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.

Low loading platinum nanoparticles on reduced graphene oxide-supported tungsten carbide crystallites as a highly active electrocatalyst for methanol oxidation

In this study, low loading platinum nanoparticles (Pt NPs) have been highly dispersed on reduced graphene oxide-supported WC nanocrystallites (Pt-WC/RGO) via program-controlled reduction-carburization technique and microwave-assisted method. The scanning electron microscopy and transmission electron microscopy results show that WC nanocrystallites are homogeneously decorated on RGO, and Pt NPs with a size of ca. 3 nm are dispersed on both RGO and WC. The prepared Pt-WC/RGO is used as an electrocatalyst for methanol oxidation reaction (MOR). Compared with the Pt/RGO, commercial carbon-supported Pt (Pt/C) and PtRu alloy (PtRu/C) electrocatalysts, the Pt-WC/RGO composites demonstrate higher electrochemical active surface area and excellent electrocatalytic activity toward the methanol oxidation, such as better tolerance toward CO, higher peak current density, lower onset potential and long-term stability, which could be attributed to the characterized RGO support, highly dispersed Pt NPs and WC nanocrystallites and the valid synergistic effect resulted from the increased interface between WC and Pt. The present work proves that Pt-WC/RGO composites could be a promising alternative catalyst for direct methanol fuel cells where WC plays the important role as a functional additive in preparing Pt-based catalysts because of its CO tolerance and lower price. 

Effects of buried high-Z layers on fast electron propagation

By extending a prior model [A. R. Bell, J.R. Davies, S. M. Guerin, Phys. Rev. E 58, 2471 (1998)], the magnetic field generated during the transport of a fast electron beam driven by an ultraintense laser in a solid target is derived analytically and applied to estimate the effect of such field on fast electron propagation through a buried high-Z layer in a lower-Z target. It is found that the effect gets weaker with the increase of the depth of the buried layer, the divergence of the fast electrons, and the laser intensity, indicating that magnetic field effects on the fast electron divergence as measured from K-a X-ray emission may need to be considered for moderate laser intensities. On the basis of the calculations, some considerations are made on how one can mitigate the effect of the magnetic field generated at the interface.

Copper(I)/ketoABNO Catalysed Aerobic Alcohol Oxidation

A Cu(I)/9-azabicyclo[3.3.1]nonan-3-one N-oxyl (ketoABNO) aerobic catalyst system is highly effective for the oxidation of secondary alcohols, including unactivated aliphatic substrates. The effects of pressure and gas composition on catalyst performance are examined. The radical can be employed at low loadings and is also amenable to immobilisation on to solid supports.

Unraveling the synergy between gold nanoparticles and chromium- hydrotalcites in aerobic oxidation of alcohols

The combination of gold nanoparticles (AuNPs) with chromium-substituted hydrotalcite (Cr-HT) supports makes very efficient heterogeneous catalysts (Au/Cr-HT) for aerobic alcohol oxidation under soluble-base-free conditions. The Au-support synergy increases with increasing Cr content of the support and decreasing AuNP size. In situ UV-Raman, X-ray absorption and photoelectron spectroscopic studies firmly establish that the strong Au-Cr synergy is related to a Cr ↔ Cr redox cycle at the Au/Cr-HT interface, where O activation takes place accompanied by electron transfer from Cr-HT to Au. The interfacial Cr species can be reduced by surface Au-H hydride and negative-charged Au species to close the catalytic cycle. A study of kinetic isotope effect indicates that alcohol O-H cleavage is facilitated by the presence of Cr, making a-C-H bond cleavage step more rate-controlling. Accordingly, a dual synergistic effect of Au/Cr-HT catalysts on the activation of O2 and alcohol reactants is proposed.

Inhibitory Effect of Phosphonium-Based Ionic Liquids on Coal Oxidation

To develop a chemical inhibitor that can efficiently suppress coal oxidation, nine tetraalkylphosphonium-based ionic liquids (ILs) and one imidazolium-based IL [1-allyl-3-methylimidazolium chloride ([AMIm]Cl)] were examined as additives. These ILs were used to treat and investigate the inhibitory effect on the oxidation activity and the structure of lignite coal. Characterization using thermogravimetric analysis showed that phosphonium-based ILs are able to inhibit coal oxidation up to 400 degrees C with the tributylethylphosphonium diethylphosphate ([P-4,P-4,P-4,P-2][DEP]) found to be the most effective. In contrast to the tetraalkylphosphonium-based ILs, inhibition using [AMIm]Cl was only found to be effective at temperatures below 250 degrees C, indicating that the tetraallcylphosphonium-based ILs may be more suitable for the future application of suppressing coal spontaneous combustion over a wide range of temperatures. Fourier transform infrared spectroscopic data showed that the various functional groups change in the coal following IL treatment, which are a decrease in the minerals and hydrogen bonds in all treated coals, while decreased aliphatic hydrocarbon and increased carbonyl bonds only appeared in some samples. During the oxidation of coal, the decomposition of aliphatic hydrocarbon groups is inhibited and the formation of carbonyl groups is delayed, so that the evolved gas concentration decreased, as shown by the temperature-programmed oxidation-mass spectrometry results. The deployment of the [P-4,P-4,P-4,P-2][ DEP] and tributylmethylphosphonium methylsulfate Its as additives also show good inhibitory effect on coal oxidation over the temperature range studied, and a relatively stronger interaction between [P-4,P-4,P-4,P-2] [DEP] and coal is demonstrated by the additive model.

Electron-Impact Excitation of Fe-peak Ions for Astrophysical Applications

This paper discusses one of the major outstanding problems in atomic collision physics, namely the accurate theoretical treatment of electron scattering from open d-shell systems, and explores how this issue has been addressed over recent years with the development of the new parallel R-matrix suite of codes. It focuses on one code in particular - the new parallel R-matrix package PRMAT, which has recently been extended to account for relativistic fine-structure effects. This program facilitates the determination of accurate electron-impact excitation rates for complex open 3d-shell systems including the astrophysically important Fe-peak ions such as Ni II, Fe II and Fe III. Results are presented for collision strengths and Maxwellian averaged effective collision strengths for the optically forbidden fine-structure transitions of Ni II. To our knowledge this is the most extensive calculation completed to date for this ion.

Hydrogen peroxide enhanced photocatalytic oxidation of microcystin-lR using titanium dioxide

Cyanobacterial toxins present in drinking water sources pose a considerable threat to human health. Conventional water treatment systems have proven unreliable for the removal of these toxins and hence new techniques have been investigated. Previous work has shown that TiO₂ photocatalysis effectively destroys microcystin-LR in aqueous solutions, however non-toxic by-products were detected. It has been shown that photocatalytic reactions are enhanced by utilisation of alternative electron acceptors. We report here enhanced photocatalytic degradation of microcystin-LR following the addition of hydrogen peroxide to the system. It was also found that hydrogen peroxide with UV illumination alone was capable of decomposing microcystin-LR although at a much slower rate than found for TiO₂. No HPLC detectable by-products were found when the TiO₂/UV/H₂O₂ system was used indicating that this method is more effective than TiO₂/UV alone. Results however indicated that only 18% mineralisation occurred with the TiO₂/UV/H₂O₂ system and hence undetectable by-products must still be present. At higher concentrations hydrogen peroxide was found to compete with microcystin-LR for surface sites on the catalyst but at lower peroxide concentrations this competitive adsorption was not observed. Toxicity studies showed that both in the presence and absence of H₂O₂ the microcystin solutions were detoxified. These findings suggest that hydrogen peroxide greatly enhances the photocatalytic oxidation of microcystin-LR.

Relativistic theory for localized electrostatic excitations in degenerate electron-ion plasmas

A self-consistent relativistic two-fluid model is proposed for electron-ion plasma dynamics. A one-dimensional geometry is adopted. Electrons are treated as a relativistically degenerate fluid, governed by an appropriate equation of state. The ion fluid is also allowed to be relativistic, but is cold, nondegenerate, and subject only to an electrostatic potential. Exact stationary-profile solutions are sought, at the ionic scale, via the Sagdeev pseudopotential method. The analysis provides the pulse existence region, in terms of characteristic relativistic parameters, associated with the (ultrahigh) particle density.

Toluene dioxygenase-catalysed oxidation route to angular cis-monohydrodiols and other bioproducts from bacterial metabolism of 1,2-dihydrobenzocyclobutene and derivatives

A mutant strain (UV4) of the soil bacterium Pseudomonas putida, containing toluene dioxygenase, has been used in the metabolic oxidation of 1,2-dihydrobenzocyclobutene 12 dagger and the related substrates 1,2-dihydrobenzocyclobuten-1-ol 13 and biphenylene 33. Stable angular cis-monohydrodiol metabolites (1R,2S)-bicyclo[4.2.0]octa-3,5-diene-1,2 7, (1S,2S,8S)-bicyclo[4.2.0]octa-3,5-diene-1,2,8-triol 8 and biphenylene-cis-1,8b-diol 9, isolated from each of these substrates, have been structurally and stereochemically assigned. The structure, enantiopurity and absolute configuration of the other cis-diol metabolites, (2R,3S)-bicyclo[4.2.0]octa-1(6),4-diene-2,3-diol 14 and cis-1,2-dihydroxy-1,2-dihydrobenzocyclobutene 16, and the benzylic oxidation bioproducts, 1,2-dihydrobenzocyclobuten-1-ol 13, 1,2-dihydrobenzocyclobuten-1-one 15 and 2-hydroxy-1,2-dihydrobenzocyclobuten-1-one 17, obtained from 1,2-dihydrobenzocyclobutene and 1,2-dihydrobenzocyclobuten-1-ol, have been determined with the aid of chiral stationary-phase HPLC, NMR and CD spectroscopy, and stereochemical correlation. X-Ray crystallographic methods have been used in the determination of absolute configuration of the di-camphanates 27 (from diol 7) and 32 (from diol 9), and the di-MTPA ester 29 (from diol 14) of the corresponding cis-diol metabolites. The metabolic sequence involved in the formation of bioproducts derived from 1,2-dihydrobenzocyclobutene 12 has been investigated.

Preparation of Dess-Martin periodinane - The role of the morphology of 1-hydroxy-1,2-benziodoxol-3(1H)-one 1-oxide precursor

1-Hydroxy-1,2-benziodoxol-3(1H)-one I-oxide prepared by oxidation of o-iodobenzoic acid with potassium bromate forms either a microcrystalline powder, a macrocrystalline material, or a mixture of both forms. This difference in physical form is the source of the difficulty in reproducibly converting 1-hydroxy-1,2-benziodoxol-3(1H)-one 1-oxide to the corresponding I-triacetoxy derivative. A simple method is given for conversion of crystalline 1-hydroxy-1,2-benziodoxol-3(1H)-one 1-oxide to the more reactive powder form, The microcrystalline powder and macrocrystalline material are characterised by X-ray diffraction.

Mapping neutral, ion and electron number densities within laser ablated plasma plumes

Spatially and temporally varying neutral, ion and electron number densities have been mapped out within laser ablated plasma plumes expanding into vacuum. Ablation of a magnesium target was performed using a KrF laser, 30 ns pulse duration and 248 nm wavelength. During the initial stage of plasma expansion (t <EQ 100 ns) interferometry has been used to obtain line averaged electron number densities, for laser power densities on target in the range 1.3 - 3.0 X 108 W/cm2. Later in the plasma expansion (t equals 1 microsecond(s) ) simultaneous absorption and laser induced fluorescence spectroscopy has been used to determine 3D neutral and ion number densities, for a power density equal to 6.7 X 107 W/cm2. Two distinct regions within the plume were identified. One is a fast component (approximately 106 cm-1) consisting of ions and neutrals with maximum number densities observed to be approximately 30 and 4 X 1012 cm-3 respectively, and the second consists of slow moving neutral material at a number density of up to 1015 cm-3. Additionally a Langmuir probe has been used to obtain ion and electron number densities at very late times in the plasma expansion (1 microsecond(s) <EQ t <EQ 15 microsecond(s) ). A copper target was ablated using a Nd:YAG laser, 7.5 ns duration and 532 nm (2 (omega) ) wavelength, with a power density on target equal to 6 X 108 W/cm2. Two regions within the plume with different velocities were observed. Within a fast component (approximately 3 X 106 cms-1) electron and ion number densities of the order 5 X 1012 cm-3 were observed and within the second slower component (approximately 106 cms-1) electron and ion number densities of the order 1 - 2 X 1013 cm-3 were determined.

Origin of extraordinarily high catalytic activity of Co3O4 and its morphological chemistry for CO oxidation at low temperature

Understanding and then designing efficient catalysts for CO oxidation at low temperature is one of the hottest topics in heterogeneous catalysis. Among the existing catalysts. Co3O4 is one of the most interesting systems: Morphology-controlled Co3O4 exhibits exceedingly high activity. In this study, by virtue of extensive density functional theory (OFT) calculations, the favored reaction mechanism in the system is identified. Through careful analyses on the energetics of elementary reactions on Co3O4(1 1 0)-A, Co3O4(1 1 0)-B, Co3O4(1 1 1) and Co3O4(1 0 0), which are the commonly exposed surfaces of Co3O4, we find the following regarding the relation between the activity and structure: (i) Co3+ is the active site rather than Co2+: and (ii) the three-coordinated surface oxygen bonded with three Co3+ may be slightly more reactive than the other two kinds of lattice oxygen, that is, the two-coordinated 0 bonded with one Co2+ and one Co3+ and the three-coordinated 0 bonded with one Co2+ and two Co3+. Following the results from Co3O4, we also extend the investigation to MnO2(1 1 0), Fe3O4(1 1 0), CuO(1 1 0) and CuO(1 1 1), which are the common metal oxide surfaces, aiming to understand the oxides in general. Three properties, such as the CO adsorption strength, the barrier of CO reacting with lattice 0 and the redox capacity, are identified to be the determining factors that can significantly affect the activity of oxides. Among these oxides, Co3O4 is found to be the most active one, stratifying all the three requirements. A new scheme to decompose barriers is introduced to understand the activity difference between lattice O-3c and O-2c on (1 1 0)-B surface. By utilizing the scheme, we demonstrate that the origin of activity variance lies in the geometric structures. (C) 2012 Elsevier Inc. All rights reserved.

Identification of MnCr2O4 nano-octahedron in catalysing pitting corrosion of austenitic stainless steels

Pitting corrosion of stainless steels, one of the classical problems in materials science and electrochemistry, is generally believed to originate from the local dissolution in MnS inclusions, which are more or less ubiquitous in stainless steels. However, the initial location where MnS dissolution preferentially occurs is known to be unpredictable, which makes pitting corrosion a major concern. In this work we show, at an atomic scale, the initial site where MnS starts to dissolve in the presence of salt water. Using in situ ex-environment transmission electron microscopy (TEM), we found a number of nano-sized octahedral MnCr2O4 crystals (with a spinel structure and a space group of Fd (3) over barm) embedded in the MnS medium, generating local MnCr2O4/MnS nano-galvanic cells. The TEM experiments combined with first-principles calculations clarified that the nano-octahedron, enclosed by eight {1 1 1} facets with metal terminations, is "malignant", and this acts as the reactive site and catalyses the dissolution of MnS. This work not only uncovers the origin of MnS dissolution in stainless steels, but also presents an atomic-scale evolution in a material's failure which may occur in a wide range of engineering alloys and biomedical instruments serving in wet environments. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.