CoTPP电化学催化原溴代环己烷的机理

以电化学循环伏安、现场ＥＳＲ电化学以及现场薄层电化学方法研究了电生Ｃｏ（Ｉ）ＴＰＰ与溴代五己烷的反机制。在ＤＭＦ中，Ｃｏ（Ⅱ）／Ｃｏ（Ⅰ）的氧化还原有明显的催化溴代环己烷还原的特片，反现场有自由基生成，反应产物之一是Ｃｏ－Ｃ键化合物，可以在１．３０Ｖ（ＳＣＥ）－电子还原，当存在ＣＨ２－ＣＨＣＮ时，。生成另一种Ｃｏ－Ｃ键化合物，该化合物在－１．１０Ｖ（ＳＣＥ）处一电子还原，证明溴代环己烷与Ｃｏ（Ｉ）     

电沉积AuInSe2半导体薄膜上的电化学振荡现象

研究了电沉积制得的ＡｕＩｎＳｅ２半导体薄膜上过氧化氢阴极还原过程中产生的电化学振荡行为，对影响该振荡行为的一些因素如半导体薄膜的后处理、溶液组成、传质、光照、化学浸渍作用等进行了分析，同时采用外界周期性光照和外接小幅度正弦波电位来调节振荡频率，为金铟硒半导体薄膜发展成为光电传感器件提供了一定的理论与实践基础．     

[Cu(PTA)(Phen)2](p-MBA)(H6O)配合物的合成、晶体结构及电化学分析

The crystal structure of the title complex with the stoichiometric formula [Cu(PTA)(Phen)₂](p-MBA)(H₆O) (Phen=1,10-phenanthroline, PTA=terephthalic acid, p-MBA=p-toluic acid) has been determined by single-crystal X-ray diffraction. The crystal (C₄₈H₄₀CuN₄O₁₀, M_r=896.38) belongs to the monoclinic space group C2/c, with the following crystallographic parameters: a=1.778 6(3) nm, b=1.912 5(3) nm, c=1.389 9(2) nm, β=114.686(2)°, V=4.295 7(12) nm³, D_c=1.386 g·cm^-3, Z=4, μ(Mo Kα)=0.574 mm^-1, F(000)=1 860, final GooF=1.019, R=0.054 0, wR=0.148 3 for 2 644 observed reflections (I>2σ(I)). The crystal structure shows that the copper(Ⅱ) ion is coordinated with two oxygen atoms from one terephthalic acid molecule and four nitrogen atoms from two 1,10-phenanthroline molecules, forming a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex is also reported. CCDC: 298809.     

Kinetic Regularities Governing the Reaction of Electrodeposition of Iron from Solutions of Citrate Complexes of Iron(III)

The kinetics of a multistep reaction of electrodeposition of iron out of aqueous citrate-containing solutions of trivalent iron is investigated. It is shown that concentrations of major solution components affect the partial current density of discharge of ions of divalent iron. It is established that the deposition of metallic iron occurs as a result of discharge of intermediates, which are hydroxy complexes of divalent iron. Kinetic parameters and mechanism of the reaction of discharge of complexes [FeOH]⁺ to a metallic state are determined. It is mentioned that the formation of poorly soluble hydroxy compounds of trivalent iron in a near-electrode layer leads to a decrease in the iron deposition current.     

Tricarbonyl(N,N-Disubstituted-Cyclohexadienecarboxamide)iron Complexes: Investigation of the Possible Intramolecular Interaction between the Iron Center and the Amide Substituent

Direct reaction of iron pentacarbonyl with 1-N,N-disubstituted-cyclohexa-2,5-dicnecarboxamide and 1-N,N-disubstituted-cyclohexa-1,3-dienecarboxamide mixture (in which the disubstkuted group is diethyl or diphenyl) gave the isomeric tricarbonyl iron complexes of 2-N,N-disubstituted-1,4-η-cyclohexa-1,3-dienccarboxamide (1), 1-N,N-disubslituted-1,4-η-cyclohexa-1,3-dienecarboxamide (2), and 5-N,N-disubstituted-1,4-η-cyclohexa-1,3-dienecarboxamide (3) and tricarbonyliron complexes of l-N,N-disubstituted-cyclohexenecarboxamide (4). These complexes were separated and characterized by IR, UV-VIS, ¹H NMR, elemental analysis, and mass spectra. Only 1 isomerized to give 2 under acidic conditions; both 1 and 2 undergo hydride abstraction with triphenylmethyl hexafluorophosphatc. Complexes 3, undergo neither isomcrization nor hydride abstraction. According to the spectral data, the possible interaction between carboxamide and iron carbonyl moiety was investigated. The irreversible electrochemical behavior of these complexes were studied.     

Hydrothermal Synthesis and Electrochemical Properties of Complex Cu(CH3C6H4COOH)2(2,2''-bipy)·(H2O)

The title complex has been synthesized by 4-methylbenzoic acid and 2,2'-bipyridine (bipy) in the mixed solvent of water and methanol. It crystallizes in the triclinic system, space group (P1-) with a = 0.7047(3), b = 1.1217(5), c = 1.6718(7) nm, α = 103.826(7), β = 90.772(6), γ = 104.195(6)°, C26H25CuN2O5.50, Mr = 517.02, V = 1.2404(9) nm3, Dc = 1.384 g/cm3, Z = 2, F(000) = 536, μ(MoKα= 0.921 mm-1, R = 0.0782 and wR = 0.2172. Structural analysis shows that the copper atom is coordinated with three oxygen atoms from two 4-methylbenzoic acids and one water molecule together with two nitrogen atoms from 2,2'-bipyridine, giving a distorted square-pyramid coordination geometry. The cyclic voltametric behavior of the complex has also been described.     

The rhodium complex of a tris(bipyridine) ligand—Its electrochemical behaviour and function as mediator for the regeneration of NADH from NAD+

The tris-bipyridine ligand3a and its stoichiometric Rh³⁺ complex have been prepared. Cyclovoltammograms of the complex at pH 7.4 using a glassy carbon disk electrode reveal a strong reduction peak at –620 mV and two weak reduction peaks at more negative voltage. The reduction potential of the new complex is shifted by 300 mV to more positive values as compared to [Rh(bipy)₃]³⁺. There is no reversible reoxidation peak of the Rh(I) complex formed due to the decomplexation of one of the three bipyridine units in the course of the transition Rh(III)Rh(I). The Rh(III) complex of3a was also studied with respect to its function as a possible redox mediator for the electrochemical regeneration of NADH from NAD⁺. The preparative electrolysis of the Rh³⁺ complex of3a in the presence of NAD⁺ yields a selective formation of NADH, whereas NAD dimers were not detected. On the other hand, a significant acceleration of this reaction compared to [Rh(bipy)₃]³⁺ was not observed.     

Determination of Inorganic Arsenic Species by Electrochemical Hydride Generation Atomic Absorption Spectrometry with Selective Electrochemical Reduction

A new direct procedure for the determination of inorganic arsenic species was developed by electrochemical hydride generation atomic absorption spectrometry （EcHG-AAS） with selective electrochemical reduction. The determination of inorganic arsenic species is based on the fact that As（Ⅲ） shows significantly higher absorbance at low electrolytic currents than As（Ⅴ） in 0.3 mol·L^-1 H2SO4. The electrolytic current used for the determination of As（Ⅲ） without considerable interferences of As（Ⅴ） was 0.4 A, whereas the current for the determination of As（Ⅲ） and As（Ⅴ） was 1.2 A. For equal concentrations of As（Ⅲ） and As（Ⅴ） in a sample, the interferences of As（Ⅴ） during the As（Ⅲ） determination were smaller than 5%. The absorbance for As（Ⅴ） could be calculated by subtracting that for As（Ⅲ） measured at 0.4 A from the total absorbance for As（Ⅲ） and As（Ⅴ） measured at 1.2 A, and then the concentration of As（Ⅴ） can be obtained by its calibration curve at 1.2 A. The methodology developed provided the detection limits of 0.3 and 0.6 ng·mL^-1 for As（Ⅲ） and As（Ⅴ）, respectively. The relative standard deviations were of 3.5% for 20 ng·mL^-1 As（Ⅲ） and 3.2% for 20 ng·mL^-1 As（Ⅴ）. The method was successfully applied to determination of soluble inorganic arsenic species in Chinese medicine.     

Pt电极上吸附原子对仲丁醇电催化氧化性能的影响

运用电化学循环伏安和石英晶体微天平研究了HClO4溶液中仲丁醇在Pt电极及以Sb和S吸附原子修饰的Pt(Pt/Sbad和Pt/Sad)电极上的电催化氧化过程 .从电极表面质量变化可以看出 ,仲丁醇的氧化与电极表面的氧物种有着极其密切的关系 .Pt电极表面Sb吸附原子可在较低的电位下吸附氧 ,明显提高仲丁醇的氧化活性 .与Pt电极相比 ,Sb吸附原子修饰的Pt电极使仲丁醇氧化的峰电位负移约 10 0mV .相反 ,Pt电极表面S吸附原子的氧化会消耗表面氧物种 ,抑制仲丁醇的氧化 .从电极表面质量变化提供了吸附原子电催化作用的数据     

Electrochemical Characteristics of Mg0.9Ti0.1-xZrxNi （x=0.02, 0.04, 0.06） Alloys

Mg-based hydrogen storage alloys Mg0.9Ti0.1-xZrxNi (x=0.02, 0.04, 0.06) were successfully prepared by means of mechanical alloying (MA). The effects of Zr addition on the discharge capacity and the cycle performance of the Mg-based electrodes were also studied. It was found that the discharge capacities were improved with addition of a small amount of Zr and the cycle performances of the alloy were stabilized with the addition of Ti. The effects of surface modification or coating on the properties of Mg0.9Ti0.06Zr0.04Ni were also studied. The results indicated that coating with graphite improved both the discharge capacity and cycle life of the amorphous Mg0.9Ti0.06Zr0.04Ni electrode.