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This work reviews recent studies of underpotential deposition (UPD) of several metals on Pt and Au substrates performed in the Grupo de Materiais Eletroquímicos e Métodos Eletroanalíticos (IQSC -- USP, São Carlos). The UPD Cu, Cd and Pb on Pt were analysed in terms of their influence in the oxygen evolution reaction. Partial blockage of surface active sites, promoted by Pb ad-atoms, resulted in a change from water to hydrogen peroxide as the final product. The Ag UPD on Pt and Au substrates was also discussed in this work. A detailed model of charge calculation for Ag monolayer was developed and confirmed by the rotating ring-disk data. The partial charge transfer in UPD studies was analysed in the Cd/Pt and Cd/Au systems and a value of 0.5 was found for the adsorption electrovalence of Cd ad-ions. The Sn/Pt UPD systems were studied from the point of view of the valences of metallic ions in solution. The deposition from Sn(IV) generates a full monolayer with a maximum occupation of approximately 40% of the surface active sites (340 µC cm-2) plus 105 µC cm-2 of Hads (half monolayer). Changing the metallic ion for Sn(II), it was possible to deposit a full monolayer (210 µC cm-2) without any detectable Hads. Finally, the effect of anions was discussed in the Zn/Pt and Zn/Au systems. Here, the hydrogen evolution reaction (her) and the hydrogen adsorption/desorption were used in order to investigate the maximum coverage of the surface with Zn ad-atoms. The full monolayer, characterised by the complete absence of Hads, was achieved only in 0.5 M HF solutions.

This work reports a comparative electrochemical behaviour study and p-nitrophenol analytical detection using silver solid amalgam, hanging dropping mercury, and silver electrodes. For this, square wave voltammetry was employed, where the analytical responses and the redox mechanisms could be compared for reduction processes of 4-nitrophenol by analysis of the voltammetric responses. The analytical performance of the electrode was evaluated and detection and quantification limits, recovery percentages, repeatability, and reproducibility for the silver solid amalgam and hanging dropping mercury electrodes presented similar values; the results presented for the silver electrode indicated worse analytical parameters than the other electrodes. The results indicate that the silver solid amalgam electrode can be considered a suitable tool and an interesting alternative for the analytical determination of 4-nitrophenol, as well as for the determination of other biological and environmentally interesting compounds that present analytical responses on mercury surfaces.

The copolymerization of o-aminophenol (OAP) and aniline (ANI) on Pt and ITO electrodes was studied using cyclic voltammetry in 0.1 M HCl/0.4 M NaCl solution. The films were characterized by SEM, cyclic voltammetry, and UV-Vis spectroscopy. The properties of the copolymer were compared with PANI and POAP films. The results strongly suggest that the growth of PANI-POAP films does not consist of the simple buildup of layers of homopolymers on the electrode surface as a result of OAP or ANI oxidation products in the monomer mixture, but that a new conducting polymer is formed by copolymerization.