Electro-oxidation of CO at the Ru(0001) single-crystal electrode surface

In situ FTIR spectroscopic and electrochemical data and ex situ (emersion) electron diffraction (LEED) and RHEED) and Auger spectroscopic data are presented on the structure and reactivity, with respect to the electro-oxidation of CO, of the Ru(0001) single-crystal surface in perchloric acid solution. In both the absence and the presence of adsorbed CO, the Ru(0001) electrode shows the potential-dependent formation of well-defined and ordered oxygen-containing adlayers. At low potentials (e.g., from -80 to +200 mV vs Ag/AgCl), a (2 × 2)-O phase, which is unreactive toward CO oxidation, is formed, in agreement with UHV studies. Increasing the potential results in the formation of (3 × 1) and (1 × 1) phases at 410 and 1100 mV, respectively, with a concomitant increase in the reactivity of the surface toward CO oxidation. Both linear (CO ) and three-fold-hollow (CO ) binding CO adsorbates (bands at 2000-2040 and 1770-1800 cm , respectively) were observed on the Ru(0001) electrode. The in situ FTIR data show that the adsorbed CO species remain in compact islands as CO oxidation proceeds, suggesting that the oxidation occurs at the boundaries between the CO and O domains. At low CO coverages, reversible relaxation (at lower potentials) and compression (at higher potentials) of the CO adlayer were observed and rationalized in terms of the reduction and formation of surface O adlayers. The data obtained from the Ru(0001) electrode are in marked contrast to those observed on polycrystalline Ru, where only linear CO is observed.

Electrochemical versus gas-phase oxidation of ru single-crystal surfaces

The electrochemical uptake of oxygen on a Ru(0001) electrode was investigated by electron diffraction, Auger spectroscopy, and cyclic voltammetry. An ordered (2 × 2)-O overlayer forms at a potential close to the hydrogen region. At +0.42 and +1.12 V vs Ag/AgCl, a (3 × 1) phase and a (1 × 1)-O phase, respectively, emerge. When the Ru electrode potential is maintained at +1.12 V for 2 min, RuO2 grows epitaxially with its (100) plane parallel to the Ru(0001) surface. In contrast to the RuO domains, the non-oxidized regions of the Ru electrode surface are flat. If, however, the electrode potential is increased to +1.98 V for 2 min, the remaining non-oxidized Ru area also becomes rough. These findings are compared with O overlayers and oxides on the Ru(0001) and Ru(101¯1) surfaces created by exposure to gaseous O under UHV conditions. On the other hand, gas-phase oxidation of the Ru(101¯0) surface leads to the formation of RuO with a (100) orientation. It is concluded that the difference in surface energy between RuO(110) and RuO(100) is quite small. RuO again grows epitaxially on Ru(0001), but with the (110) face oriented parallel to the Ru(0001) surface. The electrochemical oxidation of the Ru(0001) electrode surface proceeds via a 3-dimensional growth mechanism with a mean cluster size of 1.6 nm, whereas under UHV conditions, a 2-dimensional oxide film (1-2 nm thick) is epitaxially formed with an average domain size of 20 µm. © 2000 American Chemical Society.

Electrocatalytic activity of Ru-modified Pt(111) electrodes toward CO oxidation

The electrochemical deposition of Ru on Pt(111) electrodes has been investigated by electron diffraction, Auger spectroscopy, and cyclic voltammetry in a closed UHV transfer system. At small coverages Ru formed a monatomic commensurate layer, at higher coverage mostly small islands with a bilayer height were detected. When the Pt was almost completely covered by Ru, three-dimensional clusters developed. The island structure of Ru changed upon electrooxidation of CO, reflecting an enhanced mobility of Ru. Adsorption and electrooxidation of CO have been studied on such Ru-modified Pt(111) electrodes using cyclic voltammetry and in situ FTIR spectroscopy. Compared to the pure metals, the Ru-CO bond is weakened, the Pt-CO bond strengthened on the modified electrodes. The catalytic activity of the Ru/Pt(111) electrode toward CO adlayer oxidation is higher than that of pure Ru and a PtRu alloy (50:50). It is concluded that the electrooxidation of CO takes place preferentially at the Ru islands, while CO adsorbed on Pt migrates to them. © 1999 American Chemical Society.

Identification of the structure of a CO adlayer on a Pt(111) electrode

The structure of a Pt(111) electrode after treatment in an electrolyte and subsequent transfer to an UHV chamber was investigated ex situ by combined low energy electron diffraction (LEED), reflection high energy electron diffraction (RHEED), and Auger electron spectroscopy (AES). Treatment of the sample in a CO saturated 0.1 M HClO solution at potentials between -0.2 and 0.2 V versus Ag/AgCl caused a maximum CO coverage of about 0.75 as probed by cyclic voltammetry, which dropped by partial desorption to about 0.25 upon transfer to the UHV chamber. This adlayer exhibited a (distorted) 3×3 R30° pattern by RHEED (but not with LEED) exhibiting an average domain size of 2.3 nm at room temperature. This is identified with the same phase reported before from gas phase studies, as also corroborated by the similarities of the vibrational spectroscopic data. The same structure (albeit even more poorly ordered) was found after dissociative adsorption of methanol.

Methanol oxidation on PtRu electrodes. Influence of surface structure and Pt-Ru atom distribution

The activities of different types of PtRu catalysts for methanol oxidation are compared. Materials used were: UHV-cleaned PtRu alloys, UHV-evaporated Ru onto Pt(111) as well as adsorbed Ru on Pt(111) prepared with and without additional reduction by hydrogen. Differences in the catalytic activity are observed to depend on the preparation procedure of the catalysts. The dependence of the respective catalytic activities upon the surface composition is reported. UHV-STM data for Pt(111)/Ru show the formation of two- and three-dimensional structures depending on surface coverage. A molecular insight on the electrochemical reaction is given via in situ infrared spectroscopy. Analysis of the data indicates that the most probable rate-determining step is the reaction of adsorbed CO with Ru oxide.

Characterization of optical properties of PtSi at 3.392 mu m from 300 K to 85 K and relation of morphological effects

PtSi/Si Schottky junctions, fabricated using a conventional technique of Pt deposition with a subsequent thermal anneal, are examined using X-ray diffraction, atomic force microscopy and a novel prism/gap/sample optical coupling system. With the aid of X-ray diffraction and atomic farce microscopy it is shown that a post-anneal etch in aqua regia is essential for the removal of an unreacted, rough surface layer of Pt, to leave a much smoother PtSi film. The prism/gap/sample or Otto coupling rig is mounted in a small UHV chamber and has facilities for remote variation of the gap (by virtue of a piezoactuator system) and variation of the temperature in the range of similar to 300 K - 85 K. The system is used to excite surface plasmon polaritons on the outer surface of the PtSi and thus produce sensitive optical characterisation as a function of temperature. This is performed in order to yield an understanding of the temperature dependence of phonon and interface scattering of carriers in the PtSi.

A density functional theory study of CO oxidation on Ru(0001) at low coverage

We have performed ab initio density functional theory calculations with the generalized gradient approximation to investigate CO oxidation on Ru(0001). Several reaction pathways and transition states are identified. A much higher reaction barrier compared to that on Pt(111) is determined, confirming that the Ru is very inactive for CO oxidation under UHV conditions. The origin of the reaction barrier was analyzed. It is found that in the transition state the chemisorbed O atom sits in an unfavorable bonding site and a significant competition for bonding with the same substrate atoms occurs between the CO and the chemisorbed O, resulting in the high barrier. Ab initio molecular dynamics calculations show that the activation of the chemisorbed O atom from the initial hcp hollow site (the most stable site) to the bridge site is the crucial step for the reaction. The CO oxidation on Ru(0001) via the Eley-Rideal mechanism has also been investigated. A comparison with previous theoretical work has been made. (C) 2000 American Institute of Physics. [S0021-9606(00)31223-5].