Nitrogen Vacancy-Modulated Peroxymonosulfate Nonradical Activation for Organic Contaminant Removal via High-Valent Cobalt-Oxo Species

Jiang, Jingjing; Zhao, Ziqing; Gao, Jiaying; Li, Tianren; Li, Mingyu; Zhou, Dandan; Dong, Shuangshi

doi:10.1021/acs.est.2c01913

Cited by 153 publications

(53 citation statements)

References 50 publications

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“…The value of η in the Mn(VII) alone was determined to be 99.0%, but the value of η was 81.3% by UVA-LED/Mn(VII). The discrepancy of η in two processes confirmed the role of HO• in UVA-LED/Mn(VII), because sulfoxides (e.g., PMSO) are oxidized to their sulfones by high-valent metal-oxo species through an oxygen-transfer step, with the formation of PMSO 2 . ,− In contrast, HO• converted PMSO to hydroxylated products by attacking on the aromatic ring . In addition, the yield of PMSO 2 was 81.3, 87.9, 93.0, and 98.0% at 365, 385, 400, and 405 nm, respectively (Figure S17).…”

Section: Results and Discussionmentioning

confidence: 85%

Enhanced Permanganate Activation under UVA-LED Irradiation: Unraveled Mechanism Involving Manganese Species and Hydroxyl Radical

Yang

Mai

Zhu

et al. 2022

Environ. Sci. Technol.

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Permanganate [Mn(VII)] has gained broad attention in water treatment. However, its limited reactivity toward some refractory micropollutants hinders its application for micropollutant degradation. Herein, we introduced UVA-LED photolysis of Mn(VII) (UVA-LED/Mn(VII)) to degrade micropollutants (diclofenac (DCF), 4-chlorophenol (4-CP), atrazine, and nitrobenzene) by selecting DCF and 4-CP as target micropollutants. The effects of operating conditions (e.g., light intensity, radiation wavelengths, pH, and water constituents) on DCF and 4-CP degradation as well as the underlying mechanisms were systematically studied. The degradation rates of DCF and 4-CP linearly decreased with increasing radiation wavelengths (from 365 to 405 nm), likely due to the decreased molar absorption coefficients and quantum yields of Mn(VII). Reactive manganese species (RMnS), including Mn(V), Mn(III), and HO•, were generated in the UVA-LED/Mn(VII) process. Mn(V) and HO• were responsible for DCF degradation, while Mn(III), HO•, and likely Mn(V) accounted for 4-CP degradation. Competitive kinetic results revealed that contributions of RMnS and HO• decreased with increasing radiation wavelengths, wherein RMnS played the dominant role. Increasing pH displayed opposite effects on DCF and 4-CP degradation with higher degradation efficiency obtained at acidic pH for the former one but alkaline pH for the latter one. The presence of water background ions (e.g., Cl–, HCO3 –, and Ca2+) barely influenced DCF and 4-CP degradation. Finally, in comparison with Mn(VII) alone, enhanced degradation of DCF and 4-CP by UVA-LED/Mn(VII) was observed in real waters. This work advances the understanding of the photochemistry of manganese species in micropollutant degradation and facilitates Mn(VII) oxidation in practical application.

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Section: Results and Discussionmentioning

confidence: 85%

Enhanced Permanganate Activation under UVA-LED Irradiation: Unraveled Mechanism Involving Manganese Species and Hydroxyl Radical

Yang

Mai

Zhu

et al. 2022

Environ. Sci. Technol.

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“…The three peaks at 1060, 982, and 884 cm –1 were assigned to the HSO 5 – , SO 4 2– , and O–O in PMS, respectively. Upon the addition of catalysts, PMS adsorption was initiated to form the metastable metal-PMS* complexes, as evidenced by the new peaks at around 830 cm –1 . , The peak intensity was more moderate in the presence of FeCo–N/C compared to other catalysts. Correspondingly, the minimum value of I 1060 / I 982 was observed for the FeCo–N/C + PMS system, indicating that intermediate-spin-state FeCo–N/C facilitated the optimal PMS adsorption and rapid decomposition of HSO 5 – to SO 4 2– .…”

Section: Resultsmentioning

confidence: 99%

Improved Electronic Structure from Spin-State Reconstruction of a Heteronuclear Fe–Co Diatomic Pair to Boost the Fenton-like Reaction

Zhao

Nie³

et al. 2023

Environ. Sci. Technol.

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Dual-atom catalysts (DACs) are promising candidates for various catalytic reactions, including electrocatalysis, chemical synthesis, and environmental remediation. However, the high-activity origin and mechanism underlying intrinsic activity enhancement remain elusive, especially for the Fenton-like reaction. Herein, we systematically compared the catalytic performance of dual-atom FeCo–N/C with its single-atom counterparts by activating peroxymonosulfate (PMS) for pollutant abatement. The unusual spin-state reconstruction on FeCo–N/C is demonstrated to effectively improve the electronic structure of Fe and Co in the d orbital and enhance the PMS activation efficiency. Accordingly, the dual-atom FeCo–N/C with an intermediate-spin state remarkably boosts the Fenton-like reaction by almost 1 order of magnitude compared with low-spin Co–N/C and high-spin Fe–N/C. Moreover, the established dual-atom-activated PMS system also exhibits excellent stability and robust resistance against harsh conditions. Combined theoretical calculations reveal that unlike unitary Co atom or Fe atom transferring electrons to the PMS molecule, the Fe atom of FeCo–N/C provides extra electrons to the neighboring Co atom and positively shifts the d band of the Co center, thereby optimizing the PMS adsorption and decomposition into a unique high-valent FeIV–O–CoIV species via a low-energy barrier pathway. This work advances a conceptually novel mechanistic understanding of the enhanced catalytic activity of DACs in Fenton-like reactions and helps to expand the application of DACs in various catalytic reactions.

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“…79 TC is the most widely used broad-spectrum antibiotic, which has been considered an emerging environmental concern due to its significant mutagenicity and toxicity. 80,81 In addition, the generated much more toxic intermediates during the TC degradation process is a long-debated issue, thus greatly hampering the broad application of the existing TC degradation technology. 81 Hence, the developmental toxicity and mutagenicity of TC and its degradation products were further assessed by the Toxicity Estimation Software Tool (T.E.S.T.)…”

Section: •−mentioning

confidence: 99%

Metal-Free Activation of Sulfite by Benzoquinone-Derived Carbon for Efficient Organic Contaminant Degradation: Identification and Regulation of Active Sites

et al. 2023

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Sulfite [S(IV)]-based advanced oxidation processes (AOPs) driven by carbon materials provide an environmentally friendly, economical route for environmental remediation. However, the active sites and involved radical mechanisms are still controversial due to the complexity of the carbon structure, thus greatly hampering the development of highly efficient systems. Herein, a benzoquinone-derived carbon (BQC)/S(IV) system was developed for organic pollutant degradation in an acidic medium for the first time. The quinone groups and conductivity were confirmed as the key factors for S(IV) activation through cyclic voltammetry, antitheses, specific site masking, and quantitative structure−activity relationship methods. Benefiting from the high content of quinone groups and excellent conductivity, the BQC catalyst exhibited much more effective in activating Na 2 SO 3 for organic pollutant degradation compared to most traditional carbon or even metal catalysts. The chronopotentiometry and in situ Raman results revealed that the formation of C−S(IV)* complexes was the primary step to produce SO 3•− , followed by the production of SO 4•− via a chain reaction, in which the SO 4•− radical was responsible for pollutant degradation. The findings may provide novel insights into reaction mechanisms in S(IV)-AOP systems and pave the way toward highly efficient carbon catalysts to activate S(IV) for the elimination of organic contaminants.

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Nitrogen Vacancy-Modulated Peroxymonosulfate Nonradical Activation for Organic Contaminant Removal via High-Valent Cobalt-Oxo Species

Cited by 153 publications

References 50 publications

Enhanced Permanganate Activation under UVA-LED Irradiation: Unraveled Mechanism Involving Manganese Species and Hydroxyl Radical

Enhanced Permanganate Activation under UVA-LED Irradiation: Unraveled Mechanism Involving Manganese Species and Hydroxyl Radical

Improved Electronic Structure from Spin-State Reconstruction of a Heteronuclear Fe–Co Diatomic Pair to Boost the Fenton-like Reaction

Metal-Free Activation of Sulfite by Benzoquinone-Derived Carbon for Efficient Organic Contaminant Degradation: Identification and Regulation of Active Sites

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