p-d Orbital Hybridization Induced by Asymmetrical FeSn Dual Atom Sites Promotes the Oxygen Reduction Reaction

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21357 - 21366

Published: July 25, 2024

With more flexible active sites and intermetal interaction, dual-atom catalysts (DACs) have emerged as a new frontier in various electrocatalytic reactions. Constructing typical p-d orbital hybridization between p-block d-block metal atoms may bring avenues for manipulating the electronic properties thus boosting activities. Herein, we report distinctive heteronuclear dual-metal atom catalyst with asymmetrical FeSn dual embedded on two-dimensional C2N nanosheet (FeSn–C2N), which displays excellent oxygen reduction reaction (ORR) performance half-wave potential of 0.914 V an alkaline electrolyte. Theoretical calculations further unveil powerful stannum ferrum sites, triggers electron delocalization lowers energy barrier *OH protonation, consequently enhancing ORR activity. In addition, FeSn–C2N-based Zn–air battery provides high maximum power density (265.5 mW cm–2) specific capacity (754.6 mA h g–1). Consequently, this work validates immense along perception into logical design DACs.

Language: Английский

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Cascade Synthesis of Fe‐N2‐Fe Dual‐Atom Catalysts for Superior Oxygen Catalysis

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 3, 2024

Dual-atom catalysts (DACs) have been proposed to break the limitation of single-atom (SACs) in synergistic activation multiple molecules and intermediates, offering an additional degree freedom for catalytic regulation. However, it remains a challenge synthesize DACs with high uniformity, atomic accuracy, satisfactory loadings. Herein, we report facile cascade synthetic strategy DAC via precise electrostatic interaction control neighboring vacancy construction. We synthesized well-defined, uniformly dispersed dual Fe sites which were connected by two nitrogen bonds (denoted as Fe-N

Language: Английский

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Enhanced PtIn Catalyst via Ce-Assisted Confinement Effect in Propane Dehydrogenation

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(11), P. 8116 - 8129

Published: May 9, 2024

The PtIn nanoalloys with high surface energy are generally in a metastable state during harsh reaction conditions, and the ordered alloy structure is not conducive to exposure of Pt active sites. Herein, strategy for restructuring unfavorable via heteroatom (Ce) doping applied advance an isolated Ptδ+ confined by InCeOx nanoislands supported on SiO2. as-synthesized catalyst optimizing PtIn(Ce) ternary components exhibits ∼92.2% selectivity toward propylene stable propane conversion ∼67.1% at 550 °C (kd 0.010 h–1). As demonstrated comprehensive characterizations, introduced proper amount Ce species leads reorganization disadvantaged nanoalloy into robustness site inhibiting In0 generation. modulate electronic interaction between Pt, In, carrier, stimulating capability activate reactive molecules same time acting as spatial physical barriers restrict migration species. This work proposed facile efficient promote against sintering coking Pt-based dehydrogenation.

Language: Английский

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Nitrogen-bridged Cu-Zn dual-atom cooperative interface sites for efficient oxygen reduction reaction in Zn-air battery

Applied Catalysis B Environment and Energy, Journal Year: 2024, Volume and Issue: 357, P. 124288 - 124288

Published: June 11, 2024

Language: Английский

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Active Hydroxyl‐Mediated Preferential Cleavage of Carbon‐Carbon Bonds in Electrocatalytic Glycerol Oxidation

Angewandte Chemie International Edition, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 8, 2025

Electrocatalytic glycerol oxidation reaction (GOR) to produce high-value formic acid (FA) is hindered by high formation potential of active species and sluggish C-C bond cleavage kinetics. Herein, Ni single-atom (NiSA) Co (CoSA) dual sites anchored on nitrogen-doped carbon nanotubes embedded with Ni0.1Co0.9 alloy (Ni0.1Co0.9@NiSACoSA-NCNTs) are constructed for electrochemical GOR. Remarkably, it can reach 10 mA cm-2 at a low 1.15 V versus the reversible hydrogen electrode (vs. RHE) realize formate selectivity 93.27 % even conversion 98.81 1.45 vs. RHE. The GOR mechanism pathway systematically elucidated via experimental analyses theoretical calculations. It revealed that hydroxyl (*OH) be produced during NiSA, CoSA, synergistically optimizes electronic structure CoSA sites, reducing energy barriers *OH-mediated bonds dehydrogenation C1 intermediates. This decreases number intermediates steps GOR-to-FA, thus increasing production efficiency. After coupling evolution in membrane assembly cell, 14.26 g 23.10 L H2 100 108 h.

Language: Английский

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The Role of Long‐Range Interactions Between High‐Entropy Single‐Atoms in Catalyzing Sulfur Conversion Reactions

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 10, 2025

Abstract Sulfur conversion reactions are the foundation of lithium–sulfur batteries but usually possess sluggish kinetics during practical battery operation. Herein, a high‐entropy single‐atom catalyst (HESAC) is synthesized for this process. In contrast to conventional dual‐atom catalysts that form metal–metal bonds, center metal atoms in HESAC not bonded exhibit long‐range interactions at sub‐nanometer distance (<9 Å). The synergistic effect between and entropy changes enables regulation d‐ π‐ electron states. This alteration electronic structure improves adsorption conductivity intermediate polysulfides, thereby accelerating their kinetics. Consequently, leads significant enhancement specific capacities by ≈40% high rates compared catalysts. resulting with demonstrates remarkable areal capacity 3.4 mAh cm −2 10 C. These findings provide valuable insights into design principle atom electrochemical reactions.

Language: Английский

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Bilayer electrified-membrane with pair-atom tin catalysts for near-complete conversion of low concentration nitrate to dinitrogen

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 28, 2025

Discharge of wastewater containing nitrate (NO3−) disrupts aquatic ecosystems even at low concentrations. However, selective and rapid reduction NO3− concentration to dinitrogen (N2) is technically challenging. Here, we present an electrified membrane (EM) loaded with Sn pair-atom catalysts for highly efficient N2 in a single-pass electrofiltration. The design facilitates coupling adsorbed N intermediates on adjacent atoms enhance selectivity, which challenging conventional fully-isolated single-atom catalyst design. EM ensures sufficient exposure the intensifies interaction through mass transfer enhancement provide more coupling. We further develop reduced titanium dioxide as anode generate free chlorines fully oxidizing residual ammonia (<1 mg-N L−1) N2. sequential cathode-to-anode electrofiltration realizes near-complete removal 10 L−1 ~100% selectivity water resident time order seconds. Our findings advance practical solution contamination authors report that mg-N/L during electro-filtration.

Language: Английский

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Refining Asymmetric Low‐Coordinated Fe‐N₃ Motif to Boost Catalytic Ozonation Activity

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(26)

Published: Feb. 28, 2024

Abstract In the quest to boost intrinsic activity of single‐atom catalysts (SACs), optimizing electronic properties metal centers and maximizing active sites play a pivotal role. Here, facile surface molten salt‐assisted approach for fabricating porous iron‐nitrogen‐carbon enriched with catalytically accessible motifs is reported. Multiple characterization analyses prove that abundant defects are generated at edge sites, resulting in formation thermally stable unstitched Fe‐N 3 motif. Theoretical investigations unveil transition from 4 induces structural alteration, convergence Fe‐3 d orbital energy Fermi energy. The low‐coordinated motif exhibits higher activation ability, reinforcing its interaction O weakening O‐O bond. This leads reduction reactivity atomic oxygen barriers (O ‐to‐*O/*OO), ultimately achieving efficient catalytic oxidation methyl mercaptan intermediates, performance 20‐fold than intact 625‐fold commercial MnO 2 . These findings present comprehensive synthesizing SACs fully boosted configurations advance ozonation activity.

Language: Английский

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Tuning the Inter‐Metal Interaction between Ni and Fe Atoms in Dual‐Atom Catalysts to Boost CO2 Electroreduction

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: Aug. 8, 2024

Abstract Dual‐atom catalysts (DACs) are promising for applications in electrochemical CO 2 reduction due to the enhanced flexibility of catalytic sites and synergistic effect between dual atoms. However, precisely controlling atomic distance identifying dual‐atom configuration DACs optimize performance remains a challenge. Here, Ni Fe pairs were constructed on nitrogen‐doped carbon support three different configurations: NiFe‐isolate, NiFe‐N bridge, NiFe‐bonding. It was found that bridge catalyst with NiN 4 FeN sharing two N atoms exhibited superior activity stability when compared NiFe‐isolate NiFe‐bonding catalysts. A series characterizations density functional theory calculations suggested N‐bridged NiFe an appropriate can exert more pronounced synergy. not only regulated suitable adsorption strength *COOH intermediate but also promoted desorption *CO, thus accelerating electroreduction CO. This work provides important implication enhancement catalysis by tailoring coordination structure DACs, identification neighboring

Language: Английский

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Theory-guided design of S-doped Fe/Co dual-atom nanozymes for highly efficient oxidase mimics

Chemical Science, Journal Year: 2024, Volume and Issue: 15(36), P. 14816 - 14828

Published: Jan. 1, 2024

In this study, we synthesized S-doped Fe/Co dual-atom nanozymes under theoretical guidance. S doping and the synergistic effect of sites optimize electronic structure active site, thus enhancing its oxidase-like activity.

Language: Английский

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