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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Almost 100 % electron transfer regime over Fe−Co dual-atom catalyst toward pollutants removal: Regulation of peroxymonosulfate adsorption mode

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 339, С. 123178 - 123178

Опубликована: Авг. 15, 2023

Язык: Английский

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Fenton-like activity and pathway modulation via single-atom sites and pollutants comediates the electron transfer process

Proceedings of the National Academy of Sciences, Год журнала: 2024, Номер 121(3)

Опубликована: Янв. 8, 2024

The studies on the origin of versatile oxidation pathways toward targeted pollutants in single-atom catalysts (SACs)/peroxymonosulfate (PMS) systems were always associated with coordination structures rather than perspective pollutant characteristics, and analysis mechanism commonality is lacking. In this work, a variety (M-SACs, M: Fe, Co, Cu) fabricated via pyrolysis process using lignin as complexation agent substrate precursor. Sixteen kinds commonly detected various references selected, their ln k obs values M-SACs/PMS correlated well ( R 2 = 0.832 to 0.883) electrophilic indexes (reflecting electron accepting/donating ability pollutants) energy gap 0.801 0.840) between complexes. Both transfer (ETP) radical can be significantly enhanced systems, while was overwhelmed by ETP lower indexes. contrast, higher represented weaker electron-donating capacity complexes, which resulted accompanied noticeable oxidation. addition, different regulated gaps complexes pollutants. As result, Fenton-like activities could modulated reaction pathways, determined both sites. This work provided strategy establish PMS-based AOP tunable capacities for high-efficiency organic decontamination.

Язык: Английский

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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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Crystallinity engineering for overcoming the activity–stability tradeoff of spinel oxide in Fenton-like catalysis

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(15)

Опубликована: Апрель 5, 2023

A precise modulation of heterogeneous catalysts in structural and surface properties promises the development more sustainable advanced oxidation water purification technologies. However, while with superior decontamination activity selectivity are already achievable, maintaining a long-term service life such materials remains challenging. Here, we propose crystallinity engineering strategy to break activity-stability tradeoff metal oxides Fenton-like catalysis. The amorphous/crystalline cobalt-manganese spinel oxide (A/C-CoMnOx) provided highly active, hydroxyl group-rich surface, moderate peroxymonosulfate (PMS)-binding affinity charge transfer energy strong pollutant adsorption, trigger concerted radical nonradical reactions for efficient mineralization, thereby alleviating catalyst passivation by intermediate accumulation. Meanwhile, surface-confined reactions, benefited from enhanced adsorption pollutants at A/C interface, rendered A/C-CoMnOx/PMS system ultrahigh PMS utilization efficiency (82.2%) unprecedented (rate constant 1.48 min-1) surpassing almost all state-of-the-art catalysts. cyclic stability environmental robustness real treatment was also demonstrated. Our work unveils critical role material modulating catalytic pathways oxides, which fundamentally improves our understanding structure-activity-selectivity relationships may inspire design application beyond.

Язык: Английский

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Generation of Fe^IV=O and its Contribution to Fenton‐Like Reactions on a Single‐Atom Iron−N−C Catalyst

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(10)

Опубликована: Янв. 10, 2023

Generating FeIV =O on single-atom catalysts by Fenton-like reaction has been established for water treatment; however, the generation pathway and oxidation behavior remain obscure. Employing an Fe-N-C catalyst with a typical Fe-N4 moiety to activate peroxymonosulfate (PMS), we demonstrate that generating is mediated Fe-N-C-PMS* complex-a well-recognized nonradical species induction of electron-transfer oxidation-and determined adjacent Fe sites specific Fe1 -Fe1 distance are required. After atoms <4 Å PMS-saturated, formed 4-5 can coordinate FeII -N4 , forming inter-complex enhanced charge transfer produce =O. enables system efficiently oxidize various pollutants in substrate-specific, pH-tolerant, sustainable manner, where its prominent contribution manifests higher one-electron potential.

Язык: Английский

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Elucidation of the mechanistic origin of spin-state-dependent P-doped Fe single-atom catalysts for the oxidation of organic pollutants through peroxymonosulfate activation

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 341, С. 123289 - 123289

Опубликована: Сен. 14, 2023

Язык: Английский

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Single-atom co sites confined in layered double hydroxide for selective generation of surface-bound radicals via peroxymonosulfate activation

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 340, С. 123218 - 123218

Опубликована: Авг. 25, 2023

Selective production of specific radical species with prolonged lifetime is challenging in advanced oxidation process. Herein, we constructed single-atom Co (SA-Co) catalytic sites confined layered double hydroxide (LDH) for selectively and sustainably generate via peroxymonosulfate (PMS) activation. The negatively charged PMS was stabilized by the positively LDH simultaneously activated nanoconfined sites, resulting oriented-production surface-bonded •OH SO4•− radicals long-term efficiency (up to 48 h), suppressed decomposition self-quenching. Ion competition experiments in-situ spectroscopic studies were applied monitor activation processes. SA-Co-LDH/PMS system outperforms benchmark homogeneous (Co2+/PMS) heterogeneous (Co3O4/PMS) systems degradation emerging organic contaminants (EOCs) lowest consumption highest efficiency.

Язык: Английский

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Enhanced H2O2 utilization efficiency in Fenton-like system for degradation of emerging contaminants: Oxygen vacancy-mediated activation of O2

Water Research, Год журнала: 2023, Номер 230, С. 119562 - 119562

Опубликована: Янв. 2, 2023

Язык: 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, Год журнала: 2023, Номер 57(37), С. 14046 - 14057

Опубликована: Сен. 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

Язык: Английский

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