单分散纳米InVO4(正交相)的低温合成

InVO₄ is a new developed visible light responding photocatalyst for water decomposition, which is obtained by a solid-state reaction at high temperature traditionally. In this paper, pure InVO₄ nano-crystalline powder has been prepared by a hydrothermal process at low temperature and was characterized by TEM, IR, and X-ray diffraction. Many factors such as pH value, reaction time and temperature have been investigated. It is found that the optimal conditions for the preparation is: n_InCl3∶n_NaVO3=1∶2; temperature : 150 ℃; Reaction time: 4～8 h; pH=7.9～8.0. And the experimental result shows that it is a convenient way to get single dispersing InVO₄ nano-crystalline powder by flux in alkyl alcohol.     

Partial molar volumes of cryptand-222 in organic solvents at 25°C

The partial molar volumes at infinite dilution of cryptand-222 (C-222) in water, methanol, acetonitrile, ethanol, dimethylsulfoxide, propanol, 2-propanol, chloroform, benzene, 1-butanol, cyclohexane, butyl-methylketone, hexane, tetrahydronaphthalene, heptane, octane, cyclohexylbenzene and decane were measured at concentrations ranging from 0.01 to 0.1 mol-L^–1 at 25°C. The partial molar volumes at infinite dilution showed remarkable dependency on the molar volume of the solvent. The partial molar volumes at infinite dilution for C-222 increase as the solvent molar volume increases.     

Quantitative surface analysis by Auger and x-ray photoelectron spectroscopy

Recent developments in quantitative surface analysis by Auger (AES) and x-ray photoelectron (XPS) spectroscopies are reviewed and problems relating to a more accurate quantitative interpretation of AES/XPS experimental data are discussed. Special attention is paid to consideration of elementary physical processes involved and influence of multiple scattering effects on signal line intensities. In particular, the major features of core-shell ionization by electron impact, Auger transitions and photoionization are considered qualitatively and rigorous approaches used to calculate the respective transition probabilities are analysed. It is shown that, in amorphous and polycrystalline targets, incoherent scattering of primary and signal Auger and photoelectrons can be described by solving analytically a kinetic equation with appropriate boundary conditions. The analytical results for the angular and energy distribution, the mean escape depth, and the escape probability as a function of depth of origin of signal electrons as well as that for the backscattering factor in AES are in good agreement with the corresponding Mote Carlo simulation data. Methods for inelastic background subtraction, surface composition determination and depth-profile reconstructions by angle-resolved AES/XPS are discussed. Examples of novel techniques based on x-ray induced photoemission are considered.     

Phosphorescence lifetime of naphthalene and phenanthrene in aggregated aromatic molecule-β-cyclodextrin-precipitant complexes

Aggregated aromatic molecule--cyclodextrin-precipitant complexes exhibit long-lived phosphorescence at room temperature in water after the chemical binding of oxygen. The temperature dependences of the phosphorescence lifetimes of naphthalene-h₈, naphthalene-de, and phenanthrene in the aggregates were measured. For example, the phosphorescence lifetimes of naphthalene-d₈ aggregated with -cyclodextrin and cyclohexane are equal to 25.1, 17.6, and 6.8 s at 77, 276, and 347 K, respectively, and that of phenanthrene aggregated with isooctane and -cyclodextrin are 3.24, 3.06, and 1.26 s at 268, 274, and 335 K, respectively. The temperature dependences of the phosphorescence lifetimes at room temperature are determined by the rate constants of the radiative and nonradiative transitions from the triplet state of an aromatic molecule.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2225–2228, September, 1996.     

Reduced parabolic model for radical addition reactions

The transition state of addition of free radicals and atoms to multiple bonds is considered as a result of intersecting of two parabolic potential curves. One of them characterizes the stretching vibration of the attacked multiple bond, and another curve characterizes the stretching vibration of the bond formed in the transition state. The force constant of the latter is calculated by an empirical equation that correlates the force constant with the bond dissociation energy. In the framework of this model, the thermally neutral activation energy (E _e0) and the elongation of the attacked and formed bonds (r _e) in the transition state were calculated from the experimental data (activation energy (E _e) and enthalpy of reaction (H _e)) for the addition of an H atom and methyl, alkoxyl, aminyl, triethylsilyl, and peroxyl radicals to the C=C bond and the addition of H and CH₃ to the C=O and CC bonds. Analysis of the data obtained showed that E _e0 depends linearly on the |H _e| + E_e sum, i.e., E_e0/kJ mol^–1 = 14.2 + 0.61 · (E_e – H _e), and the bond elongation in the transition state for addition of the most part of radicals to ethylene and acetylene vary within (0.65–0.87)·10_–10 m. The factors affecting the activation energy of the radical addition reactions are discussed.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1542–August, 2004.     

碳氟链与碳氢链表面活性剂在固液界面上的吸附

全氟辛酸及其钠盐和十二烷基硫酸钠在R972上的吸附等温线均为S型或LS型，指示固液界面吸附过程中有表面疏水缔合物生成．碳氟表面活性剂的饱和吸附量显著高于碳氢表面活性剂的饱和吸附量．加电解质于液相使各体系吸附量上升．对于碳氟表面活性剂，甚至引起吸附等温线类型变化．例如，不加电解质时全氟辛酸在R972上的吸附等温线为S型，而加入HCl（c＝0．05mol·dm－3）使吸附等混线变成LS型．全氟辛酸比全氟辛酸钠在R972上的吸附更强．几种表面活性剂在R972上的吸附均随温度升高而减少。应用两阶段吸附模型及通用吸附等温线公式可以很好地解释所得实验结果．     

The role of various binding materials for trace elemental analysis of powder samples using laser-induced breakdown spectroscopy

Study of various binding materials like potassium bromide, poly(vinyl alcohol), starch, silver and aluminum has been carried out using laser-induced breakdown spectroscopy (LIBS). The role of matrix effects using these five binders on LIBS signal intensity was investigated for better performance of LIBS technique as a quantitative analytical tool. For comparative study of different binders, the signal intensity of different Mg lines at 518.3, 517.2, 383.8 and 279.5 nm wavelengths were recorded for pellets prepared with known concentrations of Mg in these binders. The influence of laser energy on ablated mass under different binding materials and its correlation with LIBS signal intensity has been explored. Optical scanning microscopy images of the ablated crater were studied to understand the laser ablation process. The study revealed that the binding material plays an important role in the generation of LIBS signal. The relative signal intensity measured for a standard Mg line (at 518.3 nm) were 735, 538, 387, 227 and 130 for potassium bromide, starch, poly(vinyl alcohol), silver and aluminum as binders, respectively. This indicates clearly that potassium bromide is better as a binder for LIBS studies of powder samples.     

Reactions of bis(hexamethylbenzene)iron(0) with carbon monoxide and with unsaturated hydrocarbons

Thermal decomposition of bis(hexamethylbenzene)iron(0) in the presence of carbon monoxide yields a novel carbonyl iron complex, [C₆(CH₃)₆]Fe(CO)₂. The cyclohexadiene complex [C₆(CH₃)₆]Fe(C₆H₈) is obtained from reaction of bis(hexamethylbenzene)iron(0) with either 1,3-cyclohexadiene or benzene, and the yield is much greater in the presence of hydrogen gas. Interaction of bis-(hexamethylbenzene)iron(0) with 2-butyne induces a catalytic cyclotrimerization to give more hexamethylbenzene. Kinetic and isotope distribution studies indicate that the primary step in these reactions is not a direct loss of one ring ligand, but rather an insertion of the iron center into one of the ligand methyl CH bonds, leading to a benzyl hydride complex species. Mechanisms for the subsequent reactions of this iron hydride species are proposed.     

The crystal structure of CuVo3(II), a high-pressure ilmenite phase

The crystal structure of a second high-pressure copper vanadate phase, CuVO₃(II), has been determined and refined by full-matrix least-squares procedures using automatic diffractometer data to a residual R = 0.042 (R_w = 0.051). The space group is rhombohedral, $\text{R}\text{3}$, with hexagonal unit cell a = 4.966(2) and c = 14.084(5) Å [a_R = 5.501(2) Å and α = 53.66(3)°]. The structure is the fully ordered ilmenite-type and, on the basis of published magnetic data and the interatomic distances, the valence distribution Cu⁺V⁵⁺O₃ is proposed. This represents a unique example of Cu⁺ in an octahedral environment.     

一步室温固相化学反应合成纳米氨基酸杂多电荷转移配合物(HPhe)3PMo12O40·2H2O

以Keggin结构的钼磷酸(H3PMo12O40·13H2O)与苯丙氨酸(Phe)为原料,利用一步固相化学反应于室温合成了纳米氨基酸杂多电荷转移配合物(HPhe)3PMo12O40·2H2O,采用元素分析,IR,XRD,TEM,UV和循环伏安法等手段对其进行了结构表征及性质研究.结果表明,标题化合物纳米粒子为均匀的球状,粒径约为30～40nm.该化合物中杂多阴离子部分仍保持Keggin结构,但在钼磷酸与苯丙氨酸之间发生了显著的电荷转移.