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Kinetic Approach by Photocurrent Measurements to the Photoelectrocatalytic Oxidation of an Anionic Surfactant Using an S,N-TiO2/Ti Electrode: Distinguishing Between Direct and Indirect Mechanisms

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Abstract

The photoelectrocatalytic oxidation of an anionic surfactant (internal olefin sulfonate C20-C24, IOS) in synthetic oilfield wastewater was investigated by photocurrent measurements using a sulfur and nitrogen co-doped titanium dioxide electrode (S,N-TiO2/Ti). For the electrode preparation, S,N-TiO2 films were supported on Ti expanded meshes by sol–gel dip-coating, followed by thermal treatment at 400 °C. Photocurrent measurements were performed by linear sweep voltammetry (LSV) under UV–Vis irradiation using different IOS concentrations (20–200 ppm). The photocurrent values obtained at 0.5 V vs Ag/AgCl (iph) for each IOS concentration (CIOS) were used to plot the 1/iph vs 1/CIOS graph, in which two trends were identified. For high IOS concentrations (70–200 ppm), the values fitted well to the unimolecular Langmuir–Hinshelwood (LH1) kinetic model (R2 = 0.973), which can be associated with the direct oxidation mechanism. For low IOS concentrations (20–70 ppm), the values fitted better to a linear combination of both unimolecular and bimolecular Langmuir–Hinshelwood (LH1 and LH2) kinetic models (R2 = 0.854), which can be associated with direct and indirect oxidation mechanisms, respectively. These results suggest that at high IOS concentrations the IOS adsorption plays the main role on the photoelectrocatalytic oxidation, while at low IOS concentrations both IOS adsorption and H2O adsorption (surface hydrophilicity) play important roles on the photoelectrocatalytic oxidation.

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Acknowledgements

This work has been carried out with the financial support of Universidad Industrial de Santander—UIS and Instituto Colombiano del Petróleo—ICP, ECOPETROL through the academic agreement No. 5222395 (Convenio Marco de Cooperación Tecnológica y Científica UIS–ECOPETROL S.A.). M.I. Jaramillo-Gutierrez also thank COLCIENCIAS for the studentship under the program “Doctorados Nacionales No.647-2014”.

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  1. Grupo de Investigaciones en Minerales, Biohidrometalurgia y Ambiente - GIMBA, Universidad Industrial de Santander - UIS, Sede Guatiguará, Transv. Guatiguará, Calle 8N No. 3W-60, Barrio El Refugio, C.P. 681011, Piedecuesta (Santander), Colombia

    M. I. Jaramillo-Gutiérrez, J. S. Velasco-Rueda & J. A. Pedraza-Avella

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  1. M. I. Jaramillo-Gutiérrez
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Jaramillo-Gutiérrez, M.I., Velasco-Rueda, J.S. & Pedraza-Avella, J.A. Kinetic Approach by Photocurrent Measurements to the Photoelectrocatalytic Oxidation of an Anionic Surfactant Using an S,N-TiO2/Ti Electrode: Distinguishing Between Direct and Indirect Mechanisms. Top Catal 64, 26–35 (2021). https://doi.org/10.1007/s11244-020-01404-x

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