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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Recent advances in the applications of encapsulated transition-metal nanoparticles in advanced oxidation processes for degradation of organic pollutants: A critical review

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 342, P. 123401 - 123401

Published: Oct. 18, 2023

Language: Английский

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Asymmetrically coordinated CoB ₁ N ₃ moieties for selective generation of high‐valent Co‐oxo species via coupled electron‐proton transfer in Fenton‐like reactions

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(23)

Published: March 18, 2023

High-valence metal species generated in peroxymonosulfate (PMS)-based Fenton-like processes are promising candidates for selective degradation of contaminants water, the formation which necessitates cleavage OH and OO bonds as well efficient electron transfer. However, high dissociation energy bond makes its quite challenging, largely hampering generation reactive oxygen species. Herein, an asymmetrical configuration characterized by a single cobalt atom coordinated with boron nitrogen (CoB1 N3 ) is established to offer strong local electric field, upon thermodynamically favored via promoted coupled electron-proton transfer process, serves essential step further allow Accordingly, Co(IV)O single-atom Co/PMS system enables highly removal performance toward various organic pollutants. The proposed strategy also holds true other heteroatom doping systems configure asymmetric coordination, thus paving alternative pathways specific conversion rationalized design catalysts at atomic level environmental applications more.

Language: Английский

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CoN₁O₂ Single‐Atom Catalyst for Efficient Peroxymonosulfate Activation and Selective Cobalt(IV)=O Generation

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(27)

Published: April 26, 2023

High-valent metal-oxo (HVMO) species are powerful non-radical reactive that enhance advanced oxidation processes (AOPs) due to their long half-lives and high selectivity towards recalcitrant water pollutants with electron-donating groups. However, high-valent cobalt-oxo (CoIV =O) generation is challenging in peroxymonosulfate (PMS)-based AOPs because the 3d-orbital occupancy of cobalt would disfavor its binding a terminal oxygen ligand. Herein, we propose strategy construct isolated Co sites unique N1 O2 coordination on Mn3 O4 surface. The asymmetric configuration able accept electrons from 3d-orbital, resulting significant electronic delocalization at for promoted PMS adsorption, dissociation subsequent CoIV =O species. CoN1 /Mn3 exhibits intrinsic activity activation sulfamethoxazole (SMX) degradation, highly outperforming counterpart CoO3 configuration, carbon-based single-atom catalysts CoN4 commercial oxides. effectively oxidize target contaminants via atom transfer produce low-toxicity intermediates. These findings could advance mechanistic understanding molecular level guide rational design efficient environmental catalysts.

Language: Английский

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Fe-Mn oxycarbide anchored on N-doped carbon for enhanced Fenton-like catalysis: Importance of high-valent metal-oxo species and singlet oxygen

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 340, P. 123204 - 123204

Published: Aug. 22, 2023

Language: Английский

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Switching of radical and nonradical pathways through the surface defects of Fe3O4/MoO S in a Fenton-like reaction

Science Bulletin, Journal Year: 2023, Volume and Issue: 68(6), P. 603 - 612

Published: Feb. 25, 2023

Language: Английский

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Improved Electronic Structure from Spin-State Reconstruction of a Heteronuclear Fe–Co Diatomic Pair to Boost the Fenton-like Reaction

Environmental Science & Technology, Journal Year: 2023, Volume and Issue: 57(11), P. 4556 - 4567

Published: March 9, 2023

Dual-atom catalysts (DACs) are promising candidates for various catalytic reactions, including electrocatalysis, chemical synthesis, and environmental remediation. However, the high-activity origin mechanism underlying intrinsic activity enhancement remain elusive, especially Fenton-like reaction. Herein, we systematically compared performance of dual-atom FeCo–N/C with its single-atom counterparts by activating peroxymonosulfate (PMS) pollutant abatement. The unusual spin-state reconstruction on is demonstrated to effectively improve electronic structure Fe Co in d orbital enhance PMS activation efficiency. Accordingly, an intermediate-spin state remarkably boosts reaction almost 1 order magnitude low-spin Co–N/C high-spin Fe–N/C. Moreover, established dual-atom-activated system also exhibits excellent stability robust resistance against harsh conditions. Combined theoretical calculations reveal that unlike unitary atom or transferring electrons molecule, provides extra neighboring positively shifts band center, thereby optimizing adsorption decomposition into a unique high-valent FeIV–O–CoIV species via low-energy barrier pathway. This work advances conceptually novel mechanistic understanding enhanced DACs reactions helps expand application reactions.

Language: Английский

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Low-coordinated Co-N3 sites induce peroxymonosulfate activation for norfloxacin degradation via high-valent cobalt-oxo species and electron transfer

Journal of Hazardous Materials, Journal Year: 2023, Volume and Issue: 455, P. 131622 - 131622

Published: May 11, 2023

Language: Английский

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Cobalt-based catalysts for heterogeneous peroxymonosulfate (PMS) activation in degradation of organic contaminants: Recent advances and perspectives

Journal of Alloys and Compounds, Journal Year: 2023, Volume and Issue: 958, P. 170370 - 170370

Published: April 30, 2023

Language: Английский

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Applications of vacancy defect engineering in persulfate activation: Performance and internal mechanism

Journal of Hazardous Materials, Journal Year: 2023, Volume and Issue: 449, P. 130971 - 130971

Published: Feb. 10, 2023

Language: Английский

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