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Estudos da eletrodeposi??o de metais em regime de subtens?o

机译：在表面下进行金属电镀的研究

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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, S?o 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.
机译：这项工作回顾了在Grupo de MateriaisEletroquímicoseMétodosEletroanalíticos（IQSC-USP，S？o Carlos）中进行的几种金属在Pt和Au基底上的欠电位沉积（UPD）的最新研究。分析了UPD上Cu，Cd和Pb在Pt上对氧释放反应的影响。铅原子促进的表面活性部位的部分堵塞，导致最终产物从水变为过氧化氢。在这项工作中还讨论了在Pt和Au衬底上的Ag UPD。建立了Ag单层电荷计算的详细模型，并通过旋转环盘数据进行了证实。 UPD研究中的部分电荷转移在Cd / Pt和Cd / Au系统中进行了分析，发现Cd离子的吸附价为0.5。从溶液中金属离子的价态角度研究了Sn / Pt UPD系统。 Sn（IV）的沉积产生了一个完整的单层，最大占据了约40％的表面活性部位（340μCcm-2）加上105μCcm-2的Hads（半单层）。改变Sn（II）的金属离子，可以沉积一个完整的单层膜（210μCcm-2），而没有任何可检测到的Hads。最后，在Zn / Pt和Zn / Au系统中讨论了阴离子的作用。在此，使用氢析出反应（her）和氢吸附/解吸来研究锌原子吸附表面的最大覆盖率。仅在0.5 M HF溶液中才能达到完整的单层，其特征是完全没有Hads。

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