Water decontamination via nonradical process by nanoconfined Fenton-like catalysts

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

Published: May 19, 2023

Abstract There is an urgent need to develop effective and sustainable solutions reduce water pollution. Heterogeneous Fenton-like catalysts are frequently used eliminate contaminants from water. However, the applicability of these limited due low availability reactive species (RS). Herein, nanoconfinement strategy was applied encapsulate short-lived RS at nanoscale boost utilization efficiency in reactions. The nanoconfined catalyst fabricated by assembling Co 3 O 4 nanoparticles carbon nanotube nanochannels achieve exceptional reaction rate excellent selectivity. Experiments collectively suggested that degradation attributed singlet oxygen ( 1 2 ). Density functional theory calculations demonstrated space contributes quantum mutation alters transition state lower activation energy barriers. Simulation results revealed enrichment contaminant on reduced migration distance enhanced . synergy between shell layer core-shell structure further improved selectivity towards oxidation real waters. expected provide a viable for pollution control.

Language: Английский

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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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Multivalent metal catalysts in Fenton/Fenton-like oxidation system: A critical review

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 466, P. 143147 - 143147

Published: April 26, 2023

Language: Английский

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Electron delocalization triggers nonradical Fenton-like catalysis over spinel oxides

Proceedings of the National Academy of Sciences, Journal Year: 2022, Volume and Issue: 119(31)

Published: July 25, 2022

Nonradical Fenton-like catalysis offers opportunities to overcome the low efficiency and secondary pollution limitations of existing advanced oxidation decontamination technologies, but realizing this on transition metal spinel oxide catalysts remains challenging due insufficient understanding their catalytic mechanisms. Here, we explore origins selectivity Fe-Mn identify electron delocalization surface active site as key driver its nonradical catalysis. Through fine-tuning crystal geometry trigger superexchange interaction at octahedra, ZnFeMnO4 with high-degree Mn-O unit was created enable near 100% activation peroxymonosulfate (PMS) unprecedented utilization efficiency. The resulting surface-bound PMS* complex can efficiently oxidize electron-rich pollutants extraordinary degradation activity, selectivity, good environmental robustness favor water applications. Our work provides a molecule-level bimetallic interactions oxides, which may guide design low-cost oxides for more selective efficient

Language: Английский

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A Site Distance Effect Induced by Reactant Molecule Matchup in Single‐Atom Catalysts for Fenton‐Like Reactions

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(33)

Published: June 20, 2022

Abstract Understanding the site interaction nature of single‐atom catalysts (SACs), especially densely populated SACs, is vital for their application to various catalytic reactions. Herein, we report a distance effect, which emphasizes how well adjacent copper atoms (denoted as d Cu1−Cu1 ) matches with reactant peroxydisulfate (PDS) molecular size determine Fenton‐like reaction reactivity on carbon‐supported SACs. The optimized in range 5–6 Å, PDS, endows catalyst nearly two times higher turnover frequency than that beyond this range, accordingly achieving record‐breaking kinetics oxidation emerging organic contaminants. Further studies suggest effect originates from alteration PDS adsorption dual‐site structure Cu 1 −Cu sites when falls within significantly enhancing interfacial charge transfer and consequently resulting most efficient activation so far.

Language: Английский

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Ultrahigh Peroxymonosulfate Utilization Efficiency over CuO Nanosheets via Heterogeneous Cu(III) Formation and Preferential Electron Transfer during Degradation of Phenols

Environmental Science & Technology, Journal Year: 2022, Volume and Issue: 56(12), P. 8984 - 8992

Published: May 31, 2022

In persulfate activation by copper-based catalysts, high-valent copper (Cu(III)) is an overlooked reactive intermediate that contributes to efficient utilization and organic pollutant removal. However, the mechanisms underlying heterogeneous enhanced are not fully understood. Here, oxide (CuO) nanosheets (synthesized with a facile precipitation method) exhibited high catalytic activity for peroxymonosulfate (PMS) 100% 4-chlorophenol (4-CP) degradation within 3 min. Evidence critical role of surface-associated Cu(III) on PMS 4-CP over wide pH range (pH 3-10) was obtained using in situ Raman spectroscopy, electron paramagnetic resonance, quenching tests. directly oxidized other phenolic pollutants, rate constants inversely proportional their ionization potentials. preferentially oxidizes rather than react two molecules generate one molecule 1O2, thus minimizing this less pathway. Accordingly, much higher efficiency (77% electrons accepted ascribed mineralization) CuO/PMS radical pathway-dominated Co3O4/PMS system (27%) or 1O2 α-MnO2/PMS (26%). Overall, these results highlight potential benefits via oxidation offer mechanistic insight into ultrahigh

Language: Английский

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Coordination Number Dependent Catalytic Activity of Single‐Atom Cobalt Catalysts for Fenton‐Like Reaction

Advanced Functional Materials, Journal Year: 2022, Volume and Issue: 32(38)

Published: July 7, 2022

Abstract Single‐atom catalysts (SACs) are widely investigated in Fenton‐like reactions for environmental remediation, wherein their catalytic performance can be further improved by coordination structure modulation, but the relevant report is rare. Herein, a series of atomically dispersed cobalt with diverse numbers (denoted as CoN x , represents nitrogen number) synthesized and peroxymonosulfate (PMS) conversion explored. The specific activity found to dependent on number single atomic Co sites, where lowest‐coordinated 2 catalyst exhibits highest PMS activation, followed under‐coordinated 3 normal 4 . Experimental theoretical results reveal that reducing increase electron density atom which governs catalysts. Specifically, entire Co–pyridinic NC motif serves active centers conversion, atom, pyridinic N‐bonded C atoms along vacancy neighboring unsaturated N moiety account reduction oxidation toward radical singlet oxygen ( 1 O ) generation, respectively. These findings provide useful avenue regulation SACs applications.

Language: Английский

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Oxygen doping of cobalt-single-atom coordination enhances peroxymonosulfate activation and high-valent cobalt–oxo species formation

Proceedings of the National Academy of Sciences, Journal Year: 2023, Volume and Issue: 120(16)

Published: April 11, 2023

The high-valent cobalt-oxo species (Co(IV)=O) is being increasingly investigated for water purification because of its high redox potential, long half-life, and antiinterference properties. However, generation Co(IV)=O inefficient unsustainable. Here, a cobalt-single-atom catalyst with N/O dual coordination was synthesized by O-doping engineering. O-doped (Co-OCN) greatly activated peroxymonosulfate (PMS) achieved pollutant degradation kinetic constant 73.12 min-1 g-2, which 4.9 times higher than that Co-CN (catalyst without O-doping) those most reported single-atom catalytic PMS systems. Co-OCN/PMS realized dominant oxidation pollutants increasing the steady-state concentration (1.03 × 10-10 M) 5.9 compared Co-CN/PMS. A competitive kinetics calculation showed contribution to micropollutant 97.5% during process. Density functional theory calculations influenced charge density (increased Bader transfer from 0.68 0.85 e), optimized electron distribution Co center d-band -1.14 -1.06 eV), enhanced adsorption energy -2.46 -3.03 eV, lowered barrier key reaction intermediate (*O*H2O) formation 1.12 0.98 eV. Co-OCN fabricated on carbon felt flow-through device, continuous efficient removal micropollutants (degradation efficiency >85% after 36 h operation). This study provides new protocol activation elimination through heteroatom-doping metal-oxo purification.

Language: Английский

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A Forward Vision for Chemodynamic Therapy: Issues and Opportunities

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(7)

Published: Jan. 17, 2023

Abstract Since the insight to fuse Fenton chemistry and nanomedicine into cancer therapy, great signs of progress have been made in field chemodynamic therapy (CDT). However, exact mechanism CDT is obscured by unique tumor chemical environment inevitable nanoparticle‐cell interactions, thus impeding further development. In this Scientific Perspective, significance clarified, complex deconstructed primitive biological research directions based on kinetics signaling pathways are discussed detail. Moreover, beneficial outlooks presented enlighten evolution next‐generation CDT. Hopefully, Perspective can inspire new ideas advances for provide a reference breaking down interdisciplinary barriers nanomedicine.

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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