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

Proceedings of the National Academy of Sciences, Journal Year: 2023, Volume and Issue: 120(15)

Published: April 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.

Language: Английский

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Coupled Surface-Confinement Effect and Pore Engineering in a Single-Fe-Atom Catalyst for Ultrafast Fenton-like Reaction with High-Valent Iron-Oxo Complex Oxidation

Environmental Science & Technology, Journal Year: 2023, Volume and Issue: 57(41), P. 15667 - 15679

Published: Oct. 6, 2023

The nanoconfinement effect in Fenton-like reactions shows great potential environmental remediation, but the construction of confinement structure and corresponding mechanism are rarely elucidated systematically. Herein, we proposed a novel peroxymonosulfate (PMS) activation system employing single Fe atom supported on mesoporous N-doped carbon (FeSA-MNC, specific surface area = 1520.9 m2/g), which could accelerate catalytic oxidation process via surface-confinement effect. degradation activity confined was remarkably increased by 34.6 times compared to its analogue unconfined system. generation almost 100% high-valent iron-oxo species identified 18O isotope-labeled experiments, quenching tests, probe methods. density functional theory illustrated that narrows gap between d-band center Fermi level atom, strengthens charge transfer rate at reaction interface reduces free energy barrier for PMS activation. exhibited excellent pollutant efficiency, robust resistance coexisting matter, adaptation wide pH range (3.0-11.0) various temperature environments (5-40 °C). Finally, FeSA-MNC/PMS achieve sulfamethoxazole removal without significant performance decline after 10,000-bed volumes. This work provides insights into chemistry guides design superior systems remediation.

Language: 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, Journal Year: 2023, Volume and Issue: 62(10)

Published: Jan. 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.

Language: Английский

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Selective degradation of organic micropollutants by activation of peroxymonosulfate by Se@NC: Role of Se doping and nonradical pathway mechanism

Journal of Hazardous Materials, Journal Year: 2023, Volume and Issue: 452, P. 131202 - 131202

Published: March 15, 2023

Language: Английский

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Tailoring d-band center of high-valent metal-oxo species for pollutant removal via complete polymerization

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 14, 2024

Abstract Polymerization-driven removal of pollutants in advanced oxidation processes (AOPs) offers a sustainable way for the simultaneous achievement contamination abatement and resource recovery, supporting low-carbon water purification approach. However, regulating such process remains great challenge due to insufficient microscopic understanding electronic structure-dependent reaction mechanisms. Herein, this work probes origin catalytic pollutant polymerization using series transition metal (Cu, Ni, Co, Fe) single-atom catalysts identifies d -band center active site as key driver transfer pollutants. The high-valent metal-oxo species, produced via peroxymonosulfate activation, are found trigger transfer. Phenoxyl radicals, identified by innovative spin-trapping quenching approaches, act intermediate reactions. More importantly, capacity species can be facilely tuned their binding strength through modulation. A 100% ratio is achieved lowering center. This presents paradigm dynamically modulate structure optimize from wastewater polymerization.

Language: Английский

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Enhanced Interfacial Electron Transfer by Asymmetric Cu‐O_v‐In Sites on In₂O₃ for Efficient Peroxymonosulfate Activation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(11)

Published: Jan. 17, 2023

Enhancing the peroxymonosulfate (PMS) activation efficiency to generate more radicals is vital promote Fenton-like reaction activity, however, how PMS adsorption and accelerate interfacial electron transfer boost its kinetics remains a great challenge. Herein, we prepared Cu-doped defect-rich In2 O3 (Cu-In2 /Ov ) catalysts containing asymmetric Cu-Ov -In sites for in water purification. The intrinsic catalytic activity that side-on configuration of O-O bond (Cu-O-O-In) at significantly stretches length. Meanwhile, increase density near Fermi energy level, promoting faster generating SO4 ⋅- ⋅OH. degradation rate constant tetracycline achieved by Cu-In2 31.8 times than , it shows possibility membrane reactor practical wastewater treatment.

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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Insights into the mechanism of carbocatalysis for peracetic acid activation: Kinetic discernment and active site identification

Water Research, Journal Year: 2022, Volume and Issue: 227, P. 119346 - 119346

Published: Nov. 8, 2022

Language: Английский

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Progress in metal-organic-framework-based single-atom catalysts for environmental remediation

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 474, P. 214855 - 214855

Published: Oct. 4, 2022

Language: Английский

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Nearly zero peroxydisulfate consumption for persistent aqueous organic pollutants degradation via nonradical processes supported by in-situ sulfate radical regeneration in defective MIL-88B(Fe)

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 331, P. 122699 - 122699

Published: March 27, 2023

Language: Английский

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