63 research outputs found
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
Single-Particle Catalysis: Revealing Intraparticle Pacemakers in Catalytic H2Oxidation on Rh
Self-sustained oscillations in H2 oxidation on a Rh nanotip mimicking a single catalytic nanoparticle were studied by in situ field emission microscopy (FEM). The observed spatio-Temporal oscillations result from the coupling of subsurface oxide formation/depletion with reaction front propagation. An original sophisticated method for tracking kinetic transition points allowed the identification of local pacemakers, initiating kinetic transitions and the nucleation of reaction fronts, with much higher temporal resolution than conventional processing of FEM video files provides. The pacemakers turned out to be specific surface atomic configurations at the border between strongly corrugated Rh{973} regions and adjacent relatively flat terraces. These structural ensembles are crucial for reactivity: while the corrugated region allows sufficient oxygen incorporation under the Rh surface, the flat terrace provides sufficient hydrogen supply required for the kinetic transition, highlighting the importance of interfacet communication. The experimental observations are complemented by mean-field microkinetic modeling. The insights into the initiation and propagation of kinetic transitions on a single catalytic nanoparticle demonstrate how in situ monitoring of an ongoing reaction on individual nanofacets can single out active configurations, especially when combined with atomically resolving the nanoparticle surface by field ion microscopy (FIM)
Adsorption of Reactive Particles on a Random Catalytic Chain: An Exact Solution
We study equilibrium properties of a catalytically-activated annihilation reaction taking place on a one-dimensional chain of length () in which some segments (placed at random, with mean concentration
) possess special, catalytic properties. Annihilation reaction takes place,
as soon as any two particles land onto two vacant sites at the extremities
of the catalytic segment, or when any 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 particle. Non-catalytic segments are inert with
respect to reaction and here two adsorbed 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
Symmetry-Breaking and Percolation Transitions in a Surface Reaction Model with Superlattice Ordering
Spatial Desynchronization of Glycolytic Waves as Revealed by Karhunen−Loeve Analysis
The dynamics of glycolytic waves in a yeast extract have been investigated in an open spatial reactor. At low protein contents in the extract, we find a transition from inwardly moving target patterns at the beginning of the experiment to outwardly moving spiral- or circular-shaped waves at later stages. These two phases are separated by a transition phase of more complex spatiotemporal dynamics. We have analyzed the pattern dynamics in these three intervals at different spatial scales by means of a Karhunen−Loève (KL) decomposition. During the initial phase of the experiment, the observed patterns are sufficiently described by the two dominant KL modes independently of the spatial scale. However, during the last stage of the experiment, at least 6 KL modes are needed to account for the observed patterns at spatial scales larger than 3 mm, while for smaller scales, 2 KL modes are still sufficient. This indicates that in the course of the experiment, the local glycolytic oscillators become desynchronized at spatial scales larger than 3 mm. Possible reasons for the desynchronization of the glycolytic waves are discussed. Copyright © 2013 American Chemical Society [accessed 2013 June 14th
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