Kinetic Modeling of COad Monolayer Oxidation on Carbon-Supported Platinum Nanoparticles Full article
Journal |
The Journal of Physical Chemistry B
ISSN: 1520-6106 , E-ISSN: 1520-5207 |
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Output data | Year: 2006, Volume: 110, Number: 42, Pages: 21028-21040 Pages count : 13 DOI: 10.1021/jp063856k | ||||||||
Tags | Carbon monoxide; Catalysis; Computer simulation; Monte Carlo methods; Nanostructured materials; Oxidation | ||||||||
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Abstract:
We present a theoretical study of COad electrooxidation on Pt nanoparticles. Effects of size and surface texture of nanoparticles on the interplay of relevant kinetic processes are investigated. Thereby, strong impacts of particle size on electrocatalytic activities, observed in experiments, are rationalized. Our theoretical approach employs the active site concept to account for the heterogeneous surface of nanoparticles. It, moreover, incorporates finite rates of surface mobility of adsorbed CO. As demonstrated, the model generalizes established mean field or nucleation and growth models. We find very good agreement of our model with chronoamperometric current transients at various particle sizes and electrode potentials (Maillard, F.; Savinova, E. R.; Stimming, U. J. Electroanal. Chem., in press, doi:10.1016/j.jelechem.2006.02.024). The full interplay of on-site reactivity at active sites and low surface mobility of COad unfolds on the smallest nanoparticles (∼2 nm). In this case, the solution of the model requires kinetic Monte Carlo simulations specifically developed for this problem. For larger nanoparticles (>4 nm) the surface mobility of COad is high compared to the reaction rate constants, and the kinetic equations can be solved in the limiting case of infinite surface mobility. The analysis provides an insight into the prevailing reaction mechanisms and allows for the estimation of relevant kinetic parameters.
Cite:
Andreaus B.
, Maillard F.
, Kocylo J.
, Savinova E.R.
, Eikerling M.
Kinetic Modeling of COad Monolayer Oxidation on Carbon-Supported Platinum Nanoparticles
The Journal of Physical Chemistry B. 2006. V.110. N42. P.21028-21040. DOI: 10.1021/jp063856k WOS Scopus РИНЦ
Kinetic Modeling of COad Monolayer Oxidation on Carbon-Supported Platinum Nanoparticles
The Journal of Physical Chemistry B. 2006. V.110. N42. P.21028-21040. DOI: 10.1021/jp063856k WOS Scopus РИНЦ
Dates:
Submitted: | Jun 20, 2006 |
Accepted: | Sep 9, 2006 |
Published online: | Sep 29, 2006 |
Published print: | Oct 1, 2006 |
Identifiers:
Web of science | WOS:000241381600049 |
Scopus | 2-s2.0-33751270476 |
Elibrary | 13514341 |
Chemical Abstracts | 2006:1012231 |
Chemical Abstracts (print) | 146:14883 |
OpenAlex | W2044750078 |