The autocatalytic decomposition of acetic acid on Ni(110)

The flash decomposition of CH₃COOH was studied on a clean nickel (110) surface following adsorption at 30° C in order to access the applicability of chemical reaction rate theory to a homologous series of reactants on a well-defined surface. As was observed for formic acid, acetic acid adsorbed at 30° C to yield gaseous H₂O and to form islands of adsorbed anhydride intermediates; the decomposition proceeded by a two-dimensional auto-catalytic mechanism to form H₂, CO₂, Co and surface carbon. The decomposition of the anhydride was rate determining for the formation of CO₂ and H₂. The rate of decomposition was well described by the equation governing the formic acid decomposition on the same surface. The activation energy for this first order decomposition was determined to be 28.2 $\text{kcal}\text{gmol}$ and the pre-exponential factor, v, was found to be 6.4 × 10¹⁴ s^?1 with a fraction of initiation sites of 0.004. These values were nearly the same as those observed for the decomposition of HCOOH, suggesting identical intramolecular mechanisms for the unimolecular decomposition of the adsorbed intermediates. The relative values of v for the decomposition of HCOOH, DCOOH and CH₃COOH indicated that the motion of the H, D or CH₃ group was involved in the rate-limiting step.     

Ion-beam crystallography of clean and sulfur covered Ni(110)

Medium energy ion scattering has been used to determine the atomic structure of a Ni(110) surface covered with 0.5 monolayer of sulfur. After having confirmed that the sulfur atom resides in a fourfold-coordinated hollow site, it was found that its distance above the plane of the first Ni layer is 0.87 ± 0.03 Å. We measured a 6 ± 3% outward relaxation effect for the sulfur covered Ni(110) surface layer and an inward relaxation of 4 ± 1% when this surface is clean.     

The kinetics and mechanism of catalytic reactions by molecular beam relaxation spectroscopy: HCOOH decomposition

The reactive scattering of formic acid from Ni(110) was studied over the temperature range of 175–920 K with MBRS in the millisecond time region by employing a modulation frequency of 36.8 Hz. The steady-state carbon and oxygen composition of the surface varied over the range of temperatures studied. For beam fluxes of 10¹³ molecules/cm² sec the onset of decomposition on the steady-state surface occurred at 300 K. By 400 K decomposition was essentially complete, and the products CO₂, CO, H₂ and H₂O were detected. All reaction events were prceded by a common step, and the products were then produced by a series/parallel mechanism. The rate constants measured for H₂ and H₂O formation indicated stringent limitations on the efficiency of second-order collisions on the surface for producing gaseous products. This study illustrates the use of MBRS for surface reaction mechanistic studies in the millisecond time scale.     

Characterization of the adsorption and decomposition of methanol on Ni(110)

The chemisorption, condensation, desorption, and decomposition of methanol, both CH₃OH and CH₃OD, on a clean Ni(110) surface have been characterized using high resolution electron energy loss spectroscopy, temperature programmed reaction spectroscopy, and low energy electron diffraction. The vibrational spectrum of the saturated chemisorbed layer, 7.4 × 10¹⁴ molecules cm^?2, is almost identical to the infrared spectrum of liquid or solid methanol. Condensation of multilayers of methanol is facile at 80 K. The only quasi-stable intermediate isolated during the decomposition is a methoxy species, CH₃O, which decomposes thermally to CO and H. The evolution of both CO and H₂ occurs in desorption limited processes.     

The decomposition of H2S on Ni(110)

Adsorbed H₂S decomposes on Ni(110) to form primarily surface S and H for coverages of less than 0.5 ML. The hydrogen evolves in two separate TPD peaks, characteristic of hydrogen recombination and desorption from the clean surface and from regions perturbed by chemisorbed sulfur. XPS and HREELS indicate the presence of SH and possibly H₂S groups on the surface at 110 K. The XPS data indicates that for coverages less than about 0.5 ML, the concentration of molecular H₂S is small, but it is difficult to asess the coverage of SH groups. However, all of the molecular species decompose prior to hydrogen desorption (for high coverage, 180 K). Physisorbed H₂S is observed on the surface for coverages greater than about 0.5 ML.

The sulfur Auger lineshape was observed to be a function of both coverage and temperature. The changes in the lineshape were attributed to perturbations in local bonding interactions between the S and the Ni surface, perhaps involving some change in either bonding sites or distances but not involving SH bond scission.

The decomposition reaction was modeled using a bond order conservation method which successfully reproduced the experimental results.     

First-principles calculations of ammonia decomposition on Ni(110) surface

First-principles calculations based on density functional theory (DFT) have been performed to study the adsorption and decomposition of NH₃ on Ni(110). The adsorption sites, the adsorption energies, the transition states and the activation energies of the stepwise dehydrogenation of NH₃ and the associative desorption of N are determined, and the zero point energy correction is included, which makes it possible to compute the rate constants of the elementary steps in NH₃ decomposition. Combined DFT calculations and kinetic analysis at 350 K indicate that the associative desorption of N has a reaction rate lower than NH_x dehydrogenation and is therefore the rate determining step. The distinctly different rate constants over Ni(110), Ni(111) and Ni(211) imply that ammonia decomposition over Ni-based catalyst is a structure-sensitive reaction.     

Intermediate product identification for ammonia decomposition at Ni (110)

Ammonia decomposition at Ni(110) has been identified to proceed via NH₃(ad) → NH₂(ad) → NH(ad) → N + H. The decomposition activation of NH is determined to be 47 kcal/mol, suggesting an amazing stability of the NiNH bond. Decomposition of NH₂ occurs up from about 350 K; no kinetic data can be given yet. NH₃ decomposition is found to proceed slower than NH₃ desorption at least below 300 K.     

Angular resolved Auger emission from clean and sulfur covered Ni(110) surface

The angular dependence of the nickel M₂₃VV and of the sulfur L₂₃VV Auger transitions are studied in detail, on clean and sulfur covered Ni(110) surfaces. New experimental data are presented for the anisotropy of both transitions as a function of polar and azimuthai angles of emission. Our model, which incorporates at the same time the multiple scattering effects in the final state wave function and the intrinsic anisotropy of the Auger emitter, is found to give a satisfactory account of the observed auger anisotropy. We find a large sensitivity to the position of the sulfur adsorbed atoms. The best agreement is obtained for the hollow site. slightly less than 0.9 Å above the top nickel layer. This conclusion is consistent with previous LEED and MEIS studies, but does not agree with the long bridge site obtained from quantum chemistry calculations. Moreover the sulfur emitter on this particular Ni(110) face appears to have an intrinsic anisotropy.     

The effects of substrate oxidation on the adsorption and decomposition of HCOOH on Mo(100)

The adsorption and decomposition of HCOOH on the clean and two distinct oxygen-modified Mo(100) surfaces were studied by high resolution electron energy loss and temperature programmed reaction spectroscopies. A surface formate species with an irreversible temperature dependent orientation was seen on the three substrates. Formate stability varied with the oxygen content of the surface. Surface passivation was found to correlate directly with substrate oxidation.     

H2O interaction with clean and oxygen precovered Ni(110)

The interaction of water vapour with clean as well as with oxygen precovered Ni(110) surfaces was studied at 150 and 273 K, using UPS, ΔΦ, TDS, and ELS. The He(I) (He(II)) excited UPS indicate a molecular adsorption of H₂O on Ni(110) at 150 K, showing three water-induced peaks at 6.5, 9.5 and 12.2 eV below E_F (6.8, 9.4 and 12.7 eV below E_F). The dramatic decrease of the Ni d-band intensity at higher exposures, as well as the course of the work function change, demonstrates the formation of H₂O multilayers (ice). The observed energy shift of all water-induced UPS peaks relative to the Fermi level (ΔE_max = 1.5 eVat 200 L) with increasing coverage is related to extra-atomic relaxation effects. The activation energies of desorption were estimated as 14.9 and 17.3 kcal/mole. From the ELS measurements we conclude a great sensitivity of H₂O for electron beam induced dissociation. At 273 K water adsorbs on Ni(110) only in the presence of oxygen, with two peaks at 5.7 and 9.3 eV below E_F (He(II)), being interpreted as due to hydroxyl species (OH)^δ? on the surface. A kinetic model for the H₂O adsorption on oxygen precovered Ni(110) surfaces is proposed, and verified by a simple Monte Carlo calculation leading to the same dependence of the maximum amount of adsorbed H₂O on the oxygen precoverage as revealed by work function measurements. On heating, some of the (OH)^δ? recombines and desorbs as H₂O at ? 320 K, leaving behind an oxygen covered Ni surface.     

The decomposition of ammonia on an oxygen-precovered Ni(110) surface studied by scanning tunneling microscopy

The decomposition of ammonia on a Ni(110) surface with preadsorbed oxygen has been investigated in ultra-high vacuum at room temperature using scanning tunneling microscopy (STM). We propose a reaction model in which the high reactivity observed at low O coverage is ascribed to a direct interaction between the NH₃ molecules and the terminating atoms of the short, mobile -Ni-O- added rows which are observed on the surface under these conditions. This model is consistent with the observation that the surface becomes inert at high O coverage. We believe that the present reaction model can also explain results from some other experiments in which preadsorbed oxygen has been found to act as a promoter for dissociation of H-containing species, such as for NH₃ on Cu(110) and H₂O on Ni(110).     

The preparation and surface structure of clean V(110)

The first quantitative determination of the surface structure of a group VB metal is reported. A procedure is described for the preparation of a clean, well-ordered surface of V(110), free from the major bulk impurity, oxygen. The clean surface exhibits the two-dimensional periodicity of the corresponding bulk plane. Experimental LEED intensity measurements are compared to the results of multiple-scattering model calculations, with very good agreement being obtained for a value of the first interlayer spacing d, close to the bulk value. Minimization of the r factor for the comparison of experimental and calculated intensity spectra leads to a value of $\text{d = 2.12 ± 0.02}\text{A}\text{?}$, compared to the bulk value of 2.14 Å.     

The adsorption and decomposition of NO on Pd(110)

The sticking probability of nitric oxide (NO) on Pd(110) and the relative selectivity of the surface to nitrogen (N₂) and nitrous oxide (N₂O) production has been measured as a function of coverage and as a function of surface and gas temperatures using a molecular beam. It is found that, at low temperatures (<440 K), molecular adsorption occurs with an initial sticking probability of 0.40 ± 0.02, rising quickly to a maximum of about 0.48 ± 0.02 as coverage increases before falling towards saturation. Following adsorption at 170 K four distinct adsorption sites can be identified by subsequent TPD. Hence, if beaming occurs at a temperature above the TPD peak due to a given site, then that site cannot be populated and the saturation coverage is found to be reduced. At higher temperatures (440–650 K) the sticking probability is seen to decrease continuously as a function of coverage. At a given NO uptake, the sticking probability falls with temperature indicating that the rate of NO desorption is significant in this temperature range. In addition, dissociation occurs leading to the desorption of nitrogen and nitrous oxide leaving only oxygen adatoms on the surface. The oxygen adatoms poison further reaction but can be cleaned off, even at the lowest temperature at which dissociation occurs, by hydrogen or carbon monoxide. At the low temperature end of this range more nitrous oxide is produced than nitrogen but this ratio falls with temperature until, above 600 K, there is 100% selectivity to the production of nitrogen which we propose is due to the low lifetime of molecular NO on the surface. However, at such high temperatures, reaction only occurs on a few sites probably located at the few step edges present on the crystal.     

AES-LEED-ellipsometry study of the kinetics of the interaction of methane with Ni(110)

The interaction of methane with Ni(110) was studied with AES, LEED and ellipsometry. Sticking coefficients were determined in the temperature range 298–600 K at methane pressures of 10^?4–10^?2 Torr. The carbon coverages were derived from Auger spectra by calibration with ellipsometry. At room temperature no detectable adsorption was observed without use of electron sources. In the temperature range 473–579 K the coverage versus exposure curves show an induction effect at low coverage followed by an almost linear increase up to a saturation coverage of about $\text{1}\text{3}$ monolayer of carbon. At these temperatures a Ni(110)-(2 × 3)-C structure was observed with streaks in the direction of constant h. The observed behaviour is explained with a nucleation and growth model in which mobile carbon species are captured at the edges of surface nickel carbide islands. At temperatures above 600 K carbon diffuses into the bulk and the Ni(110)-(4 × 5)-C superstructure is observed.     

The adsorption of water on clean and oxygen covered Cu(110)

The water adsorption on clean and oxygen precovered Cu(110) surfaces is studied by means of UPS, LEED, work function measurements and ELS. At 90 K on the clean surface molecular water adsorption is indicated by UPS. The H₂O molecules are bonded at the oxygen end and the H-O-H angle is increased as compared with the free molecule. In the temperature range between 90 and 300 K distorted H₂O molecules and adsorbed hydroxyl species (OH) are detected, which are desorbed at room temperature. On an oxygen covered surface hydroxyl groups are formed by dissociation of adsorbed water molecules at a lower temperature than on the clean surface. Multilayers of condensed water are found below 140 K in both cases.     

Phase transitions on clean Si(110) surfaces

The properties of the structure of clean Si(110) surfaces have been investigated by LEED. The phase transitions between surface structures Si(110)?(4 × 5), Si(110)?(2 × 1) and Si(110)(5 × 1) take place at about 600 and 750°C. The time of reconstruction from the high temperature phase to the low temperature phase may exceed the time of the sample cooling. That explains why the Si(110)?(2 × 1) and the Si(110)?(5 × 1) superstructures may be seen at room temperature. Surface defects favour the retaining of high temperature phases on the surface at room temperature. The transition from the Si(110)?(5 × 1) structure to the Si(110)?(2× 1) structure and conversely in the temperature range of 720–750°C apparently occurs through formation of the intermediate structures Si(110)?(7 × 1) and Si(110)?(9 × 1). The models are given of superstructures observed by LEED.