title: Adlayer inhomogeneity without lateral interactions: rationalizing correlation effects in CO oxidation at RuO2(110) with first-principles kinetic Monte Carlo.
abstract: Microkinetic modeling of surface chemical reactions still relies heavily on the mean-field based rate equation approach. This approach is expected to be most accurate for systems without appreciable lateral interactions among the adsorbed chemicals, and there in particular for the uniform adlayers resulting in poisoned regimes with predominant coverage of one species. Using first-principles kinetic Monte Carlo simulations and the CO oxidation at RuO(2)(110) as a showcase, we demonstrate that even in this limit mean-field rate equations fail to predict the catalytic activity by orders of magnitude. This deficiency is traced back to the inability to account for the vacancy pair formation that is kinetically driven by the ongoing reactions.
authors.affiliation: Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin, Germany. matera@fhi-berlin.mpg.de
authors.forename: Sebastian
authors.initials: S
authors.lastname: Matera
authors.forename: Hakim
authors.initials: H
authors.lastname: Meskine
authors.forename: Karsten
authors.initials: K
authors.lastname: Reuter
mesh_terms: D002248:Carbon Monoxide / Q000737:chemistry*; D002384:Catalysis; D007700:Kinetics; D009010:Monte Carlo Method; D010084:Oxidation-Reduction; D017975:Ruthenium Compounds / Q000737:chemistry*
chemical_list: D017975:Ruthenium Compounds; C029017:ruthenium dioxide; D002248:Carbon Monoxide