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PbO2-surfactant composites: electrosynthesis and catalytic activity

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Abstract

The electrodeposition of PbO2 from sodium laureth sulfate-containing medium has been investigated. It has been established that at low anodic polarizations, second electron transfer step is rate determining, whereas at high anodic polarizations, such step is diffusion transport of lead ions to the electrode surface. The presence of sodium laureth sulfate in the deposition electrolyte leads to a slight inhibition of the deposition of lead dioxide. It has been found that the morphology and structure of composite materials differs significantly from lead dioxide. With an increase in the additive content in the composite, there is a transition from large-grained deposits to materials with submicron and nano-sized crystals. It is shown that anionic surfactants, sodium laureth sulfate in particular, are included in the growing lead dioxide. The content of organic substance in the oxide can vary from 3.2 to 12.5 wt.%, forming a surfactant-oxide composite coating. The electrocatalytic activity of the materials involved was investigated with respect to oxygen evolution reaction and the oxidation of 4-chlorophenol. The calculated value of Tafel slope is 229 on non-modified PbO2, while on 10.2 wt.% sodium laureth sulfate-PbO2, it is 178 mV/dec. According to absorption spectra, the initial solution of chlorophenol is characterized by two peaks at 220 and 280 nm. At first, the electrolysis shows a decrease in the peak at 220 nm, as well as a slight increase in the peak at 280 nm and the appearance of the plateau at 240–270 nm, which is caused by a decrease in the concentration of 4-chlorophenol and accumulation of benzoquinone in the solution. A further increase in the time of electrolysis leads to the disappearance of the peaks at 220 and 280 nm, as well as the reduction of the plateau at 240–270 nm due to a decrease in the concentrations of both 4-chlorophenol and benzoquinone. Already after 4 h of electrolysis, the aromatic compounds are completely destroyed with the formation of only aliphatic electrolysis products (mainly maleic acid), which was evidenced by high performance liquid chromatography. The processes of electrooxidation of 4-chlorophenol on lead dioxide and PbO2-based composite materials proceed qualitatively in the same way and differ only in the rate.

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Acknowledgments

The authors are indebted to Rossano Amadelli (Universita’ degli Studi di Ferrara) for help in the discussion of obtained results.

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  1. Physical Chemistry Department, Ukrainian State University of Chemical Technology, Dnipro, Ukraine

    T. Luk’yanenko, O. Shmychkova & A. Velichenko

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  1. T. Luk’yanenko
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Luk’yanenko, T., Shmychkova, O. & Velichenko, A. PbO2-surfactant composites: electrosynthesis and catalytic activity. J Solid State Electrochem 24, 1045–1056 (2020). https://doi.org/10.1007/s10008-020-04572-8

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