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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Outlook on Single Atom Catalysts for Persulfate-Based Advanced Oxidation

ACS ES&T Engineering, Journal Year: 2022, Volume and Issue: 2(10), P. 1776 - 1796

Published: Sept. 7, 2022

Single atom catalysts (SACs) have emerged as a promising catalyst material architecture for energy, chemical, and environmental applications. In the past several years, SACs been increasingly explored persulfate-based advanced oxidation processes (AOPs) due to their superior persulfate activation pollutant degradation performance compared benchmark dissolved ion nanoparticle catalysts. However, there still exist uncertainties on mechanism of by SACs, which involves complex interplay sulfate hydroxyl radicals, singlet oxygen, high-valent metal species, and/or mediated electron transfer. Questions also remain how ions molecularly align single site, are converted into reactive what design parameters lead higher efficiency degradation. this critical review, we examine SAC materials employed AOPs discuss they function differently counterparts. We further our discussion current limitations, opportunities, future research needs in (i) filling knowledge gaps mechanisms persulfate-SAC interactions; (ii) augmenting fundamental with theoretical simulation situ characterization techniques; (iii) improving tailored applications; (iv) proactively considering challenges associated engineering practices water matrixes.

Language: Английский

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Membrane-based nanoconfined heterogeneous catalysis for water purification: A critical review✰

Water Research, Journal Year: 2023, Volume and Issue: 230, P. 119577 - 119577

Published: Jan. 5, 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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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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A polymer tethering strategy to achieve high metal loading on catalysts for Fenton reactions

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

Published: Nov. 29, 2023

The development of heterogenous catalysts based on the synthesis 2D carbon-supported metal nanocatalysts with high loading and dispersion is important. However, such practices remain challenging to develop. Here, we report a self-polymerization confinement strategy fabricate series ultrafine embedded N-doped carbon nanosheets (M@N-C) loadings up 30 wt%. Systematic investigation confirms that abundant catechol groups for anchoring ions entangled polymer networks stable coordinate environment are essential realizing high-loading M@N-C catalysts. As demonstration, Fe@N-C exhibits dual high-efficiency performance in Fenton reaction both impressive catalytic activity (0.818 min-1) H2O2 utilization efficiency (84.1%) using sulfamethoxazole as probe, which has not yet been achieved simultaneously. Theoretical calculations reveal Fe nanocrystals increase electron density frameworks, thereby facilitating continuous generation long-lasting surface-bound •OH through lowering energy barrier activation. This facile universal paves way fabrication diverse heterogeneous broad applications.

Language: Английский

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A critical review on graphene oxide membrane for industrial wastewater treatment

Environmental Research, Journal Year: 2023, Volume and Issue: 223, P. 115409 - 115409

Published: Feb. 4, 2023

Language: Английский

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High-loading of well dispersed single-atom catalysts derived from Fe-rich marine algae for boosting Fenton-like reaction: Role identification of iron center and catalytic mechanisms

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 336, P. 122951 - 122951

Published: June 2, 2023

Language: Английский

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Progress in metal-organic-framework-based single-atom catalysts for environmental remediation

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 474, P. 214855 - 214855

Published: Oct. 4, 2022

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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