钒氧酞菁(VOPc)与钒酞菁(VPc)分子的扫描隧道显微镜图像模拟

利用第一性原理方法模拟了自由钒氧酞菁(VOPc)和钒酞菁(VPc)分子的扫描隧道显微镜(STM)图像,与实验观察结果相当符合.理论STM图像都显示出亚分子内结构,外围呈四叶状.其主要差异表现在VOPc分子中心处的钒氧离子在STM图像中为一空洞,而在VPc分子的STM图像中钒离子为突起的亮斑.通过分析VOPc和VPc分子的电子结构,对模拟结果给出自洽的理论解释.造成两者图像显著不同的物理原因是VPc分子在费米能级附近有明显含dz2成分的分子轨道,导致钒离子在STM图像中央为突起的亮斑.而在VOPc分子中dz2分态密度峰位由于氧原子的加入使之远离费米能级,使STM不能“看到”VOPc分子中钒氧离子. 关键词： 钒氧酞菁 钒酞菁 STM图像模拟 电子结构     

全钒液流电池传质及电流分布

为了解决大规模蓄能全钒液流电池中传质不均衡而导致电池寿命缩短的问题,本文建立了一个三维数值模型研究全钒液流电池中的传质规律。模型耦合了Nernst-Planck方程、Butler-Volmer方程、Nernst方程、质子交换膜中的传质方程等。模型模拟了全钒液流电池中不同价态钒离子的分布规律,以及电解质电流密度和电解质电势分布规律。研究发现:在放电过程中,沿电解液流动方向,反应物的离子浓度逐渐减少,生成物的离子浓度逐渐增加;电解质电流密度在膜表面达到最大,向两侧的集流体方向逐渐降低;沿电解液流动方向和阴极指向阳极方向,电解质电势逐渐降低。结果表明:集流体附近电化学反应更剧烈,质子在Nation膜中的传递主要是依靠电渗作用和浓差作用.     

载体钒氧化物中钒—吸附物分子相互作用的ESR研究

电子自旋共振技术已经用来研究还原态V_2O_5/SiO_2催化剂和各种吸附分子的相互作用。实验指出:具有四面体配位结构的V~(4+)离子是活性中心,V~(4+)和CH_2OH,HCl,CH_3CN分子的相互作用导致形成八面体配位结构的表面VO~(2+)络合物,它们的ESR和成键参数计算指出不成对电子主要定位在钒离子的d轨道上。77 K下吸附O_2分子已经观察到氧自由基的ESR信号,但吸附乙烯和丙烯不能改变V~(4+)离子的配位结构。     

全钒液流电池非等温模型

本文基于多孔电极、电解液及集流体热物理性质的显著差异,考虑了钒离子透过膜对电池性能的影响,建立了全钒液流电池动态工作过程的非等温模型。与文献中的实验测量值相比,钒电池电压随时间变化的最大计算误差为2.91%,验证了模型的正确性。应用该模型,重点研究了正负电极与膜构成的区域,以及集流体区域的传热传质规律。结果表明,多次充放电循环后负极电解液钒离子总量增加而正极钒离子总量减少,电池容量降低。电池的电流密度对产热有较大影响,较大的电流密度下与外界达到热平衡时温度较高。此模型对发展大功率电池堆储能系统的有重要参考意义。     

氧化钒薄膜的微结构及阻变特性研究

采用射频反应溅射法于室温下在Cu/Ti/SiO₂/Si基底上制备了氧化钒薄膜. X-射线衍射、X射线光电子能谱分析仪及原子力显微镜结果表明, 室温下制备的氧化钒薄膜除微弱的V₂O₅ (101)和V₂O₃ (110)峰外, 没有明显的结晶取向, 是VO₂, V₂O₅, V₂O₃及VO的混合相薄膜, 且薄膜表面颗粒大小均匀, 表面均方根粗糙度约为1 nm. 采用半导体参数分析仪对薄膜的电开关特性进行测试. 结果表明薄膜具有较低的开关电压(V_Set<1 V, V_Reset<-0.5 V), 并且具有稳定的可逆开关特性. 薄膜从低阻态转变为高阻态的电流(I_Reset)随限流的增大而增大.通过高低阻态时I-V对数曲线的拟合(高阻态斜率>1, 低阻态斜率=1), 认为Cu离子在薄膜中扩散形成的导电细丝是该体系发生电阻转变的主要机制. 关键词： 氧化钒薄膜 电阻开关 电阻式非挥发存储器 导电细丝     

钒氧化物薄膜的拉曼散射

用射频磁控溅射以纯金属钒做靶材在氩氧混合气体中制备了钒氧化物 (VO2 (B)、V6O1 3、V2 O5)薄膜。报导了钒氧化物薄膜的拉曼光谱 ,结合这些钒氧化物不同的结构特点 ,对它们的拉曼光谱进行了分类讨论     

钼、钒的单一及混合溶液中离子存在形态的拉曼光谱研究

利用拉曼光谱研究了钼、钒单一及混合溶液在pH=10.0~1.0时的离子分布行为. 钼、钒离子在存在形式上存在着差异：当pH=9.0~7.5时钒主要以(VO₃)_n^n-形式存在,而钼主要为MoO₄^2-. 这一差异是目前现有的许多钼钒分离方法的基本原理. 通过将混合溶液体系的拉曼光谱与单一体系进行对比,分析得出了混合体系中离子的存在形式. 当pH低于6.5时,部分V-O-V基团中的V原子会被Mo原子取代,从而形成了钼钒杂多酸离子. 当pH=6.0~2.0时,钒主要以十聚钒酸盐形式存在;当pH=2.0~1.0时,混合溶液中的钼主要以具有七钼酸盐结构的杂多酸离子存在,而在相同pH的单一溶液中,钼的存在形式主要为Mo₈O₂₆^4-和Mo₃₆O₁₁₂^8-.     

盐湖卤水中微量钒的浓度测定

为了测定盐湖卤水中微量钒的浓度,开发了一个钒的分离纯化流程来降低大量的共存离子的基质效应。该分离纯化流程包括萃取和反萃两个步骤。详细地研究了影响钒纯化效率的各种因素,得到钒的最佳分离纯化条件为:以正己烷为稀释剂,有机相中D2EHPA和TBP的体积百分比分别为30%及20%,在pH为3.0时萃取30 min;然后用3 mol/L H₂SO₄反萃 10 min。基于此分离纯化流程,将两个实际盐湖卤水样品中的微量钒纯化后,再用电感耦合等离子体质谱仪(ICP-MS)测定其浓度,该ICP-MS对51V 的检测灵敏度和检测限别为53 171 cps/(μg/L) 和1.88 ng/L。所得实际盐湖卤水钒测定结果的加标回收率接近100%而相对标准偏差低于0.6%,表明该方法可用于实际复杂体系中微量钒的浓度测定,例如海水和盐湖卤水。     

钒的高压声速测量

采用反向碰撞方法进行了钒冲击实验,利用激光干涉测速技术对V/LiF窗口界面粒子速度剖面进行测量.通过对粒子速度剖面的分析获得了32—88 GPa压力范围内钒的高压声速.实验获得的声速-冲击压力关系在约60 GPa存在间断,表明钒发生了冲击相变.相变压力与静高压实验结果及第一性原理计算结果基本一致.     

钆、氟掺杂二氧化钒的晶体结构演变行为与相变机理

二氧化钒(VO₂)是一种热致相变材料,其过高的相变温度制约了其潜在应用.元素掺杂能够使VO₂的能带结构、态密度、键长和晶胞体积等晶格参数改变,引起其相变行为的变化.借助Materials Studio软件,基于第一性原理和分子轨道理论研究了钆、氟掺杂二氧化钒的晶体结构演变行为与相变机理.结果表明,无论F掺杂于VO₂(M型)中间O的位置还是两侧O位置,都会引起O—O键收缩,V—V键增长,β角增大,体系亥姆霍自由能增加,带隙相对减小,F侧位掺杂效果最好,随着V⁴⁺—V⁴⁺同极结合的减少,在1 at%F掺杂时相变温度达到最低;当Gd以0-1.8 at%掺杂于VO₂(M)中V位置时,O—O键和V—V键发生收缩,β角减小,亥姆霍自能增加,带隙减小,Gd 4f态与t_Ⅱ轨道重合,使相变能垒变低,相变温度显著降低.钆、氟两种元素掺杂VO₂相变机理更符合Peierls-Mott协同相变.     

First-principles study on electronic,magnetic properties and optical absorption of vanadium doped rutile TiO2

The electronic, magnetic properties and optical absorption of vanadium (V) doped rutile TiO₂ have been studied by the generalized gradient approximation GGA and GGA+U (Hubbard coefficient) approach respectively. On the one hand, we consider the influence of vanadium with different doping concentration on the electronic structure. On the other hand, we study double V atoms doped TiO₂, mainly study four V-doped TiO₂ configurations, and find the magnetic ground states are ferromagnetic state. For the TiO₂@V-V1, TiO₂@V-V3 and TiO₂@V-V4 configurations without O ion as bridge between V-V atoms, there will have a metastable state of antiferromagnetic configurations, while, for the TiO₂@V-V2 configurations with an O ion as bridge between V-V atoms, due to the existence of superexchange between V-O-V, there will only exist the ground state of ferromagnetic state and there are no other metastable configurations. Furthermore, the optical properties of V-doped TiO₂ are calculated. The results show that the V-doped TiO₂ has strong infrared light absorption and visible light absorption.     

XPS study of vanadium surface oxidation by oxygen ion bombardment

Oxidation of vanadium metal surfaces at room temperature by low-energy oxygen ion beams is investigated by X-ray photoelectron spectroscopy (XPS). It is observed that ion-beam irradiation of clean V results in formation of thin oxide layer containing vanadium in oxidation states corresponding to VO, V₂O₃, VO₂ and V₂O₅ oxides. The composition of the products of ion-beam oxidation depends markedly on oxygen ion fluence. The results of angle-resolved XPS measurements are consistent with a structure of oxide film with the outermost part enriched in V₂O₅ and VO₂ oxides and with V₂O₃ and VO oxides located in the inner region of the oxide layer.     

用原子吸收光谱仪研究钒的洋茉莉基荧光酮光度法

应用连续光源和原子吸收光谱仪对洋茉莉基荧光酮与钒的显色反应进行了研究,并对钢铁中的钒进行了测定。     

The metals chemical states in hydrated vanadium oxides

The X-ray photoelectron spectroscopy (XPS) spectra of hydrated vanadium oxides (VO)Mo(x)V(12-x).nH(2)O (x=0, 1, 2, 3) were studied to provide the vanadium ions reduction ratio (RR)=V(4+)/(V(4+)+V(5+)) dependence on the molybdenum ions concentration and thermal treatment. The vanadium valence does not depend on Mo doping (x相似文献   

Atmospheric pressure chemical vapour deposition of vanadium diselenide thin films

Atmospheric pressure chemical vapour deposition (APCVD) of vanadium diselenide thin films on glass substrates was achieved by reaction of [V(NMe₂)₄] and ^tBu₂Se. X-ray diffraction showed that the VSe₂ films were crystalline with preferential growth either along the (1 0 1) or the (1 1 0) direction. Energy-dispersive analysis by X-rays (EDAX) gave a V:Se ratio close to 1:2 for all films. The films were matt black in appearance, were adhesive, passed the Scotch tape test but could be scratched with a steel scalpel. SEM showed that the films were composed of plate-like crystallites orientated parallel to the substrate which become longer and thicker with increasing deposition temperature. Attempts to produce vanadium selenide films were also performed using ^tBu₂Se and two different vanadium precursors: VCl₄ and VOCl₃. Both were found to be unsuitable for producing VSe₂ from the APCVD reaction with ^tBu₂Se. The VSe₂ showed charge density wave transition at 110-115 K.     

靛蓝二磺酸钠-溴酸钾体系催化光度法测定钢铁中微量钒

基于钒对溴酸钾氧化靛蓝二磺酸钠退色反应的催化作用 ,建立了一种在室温条件下 (2 5℃ )直接测定钢铁中微量钒的高灵敏度高选择性的方法。在 1 0mol·L- 1 磷酸介质中及在 6 0 8nm波长处 ,钒含量在 0～1 0 μg·mL- 1 范围内与靛蓝二磺酸钠吸光度的减小值 (ΔA)呈线性关系 ,检测限为 0 0 2 μg·mL- 1 。在氟化钠存在下 ,大多数常见离子无干扰。由Arrhenius方程求得表观活化能为 5 0 6kJ·mol- 1 。本方法简便快速 ,用于钢铁中微量钒的直接测定     

10.6 μm Infrared light photoinduced insulator-to-metal transition in vanadium dioxide

Vanadium dioxide has excellent phase transition characteristic. Before or after phase transition, its optical, electrical, magnetic characteristic hangs hugely. It has a wide application prospect in many areas. Now, the light which can make vanadium dioxide come to pass photoinduced phase transition range from soft X-ray to medium infrared light (6.9 μm, 180 meV). However, whether 10.6 μm (117 meV) long wave infrared light can make vanadium dioxide generate photoinduced phase transition has been not studied. In this paper, we researched the response characteristic of vanadium dioxide excited by 10.6 μm infrared light. We prepared the vanadium dioxide and test the changes of vanadium dioxide thin film’s transmittance to 632.8 nm infrared light when the thin film is irradiate by CO₂ laser. We also test the resistivity of vanadium dioxide. Excluding the effect of thermal induced phase transition, we find that the transmittance of vanadium dioxide thin film to 632.8 nm light and resistivity both changes when irradiating by 10.6 μm laser. This indicates that 10.6 μm infrared light can make the vanadium dioxide come to pass photoinduced phase transition. The finding makes vanadium has a potential application in recording the long-wave infrared hologram and making infrared detector with high resolution.     

溶胶凝胶制备氧化钒薄膜的生长机理及光电特性

采用溶胶凝胶法, 在不同的退火温度下制备了不同的氧化钒薄膜. 利用扫描电子显微镜、X射线衍射仪、高阻仪、紫外-可见分光光度计和傅里叶红外光谱仪等, 对薄膜的形貌、晶态、电学和光学特性进行了分析. 结果表明, 溶胶凝胶法获取V₂O₅薄膜的最佳退火温度为430 ℃, 低于此温度不利于使有机溶剂充分分解, 高于此温度则V–O键发生裂解、形成更多的低价态氧化钒. 本文制备的氧化钒薄膜具有较高的电阻温度系数和光吸收率, 适合应用在非制冷红外探测器中. 本文揭示了溶胶凝胶法制备氧化钒薄膜的生长机理. 关键词： 氧化钒薄膜 溶胶凝胶 光电特性 生长机理     

Theoretical study of the influence of cation vacancies on the catalytic properties of vanadium antimonate

We have theoretically studied the influence of antimony and vanadium cation vacancies in the electronic structure and reactivity of vanadium antimonate, using molecular orbital methods. From the analysis of the electronic properties of the VSbO₄ crystal structure, we can infer that both antimony and vanadium vacancies increase the oxidation state of closer V cations. This would indicate that, in the rutile-type VSbO₄ phase the Sb and V cations defects stabilize the V in a higher oxidation state (V⁴⁺). Calculations of the adsorption energy for different toluene adsorption geometries on the VSbO₄(1 1 0) surface have also been performed. The oxidation state of Sb, V and O atoms and the overlap population of metal-oxygen bonds have been evaluated. Our results indicate that the cation defects influence in the toluene adsorption reactions is slight. We have computed different alternatives for the reoxidation of the VSbO₄(1 1 0) surface active sites which were reduced during the oxygenated products formation. These calculations indicate that the V cations in higher oxidation state (V⁴⁺) are the species, which preferentially incorporate lattice oxygen to the reduced Sb cations. Thus, the cation defects would stabilize the V⁴⁺ species in the VSbO₄ structure, determining its ability to provide lattice oxygen as a reactant.     

石墨炉原子吸收光谱法测定化探样品中的微量钒

采用加入基体改进剂-石墨炉原子吸收光谱法测定化探样品中微量钒.研究了不同基体改进剂对钒测定结果的影响,确定了石墨炉原子吸收测定钒的最佳条件.结果表明,采用镧为基体改进剂,在5%的HC1介质中进行钒的测定可获得满意的结果.方法的检出限为2.11μg/L,线性范围0-300.0 μg/L,相关系数r=0.9959.该方法用...