakatsuji, H., Hada, M., Nakai, H., and Anpo (1996) CO and NO adsorption on copper-containing zeolite. A theoretical ab initio study, Catal. Letters 42, 173–176.
Sayle, D. C., Catlow, C. R. A., Gale, J. D., Perrin, M.A., and Nortier, P. (1997) Computer modeling of the active-site configurations within the NO decomposition catalyst Cu-ZSM-5, J. Phys. Chem. A 101, 3331–3337.
Rodriguez-Santiago, L., Sierka, M., Branchadell, V., Sodupe, M., and Sauer, J. (1998) Coordination of Cu+ ions to zeolite framework strongly enhances their ability to bind NO2. An ab initio density functional study, J. Am. Chem. Soc. 120, 1545–1551.
Nachtigallova, D., Nachtigall, P., Sierka, M., and Sauer, J. (1999) Coordiantion and siting of Cu+ ions in ZSM-5: A combined quantum mechanics/interatomic potential function study, Phys. Chem. Chem. Phys. 1, 2019–2026.
Nachtigall, P., Nachtigallova, D., and Sauer, J. (2000) Coordination change of Cu+ sites in ZSM-5 on excitation in the triplet state: understanding of the photoluminescence spectra, J. Phys. Chem. B 104, 1738–1745.
Eichler, U., Kölmel, C. K., and Sauer, J. (1997) Combining ab initio techniques with analytical potential functions for structure predictions of large systems: Method and application to crystalline silica polymorphs, J. Comput. Chem. 18, 463–477.
Sierka, M. and Sauer J.(2000) Finding transition structures in extended systems: A strategy based on a combined quantum mechanics-empirical valence bond approach, J. Chem. Phys. 112, 6983–6996.
Dirac, P.A.M. (1930) Note on exchange phenomena in the Thomas atom, Proc. Cambridge Phil. Soc. 26, 376–385.
Vosko, S. H., Wilk, L., and Nusair, M. (1980) Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis, Can. J. Phys. 58, 1200–1211.
Parr, R.G. and Yang, W. (1989) Density-Functional Theory of Atoms and Molecules, Oxford University Press, Oxford.
Lee, C., Yang, W., and Parr, R. G. (1988) Development of the Colle-Salvetti correlation energy formula into a functional of the electron density, Phys. Rev. B 37, 785–789.
Becke, A.D. (1993) A new mixing of Hartree-Fock and local density-functional theories, J. Chem. Phys. 98, 1372–1377.
Nachtigallova, D., Davidova, M., and Nachtigall, P. (1998) Reliability of DFT methods for description of Cu sites and their interaction with NO in zeolites, Collect. Czech. Chem. Commun. 63, 1202–1212.
Hass, K. C. and Schneider, F. (1996) Reliability of Small Cluster Models for Cu-Exchanged Zeolites, J. Phys. Chem., 100, 9292–9301.
Delabie, A., Pierloot, K., Groothaert, M. H., Weckhuysen, B.M., and Schoonheydt, R. A. (2000) Study of the coordination of Cu2+ in zeolite Y: Interaction with water and ammonia, Microporous and Mesop. Materials 37, 209–222.
Yokomichi, Y., Yamabe, T., Ohtsuka, H., and Kakumoto, T. (1996) Theoretical study of NO decomposition on Cu-ZSM-5 catalyst models using the density functional method, J. Phys. Chem., 100, 14424–14429.
Broclawik, E., Datka, J., Gill, B, and Kozyra, P. (2000) T-O-T skeletal vibration in CuZSM-5 zeolite: IR study and quantum chemical modeling, Phys. Chem. Chem. Phys., 2, 401–405.
Nachtigallova, D., Nachtigall, P., and Sauer, J. (2000) Coordination of Cu+ and Cu2+ ions in ZSM-5 in the vicinity of two framework Al atoms, Phys. Chem. Chem. Phys, submitted.
Nachtigall, P., Davidova, M., and Nachtigallova, D.(2000) Computational study of interaction of Cu+ with Ferrierite: structure, coordination, and photoluminescence spectra, J. Phys. Chem. B, accepted
Schafer, A., Horn, H., and Ahlrichs, R. (1992) Fully optimized contracted gaussian-basis sets for atoms Li to Kr, J. Chem. Phys., 97, 2571–2577.
Texter, J., Strome, D. H., Herman, R. G., and Klier, K. (1977) Chemical and spectroscopic properties of copper containing zeolites, J. Phys. Chem., 81, 333–338.
Lamberti, C., Bordiga, S., Salvalaggio, M., Spoto, G.; Zecchina, A., Geobaldo, F., Vlaic, G., Bellatreccia, M. (1997) XAFS, IR, and UV-vis study of the Cu-I environment in Cu-I-ZSM-5, J. Phys. Chem. B, 101, 344–360.
Dedecek, J. and Wichterlova, B. (1999) Geometry of the Cu+ 540 nm luminescence centers in zeolites, Phys. Chem. Chem. Phys., 1, 629–637.
Schneider, W.F. and Hass, K. C. (1998) Density functional theory study of transformations of nitrogen oxides catalyzed by Cu-exchanged zeolites, J. Phys. Chem. B, 102, 3692–3705.
Schneider, W. F., Hass, K. C., Ramprasad, R., and Adams, J. B. (1996) First-principles analysis of elementary steps in the catalytic decomposition of NO by Cu-exchanged zeolites, J. Phys. Chem. B, 101, 4353–4357.
Tajima, N., Hashimoto, M., Toyama, F., El-Nahas, A.M., and Hirao, K. (1999) A theoretical study on the catalysis of Cu-exchanged zeolite for the decomposition of nitric oxide, Phys. Chem. Chem. Phys. 1, 3823–3830.
Trout, B. L, Chakraborty, A.K., and Bell, A. T. (1996) Analysis of the thermochemistry of NOX decomposition over CuZSM-5 based on quantum chemical and statistical mechanical calculations, J. Phys. Chem., 100, 17582–17592.
Nachtigall, P. and Sauer, J. (2000) Interaction of NO with Cu+ ions in ZSM-5: A combined quantum mechanics/interatomic potential function study, In preparation.
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Sauer, J., Nachtigallova, D., Nachtigall, P. (2001). Ab Initio Simulation of Cu-Species in Zeolites: Siting, Coordination, UV-Vis Spectra and Reactivity. In: Centi, G., Wichterlová, B., Bell, A.T. (eds) Catalysis by Unique Metal Ion Structures in Solid Matrices. NATO Science Series, vol 13. Springer, Dordrecht. https://doi.org/10.1007/978-94-010-0782-5_14
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DOI: https://doi.org/10.1007/978-94-010-0782-5_14
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