51 research outputs found
Field ion microscopic studies of the CO oxidation on platinum: Bistability and oscillations
The oscillating CO oxidation is investigated on a Pt‐field emitter tip by using the field ion mode of surface imaging of Oad sites with O2 as imaging gas. Based on data of the titration reactions [V. Gorodetskii, W. Drachsel, and J. H. Block, J. Chem. Phys. 100, C. E. UPDATE (1994)], external control parameters for the regions of bistability and of self‐sustained isothermal oscillations could be found. On a field emitter tip, oscillations can be generated in a rather large parameter space. The anticlockwise hysteresis of O+2 ion currents in temperature cycles occurs in agreement with results on single crystal planes. Unexpected regular oscillation sequences could occasionally be obtained on the small surface areas of a field emitter tip and measured as function of the CO partial pressure and of the temperature. Different stages within oscillating cycles were documented by field ion images. Oscillations of total ion currents are correlated with variations in the spatial brightness of field ion images. In the manifold of single crystal planes of a field emitter {331} planes around the {011} regions are starting points for oscillations which mainly proceed along [100] vicinals. This excludes the {111} regions from autonomous oscillations. With slightly increased CO partial pressures fast local oscillations at a few hundred surface sites of the Pt(001) plane display short‐living CO islands of 40 to 50 Å diameter. Temporal oscillations of the total O+2 ion current are mainly caused by surface plane specific spatial oscillations. The synchronization is achieved by diffusion reaction fronts rather than by gas phase synchronization
Response of a Model of CO Oxidation with CO Desorption and Diffusion to a Periodic External CO Pressure
We present a study of the dynamical behavior of a Ziff-Gulari-Barshad model
with CO desorption and lateral diffusion. Depending on the values of the
desorption and diffusion parameters, the system presents a discontinuous phase
transition between low and high CO coverage phases. We calculate several points
on the coexistence curve between these phases. Inclusion of the diffusion term
produces a significant increase in the CO_2 production rate. We further applied
a square-wave periodic pressure variation of the partial CO pressure with
parameters that can be tuned to modify the catalytic activity. Contrary to the
diffusion-free case, this driven system does not present a further enhancement
of the catalytic activity, beyond the increase induced by the diffusion under
constant CO pressure.Comment: 5 pages, RevTe
Macroscopic and mesoscopic characterization of a bistable reaction system: CO oxidation on Pt(111) surface
The catalytic oxidation of CO by oxygen on a platinum (111) single-crystal surface in a gas-flow reactor follows the Langmuir–Hinshelwood reaction mechanism. It exhibits two macroscopic stable steady states (low reactivity: CO-covered surface; high reactivity: O-covered surface), as determined by mass spectrometry. Unlike other Pt and Pd surface orientations no temporal and spatiotemporal oscillations are formed. Accordingly, CO+O/Pt(111) can be considered as one of the least complicated heterogeneous reaction systems. We measured both the macroscopic and mesoscopic reaction behavior by mass spectrometry and photoelectron emission microscopy (PEEM), respectively, and explored especially the region of the phase transition between low and high reactivity. We followed the rate-dependent width of an observed hysteresis in the reactivity and the kinetics of nucleation and growth of individual oxygen and CO islands using the PEEM technique. We were able to adjust conditions of the external control parameters which totally inhibited the motion of the reaction/diffusion front. By systematic variation of these conditions we could pinpoint a whole region of external control parameters in which the reaction/diffusion front does not move. Parallel model calculations suggest that the front is actually pinned by surface defects. In summary, our experiments and simulation reveal the existence of an “experimental” bistable region inside the “computed” bistable region of the reactivity diagram (S-shaped curve) leading to a novel dollar ($)-shaped curve
Numerical study of a first-order irreversible phase transition in a CO+NO catalyzed reaction model
The first-order irreversible phase transitions (IPT) of the Yaldran-Khan
model (Yaldran-Khan, J. Catal. 131, 369, 1991) for the CO+NO reaction is
studied using the constant coverage (CC) ensemble and performing epidemic
simulations. The CC method allows the study of hysteretic effects close to
coexistence as well as the location of both the upper spinodal point and the
coexistence point. Epidemic studies show that at coexistence the number of
active sites decreases according to a (short-time) power law followed by a
(long-time) exponential decay. It is concluded that first-order IPT's share
many characteristic of their reversible counterparts, such as the development
of short ranged correlations, hysteretic effects, metastabilities, etc.Comment: 17 pages, 10 figure
Efficient determiniation of multilayer relaxation in the Pt(210) stepped and densely kinked surface
The multilayer relaxation of the Pt(210) stepped and kinked surface is analyzed by low-energy-electron diffraction. This is the first application of the new real-space multiple-scattering theory of LEED, designed specifically for such open surfaces where conventional theories fail. Combined with an automated tensor LEED method, it efficiently detects nonalternating atomic relaxations which are oriented primarily perpendicular to the surface. These relaxations are in qualitative agreement with new embedded-atom-method results
Nature of phase transitions in a probabilistic cellular automaton with two absorbing states
We present a probabilistic cellular automaton with two absorbing states,
which can be considered a natural extension of the Domany-Kinzel model. Despite
its simplicity, it shows a very rich phase diagram, with two second-order and
one first-order transition lines that meet at a tricritical point. We study the
phase transitions and the critical behavior of the model using mean field
approximations, direct numerical simulations and field theory. A closed form
for the dynamics of the kinks between the two absorbing phases near the
tricritical point is obtained, providing an exact correspondence between the
presence of conserved quantities and the symmetry of absorbing states. The
second-order critical curves and the kink critical dynamics are found to be in
the directed percolation and parity conservation universality classes,
respectively. The first order phase transition is put in evidence by examining
the hysteresis cycle. We also study the "chaotic" phase, in which two replicas
evolving with the same noise diverge, using mean field and numerical
techniques. Finally, we show how the shape of the potential of the
field-theoretic formulation of the problem can be obtained by direct numerical
simulations.Comment: 19 pages with 7 figure
Oscillatory dynamics in a heterogeneous surface reaction: Breakdown of the mean-field approximation
Hydrodynamic limits for the monomer-dimer surface reaction: Chemical diffusion, wave propagation, and equistability
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