Engineering the Electronic Structure of Single‐Atom Iron Sites with Boosted Oxygen Bifunctional Activity for Zinc–Air Batteries

Advanced Materials, Journal Year: 2022, Volume and Issue: 35(9)

Published: Dec. 19, 2022

Abstract Rechargeable zinc–air batteries typically require efficient, durable, and inexpensive bifunctional electrocatalysts to support oxygen reduction/evolution reactions (ORR/OER). However, sluggish kinetics mass transportation challenges must be addressed if the performance of these catalysts is enhanced. Herein, a strategy fabricate catalyst comprising atomically dispersed iron atoms supported on mesoporous nitrogen‐doped carbon (Fe SAs/NC) with accessible metal sites optimized electronic metal–support interactions developed. Both experimental results theoretical calculations reveal that engineered structures active can regulate charge distribution Fe centers optimize adsorption/desorption oxygenated intermediates. The SAs/NC containing 1 N 4 O achieves remarkable ORR activity over entire pH range, half‐wave potentials 0.93, 0.83, 0.75 V (vs reversible hydrogen electrode) in alkaline, acidic, neutral electrolytes, respectively. In addition, it demonstrates promising low overpotential 320 mV at 10 mA cm −2 for OER alkaline conditions. battery assembled exhibits superior than Pt/C+RuO 2 counterpart terms peak power density, specific capacity, cycling stability. These findings demonstrate importance structure engineering directing catalytic activity.

Language: Английский

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Bifunctional Single Atom Catalysts for Rechargeable Zinc–Air Batteries: From Dynamic Mechanism to Rational Design

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(35)

Published: June 7, 2023

Ever-growing demands for rechargeable zinc-air batteries (ZABs) call efficient bifunctional electrocatalysts. Among various electrocatalysts, single atom catalysts (SACs) have received increasing attention due to the merits of high utilization, structural tunability, and remarkable activity. Rational design SACs relies heavily on an in-depth understanding reaction mechanisms, especially dynamic evolution under electrochemical conditions. This requires a systematic study in mechanisms replace current trial error modes. Herein, fundamental oxygen reduction is first presented combining situ and/or operando characterizations theoretical calculations. By highlighting structure-performance relationships, rational regulation strategies are particularly proposed facilitate SACs. Furthermore, future perspectives challenges discussed. review provides thorough SACs, which expected pave avenue exploring optimum effective ZABs.

Language: Английский

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Revisiting the universal principle for the rational design of single-atom electrocatalysts

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(2), P. 207 - 218

Published: Feb. 27, 2024

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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Modulating Electronic Structures of Iron Clusters through Orbital Rehybridization by Adjacent Single Copper Sites for Efficient Oxygen Reduction

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(39)

Published: July 24, 2023

The atom-cluster interaction has recently been exploited as an effective way to increase the performance of metal-nitrogen-carbon catalysts for oxygen reduction reaction (ORR). However, rational design such and understanding their structure-property correlations remain a great challenge. Herein, we demonstrate that introduction adjacent metal (M)-N4 single atoms (SAs) could significantly improve ORR well-screened Fe atomic cluster (AC) catalyst by combining density functional theory (DFT) calculations experimental analysis. DFT studies suggest Cu-N4 SAs act modulator assist O2 adsorption cleavage O-O bond on AC active center, well optimize release OH* intermediates accelerate whole kinetic. depositing with nitrogen doped mesoporous carbon nanosheet are then constructed through universal interfacial monomicelles assembly strategy. Consistent theoretical predictions, resultant exhibits outstanding half-wave potential 0.92 eV in alkali 0.80 acid, high power 214.8 mW cm-2 zinc air battery. This work provides novel strategy precisely tuning atomically dispersed poly-metallic centers electrocatalysis.

Language: Английский

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Electrocatalysts for the oxygen evolution reaction: mechanism, innovative strategies, and beyond

Materials Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 7(20), P. 4833 - 4864

Published: Jan. 1, 2023

This review provides a comprehensive of recent advances in the design OER catalysts. Specifically, it focuses on kinetics and stability catalysts, catalytic mechanism innovative strategies.

Language: Английский

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Surface Engineered Single‐atom Systems for Energy Conversion

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(16)

Published: Jan. 10, 2024

Abstract Single‐atom catalysts (SACs) are demonstrated to show exceptional reactivity and selectivity in catalytic reactions by effectively utilizing metal species, making them a favorable choice among the different active materials for energy conversion. However, SACs still early stages of conversion, problems like agglomeration low conversion efficiency hampering their practical applications. Substantial research focus on support modifications, which vital SAC stability due intimate relationship between atoms support. In this review, category supports variety surface engineering strategies employed SA systems summarized, including site (heteroatom doping, vacancy introducing, groups grafting, coordination tunning) structure (size/morphology control, cocatalyst deposition, facet engineering, crystallinity control). Also, merits single‐atom systematically introduced. Highlights comprehensive summary discussions utilization surface‐engineered diversified applications photocatalysis, electrocatalysis, thermocatalysis, devices. At end potential obstacles using field discussed. This review aims guide rational design manipulation target‐specific capitalizing characteristic benefits engineering.

Language: Английский

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Engineering MOF@LDH heterojunction with strong interfacial built-in electric field towards enhanced electrocatalytic water oxidation

Fuel, Journal Year: 2024, Volume and Issue: 377, P. 132796 - 132796

Published: Aug. 17, 2024

Language: Английский

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Atom-pair engineering of single-atom nanozyme for boosting peroxidase-like activity

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

Published: Aug. 12, 2024

Constructing atom-pair engineering and improving the activity of metal single-atom nanozyme (SAzyme) is significant but challenging. Herein, we design Zn-SA/CNCl SAzyme by simultaneously constructing Zn-N4 sites as catalytic Zn-N4Cl1 regulator. The regulators effectively boost peroxidase-like activities sites, resulting in a 346-fold, 1496-fold, 133-fold increase maximal reaction velocity, constant efficiency, compared to Zn-SA/CN without with excellent inhibits tumor cell growth vitro vivo. density functional theory (DFT) calculations reveal that facilitate adsorption *H2O2 re-exposure thus improve rate. This work provides rational effective strategy for engineering. Designing enhancing performance nanozymes (SAzymes) through important yet difficult. Here authors develop concurrently creating regulators.

Language: Английский

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A Simultaneous Modulation Strategy to Construct High Dense and Accessible Co‐N₄ Sites for Promoting Oxygen Reduction Reaction in Zn–Air Battery

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(32)

Published: April 25, 2024

Abstract Transition metal‐nitrogen‐carbon single‐atom catalysts (M─N─C SACs) exhibit outstanding catalytic activity for the oxygen reduction reaction (ORR). However, these still face dual challenges of low density and utilization active sites in practical applications. Hence, a simultaneous modulation strategy to construct high‐density accessible Co‐N 4 on nitrogen‐doped porous carbon (Co H SA/NC), is reported. As expected, optimized Co SA/NC catalyst exhibits superior ORR with half‐wave potential value 0.874 V, outperforming that benchmark Pt/C catalyst. Importantly, mass turnover frequency are 14.7 13.3 times higher than low‐density single atom L respectively. Structural characterization functional theory (DFT) reveal structure high dense synergistically improve performance, which induced redistribution d orbital, resulting z 2 orbital has enough electron interact OOH * specie, thereby facilitating kinetic process ORR. Moreover, SA/NC‐based Zn–Air Battery (ZAB) also showed excellent device including high‐power (191.7 mW cm −2 ), specific capacity, stability (250 h), significantly Pt/C‐based ZABs.

Language: Английский

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