Computational and Variable‐Temperature Infrared Spectroscopic Studies on Carbon Monoxide Adsorption on Zeolite Ca‐A

ChemPhysChem - Tập 10 Số 7 - Trang 1058-1065 - 2009
Angeles Pulido1, Petr Nachtigall1,2, M. Rodrı́guez Delgado3, C. Otero Areán3
1Center for Biomolecules and Complex Molecular Systems, Institute of Organic Chemistry and Biochemistry, Academy of Science of the Czech Republic, Flemingovo nám 2, 166 10 Praha 6, Czech Republic.
2Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 12840 Praha 2, Czech Republic
3Departamento de Química, Universidad de las Islas Baleares, E‐07122 Palma de Mallorca (Spain), Fax: (+34)  971173426

Tóm tắt

AbstractBridged Ca2+⋅⋅⋅CO⋅⋅⋅Ca2+ complexes are formed on dual‐cation sites, constituted by a pair of nearby Ca2+ cations, when CO is adsorbed on zeolite Ca‐A. Two types of such species can be formed, designated S2–S1 and S1–S1 (see picture). Ca2+⋅⋅⋅CO monocarbonyl species are also identified, and at a relatively high CO equilibrium pressure, dicarbonyl complexes can also form.magnified imageCarbon monoxide adsorption on LTA (Linde type 5A) zeolite Ca‐A is studied by using a combination of variable‐temperature infrared spectroscopy and computational methods involving periodic density functional calculations and the correlation between stretching frequency and bond length of adsorbed CO species ($\tilde \nu $CO/rCO correlation). Based on the agreement between calculated and experimental results, the main adsorption species can be identified as bridged Ca2+⋅⋅⋅CO⋅⋅⋅Ca2+ complexes formed on dual‐cation sites constituted by a pair of nearby Ca2+ cations. Two types of such species can be formed: One of them has the two Ca2+ ions located on six‐membered rings of the zeolite framework and is characterized by a CO stretching frequency in the range of 2174–2179 cm−1 and an adsorption enthalpy of −31 to −33 kJ mol−1, whereas the other bridged CO species is formed between a Ca2+ ion located on an eight‐membered ring and another one on a nearby six‐membered ring and is characterized by $\tilde \nu $CO in the range 2183–2188 cm−1 and an adsorption enthalpy of −46 to −50 kJ mol−1. Ca2+⋅⋅⋅CO monocarbonyl complexes are also identified, and at a relatively high CO equilibrium pressure, dicarbonyl species can also be formed.

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ChemPhysChem

Tập 10 Số 7

1058-1065

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