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. 2022 May 30;13:3005. doi: 10.1038/s41467-022-30560-9

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© The Author(s) 2022

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

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Fig. 4 — a Concentration profiles of PhOH at different dosage ratios of PMS to PhOH. b Regression curve of the dosage ratio of PMS to PhOH versus the removal ratio of PhOH. c Second-order kinetics fitting of the reaction with PMS to PhOH dosage ratio of 1.8. d Schematic illustration of the two-chamber galvanic cell system (marked as 1) and the single-chamber contact-type system (marked as 2). e Concentration profiles of PhOH removal in the two systems in d. f Conversion of the reactants in the analogy experiments between PhOH and KI in the two systems in d. The reactions of PhOH in the two systems exhibited the same trend as those of KI within 60 min. g Time-dependent EPR spectra of the Co₃O₄/PMS/PhOH system with DMPO as the spin trapping agent. h EPR spectra of the Fe²⁺/H₂O₂/PhOH (Fenton) and ZVI/PMS/PhOH systems recorded at a reaction time of 5 min with DMPO as the spin-trapping agent. i Fluorescence emission spectra of the Fe²⁺/H₂O₂/PhOH (Fenton) and Co₃O₄/PMS/PhOH systems for quantitative detection of radicals with benzoic acid (BA) as the probe molecule (the excitation wavelength was 310 nm). Differing from the typical radical systems (i.e., •OH in the Fe²⁺/H₂O₂/PhOH system and SO₄^•– in the ZVI/PMS/PhOH system) that exhibited DMPO-OH^• (with hyperfine couplings a_N = a_β-H = 14.9 G) or DMPO-SO₄^•– (with hyperfine splitting constants of a_N = 13.2 G, a_β-H = 9.6 G, a_γ-H1 = 1.48 G and a_γ-H2 = 0.78 G)) signals in the EPR spectra, in the Co₃O₄/PMS/PhOH system, only the DMPOX signal (with a 1:1:1 triplet (a_N = 7.2 G) of 1:2:1 triplet (a_γ-H = 4.1 G, 2H)) appeared from the beginning of the reaction and then exhibited initial increasing and later decreasing. The result of the in situ EPR experiments indicates no •OH and SO₄^•– formation in the Co₃O₄/PMS/PhOH system. _R, molar ratio of PMS to PhOH; CP, carbon paper; Reacted ratio, (1-C/C₀)*100%; ZVI, zero-valent iron solid; DMPO, .

Inline graphic — a Concentration profiles of PhOH at different dosage ratios of PMS to PhOH. b Regression curve of the dosage ratio of PMS to PhOH versus the removal ratio of PhOH. c Second-order kinetics fitting of the reaction with PMS to PhOH dosage ratio of 1.8. d Schematic illustration of the two-chamber galvanic cell system (marked as 1) and the single-chamber contact-type system (marked as 2). e Concentration profiles of PhOH removal in the two systems in d. f Conversion of the reactants in the analogy experiments between PhOH and KI in the two systems in d. The reactions of PhOH in the two systems exhibited the same trend as those of KI within 60 min. g Time-dependent EPR spectra of the Co₃O₄/PMS/PhOH system with DMPO as the spin trapping agent. h EPR spectra of the Fe²⁺/H₂O₂/PhOH (Fenton) and ZVI/PMS/PhOH systems recorded at a reaction time of 5 min with DMPO as the spin-trapping agent. i Fluorescence emission spectra of the Fe²⁺/H₂O₂/PhOH (Fenton) and Co₃O₄/PMS/PhOH systems for quantitative detection of radicals with benzoic acid (BA) as the probe molecule (the excitation wavelength was 310 nm). Differing from the typical radical systems (i.e., •OH in the Fe²⁺/H₂O₂/PhOH system and SO₄^•– in the ZVI/PMS/PhOH system) that exhibited DMPO-OH^• (with hyperfine couplings a_N = a_β-H = 14.9 G) or DMPO-SO₄^•– (with hyperfine splitting constants of a_N = 13.2 G, a_β-H = 9.6 G, a_γ-H1 = 1.48 G and a_γ-H2 = 0.78 G)) signals in the EPR spectra, in the Co₃O₄/PMS/PhOH system, only the DMPOX signal (with a 1:1:1 triplet (a_N = 7.2 G) of 1:2:1 triplet (a_γ-H = 4.1 G, 2H)) appeared from the beginning of the reaction and then exhibited initial increasing and later decreasing. The result of the in situ EPR experiments indicates no •OH and SO₄^•– formation in the Co₃O₄/PMS/PhOH system. _R, molar ratio of PMS to PhOH; CP, carbon paper; Reacted ratio, (1-C/C₀)*100%; ZVI, zero-valent iron solid; DMPO, .