Electrochemical oxidation of organics in sulfate solutions on boron-doped diamond electrode: Multiple pathways for sulfate radical generation

Yong Uk Shin, Ha Young Yoo, Yong Yoon Ahn, Min Sik Kim, Kang Lee, Seungho Yu, Changha Lee, Kangwoo Cho, Hyoung il Kim, Jaesang Lee

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

This study scrutinized the roles of sulfate radicals (SO4[rad]) and peroxydisulfate (PDS) formed from SO42− in electrochemical organic oxidation on a boron-doped diamond (BDD) electrode. The substrate-specific performance of electrochemical oxidation using SO42− as the electrolyte aligned with the reactivity of SO4[rad] produced via radiolysis- or heat-induced PDS activation, but was distinct from the non-selective oxidation efficiency observed in an aqueous ClO4 solution. A comparison of the treatment efficiencies using different electrolytes (i.e., Cl, SO42−, and ClO4) showed no pronounced enhancing effect of SO4[rad] on the anodic oxidation of diverse organics (except perfluorooctanoate), which implied that direct electron transfer and hydroxyl radical-induced oxidation proceeded as complementary reaction routes. Repeated electrolytic oxidation caused substantial electrolyte exchange from Cl to ClO4, which retarded organic oxidation accompanied by ClO4 accumulation. Conversely, high-yield PDS production observed when SO42− was used instead barely reduced treatment efficiency. Together with SO4[rad] detection in the electron paramagnetic resonance spectrum, a correlation between 4-chlorophenol oxidation rate and the faradaic efficiency for SO42− formation, monitored in PDS solutions while varying the cathode material, suggested cathodic PDS activation. The electrocatalytic performance was demonstrated to be further improved with anodically formed PDS activation through naturally occurring resistive heating or combination with UV photolysis as a post-treatment step.

Original languageEnglish
Pages (from-to)156-165
Number of pages10
JournalApplied Catalysis B: Environmental
Volume254
DOIs
Publication statusPublished - 2019 Oct 5

Fingerprint

Diamond
Boron
Electrochemical oxidation
boron
diamond
Sulfates
Diamonds
electrode
sulfate
oxidation
Oxidation
Electrodes
Electrolytes
perfluorooctanoic acid
Chemical activation
electrolyte
Radiolysis
Photolysis
Anodic oxidation
Hydroxyl Radical

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Environmental Science(all)
  • Process Chemistry and Technology

Cite this

Shin, Yong Uk ; Yoo, Ha Young ; Ahn, Yong Yoon ; Kim, Min Sik ; Lee, Kang ; Yu, Seungho ; Lee, Changha ; Cho, Kangwoo ; Kim, Hyoung il ; Lee, Jaesang. / Electrochemical oxidation of organics in sulfate solutions on boron-doped diamond electrode : Multiple pathways for sulfate radical generation. In: Applied Catalysis B: Environmental. 2019 ; Vol. 254. pp. 156-165.
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abstract = "This study scrutinized the roles of sulfate radicals (SO4[rad]−) and peroxydisulfate (PDS) formed from SO42− in electrochemical organic oxidation on a boron-doped diamond (BDD) electrode. The substrate-specific performance of electrochemical oxidation using SO42− as the electrolyte aligned with the reactivity of SO4[rad]− produced via radiolysis- or heat-induced PDS activation, but was distinct from the non-selective oxidation efficiency observed in an aqueous ClO4− solution. A comparison of the treatment efficiencies using different electrolytes (i.e., Cl−, SO42−, and ClO4−) showed no pronounced enhancing effect of SO4[rad]− on the anodic oxidation of diverse organics (except perfluorooctanoate), which implied that direct electron transfer and hydroxyl radical-induced oxidation proceeded as complementary reaction routes. Repeated electrolytic oxidation caused substantial electrolyte exchange from Cl− to ClO4−, which retarded organic oxidation accompanied by ClO4− accumulation. Conversely, high-yield PDS production observed when SO42− was used instead barely reduced treatment efficiency. Together with SO4[rad]− detection in the electron paramagnetic resonance spectrum, a correlation between 4-chlorophenol oxidation rate and the faradaic efficiency for SO42− formation, monitored in PDS solutions while varying the cathode material, suggested cathodic PDS activation. The electrocatalytic performance was demonstrated to be further improved with anodically formed PDS activation through naturally occurring resistive heating or combination with UV photolysis as a post-treatment step.",
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Electrochemical oxidation of organics in sulfate solutions on boron-doped diamond electrode : Multiple pathways for sulfate radical generation. / Shin, Yong Uk; Yoo, Ha Young; Ahn, Yong Yoon; Kim, Min Sik; Lee, Kang; Yu, Seungho; Lee, Changha; Cho, Kangwoo; Kim, Hyoung il; Lee, Jaesang.

In: Applied Catalysis B: Environmental, Vol. 254, 05.10.2019, p. 156-165.

Research output: Contribution to journalArticle

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T2 - Multiple pathways for sulfate radical generation

AU - Shin, Yong Uk

AU - Yoo, Ha Young

AU - Ahn, Yong Yoon

AU - Kim, Min Sik

AU - Lee, Kang

AU - Yu, Seungho

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AU - Cho, Kangwoo

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AU - Lee, Jaesang

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N2 - This study scrutinized the roles of sulfate radicals (SO4[rad]−) and peroxydisulfate (PDS) formed from SO42− in electrochemical organic oxidation on a boron-doped diamond (BDD) electrode. The substrate-specific performance of electrochemical oxidation using SO42− as the electrolyte aligned with the reactivity of SO4[rad]− produced via radiolysis- or heat-induced PDS activation, but was distinct from the non-selective oxidation efficiency observed in an aqueous ClO4− solution. A comparison of the treatment efficiencies using different electrolytes (i.e., Cl−, SO42−, and ClO4−) showed no pronounced enhancing effect of SO4[rad]− on the anodic oxidation of diverse organics (except perfluorooctanoate), which implied that direct electron transfer and hydroxyl radical-induced oxidation proceeded as complementary reaction routes. Repeated electrolytic oxidation caused substantial electrolyte exchange from Cl− to ClO4−, which retarded organic oxidation accompanied by ClO4− accumulation. Conversely, high-yield PDS production observed when SO42− was used instead barely reduced treatment efficiency. Together with SO4[rad]− detection in the electron paramagnetic resonance spectrum, a correlation between 4-chlorophenol oxidation rate and the faradaic efficiency for SO42− formation, monitored in PDS solutions while varying the cathode material, suggested cathodic PDS activation. The electrocatalytic performance was demonstrated to be further improved with anodically formed PDS activation through naturally occurring resistive heating or combination with UV photolysis as a post-treatment step.

AB - This study scrutinized the roles of sulfate radicals (SO4[rad]−) and peroxydisulfate (PDS) formed from SO42− in electrochemical organic oxidation on a boron-doped diamond (BDD) electrode. The substrate-specific performance of electrochemical oxidation using SO42− as the electrolyte aligned with the reactivity of SO4[rad]− produced via radiolysis- or heat-induced PDS activation, but was distinct from the non-selective oxidation efficiency observed in an aqueous ClO4− solution. A comparison of the treatment efficiencies using different electrolytes (i.e., Cl−, SO42−, and ClO4−) showed no pronounced enhancing effect of SO4[rad]− on the anodic oxidation of diverse organics (except perfluorooctanoate), which implied that direct electron transfer and hydroxyl radical-induced oxidation proceeded as complementary reaction routes. Repeated electrolytic oxidation caused substantial electrolyte exchange from Cl− to ClO4−, which retarded organic oxidation accompanied by ClO4− accumulation. Conversely, high-yield PDS production observed when SO42− was used instead barely reduced treatment efficiency. Together with SO4[rad]− detection in the electron paramagnetic resonance spectrum, a correlation between 4-chlorophenol oxidation rate and the faradaic efficiency for SO42− formation, monitored in PDS solutions while varying the cathode material, suggested cathodic PDS activation. The electrocatalytic performance was demonstrated to be further improved with anodically formed PDS activation through naturally occurring resistive heating or combination with UV photolysis as a post-treatment step.

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