Generating dual-active species by triple-atom sites through peroxymonosulfate activation for treating micropollutants in complex water

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(13)

Опубликована: Март 23, 2023

The peroxymonosulfate (PMS)-triggered radical and nonradical active species can synergistically guarantee selectively removing micropollutants in complex wastewater; however, realizing this on heterogeneous metal-based catalysts with single sites remains challenging due to insufficient electron cycle. Herein, we design asymmetric Co-O-Bi triple-atom Co-doped Bi2O2CO3 facilitate PMS oxidation reduction simultaneously by enhancing the transfer between sites. We propose that result an density increase Bi decrease Co sites, thereby undergoes a reaction generate SO4•- •OH at site 1O2 site. suggest synergistic effect of SO4•-, •OH, enables efficient removal mineralization without interference from organic inorganic compounds under environmental background. As result, achieves almost 99.3% sulfamethoxazole degradation 3 min k-value as high 82.95 min-1 M-1, which is superior existing reported so far. This work provides structural regulation approach control catalytic function, will guide rational Fenton-like catalysts.

Язык: Английский

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

Environmental Science & Technology, Год журнала: 2022, Номер 56(12), С. 8984 - 8992

Опубликована: Май 31, 2022

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

Язык: Английский

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Coordination Number Dependent Catalytic Activity of Single‐Atom Cobalt Catalysts for Fenton‐Like Reaction

Advanced Functional Materials, Год журнала: 2022, Номер 32(38)

Опубликована: Июль 7, 2022

Abstract Single‐atom catalysts (SACs) are widely investigated in Fenton‐like reactions for environmental remediation, wherein their catalytic performance can be further improved by coordination structure modulation, but the relevant report is rare. Herein, a series of atomically dispersed cobalt with diverse numbers (denoted as CoN x , represents nitrogen number) synthesized and peroxymonosulfate (PMS) conversion explored. The specific activity found to dependent on number single atomic Co sites, where lowest‐coordinated 2 catalyst exhibits highest PMS activation, followed under‐coordinated 3 normal 4 . Experimental theoretical results reveal that reducing increase electron density atom which governs catalysts. Specifically, entire Co–pyridinic NC motif serves active centers conversion, atom, pyridinic N‐bonded C atoms along vacancy neighboring unsaturated N moiety account reduction oxidation toward radical singlet oxygen ( 1 O ) generation, respectively. These findings provide useful avenue regulation SACs applications.

Язык: Английский

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A critical review on correlating active sites, oxidative species and degradation routes with persulfate-based antibiotics oxidation

Water Research, Год журнала: 2023, Номер 235, С. 119926 - 119926

Опубликована: Март 27, 2023

Язык: Английский

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The debatable role of singlet oxygen in persulfate-based advanced oxidation processes

Water Research, Год журнала: 2023, Номер 235, С. 119925 - 119925

Опубликована: Март 28, 2023

Язык: Английский

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Peroxydisulfate activation by sulfur-doped ordered mesoporous carbon: Insight into the intrinsic relationship between defects and 1O2 generation

Water Research, Год журнала: 2022, Номер 221, С. 118797 - 118797

Опубликована: Июнь 30, 2022

Язык: Английский

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The optimized Fenton-like activity of Fe single-atom sites by Fe atomic clusters–mediated electronic configuration modulation

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(15)

Опубликована: Апрель 3, 2023

The performance optimization of isolated atomically dispersed metal active sites is critical but challenging. Here, TiO2@Fe species-N-C catalysts with Fe atomic clusters (ACs) and satellite Fe-N4 were fabricated to initiate peroxymonosulfate (PMS) oxidation reaction. AC-induced charge redistribution single atoms (SAs) was verified, thus strengthening the interaction between SAs PMS. In detail, incorporation ACs optimized HSO5- SO5·- desorption steps, accelerating reaction progress. As a result, Vis/TiFeAS/PMS system rapidly eliminated 90.81% 45 mg/L tetracycline (TC) in 10 min. process characterization suggested that PMS as an electron donor would transfer species TiFeAS, generating 1O2. Subsequently, hVB+ can induce generation electron-deficient species, promoting circulation. This work provides strategy construct multiple atom assembly-enabled composite for high-efficiency PMS-based advanced processes (AOPs).

Язык: Английский

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Review of characteristics, generation pathways and detection methods of singlet oxygen generated in advanced oxidation processes (AOPs)

Chemical Engineering Journal, Год журнала: 2023, Номер 468, С. 143778 - 143778

Опубликована: Май 29, 2023

Язык: Английский

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Citrate-regulated synthesis of hydrotalcite-like compounds as peroxymonosulfate activator - Investigation of oxygen vacancies and degradation pathways by combining DFT

Applied Catalysis B Environment and Energy, Год журнала: 2022, Номер 317, С. 121704 - 121704

Опубликована: Июль 5, 2022

Язык: Английский

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Origin of the Excellent Activity and Selectivity of a Single-Atom Copper Catalyst with Unsaturated Cu-N₂ Sites via Peroxydisulfate Activation: Cu(III) as a Dominant Oxidizing Species

Environmental Science & Technology, Год журнала: 2022, Номер 56(12), С. 8765 - 8775

Опубликована: Май 12, 2022

As an efficient active oxidant for the selective degradation of pollutants in wastewater, high-valent copper species Cu(III) with persulfate activation has attracted substantial attention some Cu-based catalysts. However, systematic study a catalyst structure and mechanism about peroxydisulfate (PDS) is challenging owing to coexistence multiple Cu structural symmetry PDS. Herein, we anchored atom two pyridinic N atoms synthesize single-atom (CuSA-NC). Experimental characterizations theoretical calculations complemented each other well because uniform atomic sites. The was identified as site, unsaturated Cu-N2 configuration more conductive PDS than saturated Cu-N4 configuration. Benefiting from generation Cu(III), CuSA-NC exhibited obvious anti-interference performance pollutant complex matrix. superior catalytic activity compared that reported catalysts good durability continuous-flow experiment further revealed potential practical applications. This work strongly deepens understanding sites under develops approach actual water purification.

Язык: Английский

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