Some aspects of the kinetics of CO oxidation over Ir(111)

The steady-state kinetics of the CO oxidation reaction over the Ir(111) surface is analyzed on the basis of the data obtained earlier in transient studies.     

An XPS and UPS study of the kinetics of carbon monoxide oxidation over Ag(111)

The oxidation of carbon monoxide over a Ag(111) catalyst has been studied by XPS and UPS. The kinetics have been determined over the temperature range of 180 to 400 K and found to be of the Langmuir-Hinshelwood type, although the Eley-Rideal mechanism is mimicked. A negative activation energy, ?1.7 kcal/mole, and a preexponential, 6 × 10^?18 cm², are found. The former corresponds to the difference in the activation energies for carbon monoxide desorption and for carbon monoxide oxidation (leading to CO₂ desorption). At 90 K, upon carbon monoxide exposure to the active oxygen precovered surface, the O ls and C ls spectral regions show the formation of CO₂-like and carbonate species; the latter is stable to at least room temperature. That is, at 90 K, the residence time and mobility of CO₂ formed at the surface permits a new surface reaction — the formation of stable surface carbonate. The identifications are based on C and O coverages and on line positions from the literature for Cu/CO₂ and several bulk carbonates. With UPS, the 1π_g, the unresolved doublet 1π_u and 3σ_g, and the 4σ_g molecular orbitals of adsorbed CO₂-like species are identified, as well as the unresolved triplet 1α′₂, 1e″ and 4e′ and the unresolved triplet 3e′, 1α″₂ and 4a′ molecular orbitals of the carbonate species. Surface CO₂-like species formed by surface oxidation of CO seem to be more strongly bound than reversibly adsorbed CO₂.     

Oscillatory oxidation of co over Pd and Ir catalysts

Oscillations in the rate of CO₂ production have been observed for the first time over Pd and Ir catalysts. The experiments were conducted near atmospheric pressure in a clean flow reactor system using polycrystalline Pd or Ir wire. For Pd, sustained oscillations were found over a wide range of gas compositions and temperatures (230 < T_g < 350°C), where P_CO and P_O2 are the respective partial pressures of carbon monoxide and oxygen in the gas stream, and Tg is the temperature of the gas. For Ir, oscillations were found for and 180 < T_g < 250°C. As proposed for CO oxidation over a Pt catalyst, it is believed that the oscillations occur between two branches of a Langmuir-Hinshelwood reaction mechanism, and that the slow formation and removal of subsurface oxygen drives the reaction between these two branches. These experiments suggest that oscillations in surface reactions are more general than previously suspected.     

The oxidation and co reduction kinetics of a platinum surface

A thermogravimetric technique was used to study the oxidation and CO reduction kinetics of Pt as a function of temperature, T. The measurements were performed on Pt powder (particle sizes 0.8–2.5 μm) at 1 atm pressure. After exposure to 1 atm of oxygen at 600 K for 1 h, the total uptake of oxygen by the powder amounted to less than one oxygen atom per Pt surface atom and followed a logarithmic growth law. For 400 < T < 600 K, the logarithmic rate constant, K₀, could be described by an Arrhenius law with an apparent activation energy of 2.6 kcal/mole. Above 600 K, K₀ slowly decreased, an effect believed to be associated with the dissociation of the oxide between 650 and 850 K. Oxidation isotherms were calculated using the low pressure oxygen sticking coefficient data of Hopster et al. The calculated and measured oxidation isotherms were found to be in remarkable agreement. The CO reduction data were more difficult to analyze but showed that the reduction rate had a stronger temperature dependence (~11 kcal/mole) than the oxidation rate. For427 < T<487 K, the general time scale of the reduction process was 10–50 min. Typical durations of the oxidation and CO reduction processes are consistent with the periods observed in studies of the oscillatory rate of CO oxidation over a Pt catalyst.     

Molecular orbital study of co chemisorption and oxidation on a Pt(111) surface

A molecular orbital study was made, using an atom superposition and electron delocalization (ASED) technique, of the structures and energy levels of CO on Pt(111) surface. CO is predicted to be preferentially adsorbed at a height of 2.05 Å from the surface at a 1-fold position with the carbon end down. The calculated binding energy (1.7 eV) is in good agreement with the recent experimental result (1.5 eV) of Campbell et al. Calculated binding energies for bridging (1.3 eV) and high coordinate (1.1 eV) sites are predicted to be smaller in magnitude. Calculated results are used to discuss the ordering of energy levels of adsorbed CO. The interaction between CO (adsorbed) and O (adsorbed) has been studied to estimate the energy of activation for the oxidation of CO on Pt(111) surface. The calculated activation energy (1.6 eV) is in reasonable agreement with the recent experimental result (1 eV) of Campbell et al. The Langmuir-Hinshelwood mechanism is found to be favored. We predict CO₂ bonds vertically.     

Laser-induced oxidation of the Si(111) surface

Pulsed laser induced oxidation of clean Si(111) surfaces has been studied by Auger electron spectroscopy and electron energy loss spectroscopy. The short duration time of the pulse has allowed a precise investigation of the first stages of the oxidation. About 1–2 oxide monolayers first grow in less than 10 s. Their stoichiometry evolves from SiO_x towards SiO₂ with increasing beam energy densities. Once this superficial layer has formed, no evolution is seen with further irradiation, suggesting that oxygen diffusion during the pulse duration cannot sustain the oxide growth.     

Chemisorptive bonding and reaction of nitric oxide on Ir(100) and Ir(111) surfaces

Chemisorption of nitric oxide on single crystal Ir(111) and Ir(100)?(5 × 1) has been studied by UV-photoelectron spectroscopy, thermal desorption and low energy electron diffraction. At 300 K, partially dissociative adsorption is observed on both surfaces, confirming the borderline location of Ir in the Periodic Table with respect to molecular versus dissociative adsorption. Three different molecular chemisorption phases are distinguished in the UPS spectra through distinctly different 1π-level energies. A skewed orientation associated with a possible rehybridization and bending of the nitrosyl-metal bound for chemisorption on the Ir(111) surface is inferred both from a splitting of the 1π level and from observation of relative intensity variations in photoemission using a polarized photon source.     

Step edge diffusion and the structure of nanometer-size Ir islands on the Ir(111) surface

We report an FIM study of the structure of nanometer-size Ir islands on the Ir(111) surface. In this experiment, the number of atoms in an island is carefully controlled by field evaporation and vapor deposition. When this number can be fitted to a hexagonal atomic arrangement, the stable structure is found to be a perfect hexagon. In other cases, an addition of one ledge atom can reverse the symmetry of a small island or change its shape. We also compare diffusion of adatoms on the Ir(311) and (331) surfaces to that of ledge-atoms along the A- and B-type steps of the (111) layer, and the relative binding energies of a ledge atom at these steps.     

XPS studies for NaCl deposited on the Ni(111) surface

Vapor deposited NaCl on the Ni(111) surface was characterized by XPS. Three types of NaCl were found on the surface. First, the NaCl interacted strongly with Ni giving the Nals peak at 1072.2 eV, the C12p peak at 198.8 eV and the NaKLL peak at 494.3 eV. The 494.3 eV peak shifted to 493.4 eV when measured at ∼ 500 K. The energy of the NaKLL peak and the modified Auger parameter for sodium were nearer to those for Na metal than to those for bulk NaCl. The species was assigned to NaCl which was freed from the potential of the NaCl crystal and which had a weakened NaCl bond. The other types were characterized by using H₂O as a probe. One set of the peaks, the Nals peak at 1072.8 eV, the C12p peak at 199.6 eV and the NaKLL peak at 497.7 eV, was assigned to NaCl which was in the form of a very thin crystal. The other set, the Nals peak at 1073.5 eV, the C12p peak at 200.1 eV and the NaKLL peak at 498.5 eV, was obtained during crystal growth of NaCl as large islands upon annealing. The energies suffered from the charging effect. The effect of coadsorbing oxygen was also studied.     

Dynamical LEED analyses of the clean and the NO-adsorbed Ir(111) surface

The adsorption structure of nitric oxide (NO) on Ir(111) was studied by thermal desorption spectroscopy (TDS) and dynamical analyses of low-energy electron diffraction (LEED). At the saturation coverage at about 100 K, a 2 × 2 pattern was observed by LEED and two peaks appeared at 365 and 415 K in TDS. No change in the LEED I–V curves was observed by annealing at 280 K, which means that the NO-saturated surface was retained at this temperature. On the contrary, partial desorption and changes of the LEED I–V curves were observed by annealing at 360 K. Combined with previous vibrational studies, it is suggested that one adsorption species is not affected, while another species is partially desorbed and the rest of them are dissociated by annealing at 360 K. Dynamical analyses of LEED were performed for the 280 K-annealed and the 360 K-annealed surfaces, which correspond to the NO-saturated and the NO-dissociated Ir(111) surfaces, respectively. These revealed that NO occupies the atop, fcc-hollow and hcp-hollow sites (atop-NO + fcc-NO + hcp-NO) for the NO-saturated Ir(111) surface with the saturation coverage of 0.75 ML. For the 360 K-annealed surface, the atop-NO is not affected but the fcc-NO and the hcp-NO are partially desorbed as NO and partially dissociated to N and O, both of which occupy the fcc-hollow site on the surface.     

The steady-state kinetics of the hydrogen-oxygen reaction on a Pt(111) surface at low and moderate pressures

The steady-state kinetics of the hydrogen-oxygen reaction on a Pt(111) surface is studied at low (10⁻⁵−10⁻⁴ Pa) and moderate (5–100 Pa) pressures of the stoichiometric mixture of the reagents. The moderate-pressure kinetics is analyzed on the basis of data obtained in the transient studies at low pressures. It is found that the reaction rate, extrapolated from low to moderate pressures, exceeds the measured rate by about an order of ten.     

Structural properties of a monolayer graphite film on the (111)Ir surface

The structural properties of a monolayer graphite film prepared on the (111)Ir surface through thermal decomposition of benzene molecules were studied. The study was carried out in ultrahigh vacuum using scanning tunneling microscopy, which allowed observation of the atomic structure of the film. It is shown that, on extended smooth regions of the Ir surface, a continuous graphite film with a regular arrangement of carbon atoms in a planar hexagonal lattice is formed. The orientation of zigzag carbon atom chains coincides with the 〈110〉 direction on the Ir surface. Structural defects of the (5, 7) configuration were revealed in the film. A comparison of the topographies of the film and the (111)Ir surface shows that the graphite layer smoothly (without discontinuities) flows over subnanometer topographical features existing on the Ir surface and that the distance between the graphite film and the metal surface in this case can reach 1 nm.     

Controllable oxidation of h-BN monolayer on Ir(111) studied by core-level spectroscopies

The effect of atomic oxygen adsorption on the structure and electronic properties of monolayer hexagonal boron nitride (h-BN) grown on Ir(111) has been studied using near edge X-ray absorption fine structure spectroscopy (NEXAFS), photoelectron spectroscopy (PES), and low-energy electron diffraction (LEED). It has been shown that the oxidation of the h-BN monolayer occurs through a gradual substitution of N by O in the h-BN lattice. This process leads to the formation of defect sites corresponding to three different types of the B atom environment (BN_3 ? xO_x with x = 1,2,3). The oxidation of the h-BN monolayer is very different from the case of graphene on Ir(111), where adsorption of atomic oxygen results mainly in the formation of epoxy groups [J. Phys. Chem. C. 115, 9568 (2011)]. A post-annealing of the h-BN monolayer after oxygen exposure results in further destruction of the B–N bonds and formation of a B₂O₃-like structure.     

Adsorption of acetylene and ethylene on a clean Ir(111) surface

The adsorption of C₂H₂ and C₂H₄ on Ir(111) is studied within the temperature range 180–500 K by the HREELS and XPS methods. The absolute concentration of hydrocarbon coverage is estimated by XPS. Data are obtained on the kinetics of adsorption of the two gases at different temperatures. It is established by HREELS studies that at 180 K C₂H₄ forms ethylidyne (CCH₃ whereas C₂H₂ is adsorbed as CCH and ethylidyne species. At 300 K both kinds of species are found on the Ir(111) surface after C₂H₂ or C₂H₄ exposures. The ethylidyne decomposes completely to CCH at 500 K, which can be accompanied by polymerization of adsorbed hydrocarbon species.     

Mechanistic study of the CO oxidation reaction on the CuO (111) surface during chemical looping combustion

Cu-based oxides oxygen carriers and catalysts are found to exhibit attractive activity for CO oxidation, but the dispute with respect to the reaction mechanism of CO and O₂ on the CuO surface still remains. This work reports the kinetic study of CO oxidation on the CuO (111) surface by considering the adsorption, reaction and desorption processes based on density functional theory calculations with dispersion correction (DFT-D). The Eley–Rideal (ER) CO oxidation mechanism was found to be more feasible than the Mars-van-Krevelen (MvK) and Langmuir–Hinshelwood (LH) mechanisms, which is quite different from previous knowledge. The energy barrier of ER, LH, and MvK mechanisms are 0.557, 0.965, and 0.999 eV respectively at 0 K. The energy barrier of CO reaction with the adsorbed O species on the surface is as low as 0.106 eV, which is much more active in reacting with CO molecules than the lattice O of CuO (111) surface (0.999 eV). A comparison with the catalytic activity of the perfect Cu₂O (111) surface shows that the ER mechanism dictates both the perfect Cu₂O (111) and the CuO (111) surface activity for CO oxidation. The activity of the perfect Cu₂O (111) surface is higher than that of the perfect CuO (111) surface at elevated temperatures. A micro-kinetic model of CO oxidation on the perfect CuO (111) surface is established by providing the rate constants of elementary reaction steps in the Arrhenius form, which could be helpful for the modeling work of CO catalytic oxidation.     

The effects of surface facets on the oxidation of aluminum (111) surfaces

The initial oxidation of planar and facetted aluminum (111) surfaces was studied with low energy electron diffraction (LEED) and Auger electron spectroscopy (AES). The facetted surface was produced by rapidly heating the planar (111) surface to 773 K, and consisted of (111) and (221) planes. The planar surface showed first oxide-like aluminum at 50 L; however, the facetted surface showed first oxide at <10 L. The results are discussed in terms of the facet plane structures.     

The oxidation of Fe(111)

The oxidation of Fe(111) was studied using Auger electron spectroscopy (AES), low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), ion scattering spectroscopy (ISS) and scanning tunnelling microscopy (STM). Oxidation of the crystal was found to be a very fast process, even at 200 K, and the Auger O signal saturation level is reached within ~ 50 × 10^? 6 mbar s. Annealing the oxidised surface at 773 K causes a significant decline in apparent surface oxygen concentration and produces a clear (6 × 6) LEED pattern, whereas after oxidation at ambient temperature no pattern was observed. STM results indicate that the oxygen signal was reduced due to the nucleation of large, but sparsely distributed oxide islands, leaving mainly the smooth (6 × 6) structure between the islands. The reactivity of the (6 × 6) layer towards methanol was investigated using temperature programmed desorption (TPD), which showed mainly decomposition to CO and CO₂, due to the production of formate intermediates on the surface. Interestingly, this removes the (6 × 6) structure by reduction, but it can be reformed from the sink of oxygen present in the large oxide islands simply by annealing at 773 K for a few minutes. The (6 × 6) appears to be a relatively stable, pseudo-oxide phase, that may be useful as a model oxide surface.