Fenton-like activity and pathway modulation via single-atom sites and pollutants comediates the electron transfer process

Proceedings of the National Academy of Sciences, Год журнала: 2024, Номер 121(3)

Опубликована: Янв. 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.

Язык: Английский

---

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, Год журнала: 2023, Номер 340, С. 123224 - 123224

Опубликована: Авг. 25, 2023

Язык: Английский

---

Efficient photo-Fenton reaction for tetracycline and antibiotic resistant bacteria removal using hollow Fe-doped In2O3 nanotubes: From theoretical research to practical application

Water Research, Год журнала: 2023, Номер 240, С. 120088 - 120088

Опубликована: Май 17, 2023

Язык: Английский

---

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

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Ноя. 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.

Язык: Английский

---

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

Advanced Materials, Год журнала: 2024, Номер 36(28)

Опубликована: Апрель 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.

Язык: Английский

---

Polar electric field-modulated peroxymonosulfate selective activation for removal of organic contaminants via non-radical electron transfer process

Water Research, Год журнала: 2023, Номер 246, С. 120678 - 120678

Опубликована: Сен. 29, 2023

Язык: Английский

---

Mechanism of Particle-Mediated Inhibition of Demetalation for Single-Atom Catalytic Sites in Acidic Electrochemical Environments

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(28), С. 15528 - 15537

Опубликована: Июль 10, 2023

Demetalation, caused by the electrochemical dissolution of metal atoms, poses a significant challenge to practical application single-atom catalytic sites (SACSs) in proton exchange membrane-based energy technologies. One promising approach inhibit SACS demetalation is use metallic particles interact with SACSs. However, mechanism underlying this stabilization remains unclear. In study, we propose and validate unified which can Fe Metal act as electron donors, decreasing oxidation state increasing density at FeN4 position, thereby strengthening Fe-N bond, inhibiting dissolution. Different types, forms, contents increase bond strength varying extents. A linear correlation between state, strength, amount supports mechanism. Our screening particle-assisted led 78% reduction dissolution, enabling continuous operation for up 430 h fuel cell. These findings contribute development stable SACSs applications.

Язык: Английский

---

Unlocking Bimetallic Active Centers via Heterostructure Engineering for Exceptional Phosphate Electrosorption: Internal Electric Field-Induced Electronic Structure Reconstruction

Environmental Science & Technology, Год журнала: 2023, Номер 58(4), С. 2112 - 2122

Опубликована: Дек. 26, 2023

Development of electrode materials exhibiting exceptional phosphate removal performance represents a promising strategy to mitigate eutrophication and meet ever-stricter stringent emission standards. Herein, we precisely designed novel LaCeOx heterostructure-decorated hierarchical carbon composite (L8C2PC) for high-efficiency electrosorption. This approach establishes an internal electric field within the heterostructure, where electrons transfer from Ce atoms neighboring La through superexchange interactions in La–O–Ce coordination units. The modulatory heterostructure endows positive shift d band sites increase electron density at Fermi level, promoting stronger orbital overlap binding interactions. introduction oxygen vacancies during situ nucleation process reduces kinetic barrier phosphate-ion migration supplies additional active centers. Moreover, framework ensures electrical double-layer capacitance storage interconnected ion channels. Such synergistically multiple centers grant L8C2PC with record As expected, demonstrates highest capability among reported saturation capacity 401.31 mg P g–1 dynamic 91.83 1.2 V. electrochemical system also performs well dephosphorization natural water samples low concentration that enable effluent first-class discharge standard China (0.5 L–1). study advances efficient techniques new level offers deep understanding regulates metal orbitals densities engineering.

Язык: Английский

---

Application of 3D hierarchical porous NiCo-spinel nanosheet array for enhancement of synergistic activation of peroxymonosulfate: Degradation, Intermediates, mechanism and degradation pathway of tetracycline

Chemical Engineering Journal, Год журнала: 2024, Номер 481, С. 148506 - 148506

Опубликована: Янв. 4, 2024

Язык: Английский

---

Precise coordination of high-loading Fe single atoms with sulfur boosts selective generation of nonradicals

Proceedings of the National Academy of Sciences, Год журнала: 2024, Номер 121(4)

Опубликована: Янв. 17, 2024

Nonradicals are effective in selectively degrading electron-rich organic contaminants, which unfortunately suffer from unsatisfactory yield and uncontrollable composition due to the competitive generation of radicals. Herein, we precisely construct a local microenvironment carbon nitride–supported high-loading (~9 wt.%) Fe single-atom catalyst (Fe SAC) with sulfur via facile supermolecular self-assembly strategy. Short-distance S coordination boosts peroxymonosulfate (PMS) activation generates high-valent iron–oxo species IV =O) along singlet oxygen ( 1 O 2 ), significantly increasing yield, PMS utilization, p -chlorophenol reactivity by 6.0, 3.0, 8.4 times, respectively. The nonradicals is controllable simply changing content. In contrast, long-distance both radicals nonradicals, could not promote reactivity. Experimental theoretical analyses suggest that short-distance upshifts d -band center atom, i.e., being close Fermi level, changes binding mode between atom site generate =O high yield. S-coordinated SAC exhibits excellent application potential various water matrices. These findings can guide rational design robust SACs toward selective utilization.

Язык: Английский

---