Electrochemical behavior of redox species at carbon fibre microdisk array electrode modified with mixed-valent molybdenum(VI, V) oxide

In this study, electrode responses to a large number of electroactive species with different standard potentials at the molybdenum oxide-modified carbon fibre microdisk array (CFMA) electrode were investigated. The results demonstrated that the electrochemical behavior for those redox species with formal potentials more positive than similar to 0.0 V at the molybdenum oxide-modified CFMA electrode were affected by the range and direction of the potential scan, which were different from that at a bare CFMA electrode. If the lower limit of the potential scan was more positive than the reduction potential of the molybdenum oxide film, neither the oxidation nor the reduction peaks of the redox species tested could be observed. This indicates that electron transfer between the molybdenum oxide film on the electrode and the electroactive species in solution is blocked due to the existence of a high resistance between the film and electrolyte in these potential ranges. If the lower limit of the potential scan was more negative than the reduction potential of the molybdenum oxide film (similar to - 0.6 V), the oxidation peaks of these species occurred at the potentials near their formal potentials. In addition, the electrochemical behavior of these redox species at the molybdenum oxide-modified CFMA electrode showed a diffusionless electron transfer process. On the other hand, the redox species with formal potentials more negative than similar to - 0.2 V showed similar reversible voltammetric behaviors at both the molybdenum oxide-modified CFMA electrode and the bare electrode. This can be explained by the structure changes of the film before and after reduction of the film. In addition we also observed that the peak currents of some redox species at the modified electrode were much larger than those at a bare electrode under the same conditions, which has been explained by the interaction between these redox species and the reduction state of the molybdenum oxide film. (C) 2000 Elsevier Science Ltd. All rights reserved.

Atomic force microscopy imaging of molybdenum oxide film electrodeposited on a carbon electrode

Non-stoichiometric mixed-valent molybdenum(VI, V) oxide film was grown on carbon substrates by the electrodeposition method. Responses of the prepared molybdenum oxide thin films to potential and to different solution acidities were studied by cyclic voltammetry, and the corresponding morphological changes of the film were monitored by atomic force microscopy (AFM). AFM images of the molybdenum oxide film show that the characteristic domed structure on the film surface increased during the transition from the oxidized state to the reduced state without signification change in the KMS surface roughness value. Furthermore, AFM studies show that the solution acidity has great effect on the morphology of the films, and the films undergo a homogenizing process with increasing pH of the solutions. (C) 1999 Elsevier Science S.A. All rights reserved.

Unidirectional current flow of reversible redox couples on a MoO3 film-modified microelectrode

In this paper, we have investigated the reactivity of the molybdenum oxide film toward some standard redox systems (e.g., ferrocene (Fc) and its derivatives) and observed a few interesting phenomena. The results demonstrate that the electrochemical behaviour of Fc and its derivatives at the oxide-modified carbon fiber (CF) microelectrode differs from that at a bare CF microelectrode, The conductivity of the molybdenum oxide film is seriously affected by the range and the direction of the potential scan, which influences the electrochemical behaviour of these redox systems at the film electrode. If the cycling potential is more positive than the reduction potential of the molybdenum oxide film, the reduction and oxidation peak currents of Fc and its derivatives could not be observed. The result indicates that the molybdenum oxide film on a microelectrode surface cannot transfer electrons between the surface of the electrode and Fc or its derivatives due to the existence of a high resistance between the interface in these potential ranges. On the other hand, if the lower limit of the scan potential was extended to a potential more negative than the reduction peak potential of the film, the oxidation peak of Fc or its derivatives appeared at about the potential relative to E-0 of Fc or its derivatives on the bare electrode, and the peak current is proportional to the concentration of these couples in the electrolyte. To our surprise, the peak height on the modified electrode is much larger than that on the bare CF microelectrode under the same conditions in the range of low concentration of these couples, and the oxidation peak potential of these couples is more negative than that on the bare CF microelectrode. On the basis of the experimental observation, we propose that these redox couples may undergo an interaction with the reduction state of the molybdenum oxide film. The new phenomena that we observed have been explained by using this interaction. (C) 1997 Elsevier Science S.A.

Synthesis, properties and crystal structure of a heteropoly compound containing titanium

K4H2CoW12O40. 2Ti02 . 9H(2)O crystallizes from an aqueous solution of Na2WO4, Co(OAc)(2) and Ti(SO4)(2). The compound has very similar i.r. and u.v. spectra to those of [CoW12O40](6-) and [CoW11TiO40](8-) but its polarographic behaviour is different from that of [CoW11TiO40](8-) and exhibits only reduction of tungsten(VI). A single crystal structural analysis indicates that this compound consists of the heteropolyanion [CoW12O40](6-), titanium-oxygen chain, potassium ions and water molecules.

W-183 NMR characterization of rare earth heteropolymetalates in aqueous solution

W-183 NMR spectra were obtained for [La(AsW11O39)(2)](11-), [La(As2W17O61)(2)](17-), [La(SiW9Mo2O39)(2)](13-), [LaSb9W21O86](16-), [LaAs4W40O140](25-) and alpha-, beta-[(CeO)(3) . (SiW9O34)(2)](14-) complexes, Tungsten NMR studies showed that the C-s symmetry of the square antiprism for [La(ASW(11)O(39))(2)](11-) and [La(As2W17O61)(2)](17-) anions keep constant in aqueous solution; the lanthanide accupied the central S-1 site in [LnSb(9)W(21)O(86)](16-) and [LnAs(4)W(40)O(140)](25-) complexes, respectively, and lanthanide metal cations gave [(CeO)(3) . (SiW9O34)(3)](14-) type of complexes with SiW9O3410-.

SYNTHESIS AND CHARACTERIZATION OF TRISUBSTITUTED HETEROPOLYTUNGSTOGERMANATES CONTAINING GROUP 3A ELEMENTS

Six new compounds, alpha,beta-KaHb[GeW(9)M(3)(H2O)(3)O-37]. xH(2)O(M = Al, Ga, In; a + b = 7) and alpha-K9H5[Ge2W18Ga6(H2O)(3)O-74]. 20H(2)O, were synthesized from the lacunary precursors a and beta-GeW9O3410- and characterized by elemental analysis, spectroscopy and electrochemistry. Tungsten-183 NMR spectra of the title complexes consist of two lines with intensity ratio 2:1 as expected for trisubstituted heteropoly anions. The intensity ratio of alpha-Ga compound is 1:2, which is different from others(a:1). With the help of FAB mass spectrum, we concluded that it is a dimer with D-3h structure in aqueous, and the others exist by monomers with C-3v structures.

ELECTROCHEMICAL-BEHAVIOR OF BIS(2 /17-ARSENOTUNGSTATE) LANTHANATES AND THEIR ELECTROCATALYTIC REDUCTION FOR NITRITE

A series of new catalysts, K-14[Ln(As2W17O61)(2)]. xH(2)O (Ln = La, Pr, Sm, Eu, Gd, Tb, Dy, Tm and Yb) which can electrocatalyze reduction of nitrite are presented and their electrochemical behavior is described in this paper. Bis(2:17-arsenotungstate) lanthanates which are monovacant Dawson derivatives, exhibit two 2-electron and one 1-electron waves, attributed to electron addition and removal from the tungsten-oxide framework that comprises each anion structure. The formal potentials of redox couples are dependent on solution pH. Double-hump principle of formal potentials takes effect with increasing atomic number of lanthanide elements following their special electronic shell structure. The third waves of all the heteropolyanions have good electrocatalytic activities for nitrite reduction at pH 5.0.

ELECTROCATALYTIC PROPERTIES OF MIXED-VALENCE MOLYBDENUM OXIDE THIN-FILM MODIFIED MICROELECTRODES

A compact blue conducting mixed-valence Mo (VI,V) oxide film was grown on the surface of a carbon fibre (CF) microelectrode by cycling the potential between +0.20 and similar to 0.70 V SCE in freshly prepared Na2MoO4 solution in H2SO4 (pH 2). The thicknes

AN EFFECTIVE TRIPHASIC CATALYTIC-SYSTEM FOR OXIDATION OF BENZYL ALCOHOL UNDER PHASE-TRANSFER CONDITIONS

A tri-phasic catalytic system consisting of aqueous hydrogen peroxide, benzyl alcohol and a solid catalyst such as tungsten trioxide has been proved effective for the oxidation of benzyl alcohol in the presence of cetyl trimethyl aniline bromide (CTMAB). At first, the oxide reacts with CTMAB to form a complex, which can be oxidized by aqueous hydrogen peroxide to form a peroxide which effectively oxidizes benzyl alcohol.

Extraction behavior of Mo and W as homologs of Sg with α-benzoinoxime

Solvent extraction of molybdenum and tungsten as homologues of Sg with a-benzoinoxime from HCl solutions has been investigated. The extraction equilibration was achieved at 20s for Mo and W. Molybdenum was almost quantitatively extracted from 0.001 to 4M HCl solutions, and the extraction yields decreased at higher and lower acid concentrations due to the formation of anionic oxychloride complex and anionic species MO42-, respectively. The extraction yield of W was lower than that of Mo during the whole range of acid concentration. The composition of the extracted species was determined by using the slope method in present experiment. The elemental analysis, IR and 1H NMR spectra of the extracted species suggest that the extracted complex contain one MoO22+or WO22+ groups bonded with two a-benzoinoxime molecules.

基于人工神经网络的钛合金焊接接头机械性能预测

采用多层前向反馈神经网络模型,对钛合金钨极氩弧焊的焊接接头机械性能进行了模拟和预测。其中,输入参数包括钛合金成分、冷却速度和热处理参数;输出参数包括5个重要的机械性能,即极限抗拉强度、延伸率、断面收缩率、屈服强度和硬度。详细分析了铝和钒这2种元素对机械性能的影响。

湘南瑶岗仙钨矿床成矿流体地球化学

瑶岗仙钨矿区地处南岭中段，位于加里东隆起带与印支-燕山凹陷带的交汇地带。为了更深入地研究瑶岗仙钨矿成矿流体的性质和演化，在前人工作的基础上，本文结合流体包裹体的岩相学特征及其产出的构造特征，对瑶岗仙钨矿流体包裹体进行了显微测温和激光拉曼探针分析，从而确定了瑶岗仙钨矿成矿流体的性质，并进一步探讨了其成矿物质来源及成矿机制。 对瑶岗仙石英脉型钨矿床的石英、萤石和矽卡岩型钨矿床中石榴子石流体包裹体的岩相学特征研究表明，与成矿有关的包裹体主要有三类：富液相、富气相和含子晶多相包裹体。脉型钨矿床中石英的包裹体均一温度范围 180℃～300℃，盐度为 0.88～6.45 wt% NaCl；矽卡岩钨矿床中石榴子石包裹体均一温度范围为 190～300 ℃，盐度为 0.1～8.95 wt% NaCl，成矿溶液的密度为 0.70～1.05 g/cm3，说明形成两种类型矿床的流体均属中温、低密度、低盐度流体；两类矿床形成的压力为 32～38 MPa，成矿深度为 1～2 km，因此该矿床是在浅成、低压条件下形成的。激光拉曼探针测试表明，石榴石包裹体的气相成分以 H2O 为主，石英中包裹体的气相成分及其相对含量为 H2O＞CO2＞CH4＞N2＞H2S。由此说明，从矽卡岩型白钨矿阶段到石英脉型黑钨矿阶段，成矿流体中不断有 CH4、CO2和H2O 等挥发份的加入，此时的流体是一种介于岩浆与热液之间的过渡性流体，具有上部偏液、下部偏浆的特点。 根据前人的研究结果以及矿脉中花岗岩角砾的发现，泥盆系、寒武系岩层在花岗岩浆侵入过程中发生了混合岩化，成为成矿物质来源的基础，而真正的成矿母岩应该是深部的花岗岩体，由此推测“赋矿花岗岩并非成矿源岩”，很可能来自深部母岩浆中熔离出的流体。而 CH4 等还原组分的含量增多，推测也有可能来自相对是还原环境的地幔过渡带或软流圈中。

湘南瑶岗仙钨矿床成矿流体地球化学

瑶岗仙钨矿床位于湘东南后加里东隆起和湘、桂、粤北海西—印支坳陷带的交接部位，是南岭地区最典型的石英脉型钨矿床之一。为了深入研究瑶岗仙钨矿的成矿机制，本文在野外地质工作基础上，选取有代表性的样品，进行了氦、氩同位素以及碳、氧、硫稳定同位素研究，探讨了矿床成矿流体的来源，成岩成矿的关系，并初步讨论了矿床的成因模式。论文主要获得以下认识： （1）对瑶岗仙矿区不同硫化物中流体包裹体的氦、氩同位素系统测定表明，该矿床毒砂流体包裹体中3He/4He比值为0.58~2.60 Ra；黄铁矿和黄铜矿流体包裹体中3He/4He比值分别为0.41~1.26 Ra 和0.37~0.43 Ra，黑钨矿流体包裹体中氦同位素组成相对变化较大，其3He/4He比值为0.05~0.49 Ra，这些He同位素组成均明显高于地壳相应值；毒砂流体包裹体中的40Ar/36Ar变化范围在309.94~454.39；黄铁矿流体包裹体中的40Ar/36Ar变化范围在409.12~1822.31；黄铜矿和黑钨矿流体包裹体中的40Ar/36Ar变化范围分别为673~886和325~903，明显高于饱和大气雨水的40Ar/36Ar值。上述氦、氩同位素组成揭示瑶岗仙钨矿床中的成矿流体具有壳、幔两端元混合的特点。结合区域地质构造演化和成矿年代学的研究成果，本文认为瑶岗仙钨矿床的成矿流体是瑶岗仙花岗岩浆分异出的含有地幔He的岩浆流体与大气成因地下水二端元混合的产物。 （2）层解石和方解石的C、O同位素显示，该矿方解石的13CPDB和18OSMOW的变化范围为-2.2‰~ -7.0‰（均值为-4.8‰）和5.6‰~14.4‰（均值为11.3‰）；层解石的13CPDB和18OSMOW的变化范围为-5.5‰~ -6.3‰（均值为-5.8‰）和12.7‰~14.3‰（均值为13.8‰）；该矿方解石、层解石的C、O同位素组成与赣南西华山钨矿床非常类似。这些C、O同位素指示，该矿的成矿流体主要来自岩浆水，后期有少量大气降水的参与。 （3）对瑶岗仙矿区不同硫化物的硫同位素研究表明，该矿硫化物δ34S值的变化范围很窄，为-2.0‰~1.5‰之间，且具有明显的塔式分布。这些特征暗示，该矿的硫来源单一，主要来自岩浆。 （4）瑶岗仙花岗岩过去被视为典型的S型花岗岩，但本文研究发现该花岗岩普遍含有地幔He。结合区域构造背景的最新研究成果，本文认为，原来被认为“由地壳物质重熔形成的”瑶岗仙S型花岗岩体，实际上也是一种岩石圈伸展背景条件下壳幔相互作用的产物，地幔物质和能量的参与在该花岗岩的形成过程中发挥了重要作用。 （5）瑶岗仙钨矿床与矿区复式花岗岩体具有密切时空关系，而且该矿的主要成矿流体和成矿物质均来自矿区花岗岩，故两者亦应具成因联系。

氟、氯对热液钨、铜成矿的制约-以江西德兴铜矿、大吉山钨矿为例

矿化剂在热液矿床成矿过程中的重要作用一直为人们所关注，矿化剂地球化学行为直接影响成矿元素的富集成矿，不同的矿化剂元素可能对金属成矿具有一定的专属性。本文以著名的江西德兴铜厂超大型斑岩铜矿床和大吉山钨矿床作为研究对象，研究F、Cl与W、Cu成矿的关系。主要的认识如下：（1）F在花岗质岩浆中，可以降低岩浆的粘度、密度、固液相线温度、改变熔体结构，而Cl对熔体结构没有多大的影响。F在流体一花岗质熔体相间，绝大多数配分系数小于1.0，趋向于熔体相中配分，DF随体系中F浓度的升高而增加。Cl在流体一花岗质熔体相间的配分系数均大于1.0，且Dc1 随体系中Cl浓度的升高而增大·Cl强烈地趋向富集于流体相中。（2）Cu在流体一花岗质熔体作用过程中，铜总趋向于流体相中分布（DCu都大于1）。特别是在富Cl流体中Cu浓度较高，说明在富含Cl的热液流体能够从共存的熔体中活化迁移出大量的 Cu，S的加入DCu有降低的趋势。钨趋向于熔体相中富集，其配分系数大多小于1.0。（3）德兴铜厂花岗闪长斑岩属钙碱性系列岩石属I型花岗岩类，具有埃达克岩的特征。岩浆来源于深部，在结晶演化过程中发生了围岩物质的混染，这种高铜含量围岩的混染使成矿物质在岩浆中得到富集，有利于铜的活化、迁移。在铜厂岩体不同的蚀变带中，SiO2、K2O、Cu、Mo等从新鲜斑岩甚至弱蚀变带中带出，而在强蚀变带强烈富集，Cl同样有在强蚀变岩石中富集的趋势；而Na2O、Fe从斑岩体中带出，进入流体相中，流体中大量Fe的存在，有利于铜的沉淀、富集成矿。（4）德兴铜厂斑岩体微量元素和稀土元素地球化学特征表明，该岩体发生了流体一熔体作用，分异出来的流体是一种相对富氯的流体，同时成矿流体的流向是从岩体中心向接触带方向流动。（5）大吉山花岗岩具有高SiO2、A/CNK值，显示过铝质特点。黑云母花岗岩是壳源花岗岩但又受到慢源岩浆或慢源流体的影响。随着花岗岩的演化（从I→II→III）SiO2、K2O＋Na2O逐渐增加，ΣFe、Al2O3、CaO、F含量降低，为成矿提供了大量的矿化剂（F）和沉淀剂（Fe、Ca）。Eu负异常从I至III阶段花岗岩逐渐加强，表明该岩浆经历了高度的分异演化。（6）大吉山花岗岩类稀土元素具有“四重效应”配分的特点以及微量元素对玲Rb、Y/Ho、Zr/Hf以及Nb／Ta发生明显分异，暗示在花岗岩岩浆的演化过程中，经历了充分的流体一熔体作用，同时分异出大量富含F、W等矿化剂元素和成矿元素的热液流体，致使钨矿的形成。大吉山石英脉型钨矿的成矿年龄大约在155 Ma。（7）通过对成矿流体和花岗质岩石黑云母、白云母中卤素相对逸度的研究（log(H2O/fHCl）fluid、log（fHF/fHCl）fluid）发现，铜厂斑岩型铜矿床的成矿体系是相对富氯体系，而大吉山石英脉型钨矿床成矿体系相对富氟，同时氟可能主要迁移W、Sn、Nb、Ta等金属元素。（8）结合斑岩型铜矿床成矿流体特征，铜主要以C1的络合物形式存在和迁移，迁移形式主要是CuCl0、CuCl2等。石英脉型钨矿床中，钨主要以钨酸、钨酸盐及其离解形式存在和迁移，如WO42-、HWO4-、NaHWO4、Naw伍．等；在高度富氟的成矿流体中，钨的氟氧络合物（如WO3F-，WO2F42-等）对钨迁移也具有重要的作用。因此，不同矿化剂类型具有一定的成矿专属性，热液铜矿床主要与Cl、S有 关，而热液钨矿床大多与F有关。