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首页> 外文期刊>Electrocatalysis >In Situ IR Studies on the Electro-Oxidation of Cyanide on Ni, Cu and Au Electrodes Electrically Polarized in Dimethyl Sulfoxide (DMSO) Electrolyte Media
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In Situ IR Studies on the Electro-Oxidation of Cyanide on Ni, Cu and Au Electrodes Electrically Polarized in Dimethyl Sulfoxide (DMSO) Electrolyte Media

机译：二甲基亚砜（DMSO）电解质介质中电极化的Ni，Cu和Au电极上氰化物的电氧化原位红外研究

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Subtractively normalised Fourier transform infrared spectroscopy (SNIFTIRS) studies are reported on the electrical polarisation of nickel (Ni), copper (Cu) and gold (Au) electrodes in KCN dissolved in the polar aprotic solvent, dimethyl sulfoxide (DMSO) with tetrabutyl ammonium perchlorate (TBAP) (0.1 mol L-1) as supporting electrolyte. These studies have shown clearly that each of the metal electrodes investigated oxidised (as the applied potential was adjusted in an anodic direction) to form Ni(II), Cu(I) and Au(I)cyano complex ions of [Ni(CN)(4)](2-), [Cu(CN)(3)](2-), [Cu(CN)(2)](-) and [Au(CN)(2)](-). The distribution of other electro-oxidation products of cyanide observed, namely KOCN(s) and CO2 depended on the electrode under consideration. For Ni electrodes, DMSO-solvated CO2 and solid KOCN were observed together as the oxidation products while on Cu and Au electrodes CN- was oxidised to DMSO-solvated CO2 exclusively without any solid cyanate salt film deposition being simultaneously observed. Cu was found to be particularly electrocatalytic towards the electrooxidation of CN- ion to CO2 with high current density values being observed. It is proposed that the metal-cyano complex ion species observed in SNIFTIRS experiments are implicated in the oxidation mechanism of CN- to KOCN and/or CO2 on these electrodes, particularly on the Cu and Au electrodes. This resembled the electrochemistry observed in similar systems involving the electrochemical oxidation of cyanide on Cu electrodes in aqueous media.
机译：减法归一化傅里叶变换红外光谱（SNIFTIRS）研究报道了溶解在极性非质子溶剂，二甲亚砜（DMSO）和高氯酸四丁酯中的KCN中镍（Ni），铜（Cu）和金（Au）电极的电极化（TBAP）（0.1 mol L-1）作为支持电解质。这些研究清楚地表明，所研究的每个金属电极都被氧化了（随着在阳极方向上调节施加的电势），从而形成了[Ni（CN）]的Ni（II），Cu（I）和Au（I）氰基络合物离子。 （4）]（2-），[Cu（CN）（3）]（2-），[Cu（CN）（2）]（-）和[Au（CN）（2）]（-）。观察到的其他氰化物电氧化产物（即KOCN和CO2）的分布取决于所考虑的电极。对于Ni电极，一起观察到DMSO溶解的CO2和固体KOCN作为氧化产物，而在Cu和Au电极上，CN-仅被氧化为DMSO溶解的CO2，而没有同时观察到任何固体氰酸盐膜沉积。发现铜对CN-离子电氧化为CO2具有特别的电催化作用，并观察到高电流密度值。建议在SNIFTIRS实验中观察到的金属-氰基络合离子物种与这些电极（尤其是Cu和Au电极）上CN-转化为KOCN和/或CO2的氧化机理有关。这类似于在类似系统中观察到的电化学，涉及在水介质中的铜电极上氰化物的电化学氧化。

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