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Electrocatalytic Oxidation of Dibenzothiophene and 4,6-Dimethyldibenzothiophene at Gold-Polyaniline (Au-PANI) Composite Electrodes

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Abstract

In this study, glassy carbon electrodes modified with gold-polyaniline (Au-PANI) were evaluated for the ability to electrochemically oxidize dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT). Au-PANI was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), transmission electron micrograph (TEM), and scanning electron micrograph (SEM). The role of nitrogen groups of PANI on the formation of Au-PANI was shown by FT-IR. XPS confirmed the various electronic states and environment of oxygen, nitrogen, gold, and carbon in Au-PANI film. TEM results indicated that Au particle size is in the range of 3.50–6.97 nm, while SEM results confirmed the heterogeneous nature of PANI and Au-PANI surfaces. In this study, density functional theory (DFT) with the B3LYP functional and 6-311++G** basis set was used to examine the electronic properties of DBT/4,6-DMDBT onto the surface of PANI nanocomposite. Electrochemical tests indicate that the Au-PANI exhibits high catalytic activity for DBT and 4,6-DMDBT electrooxidation. Oxidation products such as DBTO = dibenzothiophene sulfoxide; 4,6-DMDBTO = 4,6-dimethydibenzothiophene sulfoxide; DBTO2 = dibenzothiophene sulfone; and 4,6-DMDBTO2 = 4,6-dimethydibenzothiophene sulfone were confirmed by means of gas chromatograph coupled to mass spectrometer (GC-MS), 1H, and 13C NMR.

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Acknowledgments

The authors appreciate the National Research Foundation (NRF) of South Africa for funding the project. The authors also thank the Center for High Performance Computing (CHPC) (Cape Town, South Africa) for providing the platform for DFT studies.

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  1. Department of Chemistry, Nelson Mandela University, PO Box 77000, Port Elizabeth, 6031, South Africa

    Siyabonga Shoba, Owolabi M. Bankole & Adeniyi S. Ogunlaja

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  1. Siyabonga Shoba
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Shoba, S., Bankole, O.M. & Ogunlaja, A.S. Electrocatalytic Oxidation of Dibenzothiophene and 4,6-Dimethyldibenzothiophene at Gold-Polyaniline (Au-PANI) Composite Electrodes. Electrocatalysis 11, 593–603 (2020). https://doi.org/10.1007/s12678-020-00617-8

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