Singlet oxygen in biochar-based catalysts-activated persulfate process: From generation to detection and selectivity removing emerging contaminants

Chemical Engineering Journal, Год журнала: 2024, Номер 485, С. 149724 - 149724

Опубликована: Фев. 16, 2024

Язык: Английский

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Nanoconfinement steers nonradical pathway transition in single atom fenton-like catalysis for improving oxidant utilization

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

Опубликована: Июнь 22, 2024

Abstract The introduction of single-atom catalysts (SACs) into Fenton-like oxidation promises ultrafast water pollutant elimination, but the limited access to pollutants and oxidant by surface catalytic sites intensive consumption still severely restrict decontamination performance. While nanoconfinement SACs allows drastically enhanced reaction kinetics, detailed regulatory mechanisms remain elusive. Here, we unveil that, apart from local enrichment reactants, pathway shift is also an important cause for reactivity enhancement nanoconfined SACs. electronic structure cobalt site altered confining it within nanopores mesostructured silica particles, which triggers a fundamental transition singlet oxygen electron transfer 4-chlorophenol oxidation. changed accelerated interfacial mass render system up 34.7-fold higher degradation rate raised peroxymonosulfate utilization efficiency (from 61.8% 96.6%) relative unconfined control. It demonstrates superior other electron-rich phenolic compounds, good environment robustness, high stability treating real lake water. Our findings deepen knowledge catalysis may inspire innovations in low-carbon purification technologies heterogeneous applications.

Язык: Английский

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Multi-channel electron transfer induced by polyvanadate in metal-organic framework for boosted peroxymonosulfate activation

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

Опубликована: Авг. 22, 2024

Catalytic peroxymonosulfate (PMS) activation processes don't solely rely on electron transfer from dominant metal centers due to the complicated composition and interface environment of catalysts. Herein synthesis a cobalt based metal-organic framework containing polyvanadate [V4O12]4− cluster, Co2(V4O12)(bpy)2 (bpy = 4,4'-bipyridine), is presented. The catalyst demonstrates superior degradation activity toward various micropollutants, with higher highest occupied molecular orbital (HOMO), via nonradical attack. X-ray absorption spectroscopy density functional theory (DFT) calculations demonstrate that Co sites act as both PMS trapper donor. In situ spectral characterizations DFT reveal terminal oxygen atoms in sponge could interact hydrogen form bonds, promoting generation SO5* intermediate dynamic pull direct process. Further, exhibits long-term water purification ability, up 40 h, towards actual wastewater discharged an ofloxacin production factory. This work not only presents efficient for environmental remediation pathway, but also provides fundamental insights into Fenton-like reaction mechanism. Peroxymonosulfate might centers. Here, authors found formation bond between [V4O12] 4− provided extra channel achieving activation.

Язык: Английский

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Oxidative polymerization versus degradation of organic pollutants in heterogeneous catalytic persulfate chemistry

Water Research, Год журнала: 2024, Номер 255, С. 121485 - 121485

Опубликована: Март 18, 2024

Catalytic polymerization pathways in advanced oxidation processes (AOPs) have recently drawn much attention for organic pollutant elimination owing to the rapid removal kinetics, high selectivity, and recovery of carbon from wastewater. This work presents a review on regimes AOPs their applications wastewater decontamination. The mainly highlights three critical issues reactions induced by persulfate activation (Poly-PS-AOPs), including heterogeneous catalysts, pathways, properties substrates. dominant influencing factors selection reactive oxygen species, substrates are discussed detail. Moreover, we systematically demonstrate merits challenges Poly-PS-AOPs upon degradation polymer synthesis. We particularly highlight that technology could be promising treatment industrial containing heterocyclic organics synthesis polymers polymer-functionalized materials environmental energy applications.

Язык: Английский

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Persistent free radicals on biochar for its catalytic capability: A review

Water Research, Год журнала: 2023, Номер 250, С. 120999 - 120999

Опубликована: Дек. 8, 2023

Язык: Английский

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Discriminating the Active Ru species towards the Selective Generation of Singlet Oxygen from Peroxymonosulfate: Nanoparticles Surpass Single‐Atom Catalysts

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(17)

Опубликована: Фев. 26, 2024

Abstract Singlet oxygen ( 1 O 2 ) is an exceptional reactive species in advanced oxidation processes for environmental remediation. Despite single‐atom catalysts (SACs) representing the promising candidate selective generation of from peroxymonosulfate (PMS), necessity to meticulously regulate coordination environment metal centers poses a significant challenge precisely‐controlled synthetic method. Another dilemma SACs their high surface free energy, which results inherent tendency migration and aggregation atoms. We here first time reported that Ru nanoparticles (NPs) synthesized by facile pyrolysis method behave as robust Fenton‐like catalysts, outperforming SACs, towards efficient activation PMS produce with nearly 100 % selectivity, remarkably improving degradation efficiency target pollutants. Density functional theory calculations have unveiled boosted can be attributed two aspects: (i) enhanced adsorption molecules onto NPs, (ii) decreased energy barriers offering adjacent sites promoted dimerization *O intermediates into adsorbed . This study deepens current understanding chemistry, sheds light on design optimization catalysts.

Язык: Английский

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Advancements in heterogeneous activation of persulfates: Exploring mechanisms, challenges in organic wastewater treatment, and innovative solutions

Chemical Engineering Journal, Год журнала: 2024, Номер 481, С. 148789 - 148789

Опубликована: Янв. 18, 2024

Язык: Английский

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Photothermal-synergistic peroxymonosulfate activation promoting carbamazepine degradation by Porphyra-derived porous biochar composites: Performance, mechanism, transformation pathway and practical application

Chemical Engineering Journal, Год журнала: 2024, Номер 489, С. 151263 - 151263

Опубликована: Апрель 12, 2024

Язык: Английский

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Modulating electronic structure of active sites on iron-based nanoparticles enhances peroxymonosulfate activation

Applied Catalysis B Environment and Energy, Год журнала: 2024, Номер 354, С. 124138 - 124138

Опубликована: Апрель 29, 2024

Язык: Английский

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Sulfur Vacancies in Pyrite Trigger the Path to Nonradical Singlet Oxygen and Spontaneous Sulfamethoxazole Degradation: Unveiling the Hidden Potential in Sediments

Environmental Science & Technology, Год журнала: 2024, Номер 58(15), С. 6753 - 6762

Опубликована: Март 25, 2024

Pharmaceutical residues in sediments are concerning as ubiquitous emerging contaminants. Pyrite is the most abundant sulfide minerals estuarine and coastal sediments, making it a major sink for pharmaceutical pollutants such sulfamethoxazole (SMX). However, research on adsorption redox behaviors of SMX pyrite surface limited. Here, we investigated impact nonphotochemical process fate coexisting SMX. Remarkably, sulfur vacancies (SVs) promoted generation nonradical species (hydrogen peroxide, H2O2 singlet oxygen, 1O2), thereby exhibiting prominent degradation performance under darkness. Nonradical 1O2 contributed approximately 73.1% total degradation. The SVs with high surrounding electron density showed an advanced affinity adsorbing O2 then initiated reactions sediment electron-storing geobattery pyrite, resulting extensive through two-electron oxygen reduction pathway. Surface Fe(III) (hydro)oxides facilitated decomposition to generation. Distinct products were observed all samples concentrations ranging from 1.96 2.94 μM, while ranged 4.63 × 10–15 8.93 M. This dark-redox pathway outperformed traditional photochemical routes pollutant degradation, broadening possibilities use sediments. Our study highlighted SV-triggered yet previously overlooked source species, which offered fresh insights into geochemical processes dynamics regions frequent oscillations sulfur-rich

Язык: Английский

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