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Singlet oxygen generation for selective oxidation of emerging pollutants in a flow-by electrochemical system based on natural air diffusion cathode

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Abstract

The decay of free radicals involved in side reactions is one of the challenges faced by electrochemical degradation of organic pollutants. To this end, a non-radical oxidation system was constructed by a natural air diffusion cathode (ADC) and a Ti-based dimensional stable anode coated by RuO2 (RuO2-Ti anode) for cathodic hydrogen peroxide activation by anodic chlorine evolution. The ADC fabricated by the carbon black of BP2000 produced a stable concentration of hydrogen peroxide of 339.94 mg L−1 (current efficiency of 73.4%) without aeration, which was superior to the cathode made by the XC72 carbon black. The flow-by ADC-RuO2 system consisted of an ADC and a RuO2-Ti anode showed high selectivity to aniline (AN) compared to benzoate (BA) in a NaCl electrolyte, whose degradation efficiencies were 97.72% and 1.3%, respectively. Rapid degradations of a mixture of emerging pollutants and AN were also observed in the ADC-RuO2 system, with pseudo-first-order kinetic constants of 0.51, 1.29, 0.89, and 0.99 min−1 for Bisphenol A (BPA), tetracycline (TC), sulfamethoxazole (SMX) and AN, respectively. Quenching experiments revealed the main reactive oxygen species for the pollutant degradation was singlet oxygen (1O2), which was also identified by the electron spin resonance (ESR) analysis. Finally, the steady-stable content of 1O2 was quantitatively determined to be 6.25 × 10−11 M by the method of furfuryl alcohol (FFA) probe. Our findings provide a fast, low energy consumption and well controlled electrochemical oxidation method for selective degradation of organic pollutants.

Graphical abstract

H2O2 generated on an air diffusion cathode by naturally diffused O2, reacts with ClO− produced from chloride oxidation on the RuO2-Ti anode to form singlet oxygen (1O2). The electrochemical system shows an efficient oxidation to electron-rich emerging pollutants including bisphenol A, tetracycline, sulfamethoxazole and aniline, but a poor performance on the electron-deficient compounds (e.g., benzoate).

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Acknowledgements

We would like to thank Miss Wang and Mr. Wang at the Analytical & Testing Center of Wuhan University of Science and Technology for their help on SEM and BET analysis.

Funding

This work was supported by the National Natural Science Foundation of China (No. 51808415).

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  1. Yi Li, Shiwei Xie, and Jiaxiong Yao contributed equally to this work.

Authors and Affiliations

  1. School of Urban Construction, Wuhan University of Science and Technology, Wuhan, 430065, People’s Republic of China

    Yi Li, Shiwei Xie & Jiaxiong Yao

  2. Institute of High Performance Engineering Structure, Wuhan University of Science and Technology, Wuhan, 430065, People’s Republic of China

    Shiwei Xie

  3. Shenzhen Bao’an Songgang Water Supply Co., Ltd., Shenzhen, 518100, People’s Republic of China

    Jiaxiong Yao

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All authors contributed to the study conception and design. Material preparation, experiment conduct, data collection and analysis were performed by Yi Li, and Jiaxiong Yao. The first draft of the manuscript was written by Yi Li. Supervision, reviewing editing, and validation were performed by Shiwei Xie and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to Shiwei Xie.

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Li, Y., Xie, S. & Yao, J. Singlet oxygen generation for selective oxidation of emerging pollutants in a flow-by electrochemical system based on natural air diffusion cathode. Environ Sci Pollut Res 30, 17854–17864 (2023). https://doi.org/10.1007/s11356-022-23364-3

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