Mechanisms of the catalytic carbon monoxide oxidation on Pt (110)

The kinetics of the carbon monoxide oxidation on a clean Pt (110) crystal were investigated in an ultra-high vacuum system by utilizing Auger electron spectroscopy, low-energy electron diffraction and residual gas analysis. Two different catalytic reaction mechanisms were found to prevail for the experimental conditions chosen. In the temperature range, 100 < T ? 220°C, where essentially CO was preadsorbed on the Pt surface the subsequent adsorption of O₂ was competitive and the reaction exhibited the characteristics of a Langmuir-Hinshelwood mechanism. In this case the onset of the CO₂ formation was delayed by a characteristic time which depended strongly on temperature (“induction period”). A simple model for the Langmuir-Hinshelwood reaction was developed which permitted a more detailed evaluation of the kinetic curves yielding an activation energy for the catalytic reaction of 2.9 kcal/mole. On the other hand, when oxygen was preadsorbed on the Pt surface (T > 90°C) the subsequent reaction with CO occurred immediately and was temperature independent. This behavior was interpreted in terms of an Eley-Rideal mechanism. Both reactions were used for titration of the adsorbed species. From area measurements under the titration curves it was concluded that the saturation coverage for CO and oxygen on Pt(110) is approximately the same.     

Potassium and potassium oxide monolayers on the platinum (111) and stepped (755) crystal surfaces: A LEED,AES, and TDS study

The adsorption of potassium and the coadsorption of potassium and oxygen on the Pt(111) and stepped Pt(755) crystal surfaces were studied by AES, LEED, and TDS. Pure potassium adlayers were found by LEED to be hexagonally ordered on Pt(111) at coverages of θ = _K0.9–;1. The monolayer coverage was 5.4 × 10¹⁴K atoms/cm² (0.36 times the atomic density of the Pt(111) surface). Orientational reordering of the adlayers, similar to the behavior of noble gas phase transitions on metals, was observed. The heat of desorption of K decreased, due to depolarization effects, from 60 kcal/mole at θ_K <0.1, to 25 kcal/mole at θ_K = 1 on both Pt(111) and Pt(755). Exposure to oxygen thermally stabilizes a potassium monolayer, increasing the heat of desorption from 25 to 50 kcal/mole. Both potassium and oxygen were found to desorb simultaneously indicating strong interactions in the adsorbed overlayer. LEED results on Pt(111) further indicate that a planar K₂O layer may be formed by annealing coadsorbed potassium and oxygen to 750 K.     

The oxidation of CO on the Pt(100)-(5 × 20) surface

The kinetics of the CO oxidation reaction were examined on the Pt(100)-(5 × 20) surface under UHV conditions. The transient isothermal rate of CO₂ production was examined both for exposure of an oxygen-dosed surface to a beam of CO and for exposure of a CO-dosed surface to a beam of O₂. Langmuir-Hinshelwood kinetics were found to apply in both cases. For the reaction of CO with preadsorbed oxygen atoms, the reaction rate was dependent upon the square-root of the oxygen atom coverage, suggesting that oxygen atoms were adsorbed in islands on this surface. The oxidation of preadsorbed CO was observed only when the initial CO concentrations were less than 0.5 monolayer (c(2 × 2) structure), suggesting that the dissociative adsorption of oxygen required adjacent four-fold surface sites. The activation energy calculated for the reaction of CO with preadsorbed oxygen was 31.4 kcal/mol. This value was 30 kcal/mol greater than the activation energy measured for the reaction of O₂ with preadsorbed CO. Strong attractive interactions within the oxygen islands were at least partially responsible for this difference. The reaction kinetics in both cases changed dramatically below 300 K; this change is believed to be due to phase separation at the lower temperature.     

Oxygen-induced nano-faceting of Ir(2 1 0)

The adsorption of oxygen and the nanometer-scale faceting induced by oxygen have been studied on Ir(2 1 0). Oxygen is found to chemisorb dissociatively on Ir(2 1 0) at room temperature. The molecular desorption process is complex, as revealed by a detailed kinetic analysis of desorption spectra. Pyramid-shaped facets with {3 1 1} and (1 1 0) orientations are formed on the oxygen-covered Ir(2 1 0) surface when annealed to T?600 K. The surface remains faceted for substrate temperatures T<850 K. For T>850 K, the substrate structure reverts to the oxygen-covered (2 1 0) planar state and does so reversibly, provided that oxygen is not lost due to desorption or via chemical reactions upon which the planar (2 1 0) structure remains. A clean faceted surface was prepared through the use of low temperature surface cleaning methods: using CO oxidation, or reaction of H₂ to form H₂O, oxygen can be removed from the surface while preserving (“freezing”) the faceted structure. The resulting clean faceted surface remains stable for T<600 K. For temperatures above this value, the surface irreversibly relaxes to the planar state.     

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.     

Oscillatory oxidation of Co over a Pt catalyst

We report measurements of the temporal oscillatory oxidation rates of CO over a polycrystalline Pt wire. The experiments were conducted near atmospheric pressure in a clean flow reactor system. Reproducible oscillations in both the temperature of the Pt wire and in the rate of CO₂ production were found over a wide range of gas compositions, $\text{0.001 <}\text{P}{}_{\mathrm{CO}}\text{P}{}_{\mathrm{O}}{}_2\text{< 0.045,}$ and temperatures, 150°C < T_g < 350°C, where PCO and po₂ are the respective partial pressures of carbon monoxide and oxygen in the gas stream, and T_g is the temperature of the gas. The oscillations are believed to occur between two branches of a Langmuir-Hinshelwood reaction mechanism. It is suggested that the slow formation and removal of subsurface oxygen drives the reaction between the two branches. A simple kinetic model based on this hypothesis gives excellent qualitative agreement with the observed oscillations.     

Electronic decoupling of surface layers from bulk and its influence in oxidation catalysis: A molecular beam study

Interactions between oxygen and Pd-surfaces have important implications, especially towards oxidation reactions, and influence of subsurface oxygen to oxidation reactions is the focus of the present study. In our efforts to understand the above aspects, CO oxidation reactions have been carried out with mixed molecular beam (MB), consisting CO and O₂, on Pd(1 1 1) surfaces under a wide variety of conditions (T = 400-900 K, CO:O₂ = 7:1 to 1:10). A new aspect of the above reaction observed in the transient kinetics regime is the evidence for oxygen diffusion into Pd subsurface layers, and its significant influence towards CO oxidation at high temperatures (≥600 K). Interesting information derived from the above studies is the necessity to fill up the subsurface layers with oxygen atoms to a threshold coverage (θ_O-sub), above which the reactive CO adsorption occurs on the surface and simultaneous CO₂ production begins. There is also a significant time delay (Γ) observed between the onset of oxygen adsorption and CO adsorption (and CO₂ production). Above studies suggest an electronic decoupling of oxygen covered surface and subsurface layers, which is slightly oxidized, from the metallic bulk, which induces CO adsorption at high temperatures and simultaneous oxidation to CO₂.     

Low-temperature ignition of methane-air mixtures under the action of nonequilibrium plasma

A plasma-chemical kinetic mechanism of the low-temperature (600 < T < 1000 K) oxidation/combustion of methane under conditions of nonequilibrium plasma over a wide pressure range (P = 0.1?100 atm) is developed and verified. The mechanism is comprised of three types of elementary processes: chemical reaction of neutral atoms and molecules, primary plasma-chemical processes involving electrons, and secondary plasma-chemical processes involving atomic and molecular ions and excited species. Application of the developed mechanism to describing the plasma-assisted oxidation of methane shows that this mechanism can describe the experimental results qualitatively and quantitatively.     

CO adsorption isotherms on Cu(100) at elevated pressures and temperatures using infrared reflection absorption spectroscopy

Infrared reflection-absorption spectroscopy (IRAS) has been used to study the adsorption of carbon monoxide on a Cu(100) surface. Adsorption isotherms were determined at CO pressures from 10⁻⁶ to 10 Torr, and at temperatures from 115 to 340 K, and the isosteric heats of adsorption (δE_ads) evaluated as a function of CO coverage. For increasing CO coverages between 0-0.15 monolayers (ML), δE_ads decreases sharply from 16.7 to 12.7 kcal/mol. From 0.15 to 0.35 ML, δE_ads remains approximately 12.7 kcal/mol and exhibits little coverage dependence. These results are in excellent agreement with previously reported data for the CO/Cu(100) system acquired at much lower pressures (<10⁻⁴ Torr) and temperatures (<275 K). At substrate temperatures above 240 K and at pressures > 10⁻⁴, significant bathochromic shifts of the CO frequency to lower wavenumbers are observed.     

CO和O2分子与TiO2(110)表面负载Pt单原子的相互作用

Pt单原子在低温CO氧化反应中具有很高的催化活性. 利用扫描隧道显微术与密度泛函理论，研究了Pt单原子在还原性TiO₂(110)表面的吸附行为及其与CO和O₂分子的相互作用. 研究发现在80 K低温下，TiO₂表面的氧空位缺陷是Pt单原子的最优吸附位. 将CO和O₂分子分别通入Pt单原子吸附后的TiO₂表面，研究相应的吸附构型. 实验表明在低覆盖度下，单个Pt原子会俘获一个CO分子，CO分子同时与表面次近邻的五配位Ti原子(Ti_5c)成键，进而形成非对称的Pt-CO 复合物构型. 将样品从80 K升温到100 K后，TiO₂表面的CO分子会迁移到Pt-CO处形成Pt-(CO)₂的复合结构. 对于O₂分子，单个Pt原子同样会吸附一个O₂分子，O₂分子也会与最近邻或次近邻的Ti_5c原子成键形成两种Pt-O₂构型. 这些结果在单分子尺度上揭示了CO和O₂与Pt单原子的相互作用，呈现了CO与O₂反应中的初始状态.     

Oxidised polyethylene as a paraelectric

A new experimental study of a known low temperature dielectric relaxation in oxidised polyethylene confirms that it is a manifestation of paraelectricity with certain similarities to the doped alkali halide systems. The tunnel splitting parameter (half the minimum energy splitting) is found to be 3.9 μeV ± 10%, while the strain coefficient of the double-well asymmetry is ≈ 5 meV. The multiphonon regime takes over from the one-phonon range at characteristic temperature T_o = 7.2 ± 0.5 K. A rather well oxidised sample shows a relaxation rate which varies as T^0.4 when T < 1 K, while the spread becomes markedly broader than a Debye curve. Oxidation with O₂¹⁸ leads to a 4.2 K peak at a frequency 13–15% lower than oxidation with O₂¹⁶. When the oxidised polyethylene is vacuum annealed the relaxation intensity diminishes. The half life at 126 C is about 2 hr and the activation energy of the annealing process is 40 ± 5 kcal/mole. A contaminated specimen showed accelerated oxidation kinetics and also accelerated anneal effect. These results lead to a suggested attribution of the relaxation to the rotation of the dihedral angle of isolated hydroperoxide groups. It is suggested that other hydrocarbon type materials may exhibit paraelectricity.     

A pyrolysis study on C4–C8 symmetric ethers

Pyrolysis of diethyl (C₄), di-n-propyl (C₆), di-isopropyl (C₆) and di-n-butyl (C₈) ethers were studied in a jet-stirred reactor between 720 and 1140 K, at 10 atm with an initial ether mole fraction of 0.1%. Major common pyrolysis products were observed to be CO, CH₄, H₂, and C₂H₄. All ethers produced the n/2 alcohol and olefin as products of molecular reaction to a small extent. Under pyrolysis conditions at 10 atm, hydrogen abstraction reactions by H atoms and CH₃ radicals were found to be important. Acetylene and benzene were formed for all ethers when T > 1000 K. A kinetic mechanism is used to represent these results. This study shows that there is need of systematic studies in determining site specific rate constants of important fuel related reactions of ethers.     

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.     

Island formation during CO/H coadsorption on Pt{111} studied by IR reflection-absorption spectroscopy

The reversible formation of pure CO islands during the coadsorption of CO and H on Pt{111} has been followed by monitoring the internal stretching vibration as well as the metal-carbon stretch of the CO molecule using infrared reflection-absorption spectroscopy. Island formation occurs in the temperature range 100 < T < 180 K and for average CO coverages θ_co < 0.25. This can be inferred from the appearance of bridge-bonded CO, not normally present on Pt{111} in this coverage range, and from the frequency and lineshape behaviour of the on-top absorption band. Depending on temperature and average CO coverage islands with local coverages up to θ'_CO = 0.5 occur but they always coexist with regions of lower local coverage and/or size. There is only a very weak direct interaction between the two species on the surface.     

Reactions of initiation of the autoignition of H<Subscript>2</Subscript>–O<Subscript>2</Subscript> mixtures in shock waves

The initiation of the autoignition of hydrogen–oxygen–argon mixtures behind reflected shock waves is studied by absorption and emission spectrophotometry in the temperature range of 960 < T < 1670 K at pressures of ~0.1 MPa. Introduction of Mo(CO)₆ additive in an amount of ~80 ppm made it possible to study the effect of O atoms on the shortening of the ignition delay time of H₂–O₂–Ar mixtures. A kinetic modeling of our own and published experimental data at temperatures of 930 < T < 2500 K and pressures of 0.05 < P < 8.7 MPa enabled to establish how the initiation reactions influence the process of self-ignition and to evaluate the rate constant for one of the initiation reactions: k(H₂ + O₂ → 2OH) = (3 ± 1) × 10¹¹exp(–E _a/RT), cm³ mol^–1 s^–1, where E _a = (40 ± 2) kcal/mol.     

The adsorption and decomposition of methanol on tungsten. II

A clean tungsten filament adsorbs methanol rapidly at room temperature, the initial sticking probability being 0.8. At saturation, the composition of the adsorbed layer is roughly CO:H = 1:1 and it is suggested that the hydrogen may be in the form of a surface complex. The continuous decomposition of methanol by the hot filament under steady-state conditions, or when the filament had been previously oxygenated, followed a different course from that previously reported for the newly-cleaned filament. Rather than a rapid rise in the rate of decomposition (to CO + H₂) for 600 < T_fil < 1300 K to a high plateau above 1300 K, decompositon to formaldehyde, carbon monoxide and methane was observed. The rates at which these products appeared passed through low maxima between 900 and 1100 K. The change in the relative importance of formaldehyde and carbon monoxide production with filament temperature within this range is attributed to a temperature-dependent life-time of formaldehyde molecules on the oxygenated surface. At the highest temperature (> 1500 K) the reactivity increased rapidly to join that of the clean surface, probably due to the desorption of surface oxygen.     

On the possible magnetic field dependence of the nickel carbonylation rate

The interaction of Ni with CO gas to produce Ni(CO)₄ at 1 atm pressure, has been studied as a function of time, temperature (25 < T < 95°C) and externally applied magnetic field (H ? 500 Oe). We find no significant magnetic field dependence of the nickel carbonylation rate, in sharp contrast with results previously reported by Krinchik et al. The activation energy for this reaction is found to be 0.21 ± 0.05 eV independent of magnetic field.     

The transition from surface to bulk oxide growth on Pt(1 0 0): Precursor-mediated kinetics

We investigated the kinetics governing the transition from surface (2D) to bulk (3D) oxide growth on Pt(1 0 0) in ultrahigh vacuum as a function of the surface temperature and the incident flux of an oxygen atom beam. For the incident fluxes examined, the bulk oxide formation rate increases linearly with incident flux (Φ_O) as the oxygen coverage increases to about 1.7 ML (monolayer) and depends only weakly on the surface temperature in the limit of low surface temperature (T_S < 475 K). In contrast, in the high temperature limit (T_S > 525 K), the bulk oxide formation rate increases with for oxygen coverages as high as 1.6 ML, and decreases with increasing surface temperature. We show that the measured kinetics is quantitatively reproduced by a model which assumes that O atoms adsorb on top of the 2D oxide, and that this species acts as a precursor that can either associatively desorb or react with the 2D oxide to form a 3D oxide particle. According to the model, the observed change in the flux and surface temperature dependence of the oxidation rate is due to a change in the rate-controlling steps for bulk oxide formation from reaction at low temperature to precursor desorption at high temperature. From analysis of flux-dependent uptake data, we estimate that the formation rate of a bulk oxide nucleus has a fourth-order dependence on the precursor coverage, which implies a critical configuration for oxide nucleus formation requiring four precursor O atoms. Considering the similarities in the development of surface oxides on various transition metals, the precursor-mediated transition to bulk oxide growth reported here may be a general feature in the oxidation of late transition metal surfaces.     

Bistability of the reaction rate in the oxidation of carbon monoxide by nitrogen monoxide on polycrystalline platinum

Multiplicity of the stationary reaction rate of CO oxidation by NO is observed under reducing conditions at pressures below 4×10^?4 mbar in the temperature range 500<T<525 K. The two branches of the reaction rate coalesce at a point where sustained oscillations are observed.     

The oxidation of CO on pt(100): Mechanism and structure

Using dynamic LEED measurements of spot intensities and profiles, together with thermal desorption data, we have investigated the oxidation of CO on Pt(100)?(1 × 1). At T = 355 K, either CO or O was preadsorbed and reacted off with the other species. Results from both titration sequences point to the following conclusions: Titration of preadsorbed oxygen with CO_g leads to rapid reaction, with a reaction probability of unity for each chemisorbed CO. Adsorbed CO does not accumulate on the surface until θ_o ? 0.05, i.e. an intermediate, rather clean (1 × 1) Pt surface is obtained. Further evidence for this clean intermediate is provided by the fact that characteristics of the diffraction spots of the c(2 × 2) of CO develop identically during this reaction sequence and during adsorption of CO on a clean (1 × 1) Pt surface. In the reverse case, titration of preadsorbed CO with O_2,g, the reaction rate is slower than the oxygen adsorption rate, leading to a pressure-dependent development of coexisting O_ad and CO_ad domains, which we observe directly with LEED. The stable phases coexisting are the c(2 × 2) of CO and the oxygen-related (3 × 1). Thermal desorption peak shapes, together with LEED observations, indicate that the CO in this case is held in c(2 × 2) islands by a matrix of surrounding oxygen atoms. In no case do mixed structures form, nor is an existing structure compressed by subsequent adsorption of the second species. Starting from a Langmuir-Hinshelwood mechanism, the differences between the two reaction sequences are discussed in terms of different activation barriers for reaction and different sticking coefficients of the adsorbing species. Special attention is given to the mobilities of the adsorbed reactants.