A DFT-ONIOM2 STUDY OF THE INTERACTION OF N2, O2 Y NO WITH Ce-MOR: ACTIVE SITES AND THERMODYNAMIC

Authors

  • Rodolfo Izquierdo University of Zulia image/svg+xml
  • Néstor Cubillán University of Atlántico image/svg+xml , Universidad del Atlántico image/svg+xml
  • Ana Patricia Pérez Laboratorio de Química Teórica y Computacional, Departamento de Química, Facultad Experimental de Ciencias, Universidad del Zulia, Maracaibo, Venezuela.

DOI:

https://doi.org/10.15665/rp.v19i1.2513

Keywords:

ONIOM2, DFT, deNOx, Cerium

Abstract

A theoretical study of N2, O2, NO and NO+ adsorption with cerium-modified mordenite (Ce-MOR) was carried-out. It was used the two-layer integrated molecular orbital – molecular mechanics methodology (ONIOM2) by combining Density Functional Theory (DFT) and Universal Force Field (UFF) for the high and low level model, respectively. The formation active species of Ce based on the adsorption of CeO+ on crystallographycs positions T1, T2 and T4 in H-MOR. The Geometric, vibrational and thermodynamic results indicate that the Ce atom of the CeO+ binds exothermal and spontaneously to two crystallographic non-equivalent oxygens (Om) of MOR (TnOm1Om2 ) according to: T1O1O4, T1O2O3, T2O4O7, T2O5O7 y T4O7O10 (T: Al or Si). The results of the interaction of N2 , O2 , NO and NO+ with Ce-MOR indicate that exothermic and spontaneous adsorption occurs only  on the active sites located on the main 12 membered ring (12-MR) channel, according to: T1O1O4, T2O5O7 and T4O7O10. In general, the Ce-MOR system stabilizes the electrophilic species [CeO(NO+)], with activity for NOx reactions with nucleophilic reducting agents such as NH3 , while it is reported for the CeO(NO) species adsorbed on MOR a dynamic equilibrium between the κ1NO, κ1ON, κ2NO adsorption that could be applicable for NOx catalysis in the absence of reducing agents. On the basis of the thermodynamic reaction functions, it is proposed that the most probable site for the location of the active CeO+ is T2O5O7.

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Published

2021-02-17

Issue

Vol. 19 No. 1 (2021): Enero - Junio

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Articles

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Copyright (c) 2021 Rodolfo Izquierdo, Néstor Cubillán, Ana Pérez

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