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.
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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 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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