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

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(18), P. 12414 - 12424

Published: Sept. 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.

Language: Английский

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2D surfaces twisted to enhance electron freedom toward efficient advanced oxidation processes

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 345, P. 123701 - 123701

Published: Jan. 6, 2024

Language: Английский

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Selective hydroxyl generation for efficient pollutant degradation by electronic structure modulation at Fe sites

Proceedings of the National Academy of Sciences, Journal Year: 2023, Volume and Issue: 120(26)

Published: June 20, 2023

Hydrogen peroxide (H 2 O ) is an important green oxidant in the field of sewage treatment, and how to improve its activation efficiency generate free radicals with stronger oxidation performance a key issue current research. Herein, we synthesized Cu-doped α-Fe 3 catalyst (7% Cu–Fe for H under visible light degradation organic pollutants. The introduction Cu dopant changed d-band center Fe closer Fermi level, which enhanced adsorption site , cleavage pathway from heterolytic homolytic cleavage, thereby improving selectivity •OH generation. In addition, doping also promoted absorption ability separation hole–electron pairs, photocatalytic activities. Benefiting high •OH, 7% exhibited efficient activities against ciprofloxacin, rate was 3.6 times as much that it had good variety

Language: Английский

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Single-atom Ni-N4 sites coordinate dual nonradical oxidation pathways via peroxymonosulfate activation: Computational insights and in situ spectroscopic analyses

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 346, P. 123752 - 123752

Published: Jan. 21, 2024

In this work, we revealed a dual-pathway nonradical oxidation (NRO) system catalyzed by Ni single atom catalyst (NiN4) accommodated in the carbon nitride substrate. The monatomic coordinated with four N atoms (Ni-N4) is determined as dynamic catalytic center for peroxymonosulfate (PMS) activation, showing an exceptional specific rate constant of 3.34 min-1 g-2 L-2 (29.7 times that CN/PMS system) oxidizing bisphenol A and other refractory organics. situ Raman, X-ray absorption, electrochemical analyses well theoretical simulations demonstrate Ni-N4 sites exhibit strong interaction PMS benefited from modulated electronic structures, resulting surface-bonding active complexes (NiN4-PMS*) deuterogenic high-valent Ni(IV)-Oxo species. NRO process will spontaneously coordinate both electron transfer via CN matrix direct selective organic excellent anti-interference ability adaptability.

Language: 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, Journal Year: 2023, Volume and Issue: 344, P. 123643 - 123643

Published: Dec. 21, 2023

Language: Английский

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Rapid self-heating synthesis of Fe-based nanomaterial catalyst for advanced oxidation

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

Published: Aug. 17, 2023

Abstract Iron-based catalysts are promising candidates for advanced oxidation process-based wastewater remediation. However, the preparation of these materials often involves complex and energy intensive syntheses. Further, due to inherent limitations conditions, it is challenging realise full potential catalyst. Herein, we develop an iron-based nanomaterial catalyst via soft carbon assisted flash joule heating (FJH). FJH rapid temperature increase, electric shock, cooling, process simultaneously transforms a low-grade iron mineral (FeS) into electron rich nano Fe 0 /FeS heterostructure embedded in thin-bedded graphene. The efficient consumes 34 times less than conventional pyrolysis. Density functional theory calculations indicate that delocalization FJH-derived improves its binding ability with peroxydisulfate bidentate binuclear model, thereby enhancing ·OH yield organics mineralization. Fe-based exhibits strong catalytic performance over wide pH range. Similar can be prepared using other commonly available precursors. Finally, also present strategy continuous automated production catalysts.

Language: Английский

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Insight into metal-based catalysts for heterogeneous peroxymonosulfate activation: A critical review

Separation and Purification Technology, Journal Year: 2023, Volume and Issue: 333, P. 125900 - 125900

Published: Nov. 29, 2023

Language: Английский

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