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

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(2)

Published: July 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.

Language: Английский

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

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(36)

Published: May 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.

Language: 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, Journal Year: 2023, Volume and Issue: 11(16), P. 8599 - 8646

Published: Jan. 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.

Language: 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, Journal Year: 2023, Volume and Issue: 473, P. 145348 - 145348

Published: Aug. 9, 2023

Language: Английский

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

Nano Energy, Journal Year: 2023, Volume and Issue: 113, P. 108570 - 108570

Published: May 29, 2023

Language: 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, Journal Year: 2023, Volume and Issue: 62(39)

Published: July 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.

Language: 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, Journal Year: 2024, Volume and Issue: 36(32)

Published: April 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.

Language: Английский

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Surface Engineered Single‐atom Systems for Energy Conversion

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(16)

Published: Jan. 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.

Language: Английский

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Recent Design Strategies for M‐N‐C Single‐Atom Catalysts in Oxygen Reduction: An Entropy Increase Perspective

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(36)

Published: March 18, 2024

Abstract Recently, a diverse array of novel metal‐nitrogen‐carbon (M‐N‐C) single‐atom catalysts (SACs) have rapidly evolve, particularly in the realm oxygen reduction reaction (ORR). Despite plethora proposed design and improvement strategies for SACs, comprehensive review systematically compiling components M‐N‐C from unified perspective is notably absent. For first time, thorough examination each component conducted, focusing on entropy increase active sites SACs. single M‐N 4 whole system, an implies elevated degree disorder chaos. Broadly, entropy‐increasing modification M (single mental sites) guest groups entails augmentation chaos, with most effective co‐catalytic synergy achieved by establishing multiple through “cocktail effect”. Concerning N (nitrogen other heteroatoms) C (carbon supports), induces heightened disorder, symmetry breaking more likely to drive toward adsorbing molecules attain equilibrium symmetric structure. All these innovative led remarkable ORR activity stability offer guiding criterion future preparation

Language: Английский

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