Catalytic CO Oxidation on Nanoscale Pt Facets: Effect of Inter-Facet CO Diffusion on Bifurcation and Fluctuation Behavior

We present lattice-gas modeling of the steady-state behavior in CO oxidation on the facets of nanoscale metal clusters, with coupling via inter-facet CO diffusion. The model incorporates the key aspects of reaction process, such as rapid CO mobility within each facet, and strong nearest-neighbor repulsion between adsorbed O. The former justifies our use a "hybrid" simulation approach treating the CO coverage as a mean-field parameter. For an isolated facet, there is one bistable region where the system can exist in either a reactive state (with high oxygen coverage) or a (nearly CO-poisoned) inactive state. Diffusion between two facets is shown to induce complex multistability in the steady states of the system. The bifurcation diagram exhibits two regions with bistabilities due to the difference between adsorption properties of the facets. We explore the role of enhanced fluctuations in the proximity of a cusp bifurcation point associated with one facet in producing transitions between stable states on that facet, as well as their influence on fluctuations on the other facet. The results are expected to shed more light on the reaction kinetics for supported catalysts.Comment: 22 pages, RevTeX, to appear in Phys. Rev. E, 6 figures (eps format) are available at http://www.physik.tu-muenchen.de/~natali

Fluctuation-Induced Transitions in a Bistable Surface Reaction: Catalytic CO Oxidation on a Pt Field Emitter Tip

Fluctuations which arise in catalytic CO oxidation on a Pt field emitter tip have been studied with field electron microscopy as the imaging method. Fluctuation-driven transitions between the active and the inactive branch of the reaction are found to occur sufficiently close to the bifurcation point, terminating the bistable range. The experimental results are modeled with Monte Carlo simulations of a lattice-gas reaction model incorporating rapid CO diffusion

Fluctuations and critical phenomena in catalytic CO oxidation on nanoscale Pt facets

Local fluctuations and fluctuation-induced transitions in catalytic CO oxidation are studied with field electron microscopy on the (112) facets of a [100]-oriented Pt field emitter tip. The reaction is investigated in the bistable range close to the cusp point (critical point) that terminates the bistability range in pCO, T-parameter space. The amplitude and the spatial coherence of the fluctuations increase on approaching the critical point. The fluctuations are spatially well correlated on each flat (112) facet, but their correlation decays rapidly across stepped regions that terminate the flat facets. On smaller (112) facets, an onset of fluctuation-induced transitions is observed earlier (i.e., further away from the critical point) than for larger (112) facets. The behavior of the reaction system near the cusp point appears to be similar to that of an equilibrium system near the critical point. The observed fluctuations are mimicked in a simple reaction model for CO oxidation on surfaces that incorporates both rapid diffusion of adsorbed CO, and superlattice ordering of adsorbed immobile oxygen. The steady states of the model exhibit a cusp bifurcation, from a regime of bistability to one of monostability. The fluctuations increase near this cusp point, as in experiment. This behavior is analyzed via kinetic Monte Carlo simulations and analytic procedures, focusing on the consequences for fluctuation-induced transitions

Adsorption of Reactive Particles on a Random Catalytic Chain: An Exact Solution

We study equilibrium properties of a catalytically-activated annihilation $A + A \to 0$ reaction taking place on a one-dimensional chain of length $N$ ($N \to \infty$) in which some segments (placed at random, with mean concentration $p$) possess special, catalytic properties. Annihilation reaction takes place, as soon as any two $A$ particles land onto two vacant sites at the extremities of the catalytic segment, or when any $A$ particle lands onto a vacant site on a catalytic segment while the site at the other extremity of this segment is already occupied by another $A$ particle. Non-catalytic segments are inert with respect to reaction and here two adsorbed $A$ particles harmlessly coexist. For both "annealed" and "quenched" disorder in placement of the catalytic segments, we calculate exactly the disorder-average pressure per site. Explicit asymptotic formulae for the particle mean density and the compressibility are also presented.Comment: AMSTeX, 27 pages + 4 figure

Field Stimulated Surface Diffusion of Lithium on Germanium (100) and (111) Planes

Field stimulated surface diffusion of lithium on atomically clean (100) and (111) germanium single crystal planes has been investigated by means of field emission method. Sealed-off field emission tube with a channel multiplier was used. The surface density of lithium adatoms on the germanium surface was determined applying a standard tungsten (112) crystal plane. The dependences of the surface diffusion activation energy on the applied electric field at different lithium coverages lave been obtained. The initial dipole moment of Li adatoms on the Ge (100) and (111) planes was then determined. The values 1.3 ± 0.2 and 1.0 ± 0.2 debye obtained for the Li-Ge (100) and Li-Ge (111) systems respectively are in good agreement with the ones calculated from the work function measurements. The reverse effect of the field influence on the surface diffusion of lithium on Ge (100) and (111) planes has been observed as the second lithium layer is filling. Relative contributions of the peculiarities of semiconductor substrate and alkali adsorbate on the properties of adsystems are discussed on the basis of experimental results

Fluctuation-Induced Transitions in a Bistable Surface Reaction: Catalytic CO Oxidation on a Pt Field Emitter Tip

Fluctuations which arise in catalytic CO oxidation on a Pt field emitter tip have been studied with field electron microscopy as the imaging method. Fluctuation-driven transitions between the active and the inactive branch of the reaction are found to occur sufficiently close to the bifurcation point, terminating the bistable range. The experimental results are modeled with Monte Carlo simulations of a lattice-gas reaction model incorporating rapid CO diffusion.This article is from Physical Review Letters 82 (1999): 1970, doi: 10.1103/PhysRevLett.82.1907.</p