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Rationalizing the Relation between Adlayer Structure and Observed Kinetics in Catalysis

Stamatakis, M; Piccinin, S; (2016) Rationalizing the Relation between Adlayer Structure and Observed Kinetics in Catalysis. ACS Catalysis , 6 (3) pp. 2105-2111. 10.1021/acscatal.5b02876. Green open access

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Abstract

Relating the kinetic behavior of catalytic reactions with adsorbate overlayer structure is a long-standing challenge in catalysis. Even for simple systems such as CO oxidation on Pd(111), recent studies have observed rich behavior. In particular, titration experiments by Kondoh and co-workers on this system (J. Chem. Phys. 2006, 124, 224712), demonstrated first-order reaction kinetics with respect to oxygen coverage at 190 K. Yet, the observed kinetics appeared as half-order at 320 K, a phenomenon that was attributed to island formation. We apply a theoretical approach to rationalize these observations, using first-principles kinetic Monte Carlo simulations. We employ an analysis that decomposes the overall order into two contributions: one pertaining to the adlayer structure and one quantifying coverage effects on the elementary events’ rates. It is shown that at both temperatures, the layer appears as almost well-mixed, whereas coverage effects due to adsorbate lateral interactions result in the distinct reaction orders.

Type: Article
Title: Rationalizing the Relation between Adlayer Structure and Observed Kinetics in Catalysis
Open access status: An open access version is available from UCL Discovery
DOI: 10.1021/acscatal.5b02876
Publisher version: http://dx.doi.org/10.1021/acscatal.5b02876
Language: English
Additional information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work seehttp://dx.doi.org/10.1021/acscatal.5b02876.
Keywords: catalysis, CO oxidation, titration, kinetic Monte Carlo, reaction order, island formation
UCL classification: UCL
UCL > Provost and Vice Provost Offices
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science > Dept of Chemical Engineering
URI: https://discovery.ucl.ac.uk/id/eprint/1475586
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