Construction of Co₄ Atomic Clusters to Enable Fe−N₄ Motifs with Highly Active and Durable Oxygen Reduction Performance

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Май 24, 2023

Abstract Fe−N−C catalysts with single‐atom Fe−N 4 configurations are highly needed owing to the high activity for oxygen reduction reaction (ORR). However, limited intrinsic and dissatisfactory durability have significantly restrained practical application of proton‐exchange membrane fuel cells (PEMFCs). Here, we demonstrate that constructing adjacent metal atomic clusters (ACs) is effective in boosting ORR performance stability catalysts. The integration uniform Co ACs on N‐doped carbon substrate (Co @/Fe 1 @NC) realized through a “pre‐constrained” strategy using molecular Fe(acac) 3 implanted precursors. as‐developed @NC catalyst exhibits excellent half‐wave potential ( E 1/2 ) 0.835 V vs. RHE acidic media peak power density 840 mW cm −2 H 2 −O cell test. First‐principles calculations further clarify catalytic mechanism identified modified ACs. This work provides viable precisely establishing atomically dispersed polymetallic centers efficient energy‐related catalysis.

Язык: Английский

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Decade Milestone Advancement of Defect-Engineered g-C3N4 for Solar Catalytic Applications

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

Опубликована: Янв. 4, 2024

Over the past decade, graphitic carbon nitride (g-C

Язык: Английский

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Asymmetric N, P‐Coordinated Single‐Atomic Fe Sites with Fe₂P Nanoclusters/Nanoparticles on Porous Carbon Nanosheets for Highly Efficient Oxygen Electroreduction

Advanced Energy Materials, Год журнала: 2023, Номер 13(32)

Опубликована: Июль 10, 2023

Abstract Disrupting the symmetrical electron distribution of single‐atomic Fe sites is proposed as an effective strategy for improving intrinsic activity in oxygen reduction reaction (ORR). Herein asymmetric N, P‐coordinated with 2 P nanoclusters/nanoparticles on porous carbon nanosheets (FePNC) are constructed by a soft‐template self‐sacrificing pyrolysis. The synchrotron X‐ray absorption spectroscopy confirms coexistence FeN 3 1 moieties coordination atom three nitrogen atoms and one phosphorus atom, small amount nanoclusters/nanoparticles. Benefiting from unique electronic geometric configurations, resultant FePNC catalyst exhibits excellent ORR half‐wave potential 0.76 V (0.5 m H SO 4 ) 0.90 (0.1 KOH), good Zn–air battery performance. Theoretical analysis reveals that synergistic effect nanoclusters induces asymmetrical redistribution thus optimize strength toward intermediates, which contribute to improved activity.

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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Single-Atom-Based Oxygen Reduction Reaction Catalysts for Proton Exchange Membrane Fuel Cells: Progress and Perspective

ACS Nano, Год журнала: 2023, Номер 17(20), С. 19514 - 19525

Опубликована: Окт. 9, 2023

Single-atom catalysts (SACs) are regarded as promising non-noble-metal alternatives for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells due to their high atom utilization efficiency and excellent catalytic properties. However, insufficient long-term stability issues of SACs under working conditions seriously hinder practical application. In this perspective, recent progress with optimized ORR activity is first reviewed. Then, possible degradation mechanisms process effective strategies improving durability summarized. Finally, some challenges opportunities proposed develop stable single-atom-based electrocatalysts future.

Язык: Английский

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Different Dimensionalities, Morphological Advancements and Engineering of g‐C₃N₄‐Based Nanomaterials for Energy Conversion and Storage

The Chemical Record, Год журнала: 2023, Номер 23(5)

Опубликована: Апрель 17, 2023

Abstract Graphitic carbon nitride (g‐C 3 N 4 ) has gained tremendous interest in the sector of power transformation and retention, because its distinctive stacked composition, adjustable electronic structure, metal‐free feature, superior thermodynamic durability, simple availability. Furthermore, restricted illumination extensive recombination photoexcitation electrons have inhibited photocatalytic performance pure g‐C . The dimensions may impact field electronics confinement; as a consequence, with varying shows unique features, making it appropriate for number fascinating uses. Even if there are several evaluations emphasizing on fabrication methods deployments , is certainly an insufficiency full overview, that exhaustively depicts synthesis composition diverse aspects Consequently, from standpoint numerical simulations experimentation, legitimate methodologies were employed to deliberately develop photocatalyst improve optimal result, including elements loading, defects designing, morphological adjustment, semiconductors interfacing. Herein, this evaluation initially discusses different dimensions, physicochemical modifications interfaces design development Emphasis given practical various inventory applications, such H 2 evolution, photoreduction CO source, electrocatalytic O reduction, alkali‐metal battery cells, lithium‐ion batteries, lithium–sulfur metal‐air batteries. Ultimately, current challenges potential fuel retention activities explored.

Язык: Английский

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Breaking Sabatier's vertex via switching the oxygen adsorption configuration and reaction pathway on dual active sites for acidic oxygen reduction

Energy & Environmental Science, Год журнала: 2024, Номер 17(9), С. 3077 - 3087

Опубликована: Янв. 1, 2024

Switching the oxygen adsorption configuration and reaction pathway breaks Sabatier's vertex achieves an extraordinary acidic reduction performance.

Язык: Английский

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Efficient Proton-exchange Membrane Fuel Cell Performance of Atomic Fe Sites via p–d Hybridization with Al Dopants

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(18), С. 12636 - 12644

Опубликована: Апрель 27, 2024

Orbital hybridization to regulate the electronic structures and surface chemisorption properties of transition metals is great importance for boosting oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs). Herein, we developed a core–shell rambutan-like nanocarbon catalyst (FeAl-RNC) with atomically dispersed Fe–Al atom pairs from metal–organic framework (MOF) material. Experimental theoretical results demonstrate that strong p–d orbital between Al Fe an asymmetric electron distribution moderate adsorption strength intermediates, rendering enhanced intrinsic ORR activity. Additionally, structure FeAl-RNC abundant micropores macropores can enhance density active sites, stability, transport pathways PEMFC. The FeAl-RNC-based PEMFC achieves excellent activity (68.4 mA cm–2 at 0.9 V), high peak power (1.05 W cm–2), good stability only 7% current loss after 100 h 0.7 V under H2–O2 condition.

Язык: Английский

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Single-atom tailored atomically-precise nanoclusters for enhanced electrochemical reduction of CO2-to-CO activity

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Фев. 28, 2024

Abstract The development of facile tailoring approach to adjust the intrinsic activity and stability atomically-precise metal nanoclusters catalysts is great interest but remians challenging. Herein, well-defined Au 8 modified by single-atom sites are rationally synthesized via a co-eletropolymerization strategy, in which uniformly dispersed nanocluster co-entrenched on poly-carbazole matrix. Systematic characterization theoretical modeling reveal that functionalizing single-atoms enable altering electronic structures clusters, amplifies their electrocatalytic reduction CO 2 ~18.07 fold compared isolated clusters. rearrangements structure not only strengthen adsorption key intermediates *COOH, also establish favorable reaction pathway for reaction. Moreover, this strategy fixing cross-linked polymer networks efficiently deduce performance deactivation caused agglomeration during catalytic process. This work contribute explore improvement

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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