On a new calcium vanadate: synthesis, structure and Li insertion behavior

A synthetic form of the mineral hewettite was prepared via a new route in aqueous medium, starting either from the crystalline compound Li_1.1V₃O₈, or from its amorphous precursor. The anhydrous, crystalline derivative Ca_0.5V₃O₈ was obtained by heating the synthetic hewettite at 250°C under dynamic vacuum. The diffraction studies show that the 2D structure of Ca_0.5V₃O₈ involves the same V₃O₈ layers as in the hewettite or in Li_1+αV₃O₈. The stacking of the layers is similar to that in the metahewettite. A structural model is proposed, where the Ca²⁺ ions occupy octahedral sites in the interlayer space. The electrochemical behavior of Ca_0.5V₃O₈ vs. lithium insertion is presented. It is original and reveals particularly good performances in terms of stability during cycling at C/5 rate. The homologues obtained with Mg or Ba, instead of Ca, are briefly presented.     

Lithium heptadecafluorooctanesulfonate catalyzed Mannich-type and aza-Diels-Alder reactions in supercritical carbon dioxide

The Mannich-type reaction of imines with (1-methoxy-2-methylpropenyloxy)trimethylsilane and aza-Diels-Alder reaction of imines with Danishefsky's diene can be carried out in scCO₂ in the presence of lithium heptadecafluorooctanesulfonate which offer a way to synthesize β-amino carbonyl compounds and nitrogen-containing six-membered ring compounds under environmentally benign conditions.     

Diisobutylaluminium hydride (DIBAL-H) as a molecular scalpel: a new mechanistic proposal for a spiroketal rearrangement

Taking advantage of our knowledge of the capacity of DIBAL-H to de-O-alkylate, we propose an alternative mechanism for a spiroketal rearrangement described by E. Suàrez. We also show that this proposal can account for the formation of the secondary product, whose original structure we propose to correct.     

Wavelength dependence in photochemical vapor deposition of aluminum film using dimethylaluminum hydride

In photochemical vapor deposition of aluminum film on silicon using dimethylaluminum hydride, (CH₃)₂AlH, a surface reaction dominated below a (CH₃)₂AlH pressure of 0.3 m Torr at 200°C, which was induced only with the 160 nm band emitted from a deuterium lamp. A gas-phase reaction occurred above 0.3 mTorr at 200°C, which could be induced by both 160 nm and 240 nm emission bands from the lamp. To distinguish between surface ad gas-phase reactions, a thickness profile was used. At 240°C the surface reaction could be induced even by the 240 nm band, while the deposits formed under illumination of the two bands were thinner than those obtained with only the 240 nm band, indicating occurrence of vacuum ultraviolet (VUV)-enhanced desorption. The mechanism responsible for the observed wavelength dependence in unclear. The electrical resistivity of the films deposited at 200°C was 4.5 μΩ cm, which did not change with wavelength.     

Matrix effects in the determination of butyltin compounds in environmental samples by GC AA after hydride generation

Experiments for the determination of mono-, di and tri-butyltin (MBT, DBT and TBT) by hydride generation/gas chromatography/atomic absorption spectrometry in various matrices (sediment, suspended matter, mussel, algae and water) have revealed that poor butyltin recoveries are obtained in sediments displaying high sulphur and hydrocarbon contents; very poor recoveries were also observed for TBT in sediments with high chlorophyll pigment contents as well as in algal samples. It was however not clear whether the hydride generatin was inhibited by these infering compounds, as was previously assumed in the case of hydrocarbons, or whether interferences affected the atomization rate. Further studies were performed to solve this problem in order to validate this method in the case of analyses of, for example, oil-contaminated sediment and algae. This paper presents the results obtained. It is concluded here that the poor recoveries were due to an inhibition of hydride generation rather than to interference at the atomization stage.     

Deposition conditions in tailoring the morphology of highly porous reticular films prepared by electrostatic spray deposition (ESD) technique

Spongy-like reticular structure is a unique morphology fabricated by electrostatic spray deposition (ESD) technique. The effects of solvent, substrate temperature, precursor feeding rate, static electric field strength, and deposition time on tailoring the reticular structure were investigated. Scanning electron microscopy was used to observe the film morphology. MnO_x or LiMn₂O₄ were selected as the model materials. It is found that in addition to the conventional solvent butyl carbitol, other kinds of solvents such as ethylene glycol and propylene glycol can also be used to obtain reticular films at a suitable substrate temperature. Porous films with a low cross-linking degree pore structure can be prepared by increasing precursor feeding rate or decreasing substrate temperature. Increasing the deposition time or the electric field strength helps to obtain reticular films with more homogeneous pore size distribution. In addition, the addition of a high boiling-point solvent in mixed alcohol solvent results in the increase of proper substrate temperature. It is concluded that the fluidity of the spray droplets on the surface of a hot substrate is an important factor to form a reticular film.     

Hydrothermal synthesis of FeS2 for lithium batteries

Nanocrystalline FeS₂ cathode material of lithium cell was synthesized from cheap materials of FeSO₄, Na₂S₂O₃, and sulfur by a hydrothermal process. The scanning electron microscopy analysis showed the obtained material was nano-sized, about 500 nm. The X-ray powder diffraction analysis showed that the synthetic FeS₂ material had two phases of the crystalline structure, pyrite and marcasite. The phase of marcasite seems to have no negative effect on the electrochemical performance of the material. The synthetic FeS₂ showed a significant improvement of electrochemical performance for Li/FeS₂ cells.