深共晶溶剂电沉积镍和Ni–TiO2复合材料过程中Ni(II)离子电还原的动力学和机理特征

V. Protsenko, D. Bogdanov, Tetyana Butyrina, F. Danilov
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摘要

首次研究了基于新型离子液体——深共晶溶剂的电解质中镍离子放电的动力学特性。电解质为乙炔、氯化胆碱和乙二醇的液体共晶混合物,摩尔比分别为1:2,其中溶解1 М NiCl2·6H2O。结果表明,在乙炔中Ni(II)/Ni(0)体系中,电化学过程的表观传递系数分别为α=0.309和β=0.255。在连续电化学过程的已知标准框架中,很难解释这些值。为了解释这一现象,使用了一个理论概念,这个概念是由Gileadi早期提出的。根据这一概念,金属电沉积过程中的电荷是通过金属离子而不是电子通过电极界面传递的。因此,双电层中的势垒变得非常不对称(即表观传递系数偏离0.5)。研究发现,将TiO2颗粒(0-10 g dm-3)引入基于乙炔的电解液中,由于二氧化钛胶体颗粒吸附在电极表面的部分阻断,导致镍(II)离子的电化学还原。
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Features of kinetics and mechanism of Ni(II) ion electroreduction in the course of electrodeposition of nickel and Ni–TiO2 composites from a deep eutectic solvent
Kinetic characteristics of the nickel ion discharge were investigated for the first time from electrolytes based on a new kind of ionic liquids, deep eutectic solvents. The study was carried out using electrolytes based on ethaline, a liquid eutectic mixture of choline chloride choline and ethylene glycol in a molar ratio of 1:2, respectively, in which 1 М NiCl2·6H2O was dissolved. It was shown that the apparent transfer coefficients for electrochemical process in the system Ni(II)/Ni(0) in ethaline were equal to α=0.309 and β=0.255 for anodic and cathodic reactions, respec-tively. It is difficult to interpret these values in the framework of known criteria of consecutive electrochemical pro-cesses. In order to explain this phenomenon, a theoretical conception was used, that was earlier developed by Gileadi. According to that conception, electric charge during metal electrodeposition is transferred through the electrode interface by metal ions, but not by electrons. Therefore, potential barrier in a double electrical layer be-came very asymmetric (i.e. the apparent transfer coefficient deviates from 0.5). It was found that the introduction of TiO2 particles (0–10 g dm–3) into the electrolyte based on ethaline results in declaration of electrochemical re-duction of nickel (II) ions due to a partial blocking of the electrode surface by adsorbed colloidal particles of titani-um dioxide.
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