Carbon Nitride Supported High‐Loading Fe Single‐Atom Catalyst for Activation of Peroxymonosulfate to Generate ¹O₂ with 100 % Selectivity

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(40), С. 21751 - 21755

Опубликована: Авг. 4, 2021

Abstract Singlet oxygen ( 1 O 2 ) is an excellent active species for the selective degradation of organic pollutions. However, it difficult to achieve high efficiency and selectivity generation . In this work, we develop a graphitic carbon nitride supported Fe single‐atoms catalyst (Fe /CN) containing highly uniform Fe‐N 4 sites with loading 11.2 wt %. The /CN achieves 100 % by activating peroxymonosulfate (PMS), which shows ultrahigh p‐chlorophenol efficiency. Density functional theory calculations results demonstrate that in contrast Co Ni single‐atom sites, adsorb terminal PMS, can facilitate oxidization PMS form SO 5 .− , thereafter efficiently generate selectivity. addition, exhibits strong resistance inorganic ions, natural matter, pH value during pollutants presence PMS. This work develops novel production efficient pollutants.

Язык: Английский

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

Environmental Science & Technology, Год журнала: 2021, Номер 56(1), С. 78 - 97

Опубликована: Дек. 21, 2021

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

Язык: Английский

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A critical review on graphitic carbon nitride (g-C3N4)-based materials: Preparation, modification and environmental application

Coordination Chemistry Reviews, Год журнала: 2021, Номер 453, С. 214338 - 214338

Опубликована: Дек. 4, 2021

Язык: Английский

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Unveiling the Origins of Selective Oxidation in Single-Atom Catalysis via Co–N₄–C Intensified Radical and Nonradical Pathways

Environmental Science & Technology, Год журнала: 2022, Номер 56(16), С. 11635 - 11645

Опубликована: Июль 11, 2022

Single-atom catalysts (SACs)-based peroxymonosulfate (PMS) systems are highly selective to the type of organic pollutants while mechanisms remain ambiguous. In this work, we carried out experimental and theoretical investigations reveal origins selectivity radical nonradical pathways in a designated Co–N4–C/PMS system. Two typical [bisphenol A (BPA) metronidazole (MNZ)] with different molecular structures were employed for comparison. We found that oxidation (SO4•– HO•) electron-transfer pathway (ETP) co-existed Pollutants (e.g., MNZ) high redox potential degraded primarily by free radicals rather than ETP, oxidization low-redox BPA) was dominated ETP at surface region Co–N4–C which overwhelmed contributions homogeneous phase. Intriguingly, could be manipulated PMS loading, simultaneously increased population elevated Co–N4–C-PMS* complexes ETP. Findings from work will unravel mysterious behavior SACs/PMS micropollutants.

Язык: Английский

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Spin-State-Dependent Peroxymonosulfate Activation of Single-Atom M–N Moieties via a Radical-Free Pathway

ACS Catalysis, Год журнала: 2021, Номер 11(15), С. 9569 - 9577

Опубликована: Июль 16, 2021

Transition metal catalysts are known to activate persulfate, but the properties that govern intrinsic activity of these still unknown. Here, we developed a series with transition metals anchored on carbon nanotubes (denoted M–N–CNTs, where M = Co, Fe, Mn, or Ni) containing single-atom M–N moieties, peroxymonosulfate for efficient nonradical oxidation sulfamethoxazole. The spin state M–N–CNTs strongly determined their catalytic activity. A large effective magnetic moment high (e.g., Co–N) favored overlap d orbitals oxygen-containing adsorbates (such as peroxo species) active sites and promoted electron transfer, which facilitated adsorption enhanced capacity reactive species. These findings advance mechanistic understanding metal-mediated persulfate activation inform development spintronic environmental applications.

Язык: Английский

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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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Toward Selective Oxidation of Contaminants in Aqueous Systems

Environmental Science & Technology, Год журнала: 2021, Номер 55(21), С. 14494 - 14514

Опубликована: Окт. 20, 2021

The presence of diverse pollutants in water has been threating human health and aquatic ecosystems on a global scale. For more than century, chemical oxidation using strongly oxidizing species was one the most effective technologies to destruct ensure safe clean supply. However, removal increasing amount with higher structural complexity, especially emerging micropollutants trace concentrations complicated matrix, requires excessive dosage oxidant and/or energy input, resulting low cost-effectiveness possible secondary pollution. Consequently, it is practical significance but scientifically challenging achieve selective interest for decontamination. Currently, there are variety examples concerning aqueous systems. systematic understanding relationship between origin selectivity its applicable treatment scenarios, as well rational design catalyst catalytic oxidation, still lacking. In this critical review, we summarize state-of-the-art strategies decontamination probe origins selectivity, that is, from reactivity either oxidants or target pollutants, arising accessibility via adsorption size exclusion, due interfacial electron transfer process enzymatic oxidation. Finally, challenges perspectives briefly outlined stimulate future discussion decontamination, particularly toward application real scenarios.

Язык: Английский

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Rational Regulation of Co–N–C Coordination for High-Efficiency Generation of ¹O₂ toward Nearly 100% Selective Degradation of Organic Pollutants

Environmental Science & Technology, Год журнала: 2022, Номер 56(12), С. 8833 - 8843

Опубликована: Май 26, 2022

Single oxygen-based advanced oxidation processes (1O2-AOPs) exhibit great prospects in selective degradation of organic pollutants. However, efficient production 1O2 via tailored design catalysts to achieve contaminants remains challenging. Herein, we develop a simple strategy regulate the components and coordination Co–N–C at atomic level by adjusting Zn/Co ratio bimetallic zeolitic imidazolate frameworks (ZnxCo1-ZIFs). Zn4Co1–C demonstrates 98% removal phenol mixed phenol/benzoic acid (phenol/BA) solutions. Density functional theory calculations experiments reveal that more active CoN4 sites are generated Zn4Co1–C, which beneficial peroxymonosulfate activation generate 1O2. Furthermore, correlation between origin selectivity well-defined is systematically investigated electron paramagnetic resonance test quenching experiments. This work may provide novel insights into target pollutants complicated water matrix.

Язык: Английский

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Novel Nonradical Oxidation of Sulfonamide Antibiotics with Co(II)-Doped g-C₃N₄-Activated Peracetic Acid: Role of High-Valent Cobalt–Oxo Species

Environmental Science & Technology, Год журнала: 2021, Номер 55(18), С. 12640 - 12651

Опубликована: Авг. 31, 2021

Herein, we report that Co(II)-doped g-C3N4 can efficiently trigger peracetic acid (PAA) oxidation of various sulfonamides (SAs) in a wide pH range. Quite different from the traditional radical-generating or typical nonradical-involved (i.e., singlet oxygenation and mediated electron transfer) catalytic systems, PAA activation follows novel nonradical pathway with unprecedented high-valent cobalt–oxo species [Co(IV)] as dominant reactive species. Our experiments density functional theory calculations indicate Co atom fixated into nitrogen pots serves main active site, enabling dissociation adsorbed conversion coordinated Co(II) to Co(IV) via unique two-electron transfer mechanism. Considering be highly electrophilic nature, substituents five-membered six-membered heterocyclic moieties) on SAs could affect their nucleophilicity, thus leading differences degradation efficiency transformation pathway. Also, benefiting selective Co(IV), established oxidative system exhibits excellent anti-interference capacity achieves satisfactory decontamination performance under actual water conditions. This study provides new approach degrade by activating heterogeneous cobalt-complexed 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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