Nanoconfinement steers nonradical pathway transition in single atom fenton-like catalysis for improving oxidant utilization

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

Published: June 22, 2024

Abstract The introduction of single-atom catalysts (SACs) into Fenton-like oxidation promises ultrafast water pollutant elimination, but the limited access to pollutants and oxidant by surface catalytic sites intensive consumption still severely restrict decontamination performance. While nanoconfinement SACs allows drastically enhanced reaction kinetics, detailed regulatory mechanisms remain elusive. Here, we unveil that, apart from local enrichment reactants, pathway shift is also an important cause for reactivity enhancement nanoconfined SACs. electronic structure cobalt site altered confining it within nanopores mesostructured silica particles, which triggers a fundamental transition singlet oxygen electron transfer 4-chlorophenol oxidation. changed accelerated interfacial mass render system up 34.7-fold higher degradation rate raised peroxymonosulfate utilization efficiency (from 61.8% 96.6%) relative unconfined control. It demonstrates superior other electron-rich phenolic compounds, good environment robustness, high stability treating real lake water. Our findings deepen knowledge catalysis may inspire innovations in low-carbon purification technologies heterogeneous applications.

Language: Английский

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Precisely Control Relationship between Sulfur Vacancy and H Absorption for Boosting Hydrogen Evolution Reaction

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

Published: Jan. 2, 2024

Effective and robust catalyst is the core of water splitting to produce hydrogen. Here, we report an anionic etching method tailor sulfur vacancy (V

Language: Английский

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Oxophilic Tm‐Sites in MoS₂ Trigger Thermodynamic Spontaneous Water Dissociation for Enhanced Hydrogen Evolution

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

Published: June 11, 2024

Abstract 2D MoS 2 is acknowledged as a potential alternative to Pt‐based catalysts for hydrogen evolution reaction (HER) due its suitable * H adsorption energy. However, the weak water capacity of in an alkaline solution limits performance improvement toward HER. Herein, novel rare‐earth Tm single atoms decorated (Tm SAs‐MoS ) catalyst proposed, and key role SAs on enhanced HER identified. It verified that Tm‐site contributes asymmetric [Mo‐S‐Tm] unit site, which serves electron donor disturb electronic state accelerate accumulation at surrounding Mo‐S site. The obtained exhibits significantly improved activity with low overpotential 80 mV 10 mA cm −2 , robust stability good selectivity compared pure most ‐based catalysts. In situ Raman theoretical calculations prove oxophilic sites improves migration thermodynamic spontaneous dissociation interfacial O molecules during by Tm‐4f‐OH orbital overlap. Such [Tm‐S‐Mo] site allows optimal G *H location turn reaches apex volcano plot. This work expected open up new avenues design provide valuable understanding rare earth mechanisms.

Language: Английский

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Engineering interfacial sulfur migration in transition-metal sulfide enables low overpotential for durable hydrogen evolution in seawater

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

Published: July 22, 2024

Abstract Hydrogen production from seawater remains challenging due to the deactivation of hydrogen evolution reaction (HER) electrode under high current density. To overcome activity-stability trade-offs in transition-metal sulfides, we propose a strategy engineer sulfur migration by constructing nickel-cobalt sulfides heterostructure with nitrogen-doped carbon shell encapsulation (CN@NiCoS) electrocatalyst. State-of-the-art ex situ / characterizations and density functional theory calculations reveal restructuring CN@NiCoS interface, clearly identifying dynamic migration. The NiCoS stimulates creating vacancies at Ni 3 S 2 -Co 9 8 heterointerface, while migrated atoms are subsequently captured CN via strong C-S bond, preventing sulfide dissolution into alkaline electrolyte. Remarkably, dynamically formed sulfur-doped pairing sites significantly enhances HER activity altering d -band center near Fermi level, resulting low overpotential 4.6 mV 10 mA cm −2 freshwater media, long-term stability up 1000 h. This work thus provides guidance for design high-performance electrocatalyst engineering interfacial atomic

Language: Английский

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Atomic Gap-State Engineering of MoS₂ for Alkaline Water and Seawater Splitting

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 11, 2025

Transition-metal dichalcogenides (TMDs), such as molybdenum disulfide (MoS2), have emerged a generation of nonprecious catalysts for the hydrogen evolution reaction (HER), largely due to their theoretical adsorption energy close that platinum. However, efforts activate basal planes TMDs primarily centered around strategies introducing numerous atomic vacancies, creating vacancy–heteroatom complexes, or applying significant strain, especially acidic media. These approaches, while potentially effective, present substantial challenges in practical large-scale deployment. Here, we report gap-state engineering strategy controlled activation S atom MoS2 through metal single-atom doping, effectively tackling both efficiency and stability alkaline water seawater splitting. A versatile synthetic methodology allows fabrication series single-metal atom-doped materials (M1/MoS2), featuring widely tunable densities with each dopant replacing Mo site. Among these (Mn1, Fe1, Co1, Ni1), Co1/MoS2 demonstrates outstanding HER performance media, overpotentials at mere 159 164 mV 100 mA cm–2, Tafel slopes 41 45 dec–1, respectively, which surpasses all reported TMD-based benchmark Pt/C during splitting, can be attributed an optimal modulation associated sulfur atoms. Experimental data correlating doping density identity performance, conjunction calculations, also reveal descriptor linked near-Fermi gap state modulation, corroborated by observed increase unoccupied 3p states.

Language: Английский

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Hollow Mo/MoS_Vn Nanoreactors with Tunable Built‐in Electric Fields for Sustainable Hydrogen Production

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

Published: Dec. 8, 2024

Abstract Constructing built‐in electric field (BIEF) in heterojunction catalyst is an effective way to optimize adsorption/desorption of reaction intermediates, while its precise tailor achieve efficient bifunctional electrocatalysis remains great challenge. Herein, the hollow Mo/MoS Vn nanoreactors with tunable BIEFs are elaborately prepared simultaneously promote hydrogen evolution (HER) and urea oxidation (UOR) for sustainable production. The BIEF induced by sulfur vacancies can be modulated from 0.79 0.57 0.42 mV nm −1 , exhibits a parabola‐shaped relationship HER UOR activities, V1 nanoreactor moderate presents best activity. Theoretical calculations reveal that evidently facilitate breakage N─H bond UOR. electrolyzer assembled delivers cell voltage 1.49 V at 100 mA cm −2 which 437 lower than traditional water electrolysis, also excellent durability 200 h. Life cycle assessment indicates HER||UOR system possesses notable superiority across various environment impact energy consumption. This work provide theoretical experimental direction on rational design advanced materials energy‐saving eco‐friendly

Language: Английский

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Yolk‐Shell Construction of Na₃V₂(PO₄)₂F₃ with Copper Substitution Microsphere as High‐Rate and Long‐Cycling Cathode Materials for Sodium‐Ion Batteries

Small, Journal Year: 2024, Volume and Issue: 20(31)

Published: March 8, 2024

Abstract Na 3 V 2 (PO 4 ) F (NVPF) is emerging as a promising cathode material for high‐voltage sodium‐ion batteries. Whereas, the inferior intrinsic electrical conductivity leading to poor rate performance and cycling stability. To address this issue, strategy of synthesizing unique yolk‐shell structured NVPF with copper substitution via spray drying method proposed. Besides, synergistic modulation both crystalline structure interfacial properties results in significantly enhanced NVPF. The optimized materials can possess high capacity 117.4 mAh g −1 at 0.1 C, remains high‐capacity retention 91.3% after 5000 cycles. A detailed investigation kinetic combined situ XRD technology DFT calculations, has been implemented, particularly regard electron conduction sodium ion diffusion. Consequently, composition 1.94 Cu 0.06 nitrogen‐modified carbon coating layer shows lowest polarization potential because effectively electronic + diffusion process bulk phase. robust electrochemical suggests that developing collaboration interface crystal favorable design

Language: Английский

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Enabling Ultrafine Ru Nanoparticles with Tunable Electronic Structures via a Double-Shell Hollow Interlayer Confinement Strategy toward Enhanced Hydrogen Evolution Reaction Performance

Nano Letters, Journal Year: 2023, Volume and Issue: 24(2), P. 592 - 600

Published: Dec. 1, 2023

Engineering of the catalysts' structural stability and electronic structure could enable high-throughput H

Language: Английский

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High-valent iron single-atom catalysts for improved overall water splitting via a reduced energy barrier and stabilization of the active center

Journal of Materials Chemistry A, Journal Year: 2023, Volume and Issue: 12(1), P. 121 - 127

Published: Nov. 9, 2023

We demonstrate iron (Fe) single atoms stabilized on carbon–nickel nanosheet (C–Ni) electrodes via a single-step metal–organic-framework-assisted electrochemical approach for improved water splitting.

Language: Английский

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Construction of S-doped cellulose nanocrystals with edge sulfur vacancies to enhance the generation of 1O2 and promote peroxymonosulfate (PMS) activation

Applied Surface Science, Journal Year: 2024, Volume and Issue: 671, P. 160717 - 160717

Published: July 10, 2024

Language: Английский

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