Emerging low-nuclearity supported metal catalysts with atomic level precision for efficient heterogeneous catalysis

Nano Research, Год журнала: 2022, Номер 15(9), С. 7806 - 7839

Опубликована: Июнь 2, 2022

Язык: Английский

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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

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Designing a Built-In Electric Field for Efficient Energy Electrocatalysis

ACS Nano, Год журнала: 2022, Номер 16(12), С. 19959 - 19979

Опубликована: Дек. 15, 2022

To utilize intermittent renewable energy as well achieve the goals of peak carbon dioxide emissions and neutrality, various electrocatalytic devices have been developed. However, reactions, e.g., hydrogen evolution reaction/oxygen reaction in overall water splitting, polysulfide conversion lithium–sulfur batteries, formation/decomposition lithium peroxide lithium–oxygen nitrate reduction to degrade sewage, suffer from sluggish kinetics caused by multielectron transfer processes. Owing merits accelerated charge transport, optimized adsorption/desorption intermediates, raised conductivity, regulation microenvironment, ease combine with geometric characteristics, built-in electric field (BIEF) is expected overcome above problems. Here, we give a Review about very recent progress BIEF for efficient electrocatalysis. First, construction strategies characterization methods (qualitative quantitative analysis) are summarized. Then, up-to-date overviews engineering electrocatalysis, attention on electron structure optimization microenvironment modulation, analyzed discussed detail. In end, challenges perspectives proposed. This gives deep understanding design electrocatalysts next-generation storage devices.

Язык: Английский

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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

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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

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Single‐Atom Iron Anchored Tubular g‐C₃N₄ Catalysts for Ultrafast Fenton‐Like Reaction: Roles of High‐Valency Iron‐Oxo Species and Organic Radicals

Advanced Materials, Год журнала: 2022, Номер 34(31)

Опубликована: Июнь 9, 2022

Single-atom catalysts have emerged as an efficient oxidant activator for eliminating organic pollutants in Fenton-like systems. However, the complex preparation, single active site, lack of understanding fundamental mechanism, and harsh pH conditions currently limit their practical applications. In this work, single-atom iron anchored nitrogen-rich g-C3 N4 nanotubes (FeCNs) are designed synthesized by a facile approach, eco-friendly peracetic acid (PAA) is selected reactions. The constructed heterogenous system achieves enhanced degradation various contaminants over wide range 3.0-9.0, exhibiting ultrahigh stable catalytic activity, outperforming equivalent quantities pristine 75 times. 18 O isotope-labeling technique, probe method, theoretical calculations demonstrate that activity relies on high-valency iron-oxo species coupled with radicals generated PAA. An increase electron transport from contaminant to formed "metastable PAA/FeCN catalyst surface complex" detected. A double driving mechanism tubular regulated Fe site PAA activation proposed. This work opens avenue developing novel coexistence multiple units providing opportunities significantly improving efficiency.

Язык: Английский

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The optimized Fenton-like activity of Fe single-atom sites by Fe atomic clusters–mediated electronic configuration modulation

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(15)

Опубликована: Апрель 3, 2023

The performance optimization of isolated atomically dispersed metal active sites is critical but challenging. Here, TiO2@Fe species-N-C catalysts with Fe atomic clusters (ACs) and satellite Fe-N4 were fabricated to initiate peroxymonosulfate (PMS) oxidation reaction. AC-induced charge redistribution single atoms (SAs) was verified, thus strengthening the interaction between SAs PMS. In detail, incorporation ACs optimized HSO5- SO5·- desorption steps, accelerating reaction progress. As a result, Vis/TiFeAS/PMS system rapidly eliminated 90.81% 45 mg/L tetracycline (TC) in 10 min. process characterization suggested that PMS as an electron donor would transfer species TiFeAS, generating 1O2. Subsequently, hVB+ can induce generation electron-deficient species, promoting circulation. This work provides strategy construct multiple atom assembly-enabled composite for high-efficiency PMS-based advanced processes (AOPs).

Язык: Английский

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Single-atom Mo–Co catalyst with low biotoxicity for sustainable degradation of high-ionization-potential organic pollutants

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(29)

Опубликована: Июль 10, 2023

Single-atom catalysts (SACs) are a promising area in environmental catalysis. We report on bimetallic Co–Mo SAC that shows excellent performance activating peroxymonosulfate (PMS) for sustainable degradation of organic pollutants with high ionization potential (IP > 8.5 eV). Density Functional Theory (DFT) calculations and experimental tests demonstrate the Mo sites – Co SACs play critical role conducting electrons from to sites, leading 19.4-fold increase rate phenol compared CoCl 2 PMS group. The exhibit catalytic even under extreme conditions show long-term activation 10-d experiments, efficiently degrading 600 mg/L phenol. Moreover, catalyst has negligible toxicity toward MDA-MB-231, Hela, MCF-7 cells, making it an environmentally friendly option water treatment. Our findings have important implications design efficient remediation other applications biology medicine.

Язык: Английский

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Fenton-like activity and pathway modulation via single-atom sites and pollutants comediates the electron transfer process

Proceedings of the National Academy of Sciences, Год журнала: 2024, Номер 121(3)

Опубликована: Янв. 8, 2024

The studies on the origin of versatile oxidation pathways toward targeted pollutants in single-atom catalysts (SACs)/peroxymonosulfate (PMS) systems were always associated with coordination structures rather than perspective pollutant characteristics, and analysis mechanism commonality is lacking. In this work, a variety (M-SACs, M: Fe, Co, Cu) fabricated via pyrolysis process using lignin as complexation agent substrate precursor. Sixteen kinds commonly detected various references selected, their ln k obs values M-SACs/PMS correlated well ( R 2 = 0.832 to 0.883) electrophilic indexes (reflecting electron accepting/donating ability pollutants) energy gap 0.801 0.840) between complexes. Both transfer (ETP) radical can be significantly enhanced systems, while was overwhelmed by ETP lower indexes. contrast, higher represented weaker electron-donating capacity complexes, which resulted accompanied noticeable oxidation. addition, different regulated gaps complexes pollutants. As result, Fenton-like activities could modulated reaction pathways, determined both sites. This work provided strategy establish PMS-based AOP tunable capacities for high-efficiency organic decontamination.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(27)

Опубликована: Апрель 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.

Язык: Английский

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