Isolating Single and Few Atoms for Enhanced Catalysis

Advanced Materials, Journal Year: 2022, Volume and Issue: 34(39)

Published: May 17, 2022

Abstract Atomically dispersed metal catalysts have triggered great interest in the field of catalysis owing to their unique features. Isolated single or few atoms can be anchored on substrates via chemical bonding space confinement maximize atom utilization efficiency. The key challenge lies precisely regulating geometric and electronic structure active centers, thus significantly influencing catalytic properties. Although several reviews been published preparation, characterization, application single‐atom (SACs), comprehensive understanding SACs, dual‐atom (DACs), atomic clusters has never systematically summarized. Here, recent advances engineering local environments state‐of‐the‐art DACs, for enhanced performance are highlighted. Firstly, various synthesis approaches presented. Then, special attention is focused elucidation terms state coordination structure. Furthermore, a summary isolated applications thermocatalysis, electrocatalysis, photocatalysis provided. Finally, potential challenges future opportunities this emerging This review will pave way regulate microenvironment site boosting processes.

Language: 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, Journal Year: 2023, Volume and Issue: 120(15)

Published: April 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).

Language: Английский

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Single-atom copper embedded in two-dimensional MXene toward peroxymonosulfate activation to generate singlet oxygen with nearly 100% selectivity for enhanced Fenton-like reactions

Applied Catalysis B Environment and Energy, Journal Year: 2022, Volume and Issue: 324, P. 122245 - 122245

Published: Dec. 1, 2022

Language: Английский

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Origin of the Excellent Activity and Selectivity of a Single-Atom Copper Catalyst with Unsaturated Cu-N₂ Sites via Peroxydisulfate Activation: Cu(III) as a Dominant Oxidizing Species

Environmental Science & Technology, Journal Year: 2022, Volume and Issue: 56(12), P. 8765 - 8775

Published: May 12, 2022

As an efficient active oxidant for the selective degradation of pollutants in wastewater, high-valent copper species Cu(III) with persulfate activation has attracted substantial attention some Cu-based catalysts. However, systematic study a catalyst structure and mechanism about peroxydisulfate (PDS) is challenging owing to coexistence multiple Cu structural symmetry PDS. Herein, we anchored atom two pyridinic N atoms synthesize single-atom (CuSA-NC). Experimental characterizations theoretical calculations complemented each other well because uniform atomic sites. The was identified as site, unsaturated Cu-N2 configuration more conductive PDS than saturated Cu-N4 configuration. Benefiting from generation Cu(III), CuSA-NC exhibited obvious anti-interference performance pollutant complex matrix. superior catalytic activity compared that reported catalysts good durability continuous-flow experiment further revealed potential practical applications. This work strongly deepens understanding sites under develops approach actual water purification.

Language: Английский

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Pauling-type adsorption of O2 induced electrocatalytic singlet oxygen production on N–CuO for organic pollutants degradation

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Sept. 22, 2022

Due to environmentally friendly operation and on-site productivity, electrocatalytic singlet oxygen (1O2) production via O2 gas is of immense interest in environment purification. However, the side-on configuration on catalysts surface will lead formation H2O, which seriously limits selectivity activity 1O2 production. Herein, we show a robust N-doped CuO (N-CuO) with Pauling-type (end-on) adsorption at N-Cu-O3 sites for selective generation under direct-current electric field. We propose that not only lowers overall activation energy barrier, but also alters reaction pathway form instead key feature determining dissociation Cu-O bonds rather than O-O bonds. The proposed N dopant strategy applicable series transition metal oxides, providing universal electrocatalysts design scheme existing high-performance

Language: Английский

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Almost 100 % electron transfer regime over Fe−Co dual-atom catalyst toward pollutants removal: Regulation of peroxymonosulfate adsorption mode

Applied Catalysis B Environment and Energy, Journal Year: 2023, Volume and Issue: 339, P. 123178 - 123178

Published: Aug. 15, 2023

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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Single-Atom MnN₅ Catalytic Sites Enable Efficient Peroxymonosulfate Activation by Forming Highly Reactive Mn(IV)–Oxo Species

Environmental Science & Technology, Journal Year: 2023, Volume and Issue: 57(10), P. 4266 - 4275

Published: Feb. 27, 2023

Four-nitrogen-coordinated transitional metal (MN4) configurations in single-atom catalysts (SACs) are broadly recognized as the most efficient active sites peroxymonosulfate (PMS)-based advanced oxidation processes. However, SACs with a coordination number higher than four rarely explored, which represents fundamental missed opportunity for chemistry to boost PMS activation and degradation of recalcitrant organic pollutants. We experimentally theoretically demonstrate here that five-nitrogen-coordinated Mn (MnN5) more effectively activate MnN4 sites, by facilitating cleavage O–O bond into high-valent Mn(IV)–oxo species nearly 100% selectivity. The high activity MnN5 was discerned be due formation higher-spin-state N5Mn(IV)═O species, enable two-electron transfer from organics through lower-energy-barrier pathway. Overall, this work demonstrates importance numbers informs design next-generation environmental catalysts.

Language: Английский

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Edge‐hosted Atomic Co−N₄Sites on Hierarchical Porous Carbon for Highly Selective Two‐electron Oxygen Reduction Reaction

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(51)

Published: Oct. 25, 2022

Not only high efficiency but also selectivity of the electrocatalysts is crucial for high-performance, low-cost, and sustainable energy storage applications. Herein, we systematically investigate edge effect carbon-supported single-atom catalysts (SACs) on oxygen reduction reaction (ORR) pathways (two-electron (2 e- ) or four-electron (4 )) conclude that 2 -ORR proceeding over edge-hosted atomic Co-N4 sites more favorable than basal-plane-hosted ones. As such, have successfully synthesized tuned Co-SACs with different edge-to-bulk ratios. The as-prepared edge-rich Co-N/HPC catalyst exhibits excellent performance a remarkable ≈95 % in wide potential range. Furthermore, find functional groups could saturate graphitic carbon edges under ORR operation further promote electrocatalytic performance. These findings structure-property relationship SACs offer promising direction large-scale low-cost electrochemical H2 O2 production via -ORR.

Language: Английский

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Heteroatom‐Driven Coordination Fields Altering Single Cerium Atom Sites for Efficient Oxygen Reduction Reaction

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(28)

Published: April 4, 2023

For current single-atom catalysts (SACs), modulating the coordination environments of rare-earth (RE) single atoms with complex electronic orbital and flexible chemical states is still limited. Herein, cerium (Ce) SAs supported on a P, S, N co-doped hollow carbon substrate (Ce SAs/PSNC) for oxygen reduction reaction (ORR) are reported. The as-prepared Ce SAs/PSNC possesses half-wave potential 0.90 V, turnover frequency value 52.2 s

Language: Английский

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