Hydrothermal synthesis, structure and quantum chemistry of transition metal complex supported by metal-oxo cluster [(Ni(phen)22 (ξ-Mo8O26)]

A nickel-1,10-phenanthroline complex supported on an octamolybdate, [(Ni(phen)_{2 2}(ξ-Mo₈O₂₆)], has been hydrothermally synthesized with MoO₃, H₂MoO₄, Ni(OAc)₂ 6H₃O and 1,10-phenathroline (1,10-phen) as raw materials. The crystals of the compound belong to monoclinic P2₁/n space group,a = 1.2952(2),b = 1.6659(10),c = 1.3956(12) nm, β =106.273(8)°,V = 2.8906(5) nm³,Z = 2. 5604 observable reflections (I >2σ(I)) were used for structure resolution and refinements to converge to finalR ₁ = 0.0414,wR ₂ = 0.0815. The result of structure determination shows that the compound contains octamolybdate possessing a novel structure type (named as ξ-isomer). The feature of ξ-[Mo₈O₂₆]^4- is that it is composed of Mo₆O₆ ring and two MoO₆ octahedral located at cap positions on opposite faces. The Mo₆O₆ ring contains two octahedral and four trigonal-bipyramidal Mo^VI atoms. Each ξ-[Mo₈O₂₆]^4- unit is bonded with two [Ni(phen)₂]²⁺ through terminal oxygen atoms of octahedral and neighbouring trigonal-bipyramidal Mo atom in the Mo₆O₆ ring. IR and UV-Vis spectra of the compound were measured and its electronic structure was studied by EHMO method.     

The gas phase reactions of hydroxyl radicals with a series of aliphatic ethers over the temperature range 240–440 K

Absolute rate constants were determined for the gas phase reactions of OH radicals with a series of linear aliphatic ethers using the flash photolysis resonance fluorescence technique. Experiments were performed over the temperature range 240–440 K at total pressures (using Ar diluent gas) between 25–50 Torr. The kinetic data for dimethylether (k₁), diethylether (k₂), and dipropylether (k₃) were used to derive the Arrhenius expressions and At 296 K, the measured rate constants (in units of 10^?13 cm³ molecule^?1 s^?1) were: k₁ = (24.9 ± 2.2), k₂ = (136 ± 9), and k₃ = (180 ± 22). Room temperature rate constants for the OH reactions with several other aliphatic ethers were also measured. These were (in the above units): di-n-butylether, (278 ± 36); di-n-pentylether, (347 ± 20); ethyleneoxide, (0.95 ± 0.05); propyleneoxide, (4.95 ± 0.52); and tetrahydrofuran, (178 ± 16). The results are discussed in terms of the mechanisms for these reactions and are compared to previous literature data.     

A flash photolysis resonance fluorescence investigation of the reactions of Oxygen O(3P) atoms with aliphatic ethers and diethers in the gas phase

Rate constants for the gas phase reCedex 2, Franceactions of O(³P) atoms with a series of symmetric aliphatic ethers have been determined using the flash photolysis resonance fluorescence technique over the temperature range 240–400 K. The Arrhenius parameters derived from these data are (in units of cm³ molecule ^?1 s^?1): The error limits are two standard deviations derived from the least-squares fit. Rate constants for several other ethers were determined only at 298 K. The values obtained were (in units of 10^?14 cm³ molecule^?1 s^?1): tetrahydrofuran (37.5 ± 1.1); 1,4?dioxane 1(6.81 ± 0.46); diethoxymethane (40.4 ± 1.8); ethyl -t-butyl ether (37.0 ± 1.3); and methyl-t-amylether (57.3 ± 2.3).     

物性依赖温度的热传导方程的近似解(Ⅰ)

1引言在热传导方程中式中P、C分别是介质的密度和比热,k是热传导系数。用0表示相对温度,即0—t一f＿,这里t＿表示环境温度。在很多情形下,热传导系数以幂次依赖于温度,例如等离子体中的电子热传导,即假设P,C为常数,则方程（1）变为其中a—00／pcm。本课题考虑对称物体的边界（两端）始终为环境温度,即对称区域（－－,l）上具有零边界条件0（士人,）一0（4）的近似解。关于这一问题,尽管许多中外学者对其解析解（分析解）有着很大的兴趣,然而在很多情形下,解析解是不可能得到的。同时,我们也注意到,对于半无限大和无限大固…     

Bi和O2(1△g)的化学发光研究

The emission spectra of BiO has been first obtained by studying the reaction: Bi+O_2(~1△_g)in the atomic-beam apparatus. 22 new bands has been obtained from the emission spectra of BiO (A ~2Π_g) which are attributed to the collisional energy transfer process of BiO(X,v)+O_2(b ~1Σ_g~+). The O_2(b ~1Σ_g~+) is produced by the following process: O_2(~1△_g)+O_2(~1△_g)→O_2(b ~1Σ_g~+)+O_2(X ~3Σ_g~-).     

Synthesis and magnetism of binuclear cobalt(II) complexes with the tetraacetylethene dianion as a bridging ligand

Three novel binuclear CoIIcomplexes, [Co2(TAE)-(phen)4](ClO4)2·3H2O(1),[Co2(TAE)(Nphen)4](ClO4)2 ·4H2O(2) and [CO2(TAE)(bipy)4](ClO4)2·H2O(3) (TAE=tetraacetylethene dianion, phen=1,10–phenanthroline, Nphen=5–nitro·1,10–phenanthroline, bipy =2,2-bipyridy1), have been synthesized and characterized by elemental analysis, i.r., molar conductance and electronic reflection spectra. The complexes are proposed to contain tetraacetylethene dianion bridged structures and two CoII ions. The variable-temperature magnetic susceptibility of complex (1) was measured in the 4–300 K range. The magnetic coupling parameter is consistent with antiferromagnetic exchange between the two CoII centres and the data fit a binuclear magnetic exchange model based on the Hamiltonian operator ( = –2 J12, S1=S2=3/2), giving the antiferromagnetic coupling parameter of 2J=–1.55cm–1.     

Ultrasound-assisted polyol method for the preparation of SBA-15-supported ruthenium nanoparticles and the study of their catalytic activity on the partial oxidation of methane

Metallic Ru nanoparticles have been successfully produced and incorporated into the pores of SBA-15 in situ employing a simple ultrasound-assisted polyol method. The product has been confirmed by X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy, where ultrasound provides both the energy for the reduction of the Ru(III) ion and the driving force for the loading of the Ru(0) nanoparticles into the SBA-15 pores. An ultrasound-assisted insertion mechanism has been proposed based on the microjets and shake-wave effect of the collapsed bubbles. The catalytic properties of the SBA-15-supported Ru nanoparticles have been tested by the partial oxidization of methane and show very high activity and high CO selectivity.     

Hydrothermal synthesis, structure and quantum chemistry of transition metal complex supported by metal-oxo cluster [{Ni(phen)2}2(x-Mo8O26)]

A nickel-1,10-phenanthroline complex supported on an octamolybdate, [{Ni(phen)2}2(x- Mo8O26)], has been hydrothermally synthesized with MoO3, H2MoO4, Ni(OAc)2· 6H2O and 1,10-phenathroline (1,10-phen) as raw materials. The crystals of the compound belong to monoclinic P21/n space group, a = 1.2952(2), b = 1.6659(10), c = 1.3956(12) nm, b =106.273(8)°, V = 2.8906(5) nm3, Z = 2. 5604 observable reflections (I ＞2s(I)) were used for structure resolution and refinements to converge to final R1 = 0.0414, wR2 = 0.0815. The result of structure determination shows that the compound contains octamolybdate possessing a novel structure type (named as x-isomer). The feature of x-[Mo8O26]4- is that it is composed of Mo6O6 ring and two MoO6 octahedra located at cap positions on opposite faces. The Mo6O6 ring contains two octahedral and four trigonal-bipyramidal MoVI atoms. Each x-[Mo8O26]4- unit is bonded with two [Ni(phen)2]2+ through terminal oxygen atoms of octahedral and neighbouring trigonal-bipyramidal Mo atom in the Mo6O6 ring. IR and UV-Vis spectra of the compound were measured and its electronic structure was studied by EHMO method.     

气体回流区分级着火试验研究

就回流区分级着火燃烧方式在气体燃料燃烧上的应用进行了一系列冷热态模拟试验和工业试验研究．比较了直流、钝体和开缝钝体喷口的出口速度、温度分布，以及在不同气体燃料热值时的稳焰能力。试验表明，开缝钝体喷口中缝小股射流进入喷口后低速回流区能稳定着火，进一步点燃主流，有效地形成回流区分级着火；开维钝体喷口的稳焰能力最强，特别适合低热值煤气燃烧。在大容量锅炉上进行了低热值高炉煤气燃烧的改造性工业试验，试验证明，开缝钝体燃烧器强化了低热值煤气的燃烧，有效地解决了锅炉煤气段燃烧强度不足以至锅炉尾部超温问题。     

阳离子染料在真丝绸上的光褪色机理

用电化学循环伏安法研究真丝绸上染料的光褪色，发现真丝绸中的某些氨基酸和染料、氧分子３者间可以形成电荷转移复合物。这些三元电荷转移复合物的还原电位比染料本身的还原电位明显正移。用的光照射，证明是真丝绸中的氨基酸加速了阳离子染料的光褪色。