An approach to the first stages of cobalt–nickel–molybdenum electrodeposition in sulphate–citrate medium

The first stages of Co–Ni and Co–Ni–Mo deposition in sulphate–citrate medium at pH 4.0 were analysed. In both cases, the formation of non-hydrogenated nickel on the electrode before alloy deposition was detected by linear sweep voltammetry and inductively coupled plasma mass spectrometry. Co–Ni electrodeposition was anomalous since the Co/Ni ratio in the alloy was higher than the corresponding [Co(II)]/[Ni(II)] ratio in solution. The adsorption of Co(II) over the initial nickel could explain the anomalous codeposition, which persisted with the addition of molybdate to the Co–Ni bath. However, the formation of intermediate molybdenum oxides also took place. A mechanism has been proposed to describe the sequence of steps for Co–Ni–Mo electrodeposition. Under our conditions, the alloy is formed mainly from free Co2+ and Ni2+ cations, whereas molybdate is reduced firstly to molybdenum oxide from MoO4(H3Cit)2− and, secondly, NiCit− catalyses the subsequent reduction to molybdenum metal of the intermediate [MoO2–NiCit−]ads species.