Mo-V-Te-Nb-O催化剂上丙烷选择氧化制丙烯酸Ⅰ.催化剂的制备条件及稳定性

 研究了催化剂的制备条件(焙烧方式、焙烧气氛和焙烧温度)对Mo-V-Te-Nb-O上丙烷选择氧化制丙烯酸反应的影响. 结果表明,制备条件对催化剂的催化性能具有很大的影响. 与敞开式焙烧制得的催化剂相比,封闭式焙烧制得的催化剂具有较高的丙烯酸选择性,但丙烷转化率较低. 在空气中焙烧制得的催化剂对丙烯酸无选择性,但在氮气和氩气中焙烧制得的催化剂具有很高的丙烷转化率和丙烯酸选择性. 随着焙烧温度的升高,丙烷转化率降低,丙烯酸选择性升高,适宜的焙烧温度为600 ℃. 催化剂制备条件对催化剂的晶相结构也具有重要的影响. 在惰性气氛中采用600 ℃下封闭式焙烧制得的Mo-V-Te-Nb-O催化剂经210 h反应后,丙烷转化率保持为19%,而丙烯酸选择性持续升高,由32%升至50%.     

Nanocomposites of Tantalum‐Based Pyrochlore and Indium Hydroxide Showing High and Stable Photocatalytic Activities for Overall Water Splitting and Carbon Dioxide Reduction

Nanocomposites of tantalum‐based pyrochlore nanoparticles and indium hydroxide were prepared by a hydrothermal process for UV‐driven photocatalytic reactions including overall water splitting, hydrogen production from photoreforming of methanol, and CO₂ reduction with water to produce CO. The best catalyst was more than 20 times more active than sodium tantalate in overall water splitting and 3 times more active than Degussa P25 TiO₂ in CO₂ reduction. Moreover, the catalyst was very stable while generating stoichiometric products of H₂ (or CO) and O₂ throughout long‐term photocatalytic reactions. After the removal of In(OH)₃, the pyrochlore nanoparticles remained highly active for H₂ production from pure water and aqueous methanol solution. Both experimental studies and density functional theory calculations suggest that the pyrochlore nanoparticles catalyzed the water reduction to produce H₂, whereas In(OH)₃ was the major active component for water oxidation to produce O₂.     

Catalytic and Atom‐Economic C −C Bond Formation: Alkyl Tantalum Ureates for Hydroaminoalkylation

Atom‐economic and regioselective C ?C bond formation has been achieved by rapid C?H alkylation of unprotected secondary arylamines with unactivated alkenes. The combination of Ta(CH₂SiMe₃)₃Cl₂, and a ureate N,O‐chelating‐ligand salt gives catalytic systems prepared in situ that can realize high yields of β‐alkylated aniline derivatives from either terminal or internal alkene substrates. These new catalyst systems realize C?H alkylation in as little as one hour and for the first time a 1:1 stoichiometry of alkene and amine substrates results in high yielding syntheses of isolated amine products by simple filtration and concentration.     

Structural and magnetic properties of pyrochlore solid solutions (Y,Lu)2Ti2−x(Nb,Ta)xO7±y

The synthesis and characterization of the pyrochlore solid solutions, Y₂Ti_2−xNb_xO_7−y, Lu₂Ti_2−xNb_xO_7−y, Y₂Ti_2−xTa_xO_7−y and Lu₂TiTaO_7−y (−0.4<y<0.5), is described. Synthesis at 1600 °C, and 10⁻⁵ Torr yields oxygen deficiency in all systems. All compounds are found to be paramagnetic and semiconducting, with the size of the local moments being less, in some cases substantially less, than the expected value for the number of nominally unpaired electrons present. Thermogravimetric analysis (TGA) shows that all compounds can be fully oxidized while retaining the pyrochlore structure, yielding oxygen rich pyrochlores as white powders. Powder neutron diffraction of Y₂TiNbO₇-based samples was done. Refinement of the data for oxygen deficient Y₂TiNbO_6.76 indicates the presence of a distribution of oxygen over the 8b and 48f sites. Refinement of the data for oxygen rich Y₂TiNbO_7.5 shows these sites to be completely filled, with an additional half filling of the 8a site. The magnetic and TGA data strongly suggest a preference for a Ti³⁺/(Nb,Ta)⁵⁺ combination, as opposed to Ti⁴⁺/(Nb,Ta)⁴⁺, in this pyrochlore family. In addition, the evidence clearly points to Ti³⁺ as the source of the localized moments, with no evidence for localized Nb⁴⁺ moments.     

A crystallographic and DFT study on a NHC complex of niobium oxide trifluoride

The complex [NbOF₃(Ipr)]₂, 1, was afforded in crystalline form by reaction of NbF₅ with the bulky NHC ligand 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) in toluene by slow contact with moisture air. The molecular structure of 1 was ascertained by X-ray diffraction, providing the first example of a dinuclear NbOF₃ derivative and also a rare case of niobium compound with a monodentate NHC. A DFT investigation has shown that the Nb–C bond consists of a weak NHC to Nb σ donation, reinforced by an electrostatic contribution presumably favored by the presence of the ancillary fluoride ligands. The computed enthalpy for the dissociation of one Ipr from 1 is ca. 36 kcal mol^?1. The presence of bulky 2,6-diisopropylphenyl substituents on the carbene ligand has negligible influence on the Nb–C bond, as highlighted by DFT analyses on simplified models.     

A mild,efficient, and selective procedure for the deoxygenation of sulfoxides with the TaCl5/indium system

The TaCl₅/In system was found to be a new reagent for reducing a wide range of structurally diverse sulfoxides to the corresponding sulfides with high yields under mild conditions. This protocol is chemoselective and tolerates several functional groups, such as Br, Cl, OCH₃, CHO, and CH = CH₂.     

Preparation and Characterization of Niobium Oxide Coated Cellulose Fiber

The Nb₂O₅/cellulose composite was prepared by reacting α-cellulose with NbCl_5-n(OC₂H₅)_n, in nonaqueous solvent, under nitrogen atmosphere and submitting the obtained material to hydrolysis. An increase in the crystallinity degree is observed in the composite material because the precursor reagent reacts with the amorphous phase of the cellulose fibers. Loadings between 4.5 and 16.0% of the oxide were achieved and in every case the oxide particles uniformly cover the fiber surface. Lewis and Brønsted acid sites were determined by using pyridine as the basic molecular probe.     

1．5GHz锯材超导腔的研制

介绍铌材超导腔的研制进展，重点讨论了国产铌腔的材料改性，以及相应的超导腔性能的改进．叙述了１．５ＧＨｚ铌腔的腔形设计，分析了铌材的射频性能和机械性能，制定了铌腔制作与后处理的特定工艺．最后给出了１．５ＧＨｚ铌材超导腔的低温实验结果．     

Quadrupole interaction of tantalum impurities in bismuth metal

The time differential perturbed angular correlation technique has been used in the measurement of the electric quadrupole interaction of Ta impuritiy in bismuth metal. The interaction frequencies at 293, 400 and 500 K have been observed to be 288±1.5, 266.9±3 and 244.5±4.3 MHz respectively. The electric field gradient at 293 K is 4.75±0.3 × 10¹⁷ V/cm² with the temperature coefficientB=2.2±0.2 × 10⁻⁵ (K)^−3/2.