熔盐电化学的新进展

本文主要介绍熔盐体系、熔盐电池、熔盐电沉积金属以及合金、电合成化合物材料等方面的新进展 ,预期熔盐电化学在能源、环境保护和资源利用等领域中的应用 .     

钒化合物对酸性镀锡溶液的稳定作用

研究了钒化合物稳定剂对酸性SnSO4 溶液稳定性的影响 .可见光谱分析表明稳定剂中主要含有VO2 + 和少量的V3+ ,循环伏安实验显示在 - 0 .2 0～ - 0 .55V(vs .SCE)电位范围内VO2 + 能够在阴极上还原为V3+ ,在更负的电位下V3+ 能进一步还原到V2 + .实验结果说明稳定剂中的低价钒离子有效地清除了镀液中的溶解氧 ,因而防止了Sn2 + 离子的氧化 ,显著地提高了酸性锡镀液的稳定性 .     

Theoretical study of the internal rotational barriers in nitrobenzene, 2‐nitrotoluene, 2‐nitrophenol,and 2‐nitroaniline

The molecular geometries and internal rotational barriers of the nitro group of nitrobenzene (NB), 2‐nitrotoluene (2‐NT), 2‐nitroaniline (2‐NA), and 2‐nitrophenol (2‐NP) were calculated by five different types of density functional theory (DFT) methods with three different levels of basis sets. Analysis of the torsional angles of the nitro, methyl, amino, and hydroxyl groups indicate that NB, 2‐NA, and 2‐NP are planar molecules, but 2‐NT is not a planar molecule. Internal rotational barriers of the nitro group were calculated as V₂ barriers, and the NO₂ torsional potentials for each molecule were given. The values of the V₂ barriers depend on the DFT methods and basis sets. The average values of the V₂ barriers for NB, 2‐NT, 2‐NA, and 2‐NP are 6.47 kcal/mol, 3.00 kcal/mol, 10.20 kcal/mol, and 13.26 kcal/mol, respectively. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 83: 332–337, 2001     

沸石表面有机金属化学ZSM-5外表面上——Ge(n-C4H9)x基团的接枝及其性质研究

用气体分析及IR,NMR和元素分析等方法研究了真空系统中230℃和280℃下四丁基锗在ZSM-5沸石表面上的接枝反应,并对所得沸石的热稳定性和吸附性质进行了表征,与作者曾报道的硅胶及丝光沸石上的反应类似,四丁基锗也能与ZSM-5沸石表面上的硅羟基发生缩合反应,在其外表面或孔口生成组成为(=Si-O)xGe(n-C4H9)4-x(x=2~3)的表面有机锗化合物,在２３０℃接枝丁基锗基团不影响沸石的结构和表面积,仅改变它的孔口大小,在改性后的沸石上,Ｎ２的吸附性质没有改变,而不同分子尺寸的烃,加正已烷,２-甲基戊烷,２,３-二甲基丁烷却呈现出完全不同于起始ＺＳＭ-５沸石的择形吸附效应.     

用色谱-质谱方法鉴定薄荷油中的异构体

用毛细管气相色谱－质谱联用、程序升温方法分析了一种薄荷油的化学成分、共分离出20个组分,其中含4组异构体,它们分别是：m/z=136的5个成分α－蒎烯、β－蒎烯、β－月桂烯、α－菲兰烯和柠檬烯;m/z＝154的2个成分（cis)－薄荷酮和（2R－cis)－薄荷酮;m/z＝156的2个成分（1α.2α.5β）－薄荷醇和（1α.2β.5β）－薄荷醇;以及m/z＝204的8个成分（1α,3aα,3bβ,6aβ,6bα）－十氢－3a－甲基－6－亚甲基－1－异丙基－环丁烷并[1,2:3,4]二环戊烯、[1R-(1R,4E,9S)－4,11,11－三甲基－8亚甲基－双环（7．2．0）十一碳4－烯、[1R-(1aα,7α,7aα,7bα]-1a,2,3,5,6,7,7a,7b-八氢－1,1,7,7a-四甲基－1氢－环丙烷[α]并萘、[1aR-(1aα,4aα,7α,7aβ,7bα）－十氢,1,1,7－三甲基4－亚甲基－1－氢－环丙烷[e]并奥、（1S-exo）－2－甲基－3－亚甲基－2－（4－甲基－3－戊烯基）－二环（2．2．1）庚烷、（3aα,3bα,4α,7β,7aR）－八氢－7甲基－3亚甲基－4－异丙基－1氢－不戊烷[ 1,3]并环丙烷[1,2]并苯、1－乙烯基－1－甲基－2－异丙烯基－4（1－甲基亚乙基）环己烷和绿叶烯。     

Synthesis and Structure of Dimolybdenum(I) Carbonyl Compound with Thiolate and Carboxylate Mixed-tri-bridging Ligands [Bu_4N][Mo_2(CO)_6(SC_6H_4Cl-p)_2(CF_3COO)]

1 INTRODUCTION Molybdenum(I) compounds, in particular Mo(I)-SR compounds, are rare amongst numerous Mo compounds. So far, only the following compounds [Mo2(CO)8-n(SR)2(CH_3CN)n] (R = C6H5, CH_2CO2Et, n = 0, 2)[1～5] have been reported in the literature. Recently, we make an effort to develop investigations on Mo(I) compounds on the basis of preparing new Mo(I) compounds by introducing different functional ligands into Mo2(SR)2(CO)8, then determining their structures and measur…     

Synthesis and structural characterization of a novel dimolybdenum(I) compound with mixed‐tribridging ligands: [Bu4N][Mo2(μ‐SPh)2(μ‐Cl(CO6]

A novel mixed‐tribridged dimolybdenum(I) compound [Bn₄N][Mo₂(μ‐SPh)₂(μ‐Cl)(CO)₆] (1) has been synthesized from the reaction of Mo₂(CO)₃(SPh)₂ with BU₄NCl. Compound 1 was characterized by IR, UV‐Vis and ¹H, ¹³C, ⁹⁵Mo NMR spectroscopic analyses. The electrochemical behavior was measured by cyclic voltammetry, indicating a quasi‐reversible two‐electron transfer in one step. The crystal structure determined by X‐ray crystallography shows that 1 contains a [Mo₂(μ‐S)₂(μ‐Cl)]^? core with a planar Mo₂S₂unit and a Cl bridge. The Mo? Mo distance is 0.28709(7) nm, and the Mo‐Cl‐Mo angle is 66.44(4)°. A newface‐sharing bioctahedral structure is discussed.     

Solid state reaction synthesis of filled skutterudite compounds (Ce or Y)yFexCo4-xSb12 and the effect of filling atoms Ce or Y on lattice thermal conductivity

The synthesis of filled skutterudite compounds (Ce or Y)_y(Fe)_x(Co)_(4x)(Sb)_(12), through a solidstate reaction using chloride of Ce or Y,high purity powder of Co, Fe, and Sb as starting materials,was investigated. (Ce or Y)_y(Fe)_x(Co)_(4x)(Sb)_(12) (x=0--1.0, y=0--0.15) compounds were obtained at850--1 123 K. The results of Rietveld analysis demonstrate that (Ce or Y)_y(Fe)_x(Co)_(4x)(Sb)_12synthesized by a solid state reaction possesses a filled skutterudite structure. The filling fraction ofCe or Y obtained by Rietveld analysis agrees well with the composition obtained by chemicalanalysis. The lattice constant of (Ce)_y(Fe)_x(Co)_(4x)(Sb)_(12) increases with increasing substitution of Fe at Cosites, and with an increasing Ce filling fraction in the Sb-dodecahedron voids. The lattice thermalconductivity of (Ce or Y)_y(Fe)_x(Co)_(4x)(Sb)_(12) decreases significantly with an increasing Ce or Y fillingfraction in the voids and with substitution of Fe at Co sites.     

毛细电色谱法拆分安息香手性化合物

用毛细电色谱法成功地拆分了安息手性化合物,并获得了较好的重现性和分离度。     

直链烷烃结构型和凝聚型性质的递变规律研究

用图示法和非线性规划的方法对直链烷烃同系物最高成键分子轨道能级、最低成键分子轨道能级,电离电位、氧化半波电位、正常沸点、正常熔点、临界压力、临界温度、密度、折光率、表面张力和粘度等12种结构型性质和凝聚型性质的变化规律进行研究,结果发现直链烷烃结构型性质和凝聚型性质一般能遵守同系对数递变规律,各种结构型性能和凝聚型性能均与对数递变函数呈优良的相关性,相关系数均大于0.99．用同系对数递变规律对直链烷烃各种性能进行预测的结果表明,除少数同系列起始化合物的偏差较大外,大多数预测值与实验值非常吻合,实验散点几乎与对数递变函数曲线相重合．