Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and electrochemical techniques such as cyclic voltammetry and chronoamperometry were used to study the electrodeposition and Zn nucleation mechanisms onto Fluorine-doped tin oxide (FTO) substrate from a nitrate-based electrolytic bath. The cyclic voltammetry analysis displays a reduction process (Ic) that involves three simultaneous reduction reactions: reduction of zinc neutral species ZnCl2 to Zn0, reduction of NO3− ions, and the evolution of H2 from the reduction of the medium. In addition, due to the oxidizing nature of nitrates, the surface of the recently deposited Zn0 was partially oxidized to Zn2+, which combines with OH− ions to form the Zn(OH)2 species on the surface of the deposited Zn0. Analysis of chronoamperograms showed that Zn0 nucleation onto FTO occurs via diffusion controlled 3D nucleation in the presence of NO3− ions, with the simultaneous reduction of nitrate ions on the Zn0 growth surface and the reduction of the medium occurs on the uncoated surface by the diffusion zones of Zn0 growth. SEM and XPS analysis of the deposits obtained from the chronoamperometric study evidenced the formation of the Zn(OH)2 surface species. Consequently, structures of the form Zn(OH)2/Zn0/FTO were obtained during the electrodeposition of Zn0 in the presence of nitrates.
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