Generating dual-active species by triple-atom sites through peroxymonosulfate activation for treating micropollutants in complex water

Proceedings of the National Academy of Sciences, Journal Year: 2023, Volume and Issue: 120(13)

Published: March 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.

Language: Английский

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Microenvironment Engineering of Single/Dual‐Atom Catalysts for Electrocatalytic Application

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(31)

Published: Feb. 23, 2023

Single/dual-metal atoms supported on carbon matrix can be modulated by coordination structure and neighboring active sites. Precisely designing the geometric electronic uncovering structure-property relationships of single/dual-metal confront with grand challenges. Herein, this review summarizes latest progress in microenvironment engineering single/dual-atom sites via a comprehensive comparison single-atom catalyst (SACs) dual-atom catalysts (DACs) term design principles, modulation strategy, theoretical understanding structure-performance correlations. Subsequently, recent advances several typical electrocatalysis process are discussed to get general reaction mechanisms finely-tuned SACs DACs. Finally, full-scaled summaries challenges prospects given for This will provide new inspiration development atomically dispersed electrocatalytic application.

Language: Английский

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Single-Atom MnN₅ Catalytic Sites Enable Efficient Peroxymonosulfate Activation by Forming Highly Reactive Mn(IV)–Oxo Species

Environmental Science & Technology, Journal Year: 2023, Volume and Issue: 57(10), P. 4266 - 4275

Published: Feb. 27, 2023

Four-nitrogen-coordinated transitional metal (MN4) configurations in single-atom catalysts (SACs) are broadly recognized as the most efficient active sites peroxymonosulfate (PMS)-based advanced oxidation processes. However, SACs with a coordination number higher than four rarely explored, which represents fundamental missed opportunity for chemistry to boost PMS activation and degradation of recalcitrant organic pollutants. We experimentally theoretically demonstrate here that five-nitrogen-coordinated Mn (MnN5) more effectively activate MnN4 sites, by facilitating cleavage O–O bond into high-valent Mn(IV)–oxo species nearly 100% selectivity. The high activity MnN5 was discerned be due formation higher-spin-state N5Mn(IV)═O species, enable two-electron transfer from organics through lower-energy-barrier pathway. Overall, this work demonstrates importance numbers informs design next-generation environmental catalysts.

Language: Английский

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Single-atom Mo–Co catalyst with low biotoxicity for sustainable degradation of high-ionization-potential organic pollutants

Proceedings of the National Academy of Sciences, Journal Year: 2023, Volume and Issue: 120(29)

Published: July 10, 2023

Single-atom catalysts (SACs) are a promising area in environmental catalysis. We report on bimetallic Co–Mo SAC that shows excellent performance activating peroxymonosulfate (PMS) for sustainable degradation of organic pollutants with high ionization potential (IP > 8.5 eV). Density Functional Theory (DFT) calculations and experimental tests demonstrate the Mo sites – Co SACs play critical role conducting electrons from to sites, leading 19.4-fold increase rate phenol compared CoCl 2 PMS group. The exhibit catalytic even under extreme conditions show long-term activation 10-d experiments, efficiently degrading 600 mg/L phenol. Moreover, catalyst has negligible toxicity toward MDA-MB-231, Hela, MCF-7 cells, making it an environmentally friendly option water treatment. Our findings have important implications design efficient remediation other applications biology medicine.

Language: 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, Journal Year: 2024, Volume and Issue: 121(3)

Published: Jan. 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.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(27)

Published: April 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.

Language: Английский

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Generation and identification of 1O2 in catalysts/peroxymonosulfate systems for water purification

Water Research, Journal Year: 2023, Volume and Issue: 245, P. 120614 - 120614

Published: Sept. 11, 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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Tuning Local Coordination Environments of Manganese Single‐Atom Nanozymes with Multi‐Enzyme Properties for Selective Colorimetric Biosensing

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(15)

Published: Feb. 13, 2023

Single-atom nanozymes (SAzymes) are promising in next-generation nanozymes, nevertheless, how to rationally modulate the microenvironment of SAzymes with controllable multi-enzyme properties is still challenging. Herein, we systematically investigate relationship between atomic configuration and multi-enzymatic performances. The constructed MnSA -N3 -coordinated (MnSA -C) exhibits much more remarkable oxidase-, peroxidase-, glutathione oxidase-like activities than that -N4 -C. Based on experimental theoretical results, these multi-enzyme-like behaviors highly dependent coordination number single Mn sites by local charge polarization. As a consequence, series colorimetric biosensing platforms based -C successfully built for specific recognition biological molecules. These findings provide atomic-level insight into promoting rational design other demanding biocatalysts.

Language: Английский

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Bioinspired porous three-coordinated single-atom Fe nanozyme with oxidase-like activity for tumor visual identification via glutathione

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Nov. 6, 2023

Inspired by structures of natural metalloenzymes, a biomimetic synthetic strategy is developed for scalable synthesis porous Fe-N3 single atom nanozymes (pFeSAN) using hemoglobin as Fe-source and template. pFeSAN delivers 3.3- 8791-fold higher oxidase-like activity than Fe-N4 Fe3O4 nanozymes. The high catalytic performance attributed to (1) the suppressed aggregation atomically dispersed Fe; (2) facilitated mass transfer maximized exposure active sites created mesopores thermal removal (2 ~ 3 nm); (3) unique electronic configuration oxygen-to-water oxidation pathway (analogy with cytochrome c oxidase). successfully demonstrated rapid colorimetric detection glutathione low limit (2.4 nM) wide range (50 nM-1 mM), further real-time, facile, (~6 min) precise visualization analysis methodology tumors via level, showing its potentials diagnostic clinic applications.

Language: Английский

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