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

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Nanoscale Metal Particle Modified Single‐Atom Catalyst: Synthesis, Characterization, and Application

Advanced Materials, Год журнала: 2023, Номер 36(2)

Опубликована: Июль 13, 2023

Single-atom catalysts (SACs) have attracted considerable attention in heterogeneous catalysis because of their well-defined active sites, maximum atomic utilization efficiency, and unique unsaturated coordinated structures. However, effectiveness is limited to reactions requiring sites containing multiple metal atoms. Furthermore, the loading amounts single-atom must be restricted prevent aggregation, which can adversely affect catalytic performance despite high activity individual The introduction nanoscale particles (NMPs) into SACs (NMP-SACs) has proven an efficient approach for improving performance. A comprehensive review urgently needed systematically introduce synthesis, characterization, application NMP-SACs mechanisms behind superior This first presents classifies different through NMPs enhance SACs. It then summarizes currently reported synthetic strategies state-of-the-art characterization techniques NMP-SACs. Moreover, electro/thermo/photocatalysis, reasons are discussed. Finally, challenges perspectives future design advanced addressed.

Язык: Английский

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Hetero‐Anionic Structure Activated CoS Bonds Promote Oxygen Electrocatalytic Activity for High‐Efficiency Zinc–Air Batteries

Advanced Materials, Год журнала: 2023, Номер 35(36)

Опубликована: Май 18, 2023

Abstract The electronic structure of transition metal complexes can be modulated by replacing partial ion to obtain tuned intrinsic oxygen reduction reaction (ORR) or evolution (OER) electrocatalytic activity. However, the anion‐modulated ORR activity is still unsatisfactory, and construction hetero‐anionic remains challenging. Herein, an atomic doping strategy presented prepare CuCo 2 O 4‐x S x /NC‐2 (CCSO/NC‐2) as electrocatalysts, structrual characterization results favorably demonstrate substitution atoms for in CCSO/NC‐2, which shows excellent catalytic performance durability OER 0.1 m KOH. In addition, catalyst assembled Zinc–air battery with open circuit potential 1.43 V maintains after 300 h cyclic stability. Theoretical calculations differential charges illustrate that optimizes kinetics promotes electron redistribution. superior CCSO/NC‐2 catalysis mainly due its unique modulation main body. introduction CoO covalency constructs a fast transport channel, thus optimizing adsorption degree active site Co intermediates.

Язык: Английский

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Graphitic carbon nitride (g-C₃N₄) based heterogeneous single atom catalysts: synthesis, characterisation and catalytic applications

Journal of Materials Chemistry A, Год журнала: 2023, Номер 11(16), С. 8599 - 8646

Опубликована: Янв. 1, 2023

The ease of anchoring single atoms on the g-C 3 N 4 matrix, through its abundant nitrogen sites, facilitates a variety atom catalysts for applications in multiple domains catalysis.

Язык: Английский

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Novel Pt-carbon core–shell decorated hierarchical CoMo2S4 as efficient electrocatalysts for alkaline/seawater hydrogen evolution reaction

Chemical Engineering Journal, Год журнала: 2023, Номер 473, С. 145348 - 145348

Опубликована: Авг. 9, 2023

Язык: Английский

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State-of-the-art single-atom catalysts in electrocatalysis: From fundamentals to applications

Nano Energy, Год журнала: 2023, Номер 113, С. 108570 - 108570

Опубликована: Май 29, 2023

Язык: Английский

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Modulating Electronic Structures of Iron Clusters through Orbital Rehybridization by Adjacent Single Copper Sites for Efficient Oxygen Reduction

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(39)

Опубликована: Июль 24, 2023

The atom-cluster interaction has recently been exploited as an effective way to increase the performance of metal-nitrogen-carbon catalysts for oxygen reduction reaction (ORR). However, rational design such and understanding their structure-property correlations remain a great challenge. Herein, we demonstrate that introduction adjacent metal (M)-N4 single atoms (SAs) could significantly improve ORR well-screened Fe atomic cluster (AC) catalyst by combining density functional theory (DFT) calculations experimental analysis. DFT studies suggest Cu-N4 SAs act modulator assist O2 adsorption cleavage O-O bond on AC active center, well optimize release OH* intermediates accelerate whole kinetic. depositing with nitrogen doped mesoporous carbon nanosheet are then constructed through universal interfacial monomicelles assembly strategy. Consistent theoretical predictions, resultant exhibits outstanding half-wave potential 0.92 eV in alkali 0.80 acid, high power 214.8 mW cm-2 zinc air battery. This work provides novel strategy precisely tuning atomically dispersed poly-metallic centers electrocatalysis.

Язык: Английский

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Atomic‐Level Engineered Cobalt Catalysts for Fenton‐Like Reactions: Synergy of Single Atom Metal Sites and Nonmetal‐Bonded Functionalities

Advanced Materials, Год журнала: 2024, Номер 36(32)

Опубликована: Апрель 30, 2024

Abstract Single atom catalysts (SACs) are atomic‐level‐engineered materials with high intrinsic activity. Catalytic centers of SACs typically the transition metal (TM)–nonmetal coordination sites, while functions coexisting non‐TM‐bonded functionalities usually overlooked in catalysis. Herein, scalable preparation carbon‐supported cobalt‐anchored (CoCN) controlled Co─N sites and free functional N species is reported. The role metal‐ nonmetal‐bonded for peroxymonosulfate (PMS)‐driven Fenton‐like reactions first systematically studied, revealing their contribution to performance improvement pathway steering. Experiments computations demonstrate that 3 C plays a vital formation surface‐confined PMS* complex trigger electron transfer promote kinetics because optimized electronic state Co centers, nonmetal‐coordinated graphitic act as preferable pollutant adsorption additional PMS activation accelerate transfer. Synergistically, CoCN exhibits ultrahigh activity p ‐hydroxybenzoic acid oxidation, achieving complete degradation within 10 min an turnover frequency 0.38 −1 , surpassing most reported materials. These findings offer new insights into versatile inspire rational design high‐performance complicated heterogeneous systems.

Язык: Английский

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Surface Engineered Single‐atom Systems for Energy Conversion

Advanced Materials, Год журнала: 2024, Номер 36(16)

Опубликована: Янв. 10, 2024

Abstract Single‐atom catalysts (SACs) are demonstrated to show exceptional reactivity and selectivity in catalytic reactions by effectively utilizing metal species, making them a favorable choice among the different active materials for energy conversion. However, SACs still early stages of conversion, problems like agglomeration low conversion efficiency hampering their practical applications. Substantial research focus on support modifications, which vital SAC stability due intimate relationship between atoms support. In this review, category supports variety surface engineering strategies employed SA systems summarized, including site (heteroatom doping, vacancy introducing, groups grafting, coordination tunning) structure (size/morphology control, cocatalyst deposition, facet engineering, crystallinity control). Also, merits single‐atom systematically introduced. Highlights comprehensive summary discussions utilization surface‐engineered diversified applications photocatalysis, electrocatalysis, thermocatalysis, devices. At end potential obstacles using field discussed. This review aims guide rational design manipulation target‐specific capitalizing characteristic benefits engineering.

Язык: Английский

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Advances of Synergistic Electrocatalysis Between Single Atoms and Nanoparticles/Clusters

Nano-Micro Letters, Год журнала: 2024, Номер 16(1)

Опубликована: Июль 9, 2024

Combining single atoms with clusters or nanoparticles is an emerging tactic to design efficient electrocatalysts. Both synergy effect and high atomic utilization of active sites in the composite catalysts result enhanced electrocatalytic performance, simultaneously provide a radical analysis interrelationship between structure activity. In this review, recent advances single-atomic site coupled are emphasized. Firstly, synthetic strategies, characterization, dynamics types clusters/nanoparticles introduced, then key factors controlling discussed. Next, several clean energy catalytic reactions performed over synergistic illustrated. Eventually, encountering challenges recommendations for future advancement energy-transformation electrocatalysis outlined.

Язык: Английский

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