Heterogeneous catalysis Monte Carlo simulations

K. Reuter and M. Scheffler, First-Principles Kinetic Monte Carlo Simulations for Heterogeneous Catalysis Application to the CO Oxidation at RuO2(110), Phys. Rev. B 73 (2006), 045433. 

Reuter K, Scheffler M. First-principles kinetic Monte Carlo simulations for heterogeneous catalysis application to the CO oxidation at RuC>2(110). Phys Rev B. 2006 73(4). 

The series of 10 chapters that constitute Part 3 of the book deals mainly with the use of adsorption as a means of characterizing carbons. Thus, the first three chapters in this section complement each other in the use of gas-solid or liquid-solid adsorption to characterize the porous texture and/or the surface chemistry of carbons. Porous texture characterization based on gas adsorption is addressed in Chapter 11 in a very comprehensive manner and includes a description of a number of classical and advanced tools (e.g., density functional theory and Monte Carlo simulations) for the characterization of porosity in carbons. Chapter 12 illustrates the use of adsorption at the liquid-solid interface as a means to characterize both pore texture and surface chemistry. The authon propose these methods (calorimetry, adsorption from solution) to characterize carbons for use in such processes as liquid purification or liquid-solid heterogeneous catalysis, for example. Next, the surface chemical characterization of carbons is comprehensively treated in Chapter 13, which discusses topics such as hydrophilicity and functional groups in carbon as well as the amphoteric characteristics and electrokinetic phenomena on carbon surfaces. 

The application of Monte-Carlo simulations to non-equilibrium reaction systems in heterogeneous catalysis started by Ziff, Gulari and Barshad on the lattice-gas version of a simple Langmuir-Hinshelwood model of CO oxidation on a transition metal surface. The ZGB-model is a lattice-gas version of the Langmuir-Hinshelwood-model of CO oxidation. 

More detailed studies of eleetroeatalytie processes, which incorporate heterogeneous surfaee geometries and finite surface mobilities of reactants, require kinetic Monte Carlo simulations. This stochastic method has been successfully applied in the field of heterogeneous catalysis on nanosized catalyst particles [59,60]. Since these simulations permit atomistic resolution, any level of structural detail may easily be incorporated. Moreover, kinetic Monte Carlo simulations proceed in real time. The simulation of current transients or cyclic voltammograms is, thus, straightforward [61]. 

Reuter K, Scheffler M. First-principles kinetic Monte Carlo simulations for heterogeneous catalysis Application to the CO oxidation at RuO2(110). Phys Rev B 2006 73 045433. Stegelmann C, Andreasen A, Campbell CT. Degree of rate control How much the energies of intermediates and transition states control rates. J Am Chem Soc 2009 131 8077. 

Rate constants can be estimated by means of transition-state theory. In principle all thermodynamic data can be deduced from the partion function. The molecular data necessary for the calculation of the partion function can be either obtained from quantum mechanical calculations or spectroscopic data. Many of those data can be found in tables (e.g. JANAF). A very powerful tool to study the kinetics of reactions in heterogeneous catalysis is the dynamic Monte-Carlo approach (DMC), sometimes called kinetic Monte-Carlo (KMC). Starting from a paper by Ziff et al. [16], several investigations were executed by this method. Lombardo and Bell [17] review many of these simulations. The solution of the problem of the relation between a Monte-Carlo step and real time has been advanced considerably by Jansen [18,19] and Lukkien et al. [20] (see also Jansen and Lukkien [21]). First principle quantum chemical methods have advanced to the stage where they can now offer quantitative predictions of structure and energetics for adsorbates on surfaces. Cluster and periodic density functional quantum chemical methods are used to analyze chemisorption and catalytic surface reactivity [see e.g. 24,25]. 

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