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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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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Cu-doped CoOOH activates peroxymonosulfate to generate high-valent cobalt-oxo species to degrade organic pollutants in saline environments

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 340, P. 123224 - 123224

Published: Aug. 25, 2023

Language: Английский

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Self-carbon-thermal-reduction strategy for boosting the Fenton-like activity of single Fe-N4 sites by carbon-defect engineering

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

Published: Nov. 20, 2023

Carbon-defect engineering in metal single-atom catalysts by simple and robust strategy, boosting their catalytic activity, revealing the carbon defect-catalytic activity relationship are meaningful but challenging. Herein, we report a facile self-carbon-thermal-reduction strategy for carbon-defect of single Fe-N4 sites ZnO-Carbon nano-reactor, as efficient catalyst Fenton-like reaction degradation phenol. The vacancies easily constructed adjacent to during synthesis, facilitating formation C-O bonding lowering energy barrier rate-determining-step Consequently, Fe-NCv-900 with exhibits much improved than Fe-NC-900 without abundant vacancies, 13.5 times improvement first-order rate constant phenol degradation. shows high (97% removal ratio only 5 min), good recyclability wide-ranging pH universality (pH range 3-9). This work not provides rational improving catalysts, also deepens fundamental understanding on how periphery environment affects property performance metal-N4 sites.

Language: Английский

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Heterogeneous Fe-Co dual-atom catalyst outdistances the homogeneous counterpart for peroxymonosulfate-assisted water decontamination: New surface collision oxidation path and diatomic synergy

Water Research, Journal Year: 2023, Volume and Issue: 241, P. 120164 - 120164

Published: June 1, 2023

Language: Английский

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Thermodynamic and Kinetic Behaviors of Persulfate-Based Electron-Transfer Regime in Carbocatalysis

Environmental Science & Technology, Journal Year: 2023, Volume and Issue: 57(47), P. 19012 - 19022

Published: Aug. 21, 2023

A carbon-based advanced oxidation process is featured for the nonradical electron-transfer pathway (ETP) from electron-donating organic compounds to activated persulfate complexes, enabling it as a green technology selective of pollutants in complex water environments. However, thermodynamic and kinetic behaviors regime had been ambiguous due neglect influence pH on mechanisms. In this study, three kinds were divided ETP regime: (i) physio-adsorption, (ii) adsorption-dominated (oxidation rate slightly surpasses adsorption rate), (iii) oxidation-dominated outpaces rate). The differential attributed physicochemical properties pollutants. For example, hydrophobicity, molecular radius, positive electrostatic potential controlled mass-transfer stage reactants (peroxydisulfate (PDS) organics). Meanwhile, other descriptors, including Fukui index, potential, electron cloud density regulated processes thus kinetics oxidation. Most importantly, pathways these could be altered by adjusting chemistry. This study reveals principles developing efficient systems selectively remove recycle wastewater.

Language: Английский

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Size‐Dependent Catalysis in Fenton‐like Chemistry: From Nanoparticles to Single Atoms

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(28)

Published: April 24, 2024

Abstract State‐of‐the‐art Fenton‐like reactions are crucial in advanced oxidation processes (AOPs) for water purification. This review explores the latest advancements heterogeneous metal‐based catalysts within AOPs, covering nanoparticles (NPs), single‐atom (SACs), and ultra‐small atom clusters. A distinct connection between physical properties of these catalysts, such as size, degree unsaturation, electronic structure, state, their impacts on catalytic behavior efficacy reactions. In‐depth comparative analysis metal NPs SACs is conducted focusing how particle size variations metal‐support interactions affect species pathways. The highlights cutting‐edge characterization techniques theoretical calculations, indispensable deciphering complex structural characteristics active sites downsized particles. Additionally, underscores innovative strategies immobilizing onto membrane surfaces, offering a solution to inherent challenges powdered catalysts. Recent advances pilot‐scale or engineering applications Fenton‐like‐based devices also summarized first time. paper concludes by charting new research directions, emphasizing catalyst design, precise identification reactive oxygen species, in‐depth mechanistic studies. These efforts aim enhance application potential nanotechnology‐based AOPs real‐world wastewater treatment.

Language: Английский

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Long-range interactions driving neighboring Fe–N4 sites in Fenton-like reactions for sustainable water decontamination

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

Published: Sept. 5, 2024

Language: Английский

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