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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A Site Distance Effect Induced by Reactant Molecule Matchup in Single‐Atom Catalysts for Fenton‐Like Reactions

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(33)

Опубликована: Июнь 20, 2022

Abstract Understanding the site interaction nature of single‐atom catalysts (SACs), especially densely populated SACs, is vital for their application to various catalytic reactions. Herein, we report a distance effect, which emphasizes how well adjacent copper atoms (denoted as d Cu1−Cu1 ) matches with reactant peroxydisulfate (PDS) molecular size determine Fenton‐like reaction reactivity on carbon‐supported SACs. The optimized in range 5–6 Å, PDS, endows catalyst nearly two times higher turnover frequency than that beyond this range, accordingly achieving record‐breaking kinetics oxidation emerging organic contaminants. Further studies suggest effect originates from alteration PDS adsorption dual‐site structure Cu 1 −Cu sites when falls within significantly enhancing interfacial charge transfer and consequently resulting most efficient activation so far.

Язык: Английский

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Oxygen doping of cobalt-single-atom coordination enhances peroxymonosulfate activation and high-valent cobalt–oxo species formation

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(16)

Опубликована: Апрель 11, 2023

The high-valent cobalt-oxo species (Co(IV)=O) is being increasingly investigated for water purification because of its high redox potential, long half-life, and antiinterference properties. However, generation Co(IV)=O inefficient unsustainable. Here, a cobalt-single-atom catalyst with N/O dual coordination was synthesized by O-doping engineering. O-doped (Co-OCN) greatly activated peroxymonosulfate (PMS) achieved pollutant degradation kinetic constant 73.12 min-1 g-2, which 4.9 times higher than that Co-CN (catalyst without O-doping) those most reported single-atom catalytic PMS systems. Co-OCN/PMS realized dominant oxidation pollutants increasing the steady-state concentration (1.03 × 10-10 M) 5.9 compared Co-CN/PMS. A competitive kinetics calculation showed contribution to micropollutant 97.5% during process. Density functional theory calculations influenced charge density (increased Bader transfer from 0.68 0.85 e), optimized electron distribution Co center d-band -1.14 -1.06 eV), enhanced adsorption energy -2.46 -3.03 eV, lowered barrier key reaction intermediate (*O*H2O) formation 1.12 0.98 eV. Co-OCN fabricated on carbon felt flow-through device, continuous efficient removal micropollutants (degradation efficiency >85% after 36 h operation). This study provides new protocol activation elimination through heteroatom-doping metal-oxo purification.

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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Singlet oxygen: Properties, generation, detection, and environmental applications

Journal of Hazardous Materials, Год журнала: 2023, Номер 461, С. 132538 - 132538

Опубликована: Сен. 13, 2023

Язык: Английский

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Sulfone‐Modified Covalent Organic Frameworks Enabling Efficient Photocatalytic Hydrogen Peroxide Generation via One‐Step Two‐Electron O₂ Reduction

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(26)

Опубликована: Апрель 25, 2023

Abstract Photocatalytic oxygen reduction reaction (ORR) offers a promising hydrogen peroxide (H 2 O ) synthetic strategy, especially the one‐step two‐electron (2e − ORR route holds great potential in achieving highly efficient and selectivity. However, 2e is rarely harvested underlying mechanism for regulating pathways remains greatly obscure. Here, by loading sulfone units into covalent organic frameworks (FS‐COFs), we present an photocatalyst H generation via from pure water air. Under visible light irradiation, FS‐COFs exert superb yield of 3904.2 μmol h −1 g , outperforming most reported metal‐free catalysts under similar conditions. Experimental theoretical investigation reveals that accelerate separation photoinduced electron‐hole (e ‐h + pairs, enhance protonation COFs, promote adsorption Yeager‐type, which jointly alters process two‐step to one, thereby with high

Язык: Английский

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Single-atom copper embedded in two-dimensional MXene toward peroxymonosulfate activation to generate singlet oxygen with nearly 100% selectivity for enhanced Fenton-like reactions

Applied Catalysis B Environment and Energy, Год журнала: 2022, Номер 324, С. 122245 - 122245

Опубликована: Дек. 1, 2022

Язык: Английский

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Carbon nitride based materials: more than just a support for single-atom catalysis

Chemical Society Reviews, Год журнала: 2023, Номер 52(15), С. 4878 - 4932

Опубликована: Янв. 1, 2023

Recently, the missing link between homogeneous and heterogeneous catalysis has been found it was named single-atom (SAC). However, SAC field still faces important challenges, one of which is controlling bonding/coordination single atoms support in order to compensate for increase surface energy when particle size reduced due atomic dispersion. Excellent candidates meet this requirement are carbon nitride (CN)-based materials. Metal can be firmly trapped nitrogen-rich coordination sites CN materials, makes them a unique class hosts preparing catalysts (SACs). As most promising two-dimensional supports stabilize isolated metal atoms, materials have increasingly employed SACs. Herein, we will cover recent advances single-atoms supported by In review, characterization techniques challenges faced topic discussed, commonly synthetic methods delineated different Finally, catalytic performance SACs based on nitrides reviewed with special focus their photocatalytic applications. particular, prove as non-innocent support. The relationship two-way, where change electronic properties support, while features matrix tune activity reactions. highlight frontiers field, including analytical method development, truly controlled methods, allowing fine control loading multi-element synthesis, how understanding two-way exchange behind push next level.

Язык: Английский

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Recent advances in the applications of encapsulated transition-metal nanoparticles in advanced oxidation processes for degradation of organic pollutants: A critical review

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 342, С. 123401 - 123401

Опубликована: Окт. 18, 2023

Язык: Английский

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Single-Atom MnN₅ Catalytic Sites Enable Efficient Peroxymonosulfate Activation by Forming Highly Reactive Mn(IV)–Oxo Species

Environmental Science & Technology, Год журнала: 2023, Номер 57(10), С. 4266 - 4275

Опубликована: Фев. 27, 2023

Four-nitrogen-coordinated transitional metal (MN4) configurations in single-atom catalysts (SACs) are broadly recognized as the most efficient active sites peroxymonosulfate (PMS)-based advanced oxidation processes. However, SACs with a coordination number higher than four rarely explored, which represents fundamental missed opportunity for chemistry to boost PMS activation and degradation of recalcitrant organic pollutants. We experimentally theoretically demonstrate here that five-nitrogen-coordinated Mn (MnN5) more effectively activate MnN4 sites, by facilitating cleavage O–O bond into high-valent Mn(IV)–oxo species nearly 100% selectivity. The high activity MnN5 was discerned be due formation higher-spin-state N5Mn(IV)═O species, enable two-electron transfer from organics through lower-energy-barrier pathway. Overall, this work demonstrates importance numbers informs design next-generation environmental catalysts.

Язык: Английский

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