Spatial engineering of single-atom Fe adjacent to Cu-assisted nanozymes for biomimetic O2 activation

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 12, 2024

Abstract The precise design of single-atom nanozymes (SAzymes) and understanding their biocatalytic mechanisms hold great promise for developing ideal bio-enzyme substitutes. While considerable efforts have been directed towards mimicking partial bio-inspired structures, the integration heterogeneous SAzymes configurations homogeneous enzyme-like mechanism remains an enormous challenge. Here, we show a spatial engineering strategy to fabricate dual-sites with atomic Fe active center adjacent Cu sites. Compared planar Fe–Cu dual-atomic sites, vertically stacked geometry in FePc@2D-Cu–N–C possesses highly optimized scaffolds, favorable substrate affinity, fast electron transfer. These characteristics SAzyme induces biomimetic O 2 activation through homogenous enzymatic pathway, resembling functional mechanistic similarity natural cytochrome c oxidase. Furthermore, it presents appealing alternative P450 3A4 drug metabolism drug–drug interaction. findings are expected deepen fundamental atomic-level next-generation nanozymes.

Language: Английский

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Spin effect in dual-atom catalysts for electrocatalysis

Chemical Science, Journal Year: 2024, Volume and Issue: 15(36), P. 14585 - 14607

Published: Jan. 1, 2024

The development of high-efficiency atomic-level catalysts for energy-conversion and -storage technologies is crucial to address energy shortages. spin states diatomic (DACs) are closely tied their catalytic activity. Adjusting the DACs' active centers can directly modify occupancy d-orbitals, thereby influencing bonding strength between metal sites intermediates as well transfer during electro reactions. Herein, we discuss various techniques characterizing atomic strategies modulating center states. Next, outline recent progress in study effects DACs oxygen reduction reaction (ORR), evolution (OER), hydrogen (HER), electrocatalytic nitrogen/nitrate (eNRR/NO

Language: Английский

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Current Status and Perspectives of Dual-Atom Catalysts Towards Sustainable Energy Utilization

Nano-Micro Letters, Journal Year: 2024, Volume and Issue: 16(1)

Published: Feb. 29, 2024

Abstract The exploration of sustainable energy utilization requires the implementation advanced electrochemical devices for efficient conversion and storage, which are enabled by usage cost-effective, high-performance electrocatalysts. Currently, heterogeneous atomically dispersed catalysts considered as potential candidates a wide range applications. Compared to conventional catalysts, metal atoms in carbon-based have more unsaturated coordination sites, quantum size effect, strong metal–support interactions, resulting exceptional catalytic activity. Of these, dual-atomic (DACs) attracted extensive attention due additional synergistic effect between two adjacent atoms. DACs advantages full active site exposure, high selectivity, theoretical 100% atom utilization, ability break scaling relationship adsorption free on sites. In this review, we summarize recent research advancement DACs, includes (1) comprehensive understanding synergy atomic pairs; (2) synthesis DACs; (3) characterization methods, especially aberration-corrected scanning transmission electron microscopy synchrotron spectroscopy; (4) energy-related last part focuses great catalysis small molecules, such oxygen reduction reaction, CO 2 hydrogen evolution N reaction. future challenges opportunities also raised prospective section.

Language: Английский

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Boosting Electrochemical Nitrogen Reduction via Axial Coordination Engineering on Single‐Iron‐Atom Catalysts

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: May 7, 2024

Abstract Electrocatalytic nitrogen (N 2 ) reduction reaction (NRR) presents a sustainable alternative to the Haber–Bosch process for ammonia (NH 3 synthesis. Iron phthalocyanine (FePc) is demonstrated as promising catalyst electrocatalytic NRR. However, FePc with planar symmetric Fe‐N 4 sites exhibits poor N adsorption and activation capabilities, resulting in an unsatisfactory NRR performance. Herein, axial oxygen coordination strategy developed optimize local electron distribution on improving activation. The as‐obtained FePc‐O‐CP shows superior NH yield rate (59.72 µg h −1 mg cat. considerable Faradaic efficiency (13.76%) 0.1 m HCl. Density functional theory (DFT) calculations verify that ligand inhibits of H + enhances activation, thereby greatly promoting generation. This work reveals significance regulating environment single‐atom catalysts performance provides feasible rational design atomic‐scale active sites.

Language: Английский

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Structure–Activity Relationships in Oxygen Electrocatalysis

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 30, 2024

Abstract Oxygen electrocatalysis, as the pivotal circle of many green energy technologies, sets off a worldwide research boom in full swing, while its large kinetic obstacles require remarkable catalysts to break through. Here, based on summarizing reaction mechanisms and situ characterizations, structure–activity relationships oxygen electrocatalysts are emphatically overviewed, including influence geometric morphology chemical structures electrocatalytic performances. Subsequently, experimental/theoretical is combined with device applications comprehensively summarize cutting‐edge according various material categories. Finally, future challenges forecasted from perspective catalyst development applications, favoring researchers promote industrialization electrocatalysis at an early date.

Language: Английский

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Short-range electronic engineering by coupling Fe phthalocyanines with MOF-derived N,S-doped carbon nanorods for oxygen reduction

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Language: Английский

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Molecular Strain Accelerates Electron Transfer for Enhanced Oxygen Reduction

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

Fe-N-C materials are emerging catalysts for replacing precious platinum in the oxygen reduction reaction (ORR) renewable energy conversion. However, their potential is hindered by sluggish ORR kinetics, leading to a high overpotential and impeding efficient Using iron phthalocyanine (FePc) as model catalyst, we elucidate how local strain can enhance performance of Fe-N-Cs. We use density functional theory predict mechanism four-electron water. Several key differences between mechanisms curved flat FePc suggest that molecular accelerates reductive desorption *OH decreasing barrier ∼60 meV. Our theoretical predictions substantiated experimental validation; find strained on single-walled carbon nanotubes attains half-wave (E1/2) 0.952 V versus reversible hydrogen electrode Tafel slope 35.7 mV dec-1, which competitive with best-reported values. also observe 70 change E1/2 dramatically different slopes configurations, agree well calculated energies. When integrated into zinc-air battery, our device affords maximum power 350.6 mW cm-2 mass activity 810 mAh gZn-1 at 10 mA cm-2. results indicate provides compelling tool modulating activities materials.

Language: Английский

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Fe─N₄ and Fe₇Co₃ Nanoalloy Dual‐Site Modulation by Skeleton Defect in N‐Doped Graphene Aerogel for Enhanced Bifunctional Oxygen Electrocatalyst in Zinc‐air Battery

Small, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Abstract The dual‐site electrocatalysts formed by metal single atoms combines with nanoparticles represent a promising strategy to enhance both oxygen reduction reaction (ORR) and evolution (OER) performance. Herein, defect engineering is applied ORR OER electrocatalysts. Its design, synthesis, structural properties, catalytic performance experimentally theoretically are insightfully studied for the single‐atomic Fe─N 4 adjacent Fe 7 Co 3 nanoalloy (FeCo NA ) as loading on nitrogen‐doped graphene aerogel (Fe─N/FeCo@NGA). high‐density dual‐sites, together good electronic conductivity of NGA, synergistically improve structure superior electrocatalytic activity. half‐wave potential Fe─N/FeCo@NGA in 0.92 V overpotential it 1.58 V. Corresponding all‐solid‐state Zn‐air battery demonstrates peak power density 147.6 mW cm −2 charge/discharge durability over 140 h. Theoretical calculations reveal that Fe‐N FeCo skeleton optimized further refine local structure, modulating tensile force O─O bond * OOH intermediate, leading its spontaneous dissociation facilitating significantly reduced energy barrier. This work takes shortcut application development highly efficient bifunctional atoms.

Language: Английский

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Improvement in ORR Durability of Fe Single-Atom Carbon Catalysts Hybridized with CeO₂ Nanozyme

Nano Letters, Journal Year: 2024, Volume and Issue: 24(29), P. 9034 - 9041

Published: July 11, 2024

FeNC catalysts are considered one of the most promising alternatives to platinum group metals for oxygen reduction reaction (ORR). Despite extensive research on improving ORR activity, undesirable durability is still a critical issue its practical application. Herein, inspired by antioxidant mechanism natural enzymes, CeO

Language: Английский

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Highly active air electrode catalysts for Zn‐air batteries: Catalytic mechanism and active center from obfuscation to clearness

Carbon Neutralization, Journal Year: 2024, Volume and Issue: 3(4), P. 501 - 532

Published: June 4, 2024

Abstract Carbon‐based materials have been found to accelerate the sluggish kinetic reaction and are largely subject overall Zn‐air batteries (ZABs) property, while their full catalytic mechanism is still not excavated because of indistinct internal structure immature in‐situ technology. Up now, systematic methods utilized study design promising high‐performance carbon‐based catalysts. To resolve real active units mechanism, developing molecular catalyst a significant strategy. Herein, review will initiate briefly introduce working principle composition ZABs. An important statement correspondingly provided about typical mechanisms for air cathode material. It also presents tremendous endeavors on performance stability Furthermore, combined with theoretical calculation, self‐defined sites analyzed understand character, where subsequently summarized discussed through highlighting unambiguous controllable structure, in hope surfacing optimum catalyst. Building fundamental understanding catalysts, this expected provide guidance direction toward designing future mechanistic studies ORR electrocatalysts.

Language: Английский

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