Propane dehydrogenation over extra-framework In(i) in chabazite zeolites

Indium on silica, alumina and zeolite chabazite (CHA), with a range of In/Al ratios and Si/Al ratios, have been investigated to understand the effect of the support on indium speciation and its corresponding influence on propane dehydrogenation (PDH). It is found that In₂O₃ is formed on the external surface of the zeolite crystal after the addition of In(NO₃)₃ to H-CHA by incipient wetness impregnation and calcination. Upon reduction in H₂ gas (550 °C), indium displaces the proton in Brønsted acid sites (BASs), forming extra-framework In⁺ species (In-CHA). A stoichiometric ratio of 1.5 of formed H₂O to consumed H₂ during H₂ pulsed reduction experiments confirms the indium oxidation state of +1. The reduced indium is different from the indium species observed on samples of 10In/SiO₂, 10In/Al₂O₃ (i.e., 10 wt% indium) and bulk In₂O₃, in which In₂O₃ was reduced to In(0), as determined from the X-ray diffraction patterns of the product, H₂ temperature-programmed reduction (H₂-TPR) profiles, pulse reactor investigations and in situ transmission FTIR spectroscopy. The BASs in H-CHA facilitate the formation and stabilization of In⁺ cations in extra-framework positions, and prevent the deep reduction of In₂O₃ to In(0). In⁺ cations in the CHA zeolite can be oxidized with O₂ to form indium oxide species and can be reduced again with H₂ quantitatively. At comparable conversion, In-CHA shows better stability and C₃H₆ selectivity (∼85%) than In₂O₃, 10In/SiO₂ and 10In/Al₂O₃, consistent with a low C₃H₈ dehydrogenation activation energy (94.3 kJ mol⁻¹) and high C₃H₈ cracking activation energy (206 kJ mol⁻¹) in the In-CHA catalyst. A high Si/Al ratio in CHA seems beneficial for PDH by decreasing the fraction of CHA cages containing multiple In⁺ cations. Other small-pore zeolite-stabilized metal cation sites could form highly stable and selective catalysts for this and facilitate other alkane dehydrogenation reactions.

Indium-containing chabazite zeolites show better stability and C₃H₆ selectivity for propane dehydrogenation than In₂O₃, In/SiO₂ and In/Al₂O₃. Extra-framework In⁺ is identified as the stable active site upon reduction of an impregnated sample.     

Effects of precursors on nucleation in atomic layer deposition of HfO2

Atomic layer deposition of hafnium dioxide (HfO₂) on silicon substrates was studied. It was revealed that due to low adsorption probability of HfCl₄ on silicon substrates at higher temperatures (450–600 °C) the growth was non-uniform and markedly hindered in the initial stage of the HfCl₄–H₂O process. In the HfI₄–H₂O and HfI₄–O₂ processes, uniform growth with acceptable rate was obtained from the beginning of deposition. As a result, the HfI₄–H₂O and HfI₄–O₂ processes allowed deposition of smoother, more homogeneous and denser films than the HfCl₄–H₂O process did. The crystal structure developed, however, faster at the beginning of the HfCl₄–H₂O process.     

Corticomuscular synchronization with small and large dynamic force output

Background  

Over the last few years much research has been devoted to investigating the synchronization between cortical motor and muscular activity as measured by EEG/MEG-EMG coherence. The main focus so far has been on corticomuscular coherence (CMC) during static force condition, for which coherence in beta-range has been described. In contrast, we showed in a recent study [1] that dynamic force condition is accompanied by gamma-range CMC. The modulation of the CMC by various dynamic force amplitudes, however, remained uninvestigated. The present study addresses this question. We examined eight healthy human subjects. EEG and surface EMG were recorded simultaneously. The visuomotor task consisted in isometric compensation for 3 forces (static, small and large dynamic) generated by a manipulandum. The CMC, the cortical EEG spectral power (SP), the EMG SP and the errors in motor performance (as the difference between target and exerted force) were analyzed.     

Rotational spectra of gauche perfluoro-n-butane, C4F10; perfluoro-iso-butane, (CF3)3CF; and tris(trifluoromethyl)methane, (CF3)3CH

The microwave spectra of the gauche conformer of perfluoro-n-butane, n-C₄F₁₀, of perfluoro-iso-butane, (CF₃)₃CF, and of tris(trifluoromethyl)methane, (CF₃)₃CH, have been observed and assigned. The rotational and centrifugal distortion constants for gauche n-C₄F₁₀ are: A = 1058.11750(7) MHz, B = 617.6832(1) MHz, C = 552.18794(1) MHz, Δ_J = 0.0257(5) kHz, δ_J = 0.0052(3) kHz. A C-C-C-C dihedral angle, ω, of ∼55° has been determined. These values agree well with those obtained from a coupled cluster (CCSD/cc-PVTZ) calculation. The rotational and centrifugal distortion constants for iso-C₄F₁₀ and iso-C₄HF₉ are: B_o = 816.4519(4) MHz, D_J = 0.023(2) kHz, and B_o = 903.6985(25) MHz, D_J = 0.043(4) kHz, respectively. The dipole moment of iso-C₄F₁₀ and iso-C₄HF₉ have been measured and found to be 0.0338(8) and 1.69(9) D, respectively.     

PseudoRiemannian geometry and actions of simple Lie groups

Let G be a connected noncompact simple Lie group acting isometrically on a connected compact pseudoRiemannian manifold M. Denote with $n_0$ and $m_0$ the dimension of the maximal null subspaces tangent to G and M, respectively. Then we always have $n_0?m_0$. Our main result states that, if $n_0=m_0$, then the G-action is, up to a finite covering, an algebraic action. We use this to obtain a complete characterization of a large family of G-actions, thus providing a partial positive answer to the conjecture proposed in Zimmer's program for pseudoRiemannian manifolds. To cite this article: R. Quiroga-Barranco, C. R. Acad. Sci. Paris, Ser. I 341 (2005).     

On the calculation of the minimum wave plus vortex drag of supersonic wings

Résumé Les valeurs de contour de la solution d'un problème mixte harmonique sur l'arc portant des données deNeumann sont obtenus par une représentation conforme et par évaluation d'une intégrale généralisée. Cette méthode permet de calculer le minimum du coéfficient de trainée d'une aile supersonique.

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The results presented in this paper were obtained in the course of research forConvair, A Division of General Dynamics Corporation, San Diego, Calif.     

The regiospecific Fischer indole reaction in choline chloride.2ZnCl2 with product isolation by direct sublimation from the ionic liquid

The Fischer indole synthesis occurs in high yield with one equivalent of the ionic liquid choline chloride[middle dot]2ZnCl(2); exclusive formation of 2,3-disubstituted indoles is observed in the reaction of alkyl methyl ketones, and the products readily sublime directly from the ionic liquid.     

Revisiting the Ullmann-ether reaction: a concise and amenable synthesis of novel dibenzoxepino[4,5-d]pyrazoles by intramolecular etheration of 4,5-(o,o'-halohydroxy)arylpyrazoles

A concise synthesis of a series of novel dibenzoxepino[4,5-d]pyrazoles was accomplished by implementation of an intramolecular Ullmann-ether reaction on o,o'-halohydroxy-4,5-diarylpyrazoles mediated by CuBr.DMS. An alternative useful approach based on the palladium-catalyzed biaryl-ether linkage formation (Buchwald-Hartwig reaction) was also successfully applied, offering limitations with regard to the steric demand of the substituents. The synthesis of the key o,o'-halohydroxy-4,5-diarylpyrazole intermediates proceeds through the construction of the heterocyclic ring by a tandem amine-exchange/heterocyclization sequence of 3-N,N-(dimethylamino)-1,2-diarylpropenones with phenylhydrazine followed by basic hydrolysis for deprotection. The enamino ketone precursors were conveniently prepared from the corresponding O-sulfonyloxy and O-benzoyloxy ortho-substituted 1,2-diarylethanones, starting from inexpensive salicylaldehyde or phenylacetic derivatives. Preliminary binding affinity experiments against peripheral and central nervous system receptors have been done with negative results.