Zhang Q B, Hua Y X
Key Laboratory of Ionic Liquids Metallurgy, Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, P. R. China.
Phys Chem Chem Phys. 2014 Dec 28;16(48):27088-95. doi: 10.1039/c4cp03041a.
The electrochemical nucleation and growth kinetics of copper nanoparticles on a Ni electrode have been studied with cyclic voltammetry and chronoamperometry in the choline chloride (ChCl)-urea based deep eutectic solvent (DES). The copper source was introduced into the solvent by the dissolution of Cu(I) oxide (Cu2O). Cyclic voltammetry indicates that the electroreduction of Cu(I) species in the DES is a diffusion-controlled quasi-reversible process. The analysis of the chronoamperometric transient behavior during electrodeposition suggests that the deposition of copper on the Ni electrode at low temperatures follows a progressive nucleation and three-dimensional growth controlled by diffusion. The effect of temperature on the diffusion coefficient of Cu(I) species that is present in the solvent and electron transfer rate constant obeys the Arrhenius law, according to which the activation energies are estimated to be 49.20 and 21.72 kJ mol(-1), respectively. The initial stage of morphological study demonstrates that both electrode potential and temperature play important roles in controlling the nucleation and growth kinetics of the nanocrystals during the electrodeposition process. Electrode potential is observed to affect mainly the nucleation process, whereas temperature makes a major contribution to the growth process.
在基于氯化胆碱(ChCl)-尿素的深共熔溶剂(DES)中,采用循环伏安法和计时电流法研究了铜纳米颗粒在镍电极上的电化学成核和生长动力学。通过氧化亚铜(Cu2O)的溶解将铜源引入溶剂中。循环伏安法表明,DES中Cu(I)物种的电还原是一个扩散控制的准可逆过程。对电沉积过程中计时电流瞬态行为的分析表明,低温下铜在镍电极上的沉积遵循由扩散控制的渐进成核和三维生长。温度对溶剂中存在的Cu(I)物种的扩散系数和电子转移速率常数的影响符合阿仑尼乌斯定律,据此估计活化能分别为49.20和21.72 kJ mol(-1)。形态学研究的初始阶段表明,在电沉积过程中,电极电位和温度在控制纳米晶体的成核和生长动力学方面都起着重要作用。观察到电极电位主要影响成核过程,而温度对生长过程起主要作用。