Self-carbon-thermal-reduction strategy for boosting the Fenton-like activity of single Fe-N4 sites by carbon-defect engineering

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Nov. 20, 2023

Carbon-defect engineering in metal single-atom catalysts by simple and robust strategy, boosting their catalytic activity, revealing the carbon defect-catalytic activity relationship are meaningful but challenging. Herein, we report a facile self-carbon-thermal-reduction strategy for carbon-defect of single Fe-N4 sites ZnO-Carbon nano-reactor, as efficient catalyst Fenton-like reaction degradation phenol. The vacancies easily constructed adjacent to during synthesis, facilitating formation C-O bonding lowering energy barrier rate-determining-step Consequently, Fe-NCv-900 with exhibits much improved than Fe-NC-900 without abundant vacancies, 13.5 times improvement first-order rate constant phenol degradation. shows high (97% removal ratio only 5 min), good recyclability wide-ranging pH universality (pH range 3-9). This work not provides rational improving catalysts, also deepens fundamental understanding on how periphery environment affects property performance metal-N4 sites.

Language: Английский

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Atomically Dispersed Fe Sites Regulated by Adjacent Single Co Atoms Anchored on N‐P Co‐Doped Carbon Structures for Highly Efficient Oxygen Reduction Reaction

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(17)

Published: July 27, 2023

Abstract Manipulating the coordination environment and electron distribution for heterogeneous catalysts at atomic level is an effective strategy to improve electrocatalytic performance but remains challenging. Herein, atomically dispersed Fe Co anchored on nitrogen, phosphorus co‐doped carbon hollow nanorod structures (FeCo‐NPC) are rationally designed synthesized. The as‐prepared FeCo‐NPC catalyst exhibits significantly boosted kinetics greatly upshifts half‐wave potential oxygen reduction reaction. Furthermore, when utilized as cathode, also displays excellent zinc‐air battery performance. Experimental theoretical results demonstrate that introduction of single atoms with Co‐N/P around isolated induces asymmetric distribution, resulting in suitable adsorption/desorption ability intermediates optimized reaction barrier, thereby improving activity.

Language: Английский

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Edge-Hosted Mn-N₄-C₁₂ Site Tunes Adsorption Energy for Ultralow-Temperature and High-Capacity Solid-State Zn-Air Battery

ACS Nano, Journal Year: 2023, Volume and Issue: 17(10), P. 9565 - 9574

Published: May 9, 2023

Robust operation of Zn-air batteries (ZABs) with high capacity and excellent energy efficiency is desirable for practical harsh applications, whose bottlenecks are mainly originated from the sluggish oxygen catalytic kinetics unstable Zn|electrolyte interface. In this work, we synthesized edge-hosted Mn-N4-C12 coordination supported on N-doped defective carbon (Mn1/NDC) catalyst, exhibiting a good bifunctional performance reduction/evolution reaction (ORR/OER) low potential gap 0.684 V. Theoretical calculation reveals that displayed lowest overpotential ORR/OER owing to decreased adsorption free OH*. The Mn1/NDC-based aqueous ZABs deliver impressive rate performance, ultralong discharging lifespan, stability. Notably, assembled solid-state demonstrate 1.29 Ah, large critical current density 8 mA cm-2, robust cycling stability at -40 °C, which should be attributed Mn1/NDC anti-freezing electrolyte (SSE). Meanwhile, zincophilic nanocomposite SSE polarity accounts stable Zn|SSE interface compatibility. This work not only highlights importance atomic structure design electrocatalysts ultralow-temperature high-capacity but also spurs development sustainable Zn-based conditions.

Language: Английский

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Atomic Distance Engineering in Metal Catalysts to Regulate Catalytic Performance

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(3)

Published: Oct. 2, 2023

Abstract It is very important to understand the structure–performance relationship of metal catalysts by adjusting microstructure at atomic scale. The distance has an essential influence on composition environment active atom, which a key factor for design targeted with desired function. In this review, we discuss and summarize strategies changing from three aspects relate their effects reactivity catalysts. First, regulating bond length between coordination atom one single‐atom site catalytic performance are introduced. lengths affected strain effect support high‐shell doping can evolve during reaction. Next, sites discussed. Due space matching adsorption electron transport, be adjusted shortening distance. addition, arrangement spacing surface atoms nanocatalysts studied. Finally, comprehensive summary outlook given.

Language: Английский

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Electrolyte Tuned Robust Interface toward Fast‐Charging Zn–Air Battery with Atomic Mo Site Catalyst

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(47)

Published: Sept. 3, 2023

Abstract Stable operation of sustainable Zn–air batteries (ZABs) has attracted considerable attention, but it remains a huge challenge to achieve temperature‐adaptive and fast‐charging ZABs. The poor Zn | electrolyte interface the sluggish charging kinetic are major obstacles. Here, high‐performance ZABs constructed by designing polarized zincophilic solid‐state (SSE) with unique solvation interaction 2+ ethylene glycol (EG), atomic Mo site cathode catalyst. On one hand, modulation structure ions partial substitution H 2 O EG inhibits dendrite growth parasitic reactions, leading improvement interface. Moreover, terminal groups in SSE strongly coordinated Zn/H O, which exerts profound influence on stability low‐temperature properties. other incorporated α‐Co(OH) mesoporous nanosheets decrease overpotential oxygen evolution reaction via strong electronic interaction. Consequently, assembled aqueous exhibit ten‐time ability remarkable cycling stability. show unprecedented (1400 cycles at 5 mA cm −2 ) high energy efficiency −40 °C.

Language: Английский

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D‐Orbital Manipulated Ru Nanoclusters for High‐Efficiency Overall Water Splitting at Industrial‐Level Current Densities

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(7)

Published: Oct. 30, 2023

Abstract Owing to the Pt‐like electrocatalytic capability and moderate price, Ru‐based catalysts are considered as Pt alternatives for electrochemical water splitting. However, they demonstrate limited catalytic performance under industrial‐level current densities. Herein, a novel electrocatalyst with an extremely low amount (0.85 wt.%) of Ru nanoclusters anchored on Cr‐doped Fe‐metal–organic frameworks (Ru@Cr─FeMOF) through robust Cr─O─Ru bond is presented. The study unveils that such architecture facilitates fast electron transfer manipulates highest occupied d orbital d‐band centers sites, favoring both oxygen evolution reaction (OER) hydrogen (HER) catalysis. as‐prepared catalyst performs excellent activity 21 mV@10 mA cm −2 HER 230 mV@50 OER in alkaline solution, realizes water‐splitting at densities (1.72 V@1000 ), surpassing state‐of‐the‐art literatures.

Language: Английский

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Recent advances of single-atom alloy catalyst: Properties, synthetic methods and electrocatalytic applications

Materials Today Catalysis, Journal Year: 2023, Volume and Issue: 2, P. 100009 - 100009

Published: June 27, 2023

Developing high-performance and cost-effective electrocatalysts for clean renewable energy conversion process has been proved a promising approach to deal with the global environment issues. Single-atom alloy (SAA) catalyst, foreign metal atoms atomically dispersed in surface of host metal, combines merits conventional alloys single-atom catalysts. The maximum atomic utilization active unique structural electrical properties SAA offer great potential boosting electrocatalytic activity reducing cost manufacture. Meanwhile, well-defined sites raise an opportunity shed light on structure-activity relationship further direct synthesis high-efficiency electrocatalysts. Herein, we focus recent developments advanced catalysts discussed general SAAs. Then design principle synthetic methods were summarized. Next, highlighted practical applications SAAs chemicals production, including hydrogen evolution reaction, oxygen CO2 reduction N2 reaction other representative reactions. Finally, challenges future directions are presented.

Language: Английский

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Atomic Engineering of Single‐Atom Nanozymes for Biomedical Applications

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(21)

Published: Feb. 7, 2024

Single-atom nanozymes (SAzymes) showcase not only uniformly dispersed active sites but also meticulously engineered coordination structures. These intricate architectures bestow upon them an exceptional catalytic prowess, thereby captivating numerous minds and heralding a new era of possibilities in the biomedical landscape. Tuning microstructure SAzymes on atomic scale is key factor designing targeted with desirable functions. This review first discusses summarizes three strategies for their impact reactivity biocatalysis. The effects choices carrier, different synthesis methods, modulation first/second shell, type number metal centers enzyme-like activity are unraveled. Next, attempt made to summarize biological applications tumor therapy, biosensing, antimicrobial, anti-inflammatory, other from mechanisms. Finally, how designed regulated further realization diverse reviewed prospected. It envisaged that comprehensive presented within this exegesis will furnish novel perspectives profound revelations regarding SAzymes.

Language: Английский

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Highly Reversible Zinc‐Air Batteries at −40 °C Enabled by Anion‐Mediated Biomimetic Fat

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(2)

Published: Sept. 24, 2023

Abstract The wide application of portable electrical equipment, aerial vehicles, smart robotics, etc. has boosted the development advanced batteries with safety, high energy density, and environmental adaptability. Inspired by fat layer on animal bodies, biomimetic is constructed as electrolytes solid‐state zinc‐air to achieve excellent cycling performance at low temperatures. Via tailored anion‐H 2 O interaction, antifreezing gel electrolytes, multi‐performance interface compatibility, temperature adaptability, stable power supply simultaneously, build robust Zn|electrolyte interface, thus promoting uniform interfacial electric fields Zn deposition. Excellent long‐term cyclability 120 h a current density 50 mA cm −2 are exhibited 25 °C. Moreover, −40 °C, record‐long life 205 large 10 achieved.

Language: Английский

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Ferredoxin‐Inspired Design of S‐Synergized Fe–Fe Dual‐Metal Center Catalysts for Enhanced Electrocatalytic Oxygen Reduction Reaction

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(19)

Published: Feb. 12, 2024

Abstract Dual‐metal center catalysts (DMCs) have shown the ability to enhance oxygen reduction reaction (ORR) owing their distinctive structural configurations. However, precise modulation of electronic structure and in‐depth understanding synergistic mechanisms between dual metal sites DMCs at atomic level remain challenging. Herein, mimicking ferredoxin, Fe‐based (Fe 2 N 6 ‐S) are strategically designed fabricated, in which additional Fe S synchronously installed near serve as “dual modulators” for coarse‐ fine‐tuning modulation, respectively. The as‐prepared ‐S catalyst exhibits enhanced ORR activity outstanding Zinc‐air (Zn–air) battery performance compared conventional single site catalysts. theoretical experimental results reveal that introducing second creates a adsorption alters O configuration effectively activates O─O bond, while effect downward shift d‐band center, facilitating release OH*. Additionally, local engineering heteroatom further facilitates formation rate‐determining step OOH*, thus accelerating kinetics.

Language: Английский

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