Active site engineering toward atomically dispersed M−N−C catalysts for oxygen reduction reaction

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 495, P. 215400 - 215400

Published: Aug. 21, 2023

Language: Английский

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Transformation of the Active Moiety in Phosphorus-Doped Fe–N–C for Highly Efficient Oxygen Reduction Reaction

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9427 - 9441

Published: July 3, 2023

Iron- and nitrogen-doped carbon (Fe–N–C) materials have been suggested as the most promising replacement for Pt-based catalysts in oxygen reduction reaction (ORR) owing to FeN4 active moiety. Based on relationship between binding energy catalytic activity, Fe–N–C has a very strong energy; hence, hard desorb final intermediate of *OH. Herein, we provide an effective method tuning moiety using phosphine-gas treatment Fe–N–C. Combined analyses experimental computational results reveal that conventional is transformed into FeN3PO through P-doping post-treatment. Furthermore, propose ORR mechanism unique based microkinetic model, which *OH intermediates are considered. Compared moiety, facilitates desorption, thereby enhancing activity both alkaline acidic electrolytes. The effects performance also validated anion exchange membrane fuel cells (AEMFCs) proton (PEMFCs).

Language: Английский

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Electronic structure regulation of the Fe-based single-atom catalysts for oxygen electrocatalysis

Nano Energy, Journal Year: 2024, Volume and Issue: 121, P. 109268 - 109268

Published: Jan. 9, 2024

Language: Английский

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Inhibiting Demetalation of Fe─N─C via Mn Sites for Efficient Oxygen Reduction Reaction in Zinc‐Air Batteries

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(32)

Published: May 29, 2024

Demetalation caused by the electrochemical dissolution of metallic Fe atoms is a major challenge for practical application Fe─N─C catalysts. Herein, an efficient single Mn active site constructed to improve strength Fe─N bond, inhibiting demetalation effect Fe─N─C. acts as electron donor inducing more delocalized electrons reduce oxidation state increasing density, thereby enhancing bond and Fe. The oxygen reduction reaction pathway dissociation Fe─Mn dual sites can overcome high energy barriers direct O─O modulate electronic states

Language: Английский

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Precise coordination of high-loading Fe single atoms with sulfur boosts selective generation of nonradicals

Proceedings of the National Academy of Sciences, Journal Year: 2024, Volume and Issue: 121(4)

Published: Jan. 17, 2024

Nonradicals are effective in selectively degrading electron-rich organic contaminants, which unfortunately suffer from unsatisfactory yield and uncontrollable composition due to the competitive generation of radicals. Herein, we precisely construct a local microenvironment carbon nitride–supported high-loading (~9 wt.%) Fe single-atom catalyst (Fe SAC) with sulfur via facile supermolecular self-assembly strategy. Short-distance S coordination boosts peroxymonosulfate (PMS) activation generates high-valent iron–oxo species IV =O) along singlet oxygen ( 1 O 2 ), significantly increasing yield, PMS utilization, p -chlorophenol reactivity by 6.0, 3.0, 8.4 times, respectively. The nonradicals is controllable simply changing content. In contrast, long-distance both radicals nonradicals, could not promote reactivity. Experimental theoretical analyses suggest that short-distance upshifts d -band center atom, i.e., being close Fermi level, changes binding mode between atom site generate =O high yield. S-coordinated SAC exhibits excellent application potential various water matrices. These findings can guide rational design robust SACs toward selective utilization.

Language: Английский

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Rational Design of Heteroatom-Doped Fe–N–C Single-Atom Catalysts for Oxygen Reduction Reaction via Simple Descriptor

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6952 - 6964

Published: April 18, 2024

The coordination engineering of Fe–N–C single-atom catalysts (SACs) through introducing heteroatom dopants has attracted widespread attention in the oxygen reduction reaction (ORR). However, common regularity for tuning ORR activity by coordinated and environmental heteroatoms not been sufficiently studied. Herein, we study on 100 SACs with S, P, B diverse shells density functional theory calculations. Based energy level distribution frontier orbits molecular orbital theory, it is found that origin hybridization orbitals Fe 3dz2, 3dyz (3dxz), O2*/OH* intermediates, where hybrid are adjusted heteroatoms, then protonation process O2* or OH* intermediate determined. Moreover, Fe–O bond length, d-orbital gap spin states, center, valence state site can be used as structural descriptors to predict governed potential-determining steps. Our rationalize superior performance S atoms doped second shell those first shell, well fact P more suitable a atom than enhance Fe–N–C, available experimental references. Thanks descriptors, codoping synergistic effect between predicted confirmed greatly activity. This provides unified mechanistic understanding trend among regulated heteroatoms.

Language: Английский

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Regulating the Electronic Synergy of Asymmetric Atomic Fe Sites with Adjacent Defects for Boosting Activity and Durability toward Oxygen Reduction

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

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Atomically Dispersed Dual-Metal ORR Catalyst with Hierarchical Porous Structure for Zn–Air Batteries

ACS Applied Materials & Interfaces, Journal Year: 2024, Volume and Issue: 16(10), P. 12398 - 12406

Published: Feb. 27, 2024

The metal-nitrogen-carbon (M-N-C)-based catalysts are promising to replace PGM (platinum group metal) accelerate oxygen reduction reaction due their excellent electrocatalytic performance. However, the inferior intrinsic activity and poor active site density confining further improvement in Modulating electronic structure reasonably designing pore widely acknowledged effective strategies boost of M-N-C catalysts. it is a great challenge form abundant pores regulate via facile method. Herein, hierarchical, porous dual-atom catalyst FeNi-NPC-1000 has been architectured by Na

Language: Английский

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Atomically dispersed multi-site catalysts: bifunctional oxygen electrocatalysts boost flexible zinc–air battery performance

Energy & Environmental Science, Journal Year: 2024, Volume and Issue: 17(14), P. 4847 - 4870

Published: Jan. 1, 2024

Based on the advancements in atomically dispersed multi-site catalysts for FZABs, this review discusses design methodologies to regulate performance of bifunctional oxygen electrocatalysts from electronic and geometric structures.

Language: Английский

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Salt Effect Engineering Single Fe‐N₂P₂‐Cl Sites on Interlinked Porous Carbon Nanosheets for Superior Oxygen Reduction Reaction and Zn‐Air Batteries

Advanced Science, Journal Year: 2024, Volume and Issue: 11(12)

Published: Jan. 15, 2024

Abstract Developing efficient metal‐nitrogen‐carbon (M‐N‐C) single‐atom catalysts for oxygen reduction reaction (ORR) is significant the widespread implementation of Zn‐air batteries, while synergic design matrix microstructure and coordination environment metal centers remains challenges. Herein, a novel salt effect‐induced strategy proposed to engineer N P coordinated atomically dispersed Fe atoms with extra‐axial Cl on interlinked porous carbon nanosheets, achieving superior catalyst (denoted as Fe‐NP‐Cl‐C) ORR batteries. The hierarchical nanosheet architecture can provide rapid mass/electron transfer channels facilitate exposure active sites. Experiments density functional theory (DFT) calculations reveal distinctive Fe‐N 2 ‐Cl sites afford significantly reduced energy barriers promoted kinetics ORR. Consequently, Fe‐NP‐Cl‐C exhibits distinguished performance half‐wave potential (E 1/2 ) 0.92 V excellent stability. Remarkably, assembled battery based delivers an extremely high peak power 260 mW cm −2 large specific capacity 812 mA h g −1 , outperforming commercial Pt/C most reported congeneric catalysts. This study offers new perspective structural optimization engineering electrocatalysis conversion devices.

Language: Английский

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