Explaining Cu@Pt Bimetallic Nanoparticles Activity Based on NO Adsorption

Cu@Pt nanoparticles (NPs) are experimentally regarded as improved catalysts for NO_x storage/reduction, with higher activities and selectivities compared with pure Pt or Cu NPs, and with inverse Pt@Cu NPs. Here, a density functional theory-based study on such NP models with different sizes and shapes reveals that the observed enhanced stability of Cu@Pt compared with Pt@Cu NPs is due to energetic reasons. On both types of core@shell NPs, charge is transferred from Cu to Pt, strengthening the NP cohesion energy in Pt@Cu NPs, and spreading charge along the surface in Cu@Pt NPs. The negative surface Pt atoms in the latter diminish the NO bonding owing to an energetic rise of the Pt bands, as detected by the appliance of the d-band model, although other factors, such as atomic low coordination or the presence of an immediate subsurface Pt atom do as well. A charge density difference analysis discloses a donation/back-donation mechanism in the NO adsorption.     

Organocatalytic asymmetric fulvene formation

The first catalytic asymmetric formation of a fulvene from a racemic α,α-disubstituted aldehyde has been developed. Dynamic kinetic resolution of rac-2-phenylpropanal by a simple, modularly designed supramolecular organocatalyst consisting of inexpensive components has been established, producing the desired fulvene in good yields and moderate enantioselectivities. Herein we propose a mechanistic interpretation of the observed solvent- and additive-induced stereoselectivity reversal.     

New Editor-in-Chief

Accreditation and Quality Assurance -     

Measurement of electric field strengths in a waveguide by means of the dynamic Stark effect in hydrogen and neutral helium spectral lines

The dynamic Stark effect of the spectral lines H_β and of the neutral helium lines λ=402.6 nm (2³ P ⁰−5³ D) and λ=438.8 nm (2¹ P ⁰−5¹ D) emitted from a discharge tube was used for probing rf electric fields in a transverse waveguide. Calculations accounting for the pertubation of the atomic states by strong unidirectional fields prove to be suitable in order to interprete the main experimental results. If the waveguide is terminated with a metallic reflector and the plasma in the discharge tube becomes overdense—then representing a slightly permeable mirror—a resonant enhancement of the electric field strength may be achieved by tuning. This enhancement is well recognizable in the spectral line contours.     

Angular dependent photon-stimulated desorption of ions from a V2O5(010) surface

Using a display-type analyzer, we have measured the angular and energy distribution of O⁺ ions desorbed from a V₂O₅(010) surface by incident photons. The desorbed ions were mass-analyzed using time-of-flight gating techniques. The angular distribution of desorbed ions was found to be strongly peaked in the direction of the surface normal. This strongly directional desorption pattern reflects the local bonding geometry of the topmost oxygen atoms in the surface. The observed photoexcitation spectrum of the ion yiel can be explained with the core level Auger decay model formulated by Knotek and Feibelman.     

Ultraviolet reflectivity spectra of CuInSe2, CuInTe2 and CuGaTe2

Reflectivity spectra of CuInSe₂, CuInTe₂ and CuGaTe₂ are measured in the photon energy range from 2 to 9 eV. All compounds exhibit nearly the same reflectivity structures, and a comparison with measurements on the other Cu-III-VI₂ semiconductors shows that the band structures of all Cu-III-VI₂ compounds should be very similar except the energy range near the fundamental edge.     

Spin-lattice relaxation by tunnelling motions of methyl groups in some organic compounds

The proton spin-lattice relaxation times, T₁, of methyl groups in (CH₃CO)₂O, CH₃COCl, CH₃ COBr and (CH₃)₂S₂ have been measured below melting points at 52 MHz. The observed T₁ minima display the presence of tunnelling rotation. From the fit of the experimental results the ground, the first excited state tunnelling frequencies and the energy difference between the ground and the first excited states of the compounds have been estimated.     

Plasmon dispersion in Al atk≦k F using electron energy loss spectroscopy

We find a quasi quadratic dispersion of the plasmon up to _p = 28 eV atk=1.77 Å^–1 with no levelling off contrary to other measurements. We usedk-scans at constant energy loss andE-scans at constant wave vector, which yield different dispersions of the plasmon peak maximum because of the finite halfwidth. The levelling off in plasmon dispersion observed previously is due to multiple scattering events, which obscure the plasmon dispersion inE-scans.We confirmed the anisotropy of the dispersion coefficient by investigating polycrystalline samples of different orientation.