Kinetic Constraints in the Phase Transitions of Chemisorbed Carbon Monoxide on Co{101̄0} at High Coverages

Oxidation of carbon monoxide is one of the most extensively studied heterogeneous catalysis reactions, being important among other applications in automobile-emission control. Catalytic oxidation of carbon monoxide on platinum (111) surface was simulated by the Monte Carlo technique following an extended version of the model proposed by Ziff, Gulari and Barshad (ZGB). In the simulation, a simple square two-dimensional lattice of active sites replaces the surface of the catalyst. Finite reaction rates for (i) diffusion of the reactive species on the surface, (ii) reaction of a CO molecule with an oxygen atom in a nearest neighbor site, and (iii) desorption of unreacted CO molecules, have been taken into account. The produced CO 2 desorbs instantly. The average coverage of O, CO and the CO 2 production rate for a steady state configuration, as a function of the normalized CO partial pressure (P CO ), shows two kinetic phase transitions. In the ZGB model these transitions occur at P CO ≈ 0.39 and P CO ≈ 0.53. For 0.39 < P CO < 0.53 a reactive ( CO 2 production) steady state is found. Outside of the interval, the only steady state is a poisoned catalyst of pure CO or pure O. Our results show that finite reaction rates shift the values in which these phase transitions occur.

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Coverage-Dependent Infrared Spectroscopy of Carbon Monoxide on Palladium(100) in Aqueous Solution: Adlayer Phase Transitions and Electrooxidation Pathways

Langmuir ◽

10.1021/la9817720 ◽

1999 ◽

Vol 15 (8) ◽

pp. 2931-2939 ◽

Cited By ~ 17

Author(s):

Shouzhong Zou ◽

Roberto Gómez ◽

Michael J. Weaver

Keyword(s):

Aqueous Solution ◽

Carbon Monoxide ◽

Infrared Spectroscopy ◽

Phase Transitions

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A MONTE CARLO STUDY OF CARBON MONOXIDE LAYERS ADSORBED ON IONIC SUBSTRATES: STRUCTURES AND PHASE TRANSITIONS

Surface Review and Letters ◽

10.1142/s0218625x99000664 ◽

1999 ◽

Vol 06 (05) ◽

pp. 683-690 ◽

Cited By ~ 1

Author(s):

NGOC-THANH VU ◽

DAVID B. JACK

Keyword(s):

Carbon Monoxide ◽

Monte Carlo ◽

Phase Transitions ◽

Transition Temperature ◽

Monte Carlo Study ◽

Multilayer Systems ◽

Metropolis Monte Carlo ◽

Ordered Phases ◽

Bulk Structure ◽

Monolayer Coverage

We have studied the order–disorder phase transitions of carbon monoxide layers adsorbed on sodium chloride and lithium flouride substrates using the Metropolis Monte Carlo method. The simulations have been performed in the temperature range from 5 K to 60 K. At low temperature and monolayer coverage, both of these systems form ordered phases which disorder as the temperature is increased. The transition temperature (Tc) is between 30 K and 35 K for CO/NaCl, and from 40 K to 45 K for CO/LiF. Below Tc, both systems have an ordered p(2 × 1) type structure due to correlated azimuthal orientations. Above Tc, both systems undergo a phase transition to an azimuthally disordered p(1 × 1) structure, i.e. one with no preferred orientation in the surface plane. The heat capacity shows a characteristic divergence at the transition temperature. Coverages of less than a monolayer of the CO/NaCl system have also been studied. The CO molecules are found to aggregate and form islands with an ordered structure in the middle of the islands. These islands also undergo an order–disorder transition but at lower temperatures. Multilayer systems were found to destabilize the p(2 × 1) structure of the bottommost layer in favor of a p(1 × 1) structure with the upper layers adopting the bulk structure.

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Electron Microscopy of Graphite Intercalation Compounds

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100055564 ◽

1982 ◽

Vol 40 ◽

pp. 544-545

Author(s):

G. Timp ◽

L. Salamanca-Riba ◽

L.W. Hobbs ◽

G. Dresselhaus ◽

M.S. Dresselhaus

Keyword(s):

Electron Microscopy ◽

Phase Transitions ◽

Domain Wall ◽

Intercalation Compounds ◽

Lattice Plane ◽

Wall Model ◽

Graphite Intercalation Compounds ◽

Fundamental Symmetry ◽

Graphite Intercalation

Electron microscopy can be used to study structures and phase transitions occurring in graphite intercalations compounds. The fundamental symmetry in graphite intercalation compounds is the staging periodicity whereby each intercalate layer is separated by n graphite layers, n denoting the stage index. The currently accepted model for intercalation proposed by Herold and Daumas assumes that the sample contains equal amounts of intercalant between any two graphite layers and staged regions are confined to domains. Specifically, in a stage 2 compound, the Herold-Daumas domain wall model predicts a pleated lattice plane structure.

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Multiple phase transitions investigated by high-speed TEM

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100175880 ◽

1990 ◽

Vol 48 (4) ◽

pp. 550-551

Author(s):

Oleg Bostanjoglo ◽

Peter Thomsen-Schmidt

Keyword(s):

Phase Transitions ◽

High Speed ◽

Short Exposure ◽

Semiconductor Film ◽

Time Resolved ◽

Short Exposure Time ◽

Multiple Phase ◽

Model Substance ◽

History Of ◽

Electron Image

Thin GexTe1-x (x = 0.15-0.8) were studied as a model substance of a composite semiconductor film, in addition being of interest for optical storage material. Two complementary modes of time-resolved TEM were used to trace the phase transitions, induced by an attached Q-switched (50 ns FWHM) and frequency doubled (532 nm) Nd:YAG laser. The laser radiation was focused onto the specimen within the TEM to a 20 μm spot (FWHM). Discrete intermediate states were visualized by short-exposure time doubleframe imaging /1,2/. The full history of a transformation was gained by tracking the electron image intensity with photomultiplier and storage oscilloscopes (space/time resolution 100 nm/3 ns) /3/. In order to avoid radiation damage by the probing electron beam to detector and specimen, the beam is pulsed in this continuous mode of time-resolved TEM,too.Short events ( <2 μs) are followed by illuminating with an extended single electron pulse (fig. 1c)

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