Water decontamination via nonradical process by nanoconfined Fenton-like catalysts

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

Опубликована: Май 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.

Язык: Английский

---

Cobalt Single Atoms Anchored on Oxygen‐Doped Tubular Carbon Nitride for Efficient Peroxymonosulfate Activation: Simultaneous Coordination Structure and Morphology Modulation

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(29)

Опубликована: Май 6, 2022

Abstract Simultaneous regulation of the coordination environment single‐atom catalysts (SACs) and engineering architectures with efficient exposed active sites are strategies for boosting peroxymonosulfate (PMS) activation. We isolated cobalt atoms dual nitrogen oxygen (Co−N 3 O 1 ) on oxygen‐doped tubular carbon nitride (TCN) by pyrolyzing a hydrogen‐bonded cyanuric acid melamine–cobalt acetate precursor. The theoretically constructed Co−N moiety TCN exhibited an impressive mass activity 7.61×10 5 min −1 mol high 2 selectivity. Theoretical calculations revealed that single occupied environment, PMS adsorption was promoted energy barriers reduced key *O intermediate produced . were attached to widely used poly(vinylidene fluoride) microfiltration membrane deliver antibiotic wastewater treatment system 97.5 % ciprofloxacin rejection over 10 hours, thereby revealing suitability industrial applications.

Язык: Английский

---

Rational Regulation of Co–N–C Coordination for High-Efficiency Generation of ¹O₂ toward Nearly 100% Selective Degradation of Organic Pollutants

Environmental Science & Technology, Год журнала: 2022, Номер 56(12), С. 8833 - 8843

Опубликована: Май 26, 2022

Single oxygen-based advanced oxidation processes (1O2-AOPs) exhibit great prospects in selective degradation of organic pollutants. However, efficient production 1O2 via tailored design catalysts to achieve contaminants remains challenging. Herein, we develop a simple strategy regulate the components and coordination Co–N–C at atomic level by adjusting Zn/Co ratio bimetallic zeolitic imidazolate frameworks (ZnxCo1-ZIFs). Zn4Co1–C demonstrates 98% removal phenol mixed phenol/benzoic acid (phenol/BA) solutions. Density functional theory calculations experiments reveal that more active CoN4 sites are generated Zn4Co1–C, which beneficial peroxymonosulfate activation generate 1O2. Furthermore, correlation between origin selectivity well-defined is systematically investigated electron paramagnetic resonance test quenching experiments. This work may provide novel insights into target pollutants complicated water matrix.

Язык: Английский

---

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

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(33)

Опубликована: Июнь 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.

Язык: Английский

---

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

Environmental Science & Technology, Год журнала: 2022, Номер 56(12), С. 8984 - 8992

Опубликована: Май 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

Язык: Английский

---

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

Advanced Functional Materials, Год журнала: 2022, Номер 32(38)

Опубликована: Июль 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.

Язык: Английский

---

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

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(16)

Опубликована: Апрель 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.

Язык: Английский

---

The debatable role of singlet oxygen in persulfate-based advanced oxidation processes

Water Research, Год журнала: 2023, Номер 235, С. 119925 - 119925

Опубликована: Март 28, 2023

Язык: Английский

---

Competitive Coordination‐Oriented Monodispersed Ruthenium Sites in Conductive MOF/LDH Hetero‐Nanotree Catalysts for Efficient Overall Water Splitting in Alkaline Media

Advanced Materials, Год журнала: 2022, Номер 34(12)

Опубликована: Янв. 11, 2022

Rational exploration of efficient, inexpensive, and robust electrocatalysts is critical for the efficient water splitting. Conjugated conductive metal-organic frameworks (cMOFs) with multicomponent layered double hydroxides (LDHs) to construct bifunctional heterostructure catalysts are considered as an but complicated strategy. Here, fabrication a cMOF/LDH hetero-nanotree array catalyst (CoNiRu-NT) coupled monodispersed ruthenium (Ru) sites via controllable grafted-growth strategy reported. Rich-amino hexaiminotriphenylene linkers coordinate LDH nanotrunk form cMOF nanobranches, providing numerous anchoring precisely confine stabilize RuN4 sites. Moreover, reduced Ru moieties facilitate H2 O adsorption dissociation, heterointerface between further modifies chemical electronic structures. Optimized CoNiRu-NT displays significant increase in electrochemical water-splitting properties alkaline media, affording low overpotentials 22 mV at 10 mA cm-2 255 20 hydrogen evolution reaction oxygen reaction, respectively. In actual system, drives overall splitting cell voltage 1.47 V reach . This performance comparable that pure noble-metal-based materials superior most reported MOF-based catalysts.

Язык: Английский

---

Singlet oxygen: Properties, generation, detection, and environmental applications

Journal of Hazardous Materials, Год журнала: 2023, Номер 461, С. 132538 - 132538

Опубликована: Сен. 13, 2023

Язык: Английский

---