Were Persulfate-Based Advanced Oxidation Processes Really Understood? Basic Concepts, Cognitive Biases, and Experimental Details

Environmental Science & Technology, Год журнала: 2024, Номер 58(24), С. 10415 - 10444

Опубликована: Июнь 7, 2024

Persulfate (PS)-based advanced oxidation processes (AOPs) for pollutant removal have attracted extensive interest, but some controversies about the identification of reactive species were usually observed. This critical review aims to comprehensively introduce basic concepts and rectify cognitive biases appeals pay more attention experimental details in PS-AOPs, so as accurately explore reaction mechanisms. The scientifically summarizes character, generation, different species. It then highlights complexities analysis electron paramagnetic resonance, uncertainties use probes scavengers, necessities determination scavenger concentration. importance choice buffer solution, operating mode, terminator, filter membrane is also emphasized. Finally, we discuss current challenges future perspectives alleviate misinterpretations toward mechanisms PS-AOPs.

Язык: Английский

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Rational modulation of Fe single-atom electronic structure in a Fe-N2B4 configuration for preferential 1O2 generation in Fenton-like reactions

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 344, С. 123643 - 123643

Опубликована: Дек. 21, 2023

Язык: Английский

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Tuning electronic structure of metal-free dual-site catalyst enables exclusive singlet oxygen production and in-situ utilization

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июль 9, 2024

Abstract Developing eco-friendly catalysts for effective water purification with minimal oxidant use is imperative. Herein, we present a metal-free and nitrogen/fluorine dual-site catalyst, enhancing the selectivity utilization of singlet oxygen ( 1 O 2 ) decontamination. Advanced theoretical simulations reveal that synergistic fluorine-nitrogen interactions modulate electron distribution polarization, creating asymmetric surface configurations electron-deficient nitrogen vacancies. These properties trigger selective generation from peroxymonosulfate (PMS) improve neighboring reactive species, facilitated by contaminant enrichment at fluorine-carbon Lewis-acid adsorption sites. Utilizing these insights, synthesize catalyst through montmorillonite (MMT)-assisted pyrolysis (NFC/M). This method leverages role MMT as an in-situ layer-stacked template, enabling controlled decomposition carbon, nitrogen, fluorine precursors resulting in enhanced structural adaptability, site accessibility, mass-transfer capacity. The NFC/M demonstrates impressive 290.5-fold increase phenol degradation efficiency than single-site analogs, outperforming most metal-based catalysts. work not only underscores potential precise electronic manipulations design but also advances development efficient sustainable solutions purification.

Язык: Английский

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Spin‐state Conversion by Asymmetrical Orbital Hybridization in Ni‐doped Co₃O₄ to Boost Singlet Oxygen Generation for Microbial Disinfection

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(12)

Опубликована: Янв. 25, 2024

Singlet oxygen (1 O2 ) plays a significant role in environmental and biomedical disinfection fields. Electrocatalytic processes hold great potential for 1 generation, but remain challenging. Herein, facile Ni doping converted spin-state transition approach is reported boosting production. Magnetic analysis theoretical calculations reveal that occupied at the octahedral site of Co3 O4 can effectively induce low-to-high transition. The high-spin Ni-Co3 generate appropriate binding strength enhance electron transfer between Co centers with intermediates, thereby improving catalytic activity effective generating . In neutral conditions, 1×106 CFU mL-1 Gram-negative ESBL-producing Escherichia coli (E. coli) could be inactivated by system within 5 min. Further antibacterial mechanisms indicate lead to cell membrane damage DNA degradation so as irreversible death. Additionally, developed inactivate bacteria from wastewater bioaerosols. This work provides an strategy designing electrocatalysis boost generation process.

Язык: Английский

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MOF/MXene Composites: Synthesis, Application and Future Perspectives

Advanced Sustainable Systems, Год журнала: 2024, Номер 8(8)

Опубликована: Март 19, 2024

Abstract 2D MXenes family creates an interest in environmental cleaning and energy conversion. It shows large surface functional groups, electronic transmission, electrical conductivity. This research focuses on Metal Organic Framework‐based Ti 3 C 2 heterojunctions, directing morphology control, customizable structure, high performance ‐based electrocatalytic devices, storage as a supercapacitor. In addition, future development obstacles viable possibilities are presented. MXene detailed analysis reveals fundamental study, structure‐activity connections, potential paths for applications. Specially developed MOF/MXene nanoarchitectures with remarkable features highlighted several study fields, including the chemical sciences, engineering, physics, catalysis, nanotechnology. They represent new class of cutting‐edge developing materials. Mainly, presented review describes multiple synthesis approaches by adjusting conditions varying morphologies, intriguing properties can also be electrochemical conversion storage.

Язык: Английский

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Tris(triazolo)triazine‐Based Covalent Organic Frameworks for Efficiently Photocatalytic Hydrogen Peroxide Production

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(45)

Опубликована: Июль 1, 2024

Abstract Two‐dimensional covalent organic frameworks (2D‐COFs) have recently emerged as fascinating scaffolds for solar‐to‐chemical energy conversion because of their customizable structures and functionalities. Herein, two tris(triazolo)triazine‐based COF materials (namely COF‐JLU51 COF‐JLU52) featuring large surface area, high crystallinity, excellent stability photoelectric properties were designed constructed the first time. Remarkably, gave an outstanding H 2 O production rate over 4200 μmol g −1 h with reusability in pure water under one standard sun light, that higher than its isomorphic COF‐JLU52 most reported metal‐free materials, owing to superior generation, separation transport photogenerated carriers. Experimental theoretical researches prove photocatalytic process undergoes a combination indirect 2e − reduction reaction (ORR) 4e oxidation (WOR). Specifically, ultrahigh yield 7624.7 apparent quantum 18.2 % was achieved 1 : ratio benzyl alcohol system. This finding contributes novel, nitrogen‐rich high‐quality also designate bright future solar transformations.

Язык: 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, Год журнала: 2024, Номер 121(23)

Опубликована: Май 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

Язык: Английский

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Atomically dispersed Fe-N5 sites with optimized electronic structure for sustainable wastewater purification via efficient Fenton-like catalysis

Applied Catalysis B Environment and Energy, Год журнала: 2024, Номер 358, С. 124385 - 124385

Опубликована: Июль 9, 2024

Язык: Английский

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Breaking through the oxygen hindrance effect in Fenton-like reactions to promote the generation of high-valent iron-oxo species within Fe-NxB/GCN single-atom catalysts

Applied Catalysis B Environment and Energy, Год журнала: 2025, Номер unknown, С. 125280 - 125280

Опубликована: Март 1, 2025

Язык: Английский

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Deciphering the Origin of Higher Shell Coordination on Single Iron Catalysts for Resilient Modulating Persulfate Oxidation Into Singlet Oxygen Pathway

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Янв. 28, 2025

Abstract Precise manipulation of coordination structure single‐atom sites and establishment schematic microenvironment‐oxidation pathway relations remain significant challenges in Fenton‐like chemistry. Herein, incorporating sulfur heteroatoms into the higher shell FeN 4 (Fe‐NSC) exhibited a volcano trend p ‐hydroxybenzoic acid oxidation, aligning with number positions dopant. Specifically, S moderate electronegativity larger atomic radii triggers long‐range electronic interactions, which provoke Fe 3d orbital splitting spin electron rearrangement, resulting crossover states d xy 2 yz 1 xz z 21 . As result, partial filling e g t orbitals σ/π antibonding between 2p optimized adsorption–desorption behaviors key oxygenated intermediates from peroxymonosulfate activation. Thus, optimal binding configuration weakens Fe─O bonding accelerates PMS dissociation to yield C‐S‐N Fe‐O*, subsequently couples form O nearly 100% selectivity. The Fe‐NSC‐functionalized membrane outstanding long‐term reusability continuous flow reactor further validated practical application perspective. This study provides insight at both levels for rational design spin‐polarized catalysts its functions fine‐tuning oxidation pathways environmental catalysis.

Язык: Английский

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