Study of oscillations and pattern formation in the CO + O2 reaction on Pt(1 0 0) surfaces through dynamic Monte Carlo simulation

Oscillations and pattern formation driven by a surface reconstruction are studied for the catalytic oxidation of CO on Pt(1 0 0) single-crystal surfaces through dynamic Monte Carlo simulations at low pressure and relatively high temperatures conditions. Sustained, modulated, irregular and damped oscillations are observed in our analysis as well as the formation of cellular, target, double spiral, spiral wave and turbulent patterns. The effect and the importance of the hex ? 1 × 1 surface phase transition and partial pressure of the reactants in the gas phase on the behavior of the system are discussed.     

Surface Restructuring, Kinetic Oscillations, and Chaos in Heterogeneous Catalytic Reactions

Kinetic oscillations in catalytic reactions on single-crystal surfaces often result from the interplay of the purely chemical reaction steps and adsorbate-induced surface restructuring. A classical example is CO oxidation on Pt(100). We survey evolution of the models used to simulate this reaction and show how it can be described self-consistently by employing Monte Carlo simulations combined with the lattice-gas model, taking into account substrate-substrate, substrate-adsorbate and adsorbate-adsorbate lateral interactions. Under the reactive conditions, this approach predicts formation of mesoscopic restructured well ordered islands with atomically sharp boundaries.     

Surface reconstruction in reactive dynamics: A kinetic Monte Carlo approach

The oscillatory CO oxidation reaction on the restructuring surface of Pt(1 0 0) is studied through a mesoscopic kinetic Monte Carlo (KMC) approach. The present model is an extension of the standard ZGB model with specific attention to the emergence of oscillations in surface reactions. A square and a purely hexagonal lattice are used as substrates on which the CO oxidation reaction steps take place. The dynamics of the reaction on the two substrates exhibit the ZGB kinetic phase transitions, at different kinetic parameter values for each substrate. Surface reconstruction is modelled through switching between the two lattice types. Oscillations are produced in those parametric areas where the steady state concentrations on the two substrates are considerably different. The parametric area where notable oscillations are observed is narrow, but is greatly enhanced when different sticking coefficients of oxygen are taken into account. CO diffusion introduced microscopically to the model on the hexagonal lattice shifts the kinetic transition points and increases considerably the time needed to reach the steady state.     

In-situ study of the catalytic oxidation of CO on a Pt(1 1 0) surface using ambient pressure X-ray photoelectron spectroscopy

CO and O₂ co-adsorption and the catalytic oxidation of CO on a Pt(1 1 0) surface under various pressures of CO and O₂ (up to 250 mTorr) are studied using ambient pressure X-ray photoelectron spectroscopy (APXPS) and mass spectrometry. There is no surface oxide formation on Pt under our reaction conditions. CO oxidation in this pressure (<500 mTorr), O₂ to CO ratio (<10), and temperature (150 °C) regime is consistent with the Langmuir-Hinshelwood reaction mechanism. Our findings provide in-situ surface chemical composition data of the catalytic oxidation of CO on Pt(1 1 0) at total pressures below 1 Torr.     

Coupled catalytic oscillators: Beyond the mass-action law

We present Monte Carlo simulations of the reaction kinetics corresponding to two coupled catalytic oscillators in the case when oscillations result from the interplay between the reaction steps and adsorbate-induced surface restructuring. The model used is aimed to mimic oscillations on a single nm catalyst particle with two kinds of facets or on two catalyst particles on a support. Specifically, we treat the NO reduction by H(2) on a composite catalyst containing two catalytically active Pt(100) parts connected by an inactive link. The catalyst is represented by a rectangular fragment of a square lattice. The left- and right-hand parts of the lattice mimic Pt(100). With an appropriate choice of the model parameters, these sublattices play a role of catalytic oscillators. The central catalytically inactive sublattice is considered to be able only to adsorb NO reversibly and can be viewed as a Pt(111) facet or a support. The interplay of the reactions running on the catalytically active areas occurs via NO diffusion over the boundaries between the sublattices. Using this model, we show that the coupling of the catalytically active sublattices may synchronize nearly harmonic oscillations observed on these sublattices and also may result in the appearance of aperiodic partly synchronized oscillations. The spatio-temporal patterns corresponding to these regimes are nontrivial. In particular, the model predicts that, due to phase separation, the reaction may be accompanied by the formation of narrow NO-covered zones on the left and right sublattices near the boundaries between these sublattices and the central sublattice. Such patterns cannot be obtained by using the conventional mean-field reaction-diffusion equations based on the mass-action law. The experimental opportunities to observe the predicted phenomena are briefly discussed. (c) 2001 American Institute of Physics.     

Non-equilibrium surface phase transitions during the catalytic oxidation of CO on Pt(100)

Isothermal low-pressure oscillations of the rate of catalytic CO oxidation on a Pt(100) surface could be established under appropriate conditions and were monitored through the accompanying periodic variation of the work function. Parallel observations by the Video-LEED technique demonstrated that these oscillations are associated with periodic transformations of the (long-range) surface structure from the reconstructed hex to the 1 × 1 phase and back, which is caused by varying surface concentrations of the reacting particles.     

Monte Carlo simulations of FTIR studies during CO oxidation on a Pt/SiO2 catalyst

A Monte Carlo (MC) simulation of the reaction of CO with an oxygen covered Pt surface and oxygen with a CO covered Pt surface is presented in this paper. The effect of the adsorption, desorption, reaction, and surface migration rates on the formation of CO clusters is analyzed in terms of the CO frequency shift in the IR spectrum. The MC simulation calculates the CO frequency shifts according to a dipole-dipole interaction model. The IR frequency shifts predicted by the simulation depend on the value of the various kinetic processes considered. The simulation indicates that the CO migration on the surface is important at low pressure but is inhibited at high pressure. The IR frequency shifts predicted by the simulation agree qualitatively with experimental values obtained during CO oxidation on a Pt catalyst.     

Surface restructuring, kinetic oscillations, and chaos in heterogeneous catalytic reactions

We present comprehensive Monte Carlo simulations of isothermal kinetic oscillations and chaos in catalytic reactions accompanied by adsorbate-induced surface restructuring. Our analysis is based on the lattice-gas model describing surface restructuring in terms of the statistical theory of first-order phase transitions. As an example, we treat the kinetics of the NO-H2 reaction on the Pt(100) surface. A proposed reduced mechanism of this reaction includes NO adsorption, desorption, and decomposition occurring on the restructured patches of the surface (the decomposition products are rapidly removed from the surface via N2 desorption and H2O formation and desorption). Calculations are performed with a qualitatively realistic ratio between the rates of different elementary steps. In particular, NO diffusion is several orders of magnitude faster compared to the other steps. On the nm scale, the model predicts formation of restructured islands with atomically sharp boundaries. The shape of the islands is found to change dramatically with varying reaction conditions. Despite phase separation on the surface, the transition from almost harmonic oscillations (with relatively small separate islands) to chaos (with merging islands) is demonstrated to occur via the standard Feigenbaum scenario. Near the critical point, the dependence of the amplitude of oscillations on the governing parameter is shown to be close to that predicted for the Hopf supercritical bifurcation.     

Fabrication of nanosized Pt on rutile TiO2 using a standing wave sonochemical reactor (SWSR) – observation of an enhanced catalytic oxidation of CO

Fine particles of rutile TiO₂ supporting nanosized particles of Pt were prepared by a simultaneous in situ sonochemical reduction and deposition method using a standing wave sonochemical reactor (SWSR). The mean diameter of sonochemically obtained Pt particles are of 2 nm. Following this sonochemical technique, rutile TiO₂ was also deposited with different weight percentages of Pt. Catalytic function of the prepared composite catalysts were tested by the oxidation of CO to CO₂. From the catalytic activity results, it has been found out that the catalysts prepared by the sonochemical method exhibited higher catalytic activity for CO oxidation, probably attributed to the higher Pt particle distribution achieved under sonication. Transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), and diffuse reflectance spectroscopy (DRS) were employed to characterize the resulting material.     

Influence of the spacing between metal particles on the kinetics of reaction with spillover on the supported metal catalyst

The influence of the spacing between active metal particles placed on the supported metal catalyst on the kinetics of the catalytic reaction with spillover was investigated. The 2A+B₂→2AB reaction, modelling the CO oxidation on Pd/Al₂O₃ catalyst, was studied using Dynamic Monte Carlo simulations. It was shown that there exists an optimal spacing, that provides the maximum reaction rate. It was postulated that this optimum is a consequence of both competition and cooperative effects occurring between metal particles.     

The UBI-QEP method: Mechanistic and kinetic studies of heterogeneous catalytic reactions

Applications of the unity bond index-quadratic exponential potential (UBI-QEP) method in mechanistic and kinetic studies of complex heterogeneous catalytic reactions are discussed. It is shown how UBI-QEP energetics helps to answer specific questions regarding the mechanisms of various reactions on metal surfaces. Examples of the following reactions are considered: elementary reactions of hydrogen transfer (from one carbon atom connected to the metal surface to another such atom in a different surface species), H-X bond breaking with the assistance of coadsorbed oxygen, methanol synthesis, Fischer-Tropsch synthesis, ammonia synthesis and decomposition, and partial methanol oxidation to formaldehyde. Then, examples of kinetic simulations using UBI-QEP energetics are considered for the following processes: ethane hydrogenolysis, watergas shift reaction, selective hydrogenation of acetylene in ethylene-rich mixtures, oxidative conversions of hydrogen and methane on Pt and Rh surfaces, ammonia decomposition, C₁–C₂ product formation in Fischer-Tropsch synthesis over cobalt, and steam reforming of methane. It is shown how the use of UBI-QEP and Monte Carlo methods makes it possible to calculate reaction parameters that depend on temperature in the equilibrium and kinetic regimes. To increase the accuracy of simulations, we added nonenergetic parameters affecting energetics at nonzero coverages: a spatial constraint on the distance between adsorbed atoms and the distance of hot atom traveling upon oxygen dissociation on metal surfaces. The UBI-QEP/Monte Carlo simulation method is illustrated by the study of molecular oxygen adsorption on single crystalline nickel surfaces. In most UBI-QEP-based mechanistic and kinetic studies of heterogeneous catalytic reactions, good agreement is observed with experimental observations, in many cases on a quantitative level. Taking into account diversity of reactions to which the method has been applied the agreement with experiments supports the efficiency of the method in solving mechanistic and kinetic problems.     

Oscillations, period doublings, and chaos in CO oxidation and catalytic mufflers

Early experimental observations of chaotic behavior arising via the period-doubling route for the CO catalytic oxidation both on Pt(110) and Ptgamma-Al(2)O(3) porous catalyst were reported more than 15 years ago. Recently, a detailed kinetic reaction scheme including over 20 reaction steps was proposed for the catalytic CO oxidation, NO(x) reduction, and hydrocarbon oxidation taking place in a three-way catalyst (TWC) converter, the most common reactor for detoxification of automobile exhaust gases. This reactor is typically operated with periodic variation of inlet oxygen concentration. For an unforced lumped model, we report results of the stoichiometric network analysis of a CO reaction subnetwork determining feedback loops, which cause the oscillations within certain regions of parameters in bifurcation diagrams constructed by numerical continuation techniques. For a forced system, numerical simulations of the CO oxidation reveal the existence of a period-doubling route to chaos. The dependence of the rotation number on the amplitude and period of forcing shows a typical bifurcation structure of Arnold tongues ordered according to Farey sequences, and positive Lyapunov exponents for sufficiently large forcing amplitudes indicate the presence of chaotic dynamics. Multiple periodic and aperiodic time courses of outlet concentrations were also found in simulations using the lumped model with the full TWC kinetics. Numerical solutions of the distributed model in two geometric coordinates with the CO oxidation subnetwork consisting of several tens of nonlinear partial differential equations show oscillations of the outlet reactor concentrations and, in the presence of forcing, multiple periodic and aperiodic oscillations. Spatiotemporal concentration patterns illustrate the complexity of processes within the reactor.     

Preparation of nano-sized platinum metal catalyst using photo-assisted deposition method on mesoporous silica including single-site photocatalyst

Pt particles in a uniform dispersion were successfully synthesized on single-site photocatalyst (Ti-containing mesoporous silica (Ti-HMS)) under UV-light irradiation by a photo-assisted deposition (PAD) method. Using an aqueous solution of H₂PtCl₆ as a precursor, the nano-sized Pt metal particles were deposited directly on the photo-excited tetrahedrally coordinated titanium oxide moieties within the framework of mesoporous silica (PAD-Pt/Ti-HMS). The Pt catalysts were characterized by means of XRD, Pt L_III-edge XAFS, CO adsorption, and TEM analysis. It was demonstrated that Pt particles had mean diameter of 4 nm in a narrow size distribution. Meanwhile, Pt particles loaded by a conventional impregnation method (imp-Pt/Ti-HMS) showed a wide size distribution ranging from 2 to 30 nm. The PAD-Pt/Ti-HMS catalyst was more active in the CO oxidation than the conventional impregnated imp-Pt/Ti-HMS catalyst. It is suggested that the PAD method using single-site photocatalyst is a useful and unique technique to prepare fine and uniform Pt nanoparticles.     

Highly active surfaces for CO oxidation on Rh, Pd, and Pt

Studies show that the rate of CO oxidation on Pt-group metals at temperatures between 450 and 600 K and pressures between 1 and 300 Torr increases markedly with an increase in the O₂/CO ratio above 0.5. The catalytic surfaces, formed at discrete O₂/CO ratios >0.5, exhibit rates 2-3 orders of magnitude greater than those rates observed for stoichiometric reaction conditions and similar reactant pressures or previously in ultrahigh vacuum studies at any reactant conditions and extrapolate to the collision limit of CO in the absence of mass transfer limitations. The O₂/CO ratios required to achieve these so-called “hyperactive” states (where the reaction probabilities of CO are thought to approach unity) for Rh, Pd, and Pt relate directly to the adsorption energies of oxygen, the heats of formation of the bulk oxides, and the metal particle sizes. Auger spectroscopy and X-ray photoemission spectroscopy reveal that the hyperactive surfaces consist of approximate 1 ML of surface oxygen. In situ polarization modulation reflectance absorption infrared spectroscopy measurements coupled with no detectable adsorbed CO. In contrast, under stoichiometric O₂/CO conditions and similar temperatures and pressures, Rh, Pd, and Pt are essentially saturated with chemisorbed CO and exhibit far less activity for CO oxidation.     

CO adsorption and dissociation on iron oxide supported Pt particles

We studied CO adsorption on Pt particles deposited on well-ordered Fe₃O₄(1 1 1) thin films grown on Pt(1 1 1) by temperature programmed desorption (TPD). A highly stepped Pt(1 1 1) surface produced by ion sputtering and annealing at 600 K was studied for comparison. Structural characterization was performed by scanning tunneling microscopy and Auger electron spectroscopy. The TPD spectra revealed that in addition to the desorption peaks at ∼400 and 480 K, assigned to CO adsorbed on Pt(1 1 1) facets and low-coordination sites respectively, the Pt nanoparticles annealed at 600 K exhibit a desorption state at ∼270 K. This state is assigned to initial stages of strong metal support interaction resulting in partial Fe-Pt intermixing. On both Pt/Fe₃O₄(1 1 1) and stepped Pt(1 1 1) surfaces CO is found to dissociate at 500 K. The results suggest that CO dissociation and carbon accumulation occur on the low-coordinated Pt sites.     

Lifted reconstruction as a feedback mechanism in the oscillating CO oxidation on Pt nanofacets: Microscopic evidences

Global and local oscillations in the CO oxidation reaction have been visualized in situ on the apex of a [1 0 0]-oriented Pt field emitter tip used as a well-defined model for catalytically active, nm-sized particles by Field Emission (FEM) and Lithium Field Desorption (Li-FDM) Microscopes. For the first time experimental evidence is provided that the reconstruction feedback mechanism of the self-maintained oscillations for the [1 0 0] and [1 1 0] orientations, which is well established on macroscopic single crystals, is also valid in the heterogeneous, nm-sized system with its different crystallographic orientations which are coupled by surface diffusion.     

Electrochemical properties of palladium adlayers on Pt(1 0 0) substrates

The formation of submonolayers of palladium on well-defined Pt(1 0 0) electrodes is described. It has been found that the adsorption of NO at open circuit and its further reductive stripping enable the possibility to prepare Pt(1 0 0) electrodes fully covered by the first palladium layer, without contributions coming from palladium in the subsequent layers. This method enables a better characterization of the palladium islands formed in the submonolayer range. The CO displacement method points out that hydrogen and anion adsorption play a role in the charge transfer processes involved in the voltammetric profile. The analysis of the charge-potential curves is used to determine the values of the potentials of zero total charge (pztc) of the different adelectrodes. The pztc diminishes almost linearly with palladium coverage, this shift being related to increasing anion adsorption at low potentials. Adsorbed palladium does not electrocatalyze the oxidation of adsorbed CO.     

Electrochemical promotion in emission control catalysis

Electrochemical promotion for the catalytic reduction of NO by CO and of NO by ethylene over a Pt catalyst are reported for the first time. Both reactions are of importance in the catalytic control of automotive emissions and both exhibit strong rate enhancement when Na is pumped to the Pt catalyst electrode from a β″ solid electrolyte. Complementary data obtained with a Pt(111)/Na model system indicate that electrochemically-pumped Na acts by inducing dissociation of chemisorbed NO, which is the reaction initiating step. Paper presented at the 1st Euroconference on Solid State Ionics, Zakynthos, Greece, 11 – 18 Sept. 1994.     

Surface (electro-)chemistry on Pt(1 1 1) modified by a Pseudomorphic Pd monolayer

The formic acid and methanol oxidation reaction are studied on Pt(1 1 1) modified by a pseudomorphic Pd monolayer (denoted hereafter as the Pt(1 1 1)-Pd_1 ML system) in 0.1 M HClO₄ solution. The results are compared to the bare Pt(1 1 1) surface. The nature of adsorbed intermediates (CO_ad) and the electrocatalytic properties (the onset of CO₂ formation) were studied by FTIR spectroscopy. The results show that Pd has a unique catalytic activity for HCOOH oxidation, with Pd surface atoms being about four times more active than Pt surface atoms at 0.4 V. FTIR spectra reveal that on Pt atoms adsorbed CO is produced from dehydration of HCOOH, whereas no CO adsorbed on Pd can be detected although a high production rate of CO₂ is observed at low potentials. This indicates that the reaction can proceed on Pd at low potentials without the typical “poison” formation. In contrast to its high activity for formic acid oxidation, the Pd film is completely inactive for methanol oxidation. The FTIR spectra show that neither adsorbed CO is formed on the Pd sites nor significant amounts of CO₂ are produced during the electrooxidation of methanol.