Asymmetric Coordination Regulating D‐Orbital Spin‐Electron Filling in Single‐Atom Iron Catalyst for Efficient Oxygen Reduction DOI
Yizhe Li, Hao Sun,

Longtao Ren

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(28)

Published: May 9, 2024

Abstract The single‐atom Fe−N−C catalyst has shown great promise for the oxygen reduction reaction (ORR), yet intrinsic activity is not satisfactory. There a pressing need to gain deeper understanding of charge configuration and develop rational modulation strategies. Herein, we have prepared Fe with co‐coordination N O (denoted as Fe−N/O−C) adjacent defect, proposing strategy optimize d‐orbital spin‐electron filling sites by fine‐tuning first coordination shell. Fe−N/O−C exhibits significantly better ORR compared its counterpart commercial Pt/C, much more positive half‐wave potential (0.927 V) higher kinetic current density. Moreover, using catalyst, Zn‐air battery proton exchange membrane fuel cell achieve peak power densities up 490 1179 mW cm −2 , respectively. Theoretical studies in situ electrochemical Raman spectroscopy reveal that undergoes redistribution negative shifting d‐band center Fe−N−C, thus optimizing adsorption free energy intermediates. This work demonstrates feasibility introducing an asymmetric shell catalysts provides new optimization direction their practical application.

Language: Английский

Efficient Proton-exchange Membrane Fuel Cell Performance of Atomic Fe Sites via p–d Hybridization with Al Dopants DOI
Yarong Liu, Jiaxin Li,

Zunhang Lv

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(18), P. 12636 - 12644

Published: April 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.

Language: Английский

Citations

29
Enhanced Electron Delocalization Induced by Ferromagnetic Sulfur doped C 3 N 4 Triggers Selective H 2 O 2 Production DOI

Siran Xu,

Yue Yu, Xiaoyu Zhang

et al.

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

Published: May 21, 2024

For the 2D metal-free carbon catalysts, atomic coplanar architecture enables a large number of p

Language: Английский

Citations

26
Regulating the Electronic Synergy of Asymmetric Atomic Fe Sites with Adjacent Defects for Boosting Activity and Durability toward Oxygen Reduction DOI
Siqi Ji, Yuhao Wang, Hongxue Liu

et al.

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(29)

Published: March 17, 2024

Abstract The oxygen reduction reaction (ORR) plays a fundamental role in sustainable energy technologies. However, the creation of non‐precious metal electrocatalysts with high ORR activity and durability under all pH conditions is great significance but remains challenging. Herein, aim to overcome this challenge by creating Fe single atom catalyst on 2D defect‐containing nitrogen‐doped carbon support (Fe 1 /DNC) via microenvironment engineering strategy. Microkinetic modeling reveals that FeN 4 (OH) moieties are real active sites conditions. Due synergistic promotion effect denser accessible defect‐induced electronic properties, /DNC achieves extraordinary alkaline, acidic, neutral conditions, half‐wave potentials 0.95, 0.82, 0.70 V, respectively. Moreover, negligible performance decay observed stability methanol tolerance tests. Zn‐air battery employing delivers remarkable peak power density long‐term operational durability. Theoretical analysis provides compelling evidence defects adjacent can endow an inductive reshape properties balance OOH* formation OH* reduction. This work offers insight into regulation asymmetric coordination structure for boosting electrocatalytic stability.

Language: Английский

Citations

25
Oxygen Doping Cooperated with Co‐N‐Fe Dual‐Catalytic Sites: Synergistic Mechanism for Catalytic Water Purification within Nanoconfined Membrane DOI Creative Commons
Ziwei Wang,

Zhigang Yi,

Lok Wing Wong

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(30)

Published: May 14, 2024

Abstract Atom‐site catalysts, especially for graphitic carbon nitride‐based represents one of the most promising candidates in catalysis membrane water decontamination. However, unravelling intricate relationships between synthesis‐structure–properties remains a great challenge. This study addresses impacts coordination environment and structure units metal central sites based on Mantel test, correlation analysis, evolution sites. An optimized unconventional oxygen doping cooperated with Co‐N‐Fe dual‐sites (OCN Co/Fe) exhibits synergistic mechanism efficient peroxymonosulfate activation, which benefits from significant increase charge density at active regulation natural population orbitals, leading to selective generation SO 4 •− . Building upon these findings, OCN‐Co/Fe/PVDF composite demonstrates 33 min −1 ciprofloxacin (CIP) rejection efficiency maintains over 96% CIP removal (over 24 h) an average permeance 130.95 L m −2 h work offers fundamental guide elucidating definitive origin catalytic performance advance oxidation process facilitate rational design separation improved enhanced stability.

Language: Английский

Citations

24
One‐Pot Etching Pyrolysis to Defect‐Rich Carbon Nanosheets to Construct Multiheteroatom‐Coordinated Iron Sites for Efficient Oxygen Reduction DOI
Shichao Peng,

Xilan Ma,

Jiachen Tian

et al.

Small, Journal Year: 2024, Volume and Issue: 20(33)

Published: April 9, 2024

Constructing multiheteroatom coordination structure in carbonaceous substrates demonstrates an effective method to accelerate the oxygen reduction reaction (ORR) of supported single-atom catalyst. Herein, novel etching route assisted by potassium thiocyanate (KCNS) is developed convert metal-organic framework 2D defect-rich porous N,S-co-doped carbon nanosheets for anchoring atomically dispersed iron sites as high-performance ORR catalysts (Fe-SACs). The well-designed KCNS-assisted can generate spatial confinement template direct nanosheet formation, condition form structure, and additional sulfur atoms coordinate species. Spectral microscopy analysis reveals that element Fe-SACs highly isolated on anchored nitrogen unsymmetrical Fe-S

Language: Английский

Citations

23
Asymmetric Coordination Regulating D‐Orbital Spin‐Electron Filling in Single‐Atom Iron Catalyst for Efficient Oxygen Reduction DOI
Yizhe Li, Hao Sun,

Longtao Ren

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(28)

Published: May 9, 2024

The single-atom Fe-N-C catalyst has shown great promise for the oxygen reduction reaction (ORR), yet intrinsic activity is not satisfactory. There a pressing need to gain deeper understanding of charge configuration and develop rational modulation strategies. Herein, we have prepared Fe with co-coordination N O (denoted as Fe-N/O-C) adjacent defect, proposing strategy optimize d-orbital spin-electron filling sites by fine-tuning first coordination shell. Fe-N/O-C exhibits significantly better ORR compared its counterpart commercial Pt/C, much more positive half-wave potential (0.927 V) higher kinetic current density. Moreover, using catalyst, Zn-air battery proton exchange membrane fuel cell achieve peak power densities up 490 1179 mW cm

Language: Английский

Citations

22
Hydrogen Peroxide Spillover on Platinum–Iron Hybrid Electrocatalyst for Stable Oxygen Reduction DOI

Huiting Niu,

Lei Huang,

Yanyang Qin

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22650 - 22660

Published: July 30, 2024

Iron-nitrogen-carbon (Fe-N-C) catalysts, although the most active platinum-free option for cathodic oxygen reduction reaction (ORR), suffer from poor durability due to Fe leaching and consequent Fenton effect, limiting their practical application in low-temperature fuel cells. This work demonstrates an integrated catalyst of a platinum-iron (PtFe) alloy planted Fe-N-C matrix (PtFe/Fe-N-C) address this challenge. novel exhibits both high-efficiency activity stability, as evidenced by its impressive half-wave potential (

Language: Английский

Citations

22
Single-zinc vacancy unlocks high-rate H2O2 electrosynthesis from mixed dioxygen beyond Le Chatelier principle DOI Creative Commons
Qi Huang,

Baokai Xia,

Ming Li

et al.

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

Published: May 16, 2024

Le Chatelier's principle is a basic rule in textbook defining the correlations of reaction activities and specific system parameters (like concentrations), serving as guideline for regulating chemical/catalytic systems. Here we report model breaking this constraint O

Language: Английский

Citations

19
Regulating Reactive Oxygen Intermediates of Fe−N−C SAzyme via Second‐Shell Coordination for Selective Aerobic Oxidation Reactions DOI

Yuan Xu,

Yuanjie Ma,

Xinghua Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 19, 2024

Reactive oxygen species (ROS) regulation for single-atom nanozymes (SAzymes), e.g., Fe-N-C, is a key scientific issue that determines the activity, selectivity, and stability of aerobic reaction. However, poor understanding ROS formation mechanism on SAzymes greatly hampers their wider deployment. Herein, inspired by cytochromes P450 affording bound intermediates in O

Language: Английский

Citations

18
CeO2 Boosted Fe‐N5 Electrocatalyst via Relay Catalysis for Modulating Oxygen Reduction Reaction in Al‐Air Batteries DOI Open Access
Yumeng Zhang, Fei He, Yijun Gao

et al.

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

Published: March 3, 2025

Abstract Atomically dispersed iron‐nitrogen‐carbon (Fe‐N‐C) catalysts have demonstrated promising oxygen reduction reaction (ORR) activity. It poses a formidable challenge to simultaneously optimize the adsorption energies of multiple intermediates at single active site. In addition, lack long‐term stability remains significant problem due unavoidable 2‐electron by‐product hydrogen peroxide (H 2 O ). Here, sites are achieved modulate energy while removing by growing second site CeO nanoparticles in situ on surface hollow‐structured Fe‐N 5 , thus improving efficiency and /CeO . Density functional theory (DFT) calculations employed probe into synergistic catalytic interaction between proposing relay mechanism underlying enhanced Furthermore, catalyst is ability scavenge inhibit its destructive effects Additionally, liquid Al – air batteries equipped with display higher power density. This work proffers an innovative vista for conception refinement multi‐active‐site excellent performance prolonged lifespan.

Language: Английский

Citations

2