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Computational and experimental investigations into N2O decomposition over MgO nanocrystals from thorough molecular mechanism to ab initio microkinetics

Piskorz W, Zasada F, Stelmachowski P, Diwald O, Kotarba A, Sojka Z (2011)

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Publication Language: English

Publication Status: Published

Publication Type: Journal article, Original article

Publication year: 2011

Journal

Book Volume: 115

Pages Range: 22451-22460

Journal Issue: 45

DOI: 10.1021/jp2070826

Abstract

In this article a comprehensive molecular modeling of the reaction mechanism complemented by ab initio microkinetic modeling of the catalytic decomposition of N₂O on MgO nanocrystals is discussed. The density functional level of theory was used to study the molecular mechanism of conceivable elementary steps of the deN₂O reaction over the most stable (100) surface, including the effect of surface morphology. It is shown that terrace sites are responsible for steady state reactivity, whereas the more basic and reactive sites located on edges and corners are involved only in the initial stages of the reaction because of poisoning. Detailed analysis of the reaction progress in terms of the energy profiles and the evolution of partial charges and bond orders for each step allowed for an in-depth insight at the atomic scale into the nature of the catalytic N₂O decomposition over anionic redox active sites constituted by surface O^2– ions. The harmonic transition state theory along with the calculated free enthalpies of activation were used to model the reaction progress in pulse (transient) and steady state regimes as well as to predict the kinetic isotopic effects (KIE) for ¹⁵N and ¹⁸O labeled reactants. The proposed kinetic scheme was able to reproduce the results of temperature-programmed surface reaction and KIE experiments with high accuracy without fitting of any parameters.

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How to cite

APA:

Piskorz, W., Zasada, F., Stelmachowski, P., Diwald, O., Kotarba, A., & Sojka, Z. (2011). Computational and experimental investigations into N2O decomposition over MgO nanocrystals from thorough molecular mechanism to ab initio microkinetics. Journal of Physical Chemistry C, 115(45), 22451-22460. https://doi.org/10.1021/jp2070826

MLA:

Piskorz, Witold, et al. "Computational and experimental investigations into N2O decomposition over MgO nanocrystals from thorough molecular mechanism to ab initio microkinetics." Journal of Physical Chemistry C 115.45 (2011): 22451-22460.

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