Cooperative Cation Migrations upon CO Addition in CuI- and Alkali-Exchanged Faujasite: A DFT Study
| Autor: | Zalfa Nour, Dorothée Berthomieu, Hugo Petitjean |
|---|---|
| Přispěvatelé: | Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), D.B. acknowledges a Z. N. fellowship financially supported by the CNRS and the Region Languedoc- Roussillon. HPC resources from GENCI-[CCRT/CINES/IDRIS] (Grant No. 2010- x2010081071). |
| Rok vydání: | 2010 |
| Předmět: |
Chemistry
Inorganic chemistry Infrared spectroscopy chemistry.chemical_element 02 engineering and technology Faujasite engineering.material 010402 general chemistry 021001 nanoscience & nanotechnology Alkali metal 01 natural sciences Copper 0104 chemical sciences Surfaces Coatings and Films Electronic Optical and Magnetic Materials [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Crystallography General Energy Adsorption engineering Cluster (physics) Physical and Theoretical Chemistry 0210 nano-technology Zeolite Periodic model |
| Zdroj: | Journal of Physical Chemistry C Journal of Physical Chemistry C, American Chemical Society, 2010, 114 (41), pp.17802-17811. ⟨10.1021/jp106630m⟩ |
| ISSN: | 1932-7455 1932-7447 |
| DOI: | 10.1021/jp106630m |
| Popis: | International audience; CO adsorption in Al-rich faujasite zeolite containing copper and alkali cations has been investigated using DFT methods in order to determine how CO interacts and may modify the original position of the cations. Whether a cluster or a periodic model is used, addition of CO induces the formation of stable complexes labeled DI(CO) in which CO interacts by both its C-end and its O-end, resulting from a cooperative rearrangement of cations. In addition to a CuI migration from site II to the supercage, a migration of alkali from site III′ to site III may occur. DI(CO) also induces a downshift of the νCO mode in comparison with the complex containing CO interacting with a single cation, SI(CO). These results suggest a new assignment of the IR spectra of CO adsorbed in YCuI and YNa+: for YCuI, the upshifted signal at ca. 2160 cm-1 in comparison with νCOgas at 2143 cm-1 could be assigned to a SI(CO) structure, whereas the downshifted signal at ca. 2140 cm-1 could be assigned to a DI(CO) complex. For YNa+, the upshifted signal at ca. 2170 cm-1 could be assigned to SI(CO) NaSII · · ·CO and/or to DI(CO) NaSII · · ·OC· · · NaSIII′, whereas the downshifted signal at ca. 2122 cm-1 could be assigned to DI(CO) complex NaSII · · ·CO· · ·NaSIII′. This study shows that the DI(CO) interaction is a key ingredient for understanding the metal-exchanged zeolite properties. |
| Databáze: | OpenAIRE |
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