CO oxidation: The electrocatalytic oxidation of carbon monoxide on a platinum electrode is one of the most intensively studied systems in electrocatalysis.

The electrochemical understanding of of the CO adsorption is of and

oxidation

poisonous

paramount

importance in the development of improved low temperature fuel cells. The most detailed experiments have been done with the oxidation of CO on Pt 110 and have revealed complex kinetic oscillations and the formation of a rich variety of spatiotemporal patterns, including propagating reaction fronts, standing waves, and even spatiotemporal chaos. Similarly, the oxidation of CO on a Pt 100 surface shows oscillatory kinetics accompanied by the propagation of wave fronts of adsorbed CO or O, respectively. It has been established that the reaction CO oxidation reaction on surfaces of the platinum-group metals proceeds via the Langmuir

Hinshelwood mechanism. [1] CO is a relatively simple molecule which is ideally suited for model studies of molecular coadsorption at the metal surface Monte Carlo simulation: Monte Carlo methods (or Monte Carlo experiments) are a class of computational algorithms that rely on repeated random sampling to compute their results. Monte Carlo methods are especially useful for simulating systems with many coupled degrees of freedom, such as fluids, disordered materials, strongly coupled solids, and cellular structures. With the advent of fast computers, Monte Carlo simulations have become an increasingly popular method to analyze the behavior of adsorbates on a surface. In the past, Monte Carlo methods have been successfully employed to study systems at equilibrium. Because the observed phenomena are typical for

systems not at equilibrium, these classical Monte Carlo methods are not well suited. So-called dynamical Monte Carlo methods, in which the behavior of the system over time is simulated, are used instead. In order to perform such a simulation, a stochastic model of the chemical system is built. Elements of such a model are the crystal surface, the adsorbates, and the microscopic reaction steps that change the surface configuration over time. The behavior of this system over time is determined by the rates of these reactions. These rates are specified as probabilities and the surface

configuration over time is then given by a master equation, describing the time evolution of the probability distribution of system configurations. Since the simulation follows the real timedependent behavior, experimental results can be reproduced if the model is precise enough.

Statistical models of reactions:

The most widely used statistical model for CO oxidation on metal surface is Ziff-Gulari-Barshad (ZGB) model. [3] The original paper presented ZGB as a deviation from the classical approach to catalyst kinetics to consider only average concentrations of the adsorbed species, and to write systems of differential equations of varying complexity with multiple parameters. The reaction occurs as follows: CO CO(ads) O2 2O(ads) CO(ads) + O(ads) CO2 In the reactions above, ads indicates a molecule that is adsorbed on the catalyst surface. When adsorbed, the O2 disassociates into two oxygen atoms which occupy two separate catalyst surface sites.

The CO molecule occupies a single surface site. In the final step, CO2 is produced and desorbs from the surface. The ZGB model treats the catalyst in this reaction as a "simple square two-dimensional lattice" of active sites. In order to simplify the kinetics, the model also assumes that: molecules of CO or O2 strike a when gas-phase surface site,

blank

they adsorb immediately; when O and CO occupy adjacent sites, they react immediately; the CO2 produced desorbs immediately and does not have further interactions with the system; the composition in the gas phase is not changed by the reaction. Following images shows the scheme of the model.

Figure 1 (a) CO molecule strikes the blank site in ihe center, adsorbss, (b) sees a neighbor O, and (c) the two reactand desorb. Open symbols denote oxygen and closed symbols carbon monoxide.

Figure 2 (a) An O2 molecule strikes the two blank sites, indicated by dotted lines, and adsorbs. (b) One of the O atoms sees a neighboring CO; (c) the iwo react, and desorb. Open symbols denote oxygen and closed symbols carbon monoxide.

More complex models have been proposed in the later studies and simulation works. For instance, in Yakovkins work [4], they assume the CO adsorbs on Pt atom top, while O adsorbs on hollow sites, where only the hcp site is active and can react with the adjacent adsorbed CO as shown in Figure 3. A good agreement of the results of Monte Carlo simulations with experiment suggests validity of the concepts of the precursor states in the dissociative adsorption,

indirect lateral interaction between adsorbed particles, and reveals an important role of mobility of the species in formation of film structures and in reaction between adsorbed CO molecules and O atoms.

Figure 3 A snapshot of the segment of the surface in the course of the reaction at T = 230 K. Mobility of oxygen atoms is favored in vicinity of the domain wall, and some oxygens occur in the hcp sites. These oxygen atoms can react with a neighboring CO molecule (such a pair is denoted as reactive). In contrast, oxygen atoms in the domains stay in the inactive fcc sites and will not react with the nearby CO molecule (such a COO pair is marked as non-reactive).

[1] Francisco Chvez, Luis Vicente, Aurlien Perera, and Michel Moreau, J. Chem. Phys. 110, 8119 (1999); [2] J. J. Lukkien,* J. P. L. Segers, P. A. J. Hilbers, R. J. Gelten and A. P. J. Jansen, Phys, Rev. 58, (1998) [3] Robert M. Ziff, Erdagon Gulari, and Yoav Barshad, J. Phys, Rev. Let. 56, (1986) [4] N.V. Petrova, I.N. Yakovkin, Surface Science 578 (2005) 162173