Bicarbonate-enhanced generation of hydroxyl radical by visible light-induced photocatalysis of H2O2 over WO3: Alteration of electron transfer mechanism

Jaemin Choi; Hak–Hyeon –H Kim; Ki–Myeong –M Lee; Na Chen; Min Sik Kim; Jiwon Seo; Donghyun Lee; Haein Cho; Hyoung il Kim; Jaesang Lee; Hongshin Lee; Changha Lee

doi:10.1016/j.cej.2021.134401

Bicarbonate-enhanced generation of hydroxyl radical by visible light-induced photocatalysis of H₂O₂ over WO₃: Alteration of electron transfer mechanism

Jaemin Choi, Hak–Hyeon –H Kim, Ki–Myeong –M Lee, Na Chen, Min Sik Kim, Jiwon Seo, Donghyun Lee, Haein Cho, Hyoung il Kim, Jaesang Lee, Hongshin Lee, Changha Lee

Department of Civil and Environmental Engineering

Research output: Contribution to journal › Article › peer-review

5 Citations (Scopus)

Abstract

The generation of hydroxyl radical (^•OH) by visible light-illuminated tungsten oxide (WO₃) was found to be significantly improved in the presence of hydrogen peroxide (H₂O₂) and bicarbonate ion (HCO₃⁻). A ternary system of hν/WO₃/H₂O₂/HCO₃⁻ showed synergistic enhancement in oxidation of benzoic acid (BA, a ^•OH probe compound) into hydroxybenzoic acids (HBAs), exhibiting even less consumption of H₂O₂ than hν/WO₃/H₂O₂. Analyses of HBAs from BA oxidation (three HBA isomers and ¹⁸O-labelled HBA from H₂¹⁸O₂) suggested that hν/WO₃/H₂O₂/HCO₃⁻, contrary to hν/WO₃/H₂O₂, generated ^•OH mainly via one-electron transfer from the conduction band of WO₃ to H₂O₂. The dominant one-electron reduction of H₂O₂ over HCO₃⁻-treated WO₃ was further evidenced by Koutecký–Levich plots obtained with a rotating disk electrode setup. Based on different experiments using electron paramagnetic resonance spectroscopy, radical scavengers and probes, (photo-)electrochemical measurements, and density functional theory calculations, the mechanisms underlying the enhanced generation of ^•OH by hν/WO₃/H₂O₂/HCO₃⁻ were discussed.

Original language	English
Article number	134401
Journal	Chemical Engineering Journal
Volume	432
DOIs	https://doi.org/10.1016/j.cej.2021.134401
Publication status	Published - 2022 Mar 15

Bibliographical note

Funding Information:
This work was supported by a National Research Foundation of Korea (NRF) Grant (NRF-2021R1A4A1026364), and by Korea Environment Industry & Technology Institute (KEITI) through Prospective Green Technology Innovation Project (2020003160008).

Publisher Copyright:
© 2021 Elsevier B.V.

All Science Journal Classification (ASJC) codes

Chemistry(all)
Environmental Chemistry
Chemical Engineering(all)
Industrial and Manufacturing Engineering

Access to Document

10.1016/j.cej.2021.134401

Cite this

Choi, J., Kim, HH. H., Lee, KM. M., Chen, N., Kim, M. S., Seo, J., Lee, D., Cho, H., Kim, H. I., Lee, J., Lee, H., & Lee, C. (2022). Bicarbonate-enhanced generation of hydroxyl radical by visible light-induced photocatalysis of H₂O₂ over WO₃: Alteration of electron transfer mechanism. Chemical Engineering Journal, 432, [134401]. https://doi.org/10.1016/j.cej.2021.134401

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title = "Bicarbonate-enhanced generation of hydroxyl radical by visible light-induced photocatalysis of H2O2 over WO3: Alteration of electron transfer mechanism",

abstract = "The generation of hydroxyl radical (•OH) by visible light-illuminated tungsten oxide (WO3) was found to be significantly improved in the presence of hydrogen peroxide (H2O2) and bicarbonate ion (HCO3−). A ternary system of hν/WO3/H2O2/HCO3− showed synergistic enhancement in oxidation of benzoic acid (BA, a •OH probe compound) into hydroxybenzoic acids (HBAs), exhibiting even less consumption of H2O2 than hν/WO3/H2O2. Analyses of HBAs from BA oxidation (three HBA isomers and 18O-labelled HBA from H218O2) suggested that hν/WO3/H2O2/HCO3−, contrary to hν/WO3/H2O2, generated •OH mainly via one-electron transfer from the conduction band of WO3 to H2O2. The dominant one-electron reduction of H2O2 over HCO3−-treated WO3 was further evidenced by Kouteck{\'y}–Levich plots obtained with a rotating disk electrode setup. Based on different experiments using electron paramagnetic resonance spectroscopy, radical scavengers and probes, (photo-)electrochemical measurements, and density functional theory calculations, the mechanisms underlying the enhanced generation of •OH by hν/WO3/H2O2/HCO3− were discussed.",

author = "Jaemin Choi and Kim, {Hak–Hyeon –H} and Lee, {Ki–Myeong –M} and Na Chen and Kim, {Min Sik} and Jiwon Seo and Donghyun Lee and Haein Cho and Kim, {Hyoung il} and Jaesang Lee and Hongshin Lee and Changha Lee",

note = "Funding Information: This work was supported by a National Research Foundation of Korea (NRF) Grant (NRF-2021R1A4A1026364), and by Korea Environment Industry & Technology Institute (KEITI) through Prospective Green Technology Innovation Project (2020003160008). Publisher Copyright: {\textcopyright} 2021 Elsevier B.V.",

year = "2022",

month = mar,

day = "15",

doi = "10.1016/j.cej.2021.134401",

language = "English",

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T1 - Bicarbonate-enhanced generation of hydroxyl radical by visible light-induced photocatalysis of H2O2 over WO3

T2 - Alteration of electron transfer mechanism

AU - Choi, Jaemin

AU - Kim, Hak–Hyeon –H

AU - Lee, Ki–Myeong –M

AU - Chen, Na

AU - Kim, Min Sik

AU - Seo, Jiwon

AU - Lee, Donghyun

AU - Cho, Haein

AU - Kim, Hyoung il

AU - Lee, Jaesang

AU - Lee, Hongshin

AU - Lee, Changha

N1 - Funding Information: This work was supported by a National Research Foundation of Korea (NRF) Grant (NRF-2021R1A4A1026364), and by Korea Environment Industry & Technology Institute (KEITI) through Prospective Green Technology Innovation Project (2020003160008). Publisher Copyright: © 2021 Elsevier B.V.

PY - 2022/3/15

Y1 - 2022/3/15

N2 - The generation of hydroxyl radical (•OH) by visible light-illuminated tungsten oxide (WO3) was found to be significantly improved in the presence of hydrogen peroxide (H2O2) and bicarbonate ion (HCO3−). A ternary system of hν/WO3/H2O2/HCO3− showed synergistic enhancement in oxidation of benzoic acid (BA, a •OH probe compound) into hydroxybenzoic acids (HBAs), exhibiting even less consumption of H2O2 than hν/WO3/H2O2. Analyses of HBAs from BA oxidation (three HBA isomers and 18O-labelled HBA from H218O2) suggested that hν/WO3/H2O2/HCO3−, contrary to hν/WO3/H2O2, generated •OH mainly via one-electron transfer from the conduction band of WO3 to H2O2. The dominant one-electron reduction of H2O2 over HCO3−-treated WO3 was further evidenced by Koutecký–Levich plots obtained with a rotating disk electrode setup. Based on different experiments using electron paramagnetic resonance spectroscopy, radical scavengers and probes, (photo-)electrochemical measurements, and density functional theory calculations, the mechanisms underlying the enhanced generation of •OH by hν/WO3/H2O2/HCO3− were discussed.

AB - The generation of hydroxyl radical (•OH) by visible light-illuminated tungsten oxide (WO3) was found to be significantly improved in the presence of hydrogen peroxide (H2O2) and bicarbonate ion (HCO3−). A ternary system of hν/WO3/H2O2/HCO3− showed synergistic enhancement in oxidation of benzoic acid (BA, a •OH probe compound) into hydroxybenzoic acids (HBAs), exhibiting even less consumption of H2O2 than hν/WO3/H2O2. Analyses of HBAs from BA oxidation (three HBA isomers and 18O-labelled HBA from H218O2) suggested that hν/WO3/H2O2/HCO3−, contrary to hν/WO3/H2O2, generated •OH mainly via one-electron transfer from the conduction band of WO3 to H2O2. The dominant one-electron reduction of H2O2 over HCO3−-treated WO3 was further evidenced by Koutecký–Levich plots obtained with a rotating disk electrode setup. Based on different experiments using electron paramagnetic resonance spectroscopy, radical scavengers and probes, (photo-)electrochemical measurements, and density functional theory calculations, the mechanisms underlying the enhanced generation of •OH by hν/WO3/H2O2/HCO3− were discussed.

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