Rational design of efficient metal-free catalysts for peroxymonosulfate activation: Selective degradation of organic contaminants via a dual nonradical reaction pathway

Qin, Jiaxing; Dai, Lei; Shi, Penghui; Fan, Jinchen; Xu, Qing

doi:10.1016/j.jhazmat.2020.122808

Cited by 66 publications

(14 citation statements)

References 47 publications

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“…The semicircle in the high-frequency range in the Nyquist diagram corresponds to its electron-transfer resistance: the smaller radius of semicircle, the smaller the electrochemical impedance of the catalysts (Figure d) . The sp 2 -hybridized carbons are more favorable for electron transfer than sp 3 -hybridized carbons. , Incorporating N dopants into a carbocatalyst could improve kinetics of interfacial reactions due to lower impedance in charge-migration processes. ,, Tafel slope is an important parameter to evaluate electrochemical kinetics of catalysts and to determine the corresponding rate-limiting step. Specifically, the catalyst with a larger Tafel slope would obtain a smaller current density at the same increment of overpotential, and it is controlled by the electron exchange step.…”

Section: Characterization Techniquesmentioning

confidence: 99%

“…164,165 Incorporating N dopants into a carbocatalyst could improve kinetics of interfacial reactions due to lower impedance in charge-migration processes. 32,166,167 Tafel slope is an important parameter to evaluate electrochemical kinetics of catalysts and to determine the corresponding rate-limiting step. Specifically, the catalyst with a larger Tafel slope would obtain a smaller current density at the same increment of overpotential, and it is controlled by the electron exchange step.…”

Section: •−mentioning

confidence: 99%

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Origins of Electron-Transfer Regime in Persulfate-Based Nonradical Oxidation Processes

Ren

Cheng

Shao

et al. 2021

Environ. Sci. Technol.

689

224

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Persulfate-based nonradical oxidation processes (PS-NOPs) are appealing in wastewater purification due to their high efficiency and selectivity for removing trace organic contaminants in complicated water matrices. In this review, we showcased the recent progresses of state-of-the-art strategies in the nonradical electron-transfer regimes in PS-NOPs, including design of metal and metal-free heterogeneous catalysts, in situ/operando characterization/analytical techniques, and insights into the origins of electron-transfer mechanisms. In a typical electron-transfer process (ETP), persulfate is activated by a catalyst to form surface activated complexes, which directly or indirectly interact with target pollutants to finalize the oxidation. We discussed different analytical techniques on the fundamentals and tactics for accurate analysis of ETP. Moreover, we demonstrated the challenges and proposed future research strategies for ETP-based systems, such as computation-enabled molecular-level investigations, rational design of catalysts, and real-scenario applications in the complicated water environment. Overall, this review dedicates to sharpening the understanding of ETP in PS-NOPs and presenting promising applications in remediation technology and green chemistry.

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Section: Characterization Techniquesmentioning

confidence: 99%

Section: •−mentioning

confidence: 99%

Origins of Electron-Transfer Regime in Persulfate-Based Nonradical Oxidation Processes

Ren

Cheng

Shao

et al. 2021

Environ. Sci. Technol.

689

224

View full text Add to dashboard Cite

show abstract

“…The above results confirm the ultrahigh catalytic activity of CuO for heterogeneous PMS activation (Figure c, details in Table S2 and Figure S2). ,,,− In addition to PMS, CuO can also activate PDS and H 2 O 2 to remove 4-CP, but the degradation efficiency was lower than those of PMS (41 and 7% in 20 min, respectively; Figure S3). Apparently, the symmetric structure of PDS makes it more stable and exerts higher steric hindrance than PMS, while the higher bond energy of O–O in H 2 O 2 hinders its cleavage .…”

Section: Resultsmentioning

confidence: 99%

Ultrahigh Peroxymonosulfate Utilization Efficiency over CuO Nanosheets via Heterogeneous Cu(III) Formation and Preferential Electron Transfer during Degradation of Phenols

Wei

Miao

et al. 2022

Environ. Sci. Technol.

175

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In persulfate activation by copper-based catalysts, high-valent copper (Cu(III)) is an overlooked reactive intermediate that contributes to efficient persulfate utilization and organic pollutant removal. However, the mechanisms underlying heterogeneous activation and enhanced persulfate utilization are not fully understood. Here, copper oxide (CuO) nanosheets (synthesized with a facile precipitation method) exhibited high catalytic activity for peroxymonosulfate (PMS) activation with 100% 4-chlorophenol (4-CP) degradation within 3 min. Evidence for the critical role of surface-associated Cu(III) on PMS activation and 4-CP degradation over a wide pH range (pH 3–10) was obtained using in situ Raman spectroscopy, electron paramagnetic resonance, and quenching tests. Cu(III) directly oxidized 4-CP and other phenolic pollutants, with rate constants inversely proportional to their ionization potentials. Cu(III) preferentially oxidizes 4-CP rather than react with two PMS molecules to generate one molecule of 1O2, thus minimizing this less efficient PMS utilization pathway. Accordingly, a much higher PMS utilization efficiency (77% of electrons accepted by PMS ascribed to 4-CP mineralization) was obtained with CuO/PMS than with a radical pathway-dominated Co3O4/PMS system (27%) or with the 1O2 pathway-dominated α-MnO2/PMS system (26%). Overall, these results highlight the potential benefits of PMS activation via heterogeneous high-valent copper oxidation and offer mechanistic insight into ultrahigh PMS utilization efficiency for organic pollutant removal.

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“…1 O 2 is a mild and selective oxidizing species, which exhibits high reactivity toward electron-rich compounds ( Qin et al., 2020 ). Therefore, the contribution of 1 O 2 to pollutant degradation was investigated using FFA as the scavenger.…”

Section: Resultsmentioning

confidence: 99%

Insights into singlet oxygen generation and electron-transfer process induced by a single-atom Cu catalyst with saturated Cu-N4 sites

Zhang

et al. 2022

iScience

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Rational design of efficient metal-free catalysts for peroxymonosulfate activation: Selective degradation of organic contaminants via a dual nonradical reaction pathway

Cited by 66 publications

References 47 publications

Origins of Electron-Transfer Regime in Persulfate-Based Nonradical Oxidation Processes

Origins of Electron-Transfer Regime in Persulfate-Based Nonradical Oxidation Processes

Ultrahigh Peroxymonosulfate Utilization Efficiency over CuO Nanosheets via Heterogeneous Cu(III) Formation and Preferential Electron Transfer during Degradation of Phenols

Insights into singlet oxygen generation and electron-transfer process induced by a single-atom Cu catalyst with saturated Cu-N4 sites

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