In Situ Photoelectrochemical Chloride Activation Using a WO3 Electrode for Oxidative Treatment with Simultaneous H2 Evolution under Visible Light

  • Min Seok Koo
    Min Seok Koo
    Division of Environmental Science and Engineering, Pohang University of Science and Technology (POSTECH), Pohang 37673, Korea
    More by Min Seok Koo
  • Xiaofang Chen
    Xiaofang Chen
    Guangdong Key Laboratory of Environmental Catalysis and Health Risk Control, Institute of Environmental Health and Pollution Control, Guangdong University of Technology, Guangzhou 510006, China
  • Kangwoo Cho
    Kangwoo Cho
    Division of Environmental Science and Engineering, Pohang University of Science and Technology (POSTECH), Pohang 37673, Korea
    More by Kangwoo Cho
  • Taicheng An*
    Taicheng An
    Guangdong Key Laboratory of Environmental Catalysis and Health Risk Control, Institute of Environmental Health and Pollution Control, Guangdong University of Technology, Guangzhou 510006, China
    *E-mail: [email protected] (T.A.).
    More by Taicheng An
  • , and 
  • Wonyong Choi*
    Wonyong Choi
    Division of Environmental Science and Engineering, Pohang University of Science and Technology (POSTECH), Pohang 37673, Korea
    *E-mail: [email protected] (W.C.).
    More by Wonyong Choi
Cite this: Environ. Sci. Technol. 2019, 53, 16, 9926–9936
Publication Date (Web):July 18, 2019
https://doi.org/10.1021/acs.est.9b02401
Copyright © 2019 American Chemical Society
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Abstract

Reactive chlorine species (RCS) such as HOCl and chlorine radical species is a strong oxidant and has been widely used for water disinfection. This study investigated a photoelectrochemical (PEC) method of RCS production from ubiquitous chloride ions using a WO3 film electrode and visible light. The degradation of organic substrates coupled with H2 evolution using a WO3 electrode was compared among electrochemical (EC), photocatalytic (PC), and PEC conditions (potential bias: +0.5 V vs Ag/AgCl; λ > 420 nm). The degradation of 4-chlorophenol, bisphenol A, acetaminophen, carbamazepine, humic acid, and fulvic acid and the inactivation of E. coli were remarkably enhanced by in situ RCS generated in PEC conditions, whereas the activities of the PC and EC processes were negligible. The activities of the WO3 film were limited by rapid charge recombination in the PC condition, and the potential bias of +0.5 V did not induce any significant reactions in the EC condition. The PEC activities of WO3 were limited in the absence of Cl but significantly enhanced in the presence of Cl, which confirmed the essential role of RCS in this PEC system. The PEC mineralization of organic compounds was also markedly enhanced in the presence of Cl where dark chemical chlorination by NaOCl addition induced a negligible mineralization. The H2 generation was observed only at the PEC condition and was negligible at PC and EC conditions. On the other hand, the oxidation of chloride on a WO3 photoanode produced chlorate (ClO3) as a toxic byproduct under UV irradiation, but the visible light-irradiated PEC system generated no chlorate.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.est.9b02401.

  • Cross-sectional images of WO3 thin film electrodes, Figure S1; Tauc plot for WO3 film, Figure S2; cyclic voltammograms of WO3 thin film electrode, Figure S3; fluorescence emission spectra of HA and FA, Figure S4; current time profiles, Figure S5; time profiles of 4-CP degradation, Figure S6; HPLC analysis of chlorinated intermediates production, Figure S7; time-dependent variation of inactivation of E. coli on WO3 thin film electrode, Figure S8; fluorescence emission spectra of 7-HC, Figure S9; time profiles of 4-CP degradation and accompanying current density, Figure S10; and pseudo-first-order rate constant of various pollutants in PEC, PC, and EC conditions, Table S1 (PDF)

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