钇离子在氟化物体系中的电化学还原

用循环伏安法和卷积伏安法研究钇离子在LiF-NaF-YF_3熔融盐中的阴极还原过程。结果表明,在实验条件下钇离子的电化学反应为一步还原,阴极过程受扩散控制,产物钇与铂形成合金。     

浓碱溶液中铜阳极产物的阴极还原行为研究：Ⅱ,Cu（Ⅱ）产物的阴极还原

采用恒电热氧化－动电势或恒电流还原法研究了铜在浓碱深液中二次氧化产物的阴极还原 行为，共分辨分７个阴极电流峰或相应的多个阴极是民势平阶，对各阴极峰的归属进行了指认，并探讨了铜阳极二次氧化反应历程。     

钇离子在氯化物熔盐中的电化学还原

利用循环伏安法、计时电位法和卷积伏安法研究了钇离子在LiCl-KCl熔盐体系中,钼电极上的阴极过程。结果表明,钇离子的电化学还原反应是简单的一步反应,阴极过程在较低扫描速度下接近于可逆过程,且受扩散控制。阴极产物为固态钇。     

氨苄青霉素降解产物在汞膜电极上的伏安法研究

考察了氨苄青霉素在酸、碱条件下的降解产物于玻碳汞膜电极上的伏安行为 ,降解产物在醋酸缓冲溶液 ( p H5.5)的底液中均产生了灵敏的阴极还原峰 ,以碱降解条件为好。已将方法应用于模拟样品的分析。     

氨青霉素降解产物在汞膜电极上的伏安法研究

考察了氨苄青霉素在酸、碱条件下的降解产物于玻碳汞膜电极上的伏安行为,降解产物在醋酸缓冲溶液（pH5.5)的底液中均产生了灵敏的阴极还原峰,以碱降解条件为好。已将方法应用于模拟样品的分析。     

氧气在阴极的电还原及其应用研究进展

本文综述了氧阴极电还原的研究进展，着重介绍了阴极表面修饰对该过程的影响以及氧阴极电还原在有机物电合成与废水处理方面的研究进展。     

阴极脱氯协同多孔Ti/BDD电极阳极电催化氧化对氯苯酚

本文主要研究阴极脱氯协同阳极(多孔Ti/BDD 电极)电催化氧化对于对氯苯酚的电化学降解过程. 在有无阳离子交换膜电解槽体系下电化学降解对氯苯酚的实验结果表明,对氯苯酚的矿化主要在阳极区进行;无隔膜电解槽体系下,对氯苯酚在阴极还原形成的氯离子迁移到阳极,在阳极表面进一步生成了具有强催化氧化作用的活 性氯,与阳极产生的羟基自由基协同降解对氯苯酚;在阳离子交换膜电解槽体系下,阴极产生的氯离子难以通过阳离子膜迁移至阳极区,无隔膜电解槽呈现出更好的降解效率. 结合高效液相色谱技术确定阳极室的中间产物为对苯二酚、邻苯二酚、对苯醌和苯酚等,阴极室的主要产物是苯酚,并根据中间产物提出了对氯苯酚的降解路径.     

LiCl-NaF-Na2WO4熔盐体系中电沉积钨的研究

本文用循环伏安法研究了钨酸钠在LiCl-NaF(80-20mol%)熔盐体系中的电化学还原过程, 并用X射线衍射法检测了由恒电位电解得以的阴极产物。结果表明, 钨酸钠的还原分两步进行, W(VI)首先经二电子还原成W(IV), 再经四电子还原成W(0)。     

阴阳极协同作用下对硝基苯酚的电催化降解

利用线性扫描伏安法和恒电流电解法研究了Ti/PbO2电极对于对硝基苯酚（PNP）降解的电催化活性,通过对阳极过程和阴极过程中对硝基苯酚及其降解中间产物的液相色谱测定,研究了阴阳极协同作用下对硝基苯酚电催化降解的历程。 结果表明,Ti/PbO2电极能够有效地电催化降解水溶液中的对硝基苯酚,在35 ℃,初始浓度为1 mmol/L的对硝基苯酚水溶液,恒定电流密度40×10-3 A/cm2,电解240 min,对硝基苯酚转化率为98.6%。 对硝基苯酚电催化氧化降解要经历生成对苯二酚、邻苯二酚、对苯醌、丁烯二酸和草酸,最终变成二氧化碳和水的反应历程,其中对苯二酚为第一步反应的主产物,对苯醌转化为丁烯二酸和丁烯二酸转化为草酸这两步反应是阳极氧化过程的速率控制步骤。 对硝基苯酚在阴极上发生还原反应,还原产物为对氨基苯酚（PAM）。 在无隔膜电解槽中,由于阴极还原产物对氨基苯酚很容易到阳极上发生氧化反应,阴阳两极产生协同作用,因而加速了对硝基苯酚的降解反应。     

微生物燃料电池非生物阴极催化剂的研究进展

在微生物燃料电池（MFC）中,以氧为电子受体具有很多优点,但氧阴极还原的反应动力学慢,会造成阴极电势的损失。 因此,提高阴极对氧还原的电催化活性和降低催化剂的价格是MFC非生物阴极催化剂的研究重点之一。 本文综述了近年来MFC中非生物阴极氧还原催化剂的研究进展。 重点讨论了贵金属Pt、过渡金属大环化合物以及金属氧化物催化剂对氧还原的电催化活性。 其中,非贵金属氧化物及过渡金属大环化合物催化剂具有良好的性能,而且价格低廉,有望成为MFC非生物阴极Pt基催化剂的替代催化剂。     

氯酸盐电还原机理的研究

本文利用Mo盘-Pt盘旋转电极研究了ClO_3的电还原过程, 并根据实验事实提出了一较完整的反应机理。我们首次检测到了ClO_3还原的中间产物ClO_2和Cl(或Cl_2)。其最终产物为Cl~-离子。     

C60电化学还原的稳态性质研究

自1990年9月Kratschmer等报导了C_(60)的常量制备和提纯以来,有关C_(60)及其他富勒炭分子(Fullerens)的研究报导与日俱增,成为近三年来最为活跃的研究领域之一.由于C_(60)的特殊结构,在电化学行为上也表现出十分独特的反应性质,如容易实现多电子氧化还原反应,可逆加氢及能形成离子嵌入电极材料等.本工作采用微电极方法研究了C_(60)稳态极化行为,测定了C_(60)的扩散系数和反应电子数,并通过现场紫外可见光谱电化学方     

The mechanism of electroreduction of nitrate ions on a hybrid electrode nanodispersed copper-MK-40 membrane

Based on a MK-40 sulfocation-exchange membrane, a hybride electrode material containing nanodispersed copper is prepared. The methods of scanning electron microscopy and X-ray diffraction (XRD) analysis reveal the formation of copper agglomerates measuring 250–470 nm and consisting of individual particles of 20–30 nm. The procedure of multistage chemical deposition of copper into the ion-exchange carrier makes it possible to obtain a continuous cluster of metal particles which determines the electron conducting properties of the resulting hybrid material. The electrochemical activity of the nanocomposite electrode is studied in the reaction of nitrate ion electroreduction. Nanodispersed copper deposited into the membrane is shown to intensify the electroreduction of nitrate ions by a factor of 1.5–2 as compared with a compact copper electrode. The electroreduction of nitrate ions on compact copper is shown to involve 6 electrons, whereas the electroreduction on the nanocomposite involves 8 electrons. The electroreduction products of nitrate ions are identified by the IR spectroscopy method.     

Iodate Sensing Electrodes Based on Phosphotungstate‐ Doped‐Glutaraldehyde‐Cross‐Linked Poly‐L‐lysine Coatings

Glassy carbon electrode modified with phosphotungstate‐doped‐glutaraldehyde‐cross‐linked poly‐L ‐lysine (PLL‐GA‐PW) film was employed for iodate determination. The PLL‐GA‐PW film electrode shows excellent electrocatalytic activity towards iodate reduction with significant reduction of overpotential. Under optimized experimental conditions, a linear range from 5×10^?8 to 2.27×10^?2 M with a sensitivity of 61.75 μA mM^?1 was obtained. Possible interfering species, in iodate determination, were evaluated and the applicability of proposed sensor for iodate estimation in table salt was also demonstrated. The PLL‐GA‐PW film electrode shows fast response, wider linear range, and good selectivity and stability.     

(NH_4)_(42)[Mo_(132)O_(372)(CH_3COO)_(30)(H_2O)_(72)]膜修饰电极的构筑和电化学性质的研究

由于过渡金属替代的多金属氧酸盐(polyoxometalates)的催化、磁性、电化学等性质,越来越受到人们的关注~([1-7]). 目前世界上约有10亿人生活在缺碘地区,碘的缺乏严重影响人类健康.对食物、生物临床、环境及工业中碘含量检测很有实际意义.     

乙腈中β-萘磺酸在汞电极上的电还原机理

用循环伏安法、电化学-ESR现场谱学技术和自洽场分子轨道法(CNDO/2)研究了乙腈中β-萘磺酸在汞电极上的电还原机理。结果表明该反应属ECE模式, 电还原服从直接脱磺酸基团机理, 并有萘自由基中间产物的形成。用分子轨道理论对电还原过程作了解释。     

Flow Injection Analysis of Iodate Reduction on PEDOT Modified Electrode

Poly‐(3,4‐ethylenedioxythiophene) (PEDOT) films were electrodeposited by cyclic voltammetry on glassy carbon electrode at different anodic potentials in the range of 1.0–1.5 V (Ag/AgCl) and its electrocatalytic properties towards reduction of iodate were reported. The effect of the pH of the solution on the response of PEDOT electrode towards iodate also studied. The modified electrode was employed successfully as an amperometric sensor for iodate in a flow injection apparatus. The repeatability of the method for 14 injections of a μM iodate solution was 7%. Interference from other oxidant anions such as nitrate was not noticeable, whereas bromate, chlorate and nitrite interfere at slight levels.     

Highly sensitive and selective amperometric sensors for nanomolar detection of iodate and periodate based on glassy carbon electrode modified with iridium oxide nanoparticles

Iridium oxide nanoparticles are grown on a glassy carbon electrode by electrodepositing method. The electrochemical behavior and electrocatalytic activity of modified electrode towards reduction of iodate and periodate are studied. The reductions of both ions occur at the unusual positive peak potential of 0.7 V vs. reference electrode. The modified electrode is employed successfully for iodate and periodates detection using cyclic voltammetry, hydrodynamic amperometry and flow injection analysis (FIA). In the performed experiments, flow injection amperometric determination of iodate and periodate yielded calibration curves with the following characteristics: linear dynamic range up to 100 and 80 μM, sensitivity of 140.9 and 150.6 nA μM⁻¹ and detection limits of 5 and 36 nM, respectively. The repeatability of the modified electrode for 21 injections of 1.5 μM of iodate solution is 1.5%. The interference effects of NO₂⁻, NO₃⁻, ClO₃⁻, BrO₃⁻, ClO₄⁻, SO₄²⁻, Cu²⁺, Zn²⁺, Mn²⁺, Mg²⁺, Cd²⁺, Ca²⁺, Na⁺, K⁺, NH₄⁺ and K⁺, CH₃COO⁻ and glucose were negligible at the concentration ratio of more than 1000. The obtained attractive analytical performance together with high selectivity and simplicity of the proposed method provide an effective and e novel modified electrode to develop an iodate and periodate sensor. Sensitivity, selectivity, the liner concentration range and the detection limit of the developed sensor are all much better than all known similar sensors in the literature for iodate and periodate determination.     

Electrodeposition of Ag nanoparticles on graphenized pencil lead electrode as a sensitive and low-cost sensor for iodate determination

In this study, a simple, sensitive and low-cost iodate electrochemical sensor based on graphenized pencil lead electrode (GPLE) modified with Ag nanoparticles (AgNPs) was presented. The GPLE was simply prepared via electrochemical exfoliation of pencil lead electrode (PLE) by applying an optimized potential in acidic media. Afterward, silver nanoparticles were electrochemically deposited on the surface of GPLE using chronoamperometry technique. The fabricated electrode was carefully characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM) techniques. Electrochemical behavior and also the electrocatalytic performance of the modified electrode toward the reduction of iodate were studied in details using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) techniques. The fabricated sensor responds efficiently to iodate over the concentration range of 0.05 to 75 mM with a detection limit of 0.017 mM and sensitivity of 0.26 µA µM^?1 cm^?2. Remarkably enhanced electrocatalytic performance of the modified electrode was ascribed to the synergistic effect of graphene-like nanostructures with high surface to volume ratio, excellent conductivity and also the excessive electrocatalytic behavior of silver nanoparticles. The modified electrode was successfully employed for the determination of iodate in table and sea salt samples.     

PHOTOCHEMISTRY OF HALOGEN PYRIMIDINES: IODINE RELEASE STUDIES

The feasibility of using direct iodide (I-) measurements to monitor the photochemistry of the halogenated pyrimidines 5-iodocytosine and 5-iodouracil and their corresponding deoxynucleosides was examined. Radiation from either a germicidal lamp (lambda = 254 nm) or a sunlamp (lambda greater than 290 nm) was employed to induce homolytic splitting of the carbon-iodine bond and the release of iodine atoms. These atoms combine to form I2 which reacts with water to ultimately form I- and iodate (IO3-). The formation of I- was followed using either high performance liquid chromatography with electrochemical detection or a specific ion electrode. IO3- was assayed spectroscopically following its conversion to triiodide. The yields of I- relative to starting material destroyed were either close to the theoretical limit of 83% or higher depending upon (a) the compound being irradiated, (b) the irradiation wavelength and (c) the extent of exposure. Yields of iodide greater than 83% are generally accounted for by a concomitant reduction in the yield of iodate such that the sum I(-) + IO3- is approx. 100%. Because iodate is photochemically reduced to iodide by 254 nm but not sunlamp irradiation, exhaustive irradiation at 254 nm converts all of the iodate present to iodide. These studies have application to the use of photochemical methods for quantitating the percent substitution of iodinated pyrimidines in DNA, and should be useful in following the photochemistry of IdUrd and IdCyd substituted DNA.