The first observation of Mo5+ in the passivation layer of Mo2N

Molybdenum nitride powder with sg of 115 m2·g-1 (passivated) has been prepared by a temperature programmed reaction of MoO3 in H2/N2 mixture. It exhibited high catalytic activity in CO oxidation at low temperature. XPS, EPR and LRS studies have shown the existence of mixed valence states of Mo ions, especially Mo5+ ion (g⊥=1.932, g‖=1.892) observed for the first time, in the passivation layer of molybdenum nitride. A surface superoxide species, O-2(g = 2.001, Raman band 1 124 cm-1), was found to be produced accompanying the transformation of Mo5+/Mo4+ redox pair. Evidence has been given to suggest that this surface superoxide might be responsible for CO oxidation over Mo2N catalyst.     

Pu(H2O)53+和Pu(H2O)54+ 团簇的相对论密度泛函研究

用TPSSTPSS密度泛函方法, Pu离子和H₂O分子分别采用相对论有效原子实势(RECP)和6-31g基组, 研究了Pu(H₂O)₅³⁺和Pu(H₂O)₅⁴⁺ 团簇溶剂化和非溶剂化效应中的几何结构及紫外可见吸收光谱. 计算结果表明: 水溶剂环境对Pu(H₂O)₅³⁺及Pu(H₂O)₅⁴⁺ 团簇的几何结构影响都比较明显. NBO电荷分析表明水分子与钚离子之间没有直接的电荷转移. 所研究团簇的未配对电子都占据5f轨道. 在气相及水溶剂环境下, 所研究团簇的紫外可见吸收光谱存在较大差距. 主要的吸收峰大都源于f电子之间的跃迁.     

Theoretical study on photophysical property of C60M（CO）5 （M=Cr,Mo and W）

Configurations of three η2 models of transition-metal [60]fullerene derivatives C60M（CO）5（M=Cr, Mo and W） have been optimized at B3LYP/LanL2DZ level. On the basis of the optimized geometrical structures, their electronic spectra and the frequency dependence of third-order nonlinear optical polarizabilities γ in different optical processes of third-harmonic generation （THG）, electric-field-induced second-harmonic generation （EFISHG） and degenerate four-wave mixing （DFWM） are calculated by using TDB3LYP model based on LanL2DZ level coupled with the SOS （sum-over-state） method. The obtained results show that their electronic spectra have a red shift compared with that of [60]fullerene and different transition-metal functional groups added to C60 cage may result in different spectrum properties. For the three studied species, （η^2-C60）Mo（CO）5 has the largest third-order nonlinear optical polarizability.     

A possible configuration of H 5 + cluster

On the basis of our previous work, a configuration of H ₅ ⁺ has been presented that is a square center structure, and the energy for the structure of H ₅ ⁺ has been obtained by IACQM. The result showed that there is an extreme energy E_e: −2.45981 [2 Ry] atR = 2.50a ₀. It indicates that the square center structure of H ₅ ⁺ system has the certain stability, which is a possible configuration of H ₅ ⁺ .     

Preparation and luminescence characteristics of Sr3SiO5：Eu^2＋ phosphor for white LED

The Sr3SiO5：Eu^2＋ phosphor was synthesized by high temperature solid-state reaction. The emission spectrum of Sr3SiO5：Eu^2＋ shows two bands centered at 487 and 575 nm, which well agree with the theoretic values of emission spectrum. The excitation spectrum for 575 nm emission center has several excitation bands at 365, 418, 458 and 473 nm. And the results show that the emission spectrum of Sr3SiO5：Eu^2＋ is influenced by the Eu^2＋ concentration. The relative emission spectra of the white-emitting InGaN-based YAG：Ce^3＋ LED and Sr3SiO5：Eu^2＋ LED were investigated. The results show that the color development of InGaN-based Sr3SiO5：Eu^2＋ is better than that of InGaN-based YAG：Ce^3＋, and the CIE chromaticity of InGaN-based Sr3SiO5：Eu^2＋ is （x=0.348, y=0.326）.     

Optical Properties of Ru（bipy）2 （dppx）^2＋ in Different Environments

The emission spectra of Ru（bipy）2 （dppx）^2＋ in different environments has been studied. It was found that the solvent polarity and the ability of donating and transferring proton are the important factors in predicting luminescence intensity in different systems. The increasing content of water in the organic solutions of Ru（bipy）2 （dppx）^2＋ leads to de crease in emission intensity that follows the Perrin sphere of quenching model. The effect of base content of DNA on the fluorescence spectra of Ru （bipy）2 （dppx）^2＋ has also been studied.     

The concentration quenching characteristics of 5D3-7FJ and 5D4-7FJ (J=0―6) transitions of Tb3+ in YBO3:Tb3+ phosphor

The photoluminescence quenching behaviors of ^5D3-^7Fj and ^5D4-^7Fj （J = 0—6） transitions of Tb^3＋ in YBO3：Tb under 130—290 nm excitation were systematically investigated. The results revealed that the quenching concentrations of both ^5D3-^7Fj and ^5D4-^7Fj transitions of Tb^3＋ in YBO3：Tb were mainly dependent on excitation wavelength. Particularly, the quenching concentrations of ^5D4-^7Fj transitions of Tb^3＋ under 130—290 nm excitation were correlated with excitation bands of YBO3：Tb. The quenching concentrations of ^5D3-^7Fj transitions remained at low concentration （2%） under 186—290 nm excitation and then increased gradually with energy of incoming excitation photon when excited at 130—186 nm. This dependence should be involved in their excitation mechanisms and quenching pathway in particular excitation region.[第一段]     

Harmonic mixing of Bi2Sr2CaCu2O8+x intrinsic junction at millimeter waveband

Using intrinsic Josephson junctions in Ba₂Sr₂CaCu₂O_8+x single crystal, harmonic frequency mixing at 8 and 3 mm wavebands was successfully demonstrated at liquid nitrogen temperatures with harmonic numbers up to 68 and 50 respectively. The dependences of intermediate frequency output on the local oscillator power and dc bias were carefully studied.     

Degradation of 2, 4-D acid using Mn2+ as catalyst under UV irradiation

In this paper, the oxidative degradation of 2, 4-dichlorophenoxyacetic acid (2, 4-D) using Mn²⁺/H₂O₂ reagent under UV irradiation was studied. The results show that 2, 4-D was degraded more completely in Mn²⁺/H₂O₂ solution than traditional Fenton solutions. The effects of the concentration of Mn²⁺, H₂O₂ and pH were also investigated. And under the optimal condition of 1.48×10⁻⁴ mol/L, 8.99×10⁻⁵ mol/L and pH 3.38, the formation of ·OH was the most, both the decomposition rate of H₂O₂ and the degradation rate of 2, 4-D were the fastest. In addition, the photoreaction process was monitored using spin-trapping electron paramagnetic resonance (EPR), and the results indicated that the oxidative process was predominated mainly by the hydroxyl radical (·OH) gennerated in the system. Biography: HUANG Yingping (1964–), Professor, Ph. D., research direction: pollution ecology and water pollution control.     

过渡金属离子(Fe~(3+),Co~(2+),Ni~(2+))和UO_2~(2+)与不同取代基偕胺肟络合机理的理论研究

偕胺肟基对铀酰离子具有很强的络合能力及较高的选择性,目前已成为海水提铀吸附材料研究的热点.本文运用阿姆斯特丹密度泛函(Amsterdam density functional,简称ADF)方法研究了UO_2~(2+)、Fe~(3+)、Ni~(2+)、Co~(2+)与不同取代基(—OH,—NH_2,—H,—F,—CF_3)偕胺肟的络合反应.密度泛函理论(density functional theory,简称DFT)对这些配位化合物的几何结构进行优化和相关热力学参数的计算与收集.从键能强弱方面分析,不同取代基偕胺肟螯合的基本趋势都是Fe~(3+)最稳定的,而UO_2~(2+)螯合是最不稳定的.从热力学角度分析,表明偕胺肟最容易与UO_2~(2+)和Co~(2+)进行螯合,而取代基为—CF_3的偕胺肟最难与UO_2~(2+)和Co~(2+)进行螯合.在液相环境中不同取代基偕胺肟与UO_2~(2+)和Co~(2+)离子螯合的稳定顺序均为—NH_2—OH—H—F—CF_3.在η2构型中,偕胺肟比其他取代基偕胺肟更稳定,其中UO2+2与氨基偕胺肟螯合过程中的ΔG(吉布斯自由能变)最低为-646.65 k J/mol.     

ZnGa2Se4:V3+ 光谱的理论研究

应用区分t₂和e轨道共价性的差异(包含静电部分和晶场部分)并考虑了低对称场的能量矩阵, 在考虑和忽略静电参量B₀₀的条件下, 分别研究了t₂和e轨道共价性的差异对三元半导体ZnGa₂Se₄:V ³⁺能级以及低对称分裂的影响; 计算了ZnGa₂Se₄:V ³⁺晶体的能级的低对称分裂, 并与实验值进行比较. 计算结果与实验值符合很好. 研究发现: 在对ZnGa₂Se₄:V ³⁺晶体的光学性质进行理论研究时, 在能量矩阵的静电和晶场部分同时考虑t₂和e轨道共价性的差异是非常有必要的; 晶场参量B₀₀对ZnGa₂Se₂4:V ³⁺的能级有重要影响, 因此不能忽略.     

Nb_2O_5/CdS纳米粒子的制备及其光催化性能研究

通过简单的沉淀法合成了Nb2O5/Cd S纳米粒子,利用XRD、TEM、XPS对其进行了表征,采用制备的Nb2O5/Cd S纳米粒子在可见光照射下对罗丹明B进行了降解实验.结果表明:负载在Nb2O5表面上的Cd S粒径大小较均一,约为35 nm,在可见光照射下,Cd S质量比为20%的Nb2O5/Cd S纳米粒子光催化活性最佳,可见光照射下3 h对罗丹明B降解率为98%,经过3次循环利用,发现其具有良好的光催化稳定性.     

葡萄糖-BrO3--Mn2+-H2SO4-丙酮体系的振荡反应

以葡萄糖为有机底物，与－ＢｒＯ３－－Ｍｎ２＋－Ｈ２ＳＯ４－丙酮组成振荡反应体系，在恒温条件下进行振荡反应。结果表明：反应有诱导期，体系电导（Ｌ）不随时间（ｔ）变化；振荡周期，Ｌ随ｔ发生周期变化，溶液颜色在粉红色与无色之间交替变化，有典型的振荡波型。诱导期及振荡周期反应的表观活化能分别为８４．２７５ｋＪ／ｍｏｌ和９８．１５３ｋＪ／ｍｏｌ。体系振荡反应物浓度范围［葡萄糖］０．０１～０．０２ｍｏｌ／Ｌ，［ＢｒＯ３－］０．０３～０．０４５ｍｏｌ／Ｌ，［Ｍｎ２＋］０．０６～０．０８ｍｏｌ／Ｌ，［丙酮］０．２７～０．３０ｍｏｌ／Ｌ，［Ｈ２ＳＯ４］０．８～１．２ｍｏｌ／Ｌ。振荡反应有Ｂｒ２产生，Ｂｒ２准一级消耗速率常数ｋＢｒ２＝１．６×１０－５Ｓ－。对温度、反应物浓度、丙酮、Ｍｎ２＋、Ｃｌ－、底物对振荡反应的影响作了探讨。     

EPR studies of Mn2+ in the Loess Plateau of central China: Implication for variation of the East Asia summer monsoon

Mn²⁺ EPR intensity recorded in the Chinese loess-paleosol sequence shows close correlation with magnetic susceptibility and Sr content as well as the oscillation of paleoclimate. Thus Mn²⁺ EPR signal can serve as an indicator sensitive to the East Asia summer monsoon intensity fluctuations.     

Eu~(3+)掺杂纳米TiO_2的制备及光催化性能的研究

通过溶液法制备了不同铕(Eu3+)掺杂量Ti O2纳米颗粒(Eu3+/Ti O2),利用XRD、TEM、XPS对其进行了表征.在可见光照射下,以光催化降解常用的工业染料为目标反应,探讨了Eu3+掺杂量、催化剂用量、溶液p H值和催化剂重复利用对催化活性的影响,以优化光催化条件.结果表明:煅烧温度为500℃,Eu3+/Ti O2光催化剂晶型为锐钛矿型,其晶粒尺寸为14 nm;Eu3+离子的最佳掺杂摩尔比r(Eu3+︰Ti O2)=3%,样品加入量为1.25 mg/m L,p H=10.75时样品光催件性能最佳;其3次循环降解甲基紫,60 min内降解率仍保持在约96%,说明Eu3+/Ti O2光催化剂具有良好的稳定性.     

CaCl_2-NaCl熔盐中Fe~(3+)电化学行为的循环伏安分析

利用ZrO_2(Y_2O_3)固体电解质管集成构建Pt,O_2(air)|ZrO_2作为参比电极的电化学电池,采用循环伏安法在1273、1323、1373、1393K温度下对溶解0.5%Fe2O3的CaCl2-NaCl共晶熔盐中Fe~(3+)的电化学行为进行研究,分析了Fe~(3+)在Pt电极上的还原机理,并计算了电极反应交换电子数、Fe~(3+)扩散系数与Fe~(3+)扩散活化能等电化学参数。结果表明,在实验温度范围内,熔盐中Fe~(3+)在Pt电极上还原为Fe的反应是一步还原并受扩散控制的可逆过程;随着温度升高,Fe~(3+)扩散系数增大,Fe~(3+)扩散活化能为97.91kJ·mol-1。另外,本实验测得的Fe~(3+)扩散系数与文献值基本相符,因此,可以认为利用该电化学电池装置研究溶解有Fe2O3的CaCl2-NaCl溶盐的电化学行为是可行的。     

镀镍碳纳米管对Mo_2FeB_2基金属陶瓷组织与性能的影响

采用化学镀法对碳纳米管进行表面镀镍处理,再利用真空液相烧结法制备出以镀镍碳纳米管为增强体的Mo_2FeB_2基金属陶瓷复合材料,借助SEM、EDS、硬度计等研究了添加镀镍碳纳米管对Mo_2FeB_2基金属陶瓷微观组织及力学性能的影响。结果表明,添加适量镀镍碳纳米管可细化Mo_2FeB_2基金属陶瓷组织并控制其孔洞尺寸及数量,显著提高其硬度及断裂韧性。当镀镍碳纳米管添加量为0.5%时,所得试样的晶粒最为细小,晶粒尺寸大约为1.2μm,材料的力学性能最佳,其硬度和断裂韧性分别达到1228.4HV0.3及15.90MPa·m12,相应增韧机制为裂纹偏转、桥接增韧、撕裂棱增韧和微孔洞增韧。     

添加C、Si元素对Mo_2FeB_2基金属陶瓷组织及力学性能的影响

采用真空液相反应烧结法制备Mo_2FeB_2基金属陶瓷,基于正交试验设计对金属陶瓷中C、Si添加量进行研究,选取抗弯强度和硬度为试验指标进行极差和方差分析,并借助OM、XRD、SEM、EDS等手段对金属陶瓷的物相组成和显微组织进行表征。结果表明,Si含量对Mo_2FeB_2基金属陶瓷硬度影响显著,而C含量对其抗弯强度影响显著。在烧结工艺条件相同时,添加0.5%C和0.5%Si的金属陶瓷试样具有最佳的综合力学性能,硬度和抗弯强度分别为HRA85.4和1970 MPa;此时,Mo_2FeB_2基金属陶瓷致密度高,硬质相颗粒细小且均匀地分布在Fe基黏结相中。     

Effects of La3+ and Gd3+ on Ca2+ influx in rat hepatoma H-35 cells

Effects of La³⁺ and Gd³⁺ on Ca²⁺ influx were investigated in rat hepatoma H-35 cells by measuring the initial rate of⁴⁵Ca²⁺ uptake. It was found that the maximum initial rate of Ca²⁺ uptake was increased six-to ten-fold at low concentrations of La³⁺ and Gd³⁺. Kinetic analyses by measuring the initial rate of Ca²⁺ influx at different external Ca²⁺ concentrations indicated the existence of two intracellular exchangeable components in the basal Ca²⁺ system, with low and high affinities for Ca²⁺, and only one class of Ca²⁺ binding sites was observed in the La³⁺-or Gd³⁺-treated cells. For high affinity, La³⁺ and Gd³⁺ increased both kinetic parametersK _m andV _max of basai Ca²⁺ influx. La³⁺ and Gd³⁺ compete directly with Ca²⁺ for Ca²⁺ binding site for low affinity. The kinetics is competitive.     

子长油田王家湾区长21-2小层流动单元定量研究

针对子长油田王家湾区油藏开发中面临的问题,对长21—2小层选择多参数综合法进行了流动单元的划分。首先,优选了孔隙度(Φ)、渗透率(K)、泥质含量(Vsh)、孔喉半径(R35)、流动层段指数(FZI)等能充分反映储层特征的参数,通过主因子分析和系统聚类等数学方法对取芯井进行了流动单元划分;并由此建立了各类流动单元的Bayes判别函数,在判别函数的基础上对非取芯井以测井解释数据为依据进行流动单元的划分。结果表明:长21—2小层划分为四种类型(E、G、M、P)的流动单元,研究区以E和G为主,两者主要发育在河道主体,侧向连续性好,分布面积大。单井产量与流动单元类型关系密切,高产井主要分布在优势流动单元内;受流动单元纵向组合样式影响,E和G对M和P会产生两种截然不同的吸水效果。