Abstract
The influence of existing form of different zinc compounds on the electrochemical behavior of zinc was investigated in choline chloride-urea (ChCl-urea) deep eutectic solvent (DES). Raman and ESI-MS analyses indicate that complexes [ZnCl4]−, [Zn(H2O)Cl3]− and [ZnO⋅urea⋅Cl]− are presented in the ChCl-urea DES containing ZnCl4, ZnSO4⋅7H2O and ZnO, respectively. The zinc compounds were found to vary reduction overpotential of Zn(II) ions in the order ZnO > ZnSO4⋅7H2O > ZnCl4, while their reduction and diffusion rate in a sequence ZnSO4⋅7H2O > ZnCl4 > ZnO. This may be due to the formation of various Zn(II) complexes and oligomers. The chronoamperometric transient analysis shows that Zn electrodeposition in ChCl-urea DES with ZnCl2 or ZnO as a precursor follows instantaneous nucleation mode, while ZnSO4⋅7H2O is changed to a more progressive one. Besides, the zinc compounds can alter the rate of nucleation, influencing the morphology of zinc deposits. The ChCl-urea DES containing ZnSO4⋅7H2O or ZnO is conducive to electrodeposition of a smooth and dense zinc coating. The XRD analysis of the deposits displays that part of the deposited zinc is able to alloy with copper substrate to form the Zn-Cu surface alloy, and the amount of the alloy depends on zinc compound. These findings promise a cheap and simple route for production of Zn coating directly form Zn secondary resources.
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