Density Functional Theory Molecular Cluster Study of Copper Interaction with Nitric Oxide Dimer in Cu-ZSM-5 Catalysts Full article
Journal |
The Journal of Physical Chemistry C
ISSN: 1932-7447 , E-ISSN: 1932-7455 |
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Output data | Year: 2007, Volume: 111, Number: 7, Pages: 3080-3089 Pages count : 10 DOI: 10.1021/jp0650634 | ||||
Tags | Catalysts; Copper oxides; Decomposition; Density functional theory; Dimers; Molecular interactions; Nitric oxide | ||||
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Affiliations |
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Funding (2)
1 | Netherlands Organisation for Scientific Research | 047.015.004 |
2 | Council for Grants of the President of the Russian Federation | НШ-1140.2003.3 |
Abstract:
The various quantum chemical models of catalytic active site in Cu−ZSM-5 zeolites are analyzed. The density functional theory (DFT) is used to calculate the electronic structure of molecular cluster (HO)3Al−O−Cu−O−Cu modeling the catalytic active site in Cu−ZSM-5 zeolites and study the interaction and decomposition of NO. It is assumed that the rate-determining stage of the low-temperature selective catalytic reduction of NO is the formation of the π-radical (N2O2)- on electron donor sites of Cu−ZSM-5 catalysts. This is in good agreement with the high electron affinity of the molecular dimer ONNO (Ea = −1.5 eV) and is confirmed by the experimental data on the formation of surface anion π-radical (N2O2)- on electron donor sites of supported organo−zirconium surface complex. The DFT calculated electronic structure and excitation energy spectra for the model system (HO)3Al−O−Cu−O−Cu show that it is a satisfactory model for description of experimental UV−vis spectra of Cu−ZSM-5, containing (−O−Cu−O−Cu−) chain structures in the zeolite channels. The calculated reaction energy profile of ONNO adsorption and decomposition on the model catalytic active site shows the possibility of the low-temperature decomposition of dimer (NO)2 with low activation energy and the important role of copper oxide chains (−O−Cu−O−Cu−) in the channels of Cu−ZSM-5 zeolite during selective reduction of NO.
Cite:
Zakharov I.I.
, Ismagilov Z.R.
, Ruzankin S.P.
, Anufrienko V.F.
, Yashnik S.A.
, Zakharova O.I.Z.
Density Functional Theory Molecular Cluster Study of Copper Interaction with Nitric Oxide Dimer in Cu-ZSM-5 Catalysts
The Journal of Physical Chemistry C. 2007. V.111. N7. P.3080-3089. DOI: 10.1021/jp0650634 WOS Scopus РИНЦ
Density Functional Theory Molecular Cluster Study of Copper Interaction with Nitric Oxide Dimer in Cu-ZSM-5 Catalysts
The Journal of Physical Chemistry C. 2007. V.111. N7. P.3080-3089. DOI: 10.1021/jp0650634 WOS Scopus РИНЦ
Dates:
Submitted: | Aug 7, 2006 |
Accepted: | Dec 5, 2006 |
Published online: | Jan 26, 2007 |
Published print: | Feb 22, 2007 |
Identifiers:
Web of science | WOS:000245005800036 |
Scopus | 2-s2.0-33847784933 |
Elibrary | 13548471 |
Chemical Abstracts | 2007:94191 |
Chemical Abstracts (print) | 146:385424 |
OpenAlex | W2012934393 |