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

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 468, P. 143778 - 143778

Published: May 29, 2023

Language: Английский

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Facilely Tuning the First-Shell Coordination Microenvironment in Iron Single-Atom for Fenton-like Chemistry toward Highly Efficient Wastewater Purification

Environmental Science & Technology, Journal Year: 2023, Volume and Issue: 57(37), P. 14046 - 14057

Published: Sept. 2, 2023

Precisely identifying the atomic structures in single-atom sites and establishing authentic structure-activity relationships for catalyst (SAC) coordination are significant challenges. Here, theoretical calculations first predicted underlying catalytic activity of Fe-NxC4-x with diverse first-shell environments. Substituting N C to coordinate central Fe atom induces an inferior Fenton-like efficiency. Then, Fe-SACs carrying three configurations (Fe-N2C2, Fe-N3C1, Fe-N4) fabricate facilely demonstrate that optimized environments significantly promote activity. Specifically, reaction rate constant increases from 0.064 0.318 min-1 as number Fe-N 2 4, slightly influencing nonradical mechanism dominated by 1O2. In-depth unveil modulated Fe-N2C2 Fe-N4 optimize d-band electronic regulate binding strength peroxymonosulfate on sites, resulting a reduced energy barrier enhanced The stability actual hospital sewage treatment capacity also showed strong dependency. This strategy local engineering offers vivid example modulating SACs well-regulated environments, ultimately maximizing their

Language: Английский

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Singlet oxygen in the removal of organic pollutants: An updated review on the degradation pathways based on mass spectrometry and DFT calculations

Chemosphere, Journal Year: 2023, Volume and Issue: 345, P. 140203 - 140203

Published: Sept. 19, 2023

Language: Английский

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Strategies and applications of electrocatalytic nitrate reduction towards ammonia

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 506, P. 215723 - 215723

Published: Feb. 26, 2024

Language: Английский

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Size‐Dependent Catalysis in Fenton‐like Chemistry: From Nanoparticles to Single Atoms

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(28)

Published: April 24, 2024

Abstract State‐of‐the‐art Fenton‐like reactions are crucial in advanced oxidation processes (AOPs) for water purification. This review explores the latest advancements heterogeneous metal‐based catalysts within AOPs, covering nanoparticles (NPs), single‐atom (SACs), and ultra‐small atom clusters. A distinct connection between physical properties of these catalysts, such as size, degree unsaturation, electronic structure, state, their impacts on catalytic behavior efficacy reactions. In‐depth comparative analysis metal NPs SACs is conducted focusing how particle size variations metal‐support interactions affect species pathways. The highlights cutting‐edge characterization techniques theoretical calculations, indispensable deciphering complex structural characteristics active sites downsized particles. Additionally, underscores innovative strategies immobilizing onto membrane surfaces, offering a solution to inherent challenges powdered catalysts. Recent advances pilot‐scale or engineering applications Fenton‐like‐based devices also summarized first time. paper concludes by charting new research directions, emphasizing catalyst design, precise identification reactive oxygen species, in‐depth mechanistic studies. These efforts aim enhance application potential nanotechnology‐based AOPs real‐world wastewater treatment.

Language: Английский

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The structure-performance relationships in active center size-dependent Fenton-like catalysis: From nanoparticles to single atoms

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 355, P. 124157 - 124157

Published: May 9, 2024

Language: Английский

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Synergetic Manipulation Mechanism of Single-Atom M–N₄ and M–OH (M = Mn, Fe, Co, Ni) Sites for Ozone Activation: Theoretical Prediction and Experimental Verification

Environmental Science & Technology, Journal Year: 2024, Volume and Issue: 58(21), P. 9393 - 9403

Published: May 15, 2024

Carbon-based single-atom catalysts (SACs) have been gradually introduced in heterogeneous catalytic ozonation (HCO), but the interface mechanism of O3 activation on catalyst surface is still ambiguous, especially effect a hydroxyl group (M–OH) at metal sites. Herein, we combined theoretical calculations with experimental verifications to comprehensively investigate mechanisms series conventional SAC structures N-doped nanocarbon substrates (MN4–NCs, where M = Mn, Fe, Co, Ni). The synergetic manipulation atom and M–OH pathways was paid particular attention. tends directly interact MnN4–NC, FeN4–NC, NiN4–NC catalysts, among which MnN4–NC has best activity for its relatively lower energy barrier (0.62 eV) more active surface-adsorbed oxygen species (Oads). On CoN4–NC catalyst, direct interaction site energetically infeasible, can be activated generate Oads or HO2 from indirect participation results showed that 90.7 82.3% total organic carbon (TOC) removed within 40 min during p-hydroxybenzoic acid respectively. Phosphate quenching, characterization, EPR measurement further supported prediction. This contribution provides fundamental insights into SACs, methods ideals could helpful future studies environmental catalysis.

Language: Английский

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The “4 + 1” strategy fabrication of iron single-atom catalysts with selective high-valent iron-oxo species generation

Proceedings of the National Academy of Sciences, Journal Year: 2024, Volume and Issue: 121(23)

Published: May 30, 2024

Single-atom catalysts (SACs) with atomic dispersion active sites have exhibited huge potentials in peroxymonosulfate (PMS)-based Fenton-like chemistry water purification. However, four-N coordination metal (MN 4 ) moieties often suffer from such problems as low selectivity and narrow workable pH. How to construct SACs a controllable strategy optimized electronic structures is of great challenge. Herein, an innovative (i.e., the “4 + 1” fabrication) was devised precisely modulate first-shell coordinated microenvironment FeN SAC using additional N (SA-FeN 5 ). This leads almost 100% selective formation high-valent iron-oxo [Fe(IV)═O] (steady-state concentration: 2.00 × 10 −8 M) SA-FeN /PMS system. In-depth theoretical calculations unveil that configuration optimizes electron distribution monatomic Fe sites, which thus fosters PMS adsorption reduces energy barrier for Fe(IV)═O generation. then attached polyvinylidene difluoride membrane continuous flow device, showing long-term abatement microcontaminant. work furnishes general effective activation metal-oxo species generation by high N-coordination number regulation SACs, would provide guidance rational design superior environmental

Language: Английский

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Iron Single-Atom Catalyst Actuates PMS/O₃ Activation Process: Nonradical Generation Path for Synergistic Multiperoxides

ACS Applied Engineering Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 13, 2025

Singlet oxygen (1O2) is an excellent reactive species in advanced oxidation processes for water purification due to its environmental suitability and selectivity. However, generation conversion mechanisms remain unclear. Herein, we have constructed a high-yield system 1O2 by introducing ozone (O3) into iron single-atom catalyst/peroxymonosulfate (PMS) system. The steady-state concentration of the was increased 53.2% at O3 below 0.5 mg/L. formation from high-valent iron-oxo (FeIV═O) revealed electron paramagnetic resonance analysis, where FeIV═O found probe experiment via activation PMS on sites. developed situ singlet fluorescence imaging technique observed that addition has promoted process 1O2. Density functional theory calculations further demonstrated low energy barrier key intermediate OO* this process. These findings help understand mechanism production molecular level guide design efficient reaction systems purification.

Language: Английский

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Single‐Atom Catalysts Originated from Metal–Organic Frameworks for Sulfate Radical‐Based Advanced Oxidation Processes: Critical Insights into Mechanisms

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(6)

Published: Oct. 22, 2023

Abstract The widely discussed single‐atom catalysts (SACs) are regarded as a kind of attractive material for sulfate radical‐based advanced oxidation processes (SR‐AOPs) owing to their maximum atomic utilization efficiency and outstanding stability. Currently, metal–organic frameworks (MOFs) have appeared prospective precursors building SACs due extensive chelating sites, functional adjustability, structural tunability. However, there few critical systematic reviews about the application MOF‐derived in SR‐AOPs, especially in‐depth analysis mechanisms. Therefore, this review seeks offer thorough summary development SR‐AOPs. First, unique advantages MOFs derivative thoroughly. Afterward, current synthesis strategies elaborated categorically unveil formation process single atoms coordination environments. Notably, roles different reaction sites including generation reactive species mediating electron transfer further analyzed explain mechanisms comprehensively. Thereafter, characterization techniques theoretical calculations studies also highlighted. Eventually, insights into present challenges future developments proposed, which expected enhance catalytic

Language: Английский

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