Effect of the rare earth in the perovskite-type mixed oxides AMnO3 (A=Y, La, Pr, Sm, Dy) as catalysts in methanol oxidation

The effect of the rare earth in the perovskite-type mixed oxides AMnO₃ (A=Y, La, Pr, Sm, Dy) on catalytic properties in methanol oxidation was investigated in this work. The perovskites were prepared by reactive grinding in order to enhance the specific surface area in comparison with other classical synthesis procedures. These catalysts were characterized by N₂ adsorption, X-ray diffraction, H₂ temperature-programmed reduction (TPR-H₂), O₂-, CH₃OH- and CO₂-temperature-programmed desorption (TPD). The activity of the five catalysts under study in the methanol oxidation reaction was evaluated. The behaviour of the α-O₂ from the surface of the perovskite was strongly related to the nature of the A-site cation and particularly to its electronegativity but also to its density. Concerning the β-O₂ from the bulk, the rare earth only induces an indirect effect notably due to structural modifications. As suggested in a previous study, the activity in methanol oxidation was directly linked with the surface oxygen density. Under an excess of α-oxygen, the reaction intermediate was found to be a monodentate carbonate that decomposes into CO₂. The stability of monodentate carbonates was also found to be related to the electronegativity of the rare earth during both CH₃OH- and CO₂-temperature-programmed desorption. However, as soon as a lack of α-oxygen was observed in the structure, the dominant reaction intermediate was a bidentate carbonate that induces a consumption of anion vacancies in spite of the production of CO₂. Nevertheless, the accumulation of these carbonates leads to a decrease in the oxidation rate since their desorption requires high temperatures.     

Effects of enhanced electronic correlation on magnetic properties of light non-metallic element (B,C, N,and O)-doped CuCl: A first-principles study

Based on density functional calculations within both standard generalized gradient approximation and plus on-site Coulomb interactions approaches, we have investigated the electronic structure and magnetic properties of the first-row element-doped CuCl semiconductors. The electronic correlations in both 2p and 3d orbitals are enhanced by adding the on-site Coulomb repulsion (Hubbard U and Hund exchange J). After a comparative study, we find that, for both standard and beyond approaches, B-doped CuCl is a half-metallic magnet with majority-spin impurity bands touching the Fermi level, C-doped CuCl is a magnetic semiconductor, and N-doped CuCl is a half-metallic magnet with minority-spin impurity bands crossing the Fermi level. Nevertheless, for O-doped CuCl, it transforms from a nonmagnetic semiconductor to a half-metallic magnet with metallic up-spins by considering the correlation effects. The calculation shows that the enhanced electronic correlation not only corrects the error of band-gap, but also influences the magnetic ground state and the distribution of local magnetic moments. The location of impurity bands with different dopants was understood based on the elements' electronegativity and interaction between dopant and host atoms. Strong hybridization between the dopant's 2p states and the filled 3d orbitals of adjacent Cu yields the main contribution to magnetization.     

Electronegativity Scaled as a Average Attracting Energy of Valence‐Shell Electrons in a Ground‐State Free Atom

The total capability of an atom attracting valence electrons can be measured by the sum of ionization energies of valence electron in a ground‐state free atom plus its electron affinity called Total Attracting Energy, TAE = Σn_iE_i + EA, where, E_i is the ionization energy of the ith valence‐shell electron in a ground‐state free atom, n_i is the number of valence‐shell electron bearing energy E_i, and EA is the electron affinity. And the electronegativity χ_CL is proportional to the average of TAE, AAE = TAE_av, divided by Σn_i, the number of atomic valence‐shell electrons. χ_CL = 0.1813 TAE_av = 0.1813 AAE = 0.1813 TAE/Σn_i, = 0.1813 (Σn_iE_I + EA)/Σn_i. Further, the atomic valence orbital electronegativity can be also obtained from the TAE value of an atom. Some discussions were made on several special aspects such as scale of rare gases, comparisons with Pauling's and Allen's scales, etc.     

元素电负性和硬度的密度泛函理论研究

应用密度泛函理论的DFT LDA、DFT LDA/NL和改进的Slater过渡态方法,把元素的电离能和电子亲合能的计算扩展到周期表的103种元素.并用有限差分方法计算了这103种元素的电负性和硬度.计算中考虑了相对论效应.计算结果比以前Robles等用密度泛函理论的XGL和Xα近似的交换相关泛函的计算结果有所改进,更接近实验值.     

Spectroscopically determined electronegativity values for heavy elements

A new scale of electronegativity based on X-ray spectroscopic data was earlier presented by Mande and others for the elements₃Li to₅₄Xe. The present paper reports an extension of this scale carried out for most of the heavier elements lying between₅₅Cs and₉₂U. The present approach is based on the physical interpretation of electronegativity of an atom as the attractive electrostatic force it exerts at a distance equal to its covalent radius. To estimate this force, experimental spectroscopic data have been employed. The merits of such an approach have been pointed out recently by Mullay and may be of interest in the context of the intimate relation found between electronegativity and superconducting transition temperature.     

磷酸三乙酯改性HZSM-5沸石的活性及理论研究

采用XRD表征了水蒸气和磷联合改性的HZSM-5沸石分子筛的结构．通过NH3-TPD和N2吸附脱附研究了样品的酸性和比表面．采用正庚烷的裂化反应研究了样品的裂化活性，研究结果表明，磷改性样品与母体样品相比，经过水蒸气处理后显示出较高的酸量和正庚烷裂化活性．上述结果首次用模型簇和计算量子化学方法进行了解释．采用Gaussian94软件包和PM3半经验量子化学方法对模型簇进行了全优化和频率分析．计算结果显示磷改性后样品的脱铝补硅反应热大于母体样品脱铝补硅反应热，从而显示出磷对骨架的稳定化作用．     

Halodemetallation of (Z)-1-[2-(Triarylstannyl)vinyl]-cyclooctanol and Correlation of Proton Chemical Shift with Electronegativity

IntroductionOrganotin compounds have attracted attentionas an optimal model for antitumour agents due tothe function of the interesting intramolecularO→Sn coordination[1,2 ] . Our recent concern hasbeen focused on the preparation of ( Z) - 1 - [2 -( triarylstannyl) vinyl]- cyclooctanol[3 ] .In order tofind more appropriate compounds used asanticancer agents and explore the effect of thecoordinate O→ Sn interaction to the antitumoractivity,the new compounds werehalodemetallated and characte…     

Fluorinated nitroxides as ESR probes of solvation

Some newly synthesized fluorinated nitroxides, such as t-butyl perfluoroalkyl nitroxides Bu^tN(O) R_f (R_f=CF₃, 5; C₂F₅, 6; n-C₃F₇, 7) and s-butyl perfluoroacyl nitroxides Bu^sN(O) COR_f (R_f=CF₃, 9; n-C₃F₇, 10) have been employed as ESR probes of solvation in different common organic solvents. In aprotic solvents, the measured a_N values for each of the nitroxyl probes show a linear correlation with the cybotactic polar solvent parameters E_T (Dimroth) and Z (Kosowar), i.e. a_N=bE_T+c, and a_N=b′Z+c′. The physical significance for the slope (b or b′), the slope×E_T or slope×Z, the extrapolated intercept on a_N axis, c or c′, are linked, respectively, to the sensitivity of a specific nitroxide toward solvation, the magnitude of the overall solvation effect on the a_N value, and the intrinsic a_N value of each nitroxide in the ideal gaseous state. The intercept on the a_N axis may also serve as a new measure of electronegativity for perfluoroalkyl groups, CF₃, C₂F₅, n-C₃F₇, and perfluoroacyl groups, CF₃CO, n-C₃F₇CO. In protic solvents, i.e. alcohols and carboxylic acids, however, a_N values of all the probes, kept almost no change with the increase in E_T and Z. Furthermore, the plots of a_N versus non-cybotactic solvent constants, such as dipolar moment (μ) and dielectric constant (ε), all show random variations.     

密度泛函理论下的分子电负性（Ⅳ）──大环分子的总能量和电荷分布的直接计算

以密度泛函理论表述的电负性定义及其均衡原理为基础，提出了一个修正电负性均衡方法（ＭＥＥＭ），可直接用于计算各类分子的总能量和原子电荷分布。通过对３个较大环状分子１８－ｃｒｏｗｎ－６，２４－ｃｒｏｗｎ－８和２４－ｃｒｙｐｔａｎｄ的实际计算，发现其计算结果与从头计算结果接近。