CoN₁O₂ Single‐Atom Catalyst for Efficient Peroxymonosulfate Activation and Selective Cobalt(IV)=O Generation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(27)

Опубликована: Апрель 26, 2023

High-valent metal-oxo (HVMO) species are powerful non-radical reactive that enhance advanced oxidation processes (AOPs) due to their long half-lives and high selectivity towards recalcitrant water pollutants with electron-donating groups. However, high-valent cobalt-oxo (CoIV =O) generation is challenging in peroxymonosulfate (PMS)-based AOPs because the 3d-orbital occupancy of cobalt would disfavor its binding a terminal oxygen ligand. Herein, we propose strategy construct isolated Co sites unique N1 O2 coordination on Mn3 O4 surface. The asymmetric configuration able accept electrons from 3d-orbital, resulting significant electronic delocalization at for promoted PMS adsorption, dissociation subsequent CoIV =O species. CoN1 /Mn3 exhibits intrinsic activity activation sulfamethoxazole (SMX) degradation, highly outperforming counterpart CoO3 configuration, carbon-based single-atom catalysts CoN4 commercial oxides. effectively oxidize target contaminants via atom transfer produce low-toxicity intermediates. These findings could advance mechanistic understanding molecular level guide rational design efficient environmental catalysts.

Язык: Английский

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High-efficiency degradation of carbamazepine by the synergistic electro-activation and bimetals (FeCo@NC) catalytic-activation of peroxymonosulfate

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 338, С. 123064 - 123064

Опубликована: Июль 3, 2023

Язык: Английский

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Cu-doped CoOOH activates peroxymonosulfate to generate high-valent cobalt-oxo species to degrade organic pollutants in saline environments

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 340, С. 123224 - 123224

Опубликована: Авг. 25, 2023

Язык: Английский

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Regulating the Local Electronic Structure of Copper Single Atoms with Unsaturated B,O-Coordination for Selective ¹O₂ Generation

ACS Catalysis, Год журнала: 2023, Номер 13(18), С. 12414 - 12424

Опубликована: Сен. 7, 2023

Generating singlet oxygen (1O2) on single atom catalysts (SACs) in peroxymonosulfate (PMS)-based Fenton-like reactions exhibits great potential for selective degradation of contaminants complex wastewater. Clarifying the structure–activity relationship between electronic structure SACs and 1O2 generation selectivity is crucial precise design efficient catalysts, but it challenging. Herein, Cu with different structures (namely, Cu–O2X, where X = N, S, B, P, O) investigated by density functional theory calculations using adsorption terminal atoms PMS as an activity descriptor. Significantly, affected center which electron-depleted Cu-O2B site a higher atoms. Experimentally, moiety superior catalytic activation, showing nearly 100% ciprofloxacin rate 0.2250 min–1, outperforming those other counterparts. The high attributed to asymmetric accelerating faster electron transfer O–O bond stretching, lowering energy barrier key intermediates toward generation. This work provides broader perspective regulating sites at atomic level catalysts.

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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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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Utilizing the oxygen-atom trapping effect of Co ₃ O ₄ with oxygen vacancies to promote chlorite activation for water decontamination

Proceedings of the National Academy of Sciences, Год журнала: 2024, Номер 121(11)

Опубликована: Март 5, 2024

Heterogeneous high-valent cobalt-oxo [≡Co(IV)=O] is a widely focused reactive species in oxidant activation; however, the relationship between catalyst interfacial defects and ≡Co(IV)=O formation remains poorly understood. Herein, photoexcited oxygen vacancies (OVs) were introduced into Co 3 O 4 (OV-Co ) by UV-induced modification method to facilitate chlorite (ClO 2 – activation. Density functional theory calculations indicate that OVs result low-coordinated atom, which can directionally anchor under oxygen-atom trapping effect. Chlorite first undergoes homolytic O–Cl cleavage transfers dissociated atom form with higher spin state. The rapidly extracts one electron from ClO chlorine dioxide ), accompanied returning lower As of effect, OV-Co /chlorite system achieved 3.5 times efficiency sulfamethoxazole degradation (~0.1331 min −1 than pristine system. Besides, refiled be easily restored re-exposure UV light, indicating sustainability trap. was further fabricated on polyacrylonitrile membrane for back-end water purification, achieving continuous flow pollutants low cobalt leakage. This work presents an enhancement strategy constructing OV as site heterogeneous advanced oxidation processes provides insight modulating via defect engineering.

Язык: Английский

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Polar electric field-modulated peroxymonosulfate selective activation for removal of organic contaminants via non-radical electron transfer process

Water Research, Год журнала: 2023, Номер 246, С. 120678 - 120678

Опубликована: Сен. 29, 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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Long-range interactions driving neighboring Fe–N4 sites in Fenton-like reactions for sustainable water decontamination

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

Опубликована: Сен. 5, 2024

Язык: Английский

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