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.

Quantum chemistry and in situ FTir spectroscopy studies on potential-dependent properties of CO adsorbed on Pt electrodes

The electronic and vibrational properties of CO adsorbed on Pt electrodes at different potentials have been studied, by using methods of self-consistent-charge discrete variational Xa (SCC-DV-Xa) cluster calculations and in situ FTir spectroscopy. Two new models have been developed and verified to be successful: (1) using a "metallic state cluster" to imitate a metal (electrode) surface; and (2) charging the cluster and shifting its Fermi level (e{lunate}) to simulate, according to the relation of -d e{lunate}e dE, quantitatively the variation of the electrode potential (E). It is shown that the binding of PtCO is dominated by the electric charge transfer of dp ? 2p, while that of s ? Pt is less important in this binding. The electron occupancy of the 2p orbital of CO weakens the CO bond and decreases the v. Variation of E mainly influences the charge transfer process of dp ? 2p, but hardly influences that of s ? Pt. A linear potential-dependence of v has been shown and the calculated dv/dE = 35.0 cm V. All results of calculations coincide with the ir experimental data. © 1993.

Quantum chemistry studies on electronic properties of CN adsorbed on silver electrodes

The electronic properties of CN adsorbed on Ag electrodes at different potentials have been studied by using the method of self-consistent-charge discrete variational Xa (SCC-DV-Xa) cluster calculations. It is shown that the binding of NCAg is dominated by both electrostatic and polarization effects derived from the charge of CN, and that the transfer of s charge from CN to silver is the largest donation contribution. The electrode potential influences this charge transfer process and the interaction between CN adsorbate and silver electrode. The results of quantum chemistry calculations fit well with the experimental data of in situ spectroscopic studies on the CN/Ag electrode systems. © 1991.

In situ FTIR spectroscopic studies of the oxidation of CO adsorbates on Ru(0 0 0 1) electrodes under open circuit conditions

This paper reports the first observation, using in situ FTIR spectroscopy, of the oxidation of CO adsorbates on the Ru(0001) electrode to CO under open circuit (oc) conditions in both perchloric acid and sulphuric acid solution at 20 and 55 °C. While the significant oc oxidation of the adsorbed CO on the Ru(0001) electrode was observed in perchloric acid solution, much less oc oxidation took place in sulfuric acid solution due to the specific adsorption of bisulfate at the Ru surface which inhibits the surface oxidation and reduces the reactivity of the surface towards the oxidation of CO . The oc oxidation of the CO depends strongly on the oxygen concentration in the solution and the temperature. The data so obtained are compared to those observed at the gas|solid interface, as well as to those obtained from the electro-oxidation of CO , and possible new catalytic oxidation reaction mechanisms are discussed. In addition, it is shown that the C-O frequency of the adsorbed CO may be used as an effective probe of the open circuit potential. © 2003 Elsevier B.V. All rights reserved.

ALMA hints at the presence of two companions in the disk around HD 100546

HD 100546 is a well-studied Herbig Be star-disk system that likely hosts a close-in companion with compelling observational evidence for an embedded protoplanet at 68 AU. We present ALMA observations of the HD 100546 disk which resolve, for the first time, the gas and dust structure at (sub)mm wavelengths. The CO emission (at 345.795 GHz) originates from an extensive molecular disk (390 AU in radius) whereas the continuum emission is more compact (230 AU in radius) suggesting radial drift of the mm-sized grains. The CO emission is similar in extent to scattered light images indicating well-mixed gas and um-sized grains in the disk atmosphere. Assuming an azimuthally-symmetric disk, the continuum visibilities at long baselines (> 100 klambda) are reproduced by a compact ring with a width of 21 AU centered at 26 AU. An outer component is required to fit the short baselines: assuming a flat brightness distribution, the best-fit model is a ring with a width of 75 AU centered at 190 AU. The influence of a companion and protoplanet on the dust evolution is investigated. The companion at 10 AU facilitates the accumulation of mm-sized grains within a compact ring, ~20-30 AU, by ~10 Myr. The injection of a protoplanet at 1 Myr hastens the ring formation (~1.2 Myr) and also triggers the development of an outer ring (~100-200 AU). These observations provide additional evidence for the presence of a close-in companion and hint at dynamical clearing by a protoplanet at 68 AU.

The electrochemical reduction of 1-bromo-4-nitrobenzene at zinc electrodes in a room-temperature ionic liquid: a facile route for the formation of arylzinc compounds

The electrochemical reduction of 1-bromo-4-nitrobenzene (p-BrC₆H₄NO₂) at zinc microelectrodes in the [C(₄)mPyrr][NTf₂] ionic liquid was investigated via cyclic voltammetry. The reduction was found to occur via an EC type mechanism, where p-BrC₆H₄NO₂ is first reduced by one electron, quasi-reversibly, to yield the corresponding radical anion. The radical anions then react with the Zn electrode to form arylzinc products. Introduction of carbon dioxide into the system led to reaction with the arylzinc species, fingerprinting the formation of the latter. This method thus demonstrates a proof-of-concept of the formation of functionalised arylzinc species.

Line-driven Disk Winds in Activ Galactic Nuclei: The Critical Importance of Ionization and Radiative Transfer

Accretion disk winds are thought to produce many of the characteristic features seen in the spectra of active galactic nuclei (AGNs) and quasi-stellar objects (QSOs). These outflows also represent a natural form of feedback between the central supermassive black hole and its host galaxy. The mechanism for driving this mass loss remains unknown, although radiation pressure mediated by spectral lines is a leading candidate. Here, we calculate the ionization state of, and emergent spectra for, the hydrodynamic simulation of a line-driven disk wind previously presented by Proga & Kallman. To achieve this, we carry out a comprehensive Monte Carlo simulation of the radiative transfer through, and energy exchange within, the predicted outflow. We find that the wind is much more ionized than originally estimated. This is in part because it is much more difficult to shield any wind regions effectively when the outflow itself is allowed to reprocess and redirect ionizing photons. As a result, the calculated spectrum that would be observed from this particular outflow solution would not contain the ultraviolet spectral lines that are observed in many AGN/QSOs. Furthermore, the wind is so highly ionized that line driving would not actually be efficient. This does not necessarily mean that line-driven winds are not viable. However, our work does illustrate that in order to arrive at a self-consistent model of line-driven disk winds in AGN/QSO, it will be critical to include a more detailed treatment of radiative transfer and ionization in the next generation of hydrodynamic simulations.

In situ electron holography of the dynamic magnetic field emanating from a hard-disk drive writer

The proliferation of mobile devices in society accessing data via the ‘cloud’ is imposing a dramatic increase in the amount of information to be stored on hard disk drives (HDD) used in servers. Forecasts are that areal densities will need to increase by as much as 35% compound per annum and by 2020 cloud storage capacity will be around 7 zettabytes corresponding to areal densities of 2 Tb/in2. This requires increased performance from the magnetic pole of the electromagnetic writer in the read/write head in the HDD. Current state-of-art writing is undertaken by morphologically complex magnetic pole of sub 100 nm dimensions, in an environment of engineered magnetic shields and it needs to deliver strong directional magnetic field to areas on the recording media around 50 nm x 13 nm. This points to the need for a method to perform direct quantitative measurements of the magnetic field generated by the write pole at the nanometer scale. Here we report on the complete in situ quantitative mapping of the magnetic field generated by a functioning write pole in operation using electron holography. Opportunistically, it points the way towards a new nanoscale magnetic field source to further develop in situ Transmission Electron Microscopy.

The Well-Aligned Orbit of Wasp-84b: Evidence for Disk Migration of a Hot Jupiter

We report the sky-projected orbital obliquity (spin–orbit angle) of WASP-84 b, a 0.69MJup planet in an 8.52 day orbit around a G9V/K0V star, to be λ = −0.3 ± 1.7°. We obtain a true obliquity of ψ = 17.3 ± 7.7° from a measurement of the inclination of the stellar spin axis with respect to the sky plane. Due to the young age and the weak tidal forcing of the system, we suggest that the orbit of WASP-84b is unlikely to have both realigned and circularized from the misaligned and/or eccentric orbit likely to have arisen from high-eccentricity migration. Therefore we conclude that the planet probably migrated via interaction with the protoplanetary disk. This would make it the first “hot Jupiter” (P d < 10 ) to have been shown to have migrated via this pathway. Further, we argue that the distribution of obliquities for planets orbiting cool stars (Teff < 6250 K) suggests that high-eccentricity migration is an important pathway for the formation of short-orbit, giant planets.

The use of carbon and gold electrodes in anodic stripping voltammetric heavy metal sensors.

The use of anodic stripping voltammetry (ASV)has been proven in the past to be a precise and sensitive analytical method with an excellent limit of detection. Electrochemical sensors could help to avoid expensive and time consuming procedures as sample taking and storage and provide a both sensitive and reliable method for the direct monitoring of heavy metals in the aquatic environment. Solid electrodes which have been used in this work, were produced using previously developed methods. Commercially available and newly designed, screen printed carbon and gold plated working electrodes (WE) were compared. Good results were achieved with the screen printed and plated electrodes under conditions optimized for each electrode material. The electrode stability, reproducibility of single measurements and the limit of detection obtained for Pb were satisfactory (3*10-6mol/l on screen printed carbon WEs after 60 s of deposition and 6*10-6 mol/l on gold plated WEs after 5 min of deposition). Complete 3-electrode-sets (counter, reference and working electrode) were screen printed on different substrates (glass, polycarbonate and alumina). Also here, both carbon and gold were used as WE. Using 3-electrode-sets with a gold plated WE on glass was a limit of detection of 7*10-7 mol/l was achieved after only 60 s of deposition.

One-Electron Reduction of 2-Nitrotoluene, Nitrocyclopentane, and 1-Nitrobutane in Room Temperature Ionic Liquids: A Comparative Study of Butler–Volmer and Symmetric Marcus–Hush Theories Using Microdisk Electrodes

The voltammetry for the reduction of 2-nitrotoluene at a gold microdisk electrode is reported in two ionic liquids: trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate ([P-14,P-6,P-6,P-6][FAP]) and 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Emim][NTf2]). The reduction of nitrocyclopentane (NCP) and 1-nitrobutane (BuN) was investigated using voltammetry at a gold microdisk electrode in the ionic liquid [P-14,P-6,P-6,P-6][FAP]. Simulated voltammograms, generated through the use of ButlerVolmer theory and symmetric MarcusHush theory, were compared to experimental data, with both theories parametrizing the data similarly well. An experimental value for the Marcusian parameter, 1 was also determined in all cases. For the reduction of 2-nitrotoluene, this was 0.5 +/- 0.1 eV in both solvents, while for NCP and BuN in [P-14,P-6,P-6,P-6][FAP], it was 2 +/- 0.1 and 5 +/- 0.1 eV, respectively. This is attributed to the localization of charge on the nitro group and the primary nitro alkyls increased interaction with the environment, resulting in a larger reorganization energy.

Physical Characterisation of Fast-Rotating Near-Earth Asteroids

We present VLT+VISIR mid-IR observations of fast-rotating near-Earth asteroids. Diameters and albedos are determined with thermal models. These NEAs may have unusual surface properties, e.g. from regolith transport/stripping due to the YORP effect.