Complete Oxidation of Methane over Palladium Supported on Alumina Modified with Calcium,Lanthanum,and Cerium Ions

The activity and thermal stability of Pd/Al_2O_3 and Pd/(Al_2O_3 MO_x)(M=Ca,La,Ce) palladium catalysts in the reaction of complete oxidation of methane are presented in this study.The catalyst supports were prepared by sol-gel method and they were dried either conventionally or with supercritical carbon dioxide.Then they were impregnated with palladium nitrate solution.The catalysts with unmodified alumina had a high surface area.The activity and thermal stability of the alumina- supported catalyst was also very high.The introduction of calcium,lanthanum,or cerium oxide into alumina support caused a decrease of the surface area in the way dependent on the support precursor drying method.These modifiers decreased the activity of palladium catalysts,and they required higher temperatures for the complete oxidation of methane than unmodified Pd/Al_2O_3.The improvement of the palladium activity by lanthanum and cerium support modifier was observed only at low temperatures of the reaction.     

Ultrafast photofragmentation dynamics of molecular iodine driven with timed XUV and near-infrared light pulses

Photofragmentation dynamics of molecular iodine was studied as a response to the joint illumination with femtosecond 800 nm near-infrared and 13 nm extreme ultraviolet (XUV) pulses delivered by the free-electron laser facility FLASH. The interaction of the molecular target with two light pulses of different wavelengths but comparable pulse energy elucidates a complex intertwined electronic and nuclear dynamics. To follow distinct pathways out of a multitude of reaction channels, the recoil of created ionic fragments is analyzed. The delayed XUV pulse provides a way of following molecular photodissociation of I(2) with a characteristic time-constant of (55 ± 10) fs after the laser-induced formation of antibonding states. A preceding XUV pulse, on the other hand, preferably creates a 4d(-1) inner-shell vacancy followed by the fast Auger cascade with a revealed characteristic time constant τ(A2)=(23±11) fs for the second Auger decay transition. Some fraction of molecular cationic states undergoes subsequent Coulomb explosion, and the evolution of the launched molecular wave packet on the repulsive Coulomb potential was accessed by the laser-induced postionization. A further unexpected photofragmentation channel, which relies on the collective action of XUV and laser fields, is attributed to a laser-promoted charge transfer transition in the exploding molecule.     

Etude par spectrometrie Raman des complexes de l'iode dans les alcools et les ethers

Laser Raman spectra of iodine-alcohol and iodine-ether solutions have been studied. It was found a new line at 167 cm^?1 for alcohols and at 170 cm^?1 for ethers which is tentatively attributed to an intermediate Hassel complex.     

Synthesis of transparent silica aerogels using tetraalkylammonium fluoride catalysts

Tetraalkylammonium fluoride salts have been employed as catalysts for the synthesis of silica aerogels by a two-step, sol–gel method. Aerogel materials were characterized by N₂ physisorption and SEM. The effect of the type of catalyst on the optical transparency of obtained aerogels has been examined. It has been found that such compounds allow the synthesis of silica aerogels with the highest optical transmittance ever reported for such materials. The optimal catalysts are tetrabutyl and tetraoctyl ammonium fluoride, with which aerogels with transparency as high as 96% and extinction coefficient as low as 3.5 m⁻¹ can be prepared.     

Wave-function mapping of InAs quantum dots by scanning tunneling spectroscopy

Scanning tunneling spectroscopy is used to investigate the single-electron states and the corresponding squared wave functions of single and freestanding strain-induced InAs quantum dots grown on GaAs(001). Several peaks are found in dI/dV curves, which belong to different single-electron states. Spatially resolved dI/dV images reveal (000), (100), (010), (200), and (300) states, where the numbers describe the number of nodes in [11;0], [110], and [001] directions, respectively. The total number and energetic sequence of states is different for different dots. Interestingly, the (010) state is often missing, even when (200) and (300) states are present. We interpret this anisotropy in electronic structure as a consequence of the shape asymmetry of the dots.     

Modèle électrostatique de la conformation des molécules CH2X-CH2Y

A very simple elctrostatic model is proposed for the conformation of the CH₂X-CH₂Y molecules. The mutual repulsion between the two electrical charges located on the X and Y substituents is in equilibrium with the couple of torsion arising from the C-C bond. To calculate this model, the geometrical parameters and torsion constant of the various molecules are replaced by their averaged values. The conformation angle is related: (1) to the electronegativities of the substituents; (2) to the mean value of the net charge from the two linked carbon atoms; (3) to the difference in energy between the gauche and trans compounds. This elementary model permits us to explain results, which were previously published by one of us, concerning the conformation calculated by using the EHMO method.     

Laser-Raman spectra of argon-iodine interactions

Resonance Raman spectra of iodine-argon interactions at relatively high argon pressures (1–40 atm) are presented. It is shown that the decrease in the vibrational frequency from 213 cm^-1 for iodine molecule to 197 cm^-1 for Ar-I₂ is consistent with the formation of an argon-iodine complex catalyzed by the glass surface, or possibly with a weak Ar-I vibration.