Study on the electroreduction of In(III) ions at gold from acidic bromide solutions by the rotating ring-disc electrode technique

The mechanism of the indium electrodeposition on gold from acidic KBr solutions has been investigated by means of the rotating ring-disc electrode technique. The measurements showed that the overall electrode reaction In(III) + 3 e In consists of two successive charge transfer steps, i.e. In(III) + 2 e In(I) and In(I) + e In, with soluble monovalent indium as an intermediate. The current efficiency for In(I) generation under steady-state conditions is 100% in the case of low disc current densities. The disproportionation of In(I) in the bulk of solution occurs in slightly acidified solutions,pH=2, in addition to the In(I) electrochemical reduction. Based on the ring current transients, it was established that the two-electron transfer step is preceded by the formation of a thin passive film of indium metal.

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Untersuchung der elektrochemischen Reduktion von In(III)-Ionen an Gold in sauren Bromidlösungen mit der rotierenden Ring-Scheiben-Elektrode

Zusammenfassung Mit Hilfe der rotierenden Ring-Scheiben-Elektrode wurde der Mechanismus der kathodischen Abscheidung von Indium auf Gold in sauren KBr-Lösungen untersucht. Aus den Messungen folgt, daß die Bruttoreaktion In(III) + 3e In über zwei aufeinanderfolgende Durchtrittsreaktionen, In(III) + 2 e In(I) und In(I) + e In, mit löslichem einwertigem Indium als Zwischenprodukt abläuft. Bei kleinen Stromdichten werden die In(I)-Ionen mit 100%iger Stromausbeute erzeugt. In schwächer sauren Lösungen (pH=2) konnte außer der elektrochemischen Reduktion von In(I) zusätzlich dessen Disproportionierung innerhalb der Lösung ermittelt werden. Auf Grund der Ringstrom-Zeit-Kurven wurde auch festgestellt, daß die Bildung von einer dünnen In-Metallschicht, die ein passives Verhalten aufweist, dem Zweielektronenübergang vorangegangen ist.

     

硝基苯在离子液体BMimBF4-H2O中的电还原

采用循环伏安法和恒电位电解法研究了离子液体BMimBF4-H2O 中硝基苯在微铂电极上的电还原特性. 实验表明, 在BMimBF4中, 随着硝基苯和水的浓度变化, 循环伏安曲线的峰电位和峰电流呈现复杂的变化规律; 硝基苯在铂电极上的电还原反应为双分子8 电子3 步骤电化学过程, 第一步反应为准可逆单分子单电子转移步骤, 产生阴离子自由基, 第二步为2 电子转移步骤, 并伴有随后的双分子不可逆自由基偶合化学反应, 主要产物为氧化偶氮苯, 第三步是2 电子转移产生偶氮苯的过程.     

混合价化合物的研究(Ⅱ)─—电化学及现场光谱电化学方法研究非质子介质中Dawson结构杂多阴离子[HAs_2Mo_(18)O_(62)]~(n-)的电还原性质

以电化学和现场紫外－可见－近红外及现场FTIR光谱电化学方法对Dawson结构杂多阴离子［HAS2Mo18O62］5－在非质子介质（CH3CN）中的电还原过程进行了研究．结果表明，该杂多阴离子在非质子介质中经历4步单电子还原反应，所产生的杂多蓝阴离子在近红外区出现宽广的价间电荷转移吸收带，而红外区Mo＝O端键及Mo—O—Mo桥键的特征吸收峰在还原后均有不同程度的红移．     

Effects of temperature and anion type on the two-dimensional condensation of the 4,4′-bipyridine cation radical on mercury

The reduction of 4,4′-bipyridine (BPH²⁺₂) on mercury in an acid medium gives a very narrow sharp tail-less reversible voltammetric peak that can be ascribed to the formation of a two-dimensional (2D) phase of the cation radical BPH^·+₂ at the electrode according to the reaction

BPH²⁺₂ + e⁻ |BPH^·+₂|_2D

The corresponding oxidation peak possesses similar properties and arises from the destruction (fusion) of the 2D phase.In this work we studied the influence of some experimental variables, namely the type of anion present in the medium, the concentration of 4,4′-bipyridine and temperature on the 2D phase transition peaks. Also, we tested various analytical criteria to validate this assignation and fitted both voltammetric peaks numerically to the theoretical model developed for this purpose.     

Electroreduction of tetra-coordinate phosphonium derivatives; one-pot transformation of triphenylphosphine oxide into triphenylphosphine

Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode, wherein Al³⁺, which was electrogenerated at the anode would react as a Lewis acid with triphenylphosphine dichloride to afford tetra-coordinate chlorotriphenylphosphonium species and subsequent two-electron reduction at the cathode would give triphenylphosphine. One-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide with oxalyl chloride and subsequent electroreduction. In a similar manner, some tetra-coordinate triphenylphosphonium species derived from triphenylphosphine oxide were reduced electrochemically to triphenylphosphine in moderate yields.     

Co3O4纳米片的制备及对H2O2电还原反应的催化性能简

通过恒电势电沉积和加热处理在泡沫镍基体上制备了Co3O4纳米片. 利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)等手段对纳米片的形貌和结构进行了表征. 采用线性伏安扫描和计时电流技术研究了Co3O4纳米片电极对H2O2的电还原性能. 结果表明,在3.0 mol/L KOH 和 0.4 mol/L H2O2溶液中,当电压为-0.4 V(vs. Ag/AgCl)时,线性伏安扫描电流密度达到-0.386 A/cm2,在1000 s 测试时间内,计时电流密度衰减很小,表明Co3O4纳米片电极对H2O2具有很高的活性和稳定性.     

在液镓电极上反丁烯二腈的电氢化二聚

在液镓电极上,反丁烯二腈（ＦＤＮ）的电氢化二聚（ＥＨＤ）不仅能在含离子型表面活性剂如四乙基对甲苯磺酸铵（ＴＥＡ－ＰＴＳ）溶液中发生,同样也能在含低浓度的强表面活性剂如ＴｒｉｔｏｎＸ－１００溶液中进行,在不含有机表面活性剂的溶液中,ＦＤＮ在滴镓电极上产生一个２电子还原波,生成为丁二腈的饱和单体。在水溶液中加入一定浓度的ＴＥＡ－ＰＴＳ或低浓度的ＴｒｉｔｏｎＸ－１００时,原来的２电子还原波分裂成两个连续     

新型氧化锌纳米材料在电化学检测对硝基苯酚中的应用

通过溶剂热法控制合成了花生形氧化锌纳米材料,并利用扫描电子显微镜(SEM)、X射线粉末衍射仪(XRD)和傅里叶变换红外光谱(FTIR)对材料进行了表征和分析.循环伏安和Nyquist测试结果表明,该材料具有良好的电化学导电性,且对对硝基苯酚(p-NP)具有良好的选择性.侧分脉冲伏安法(DPV)测试结果表明,在p-NP浓度为0.8~24μmol/L和32~80μmol/L这2个浓度范围内,电流强度与浓度呈线性关系,通过3倍信噪比计算得出检测限分别为0.25和0.61μmol/L.该材料修饰的电极具有良好的稳定性和重现性,用于实际样品中p-NP含量的测定显示出优良的效果.