Neodymium‐Evoked Valence Electronic Modulation to Balance Reversible Oxygen Electrocatalysis

Advanced Energy Materials, Год журнала: 2022, Номер 13(2)

Опубликована: Ноя. 23, 2022

Abstract Suffering from the competition adsorption between oxygen reduction reaction (ORR) and evolution (OER), development of high‐efficiency electrocatalysts with bifunctional properties still remains a challenge. Herein, novel effective neodymium‐evoked valence electronic perturbation strategy to improve balance reversible electrocatalysis metallic cobalt sites is proposed. To heighten coupling Nd Co, metal‐organic‐framework‐induced method chosen prepare target catalyst atomic Nd‐doped Co on an N‐doped carbon substrate. The as‐prepared presents excellent electrocatalytic low overpotential 288 mV at 10 mA cm −2 for OER high half‐wave potential 0.85 V ORR. robust stabilities both ORR are also proven. electrochemical in situ Raman spectra confirm surface dynamic change transformation intermediates by noting formation Co–OOH. Theoretical calculations verify that balanced owing strong 3d‐Nd 4f orbital effect below Fermi level. Moreover, practicability further demonstrated solid‐state rechargeable Zn‐Air batteries, which exhibit large power density long cycling life.

Язык: Английский

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Nanoscale Metal Particle Modified Single‐Atom Catalyst: Synthesis, Characterization, and Application

Advanced Materials, Год журнала: 2023, Номер 36(2)

Опубликована: Июль 13, 2023

Single-atom catalysts (SACs) have attracted considerable attention in heterogeneous catalysis because of their well-defined active sites, maximum atomic utilization efficiency, and unique unsaturated coordinated structures. However, effectiveness is limited to reactions requiring sites containing multiple metal atoms. Furthermore, the loading amounts single-atom must be restricted prevent aggregation, which can adversely affect catalytic performance despite high activity individual The introduction nanoscale particles (NMPs) into SACs (NMP-SACs) has proven an efficient approach for improving performance. A comprehensive review urgently needed systematically introduce synthesis, characterization, application NMP-SACs mechanisms behind superior This first presents classifies different through NMPs enhance SACs. It then summarizes currently reported synthetic strategies state-of-the-art characterization techniques NMP-SACs. Moreover, electro/thermo/photocatalysis, reasons are discussed. Finally, challenges perspectives future design advanced addressed.

Язык: Английский

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Carbon‐Nanotube‐Bridging Strategy for Integrating Single Fe Atoms and NiCo Nanoparticles in a Bifunctional Oxygen Electrocatalyst toward High‐Efficiency and Long‐Life Rechargeable Zinc–Air Batteries

Advanced Energy Materials, Год журнала: 2022, Номер 12(48)

Опубликована: Ноя. 6, 2022

Abstract The development of highly efficient and robust bifunctional electrocatalysts for oxygen reduction (ORR) evolution reactions (OER) is the key issue realizing high‐performance long‐life rechargeable zinc–air batteries (ZABs). However, it still a great challenge to integrate independent ORR OER sites in catalyst with high activity. Here, carbon nanotube‐bridging strategy proposed synthesize such electrocatalyst enriched active single‐atom Fe nanosized NiCo hydroxides OER. Consequently, developed shows small overpotential difference 0.686 V. When used as an electrode catalyst, corresponding ZAB exhibits large power density 219.5 mW cm −2 , charge–discharge voltage gap 0.72 V at 10 mA outstanding discharge–charge durability without attenuation after more than 700 cycles. This work proposes new idea realize multifunctional catalysts drives practical application ZABs.

Язык: Английский

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Zn-based batteries for sustainable energy storage: strategies and mechanisms

Chemical Society Reviews, Год журнала: 2024, Номер 53(10), С. 4877 - 4925

Опубликована: Янв. 1, 2024

This review systematically summarizes various redox mechanisms in Zn-based batteries and design strategies to improve their electrochemical performance, which provides a reference for future development of high-performance batteries.

Язык: Английский

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Tuning Co‐Catalytic Sites in Hierarchical Porous N‐Doped Carbon for High‐Performance Rechargeable and Flexible Zn‐Air Battery

Advanced Energy Materials, Год журнала: 2022, Номер 13(1)

Опубликована: Ноя. 6, 2022

Abstract The strategy of heteroatom doping and metal active sites can synergistically promote oxygen electrocatalysis. Especially, the combination theoretical simulations with experimental results provides new opportunities to understand electrocatalytic mechanism. Herein, 3D carbon nanosheets aggregate highly branched nanotubes cobalt (CoCNTs/PNAs) is prepared via facile self‐assembly‐pyrolysis strategy. CoCNTs/PNAs electrocatalysts exhibit superior bifunctional activities reduction ( E 1/2 = 0.925 V) evolution j 10 1.54 reactions, surpassing those Pt/C‐RuO 2 catalysts. calculations reveal that electronic interaction nitrogen‐doped matrix plays a critical role in boosting performance. Additionally, rechargeable Zn‐Air battery (ZAB) assembled aqueous electrolyte exhibits largest power density 371.6 mW cm −2 outstanding cycling durability (over 2000 h). Furthermore, all‐solid‐state cable‐type ZAB delivers high flexibility good stability energy efficiency (76.5%). This work will open avenue adjust metal‐carbon support for functional electrocatalysis hierarchical porous structure design.

Язык: Английский

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Modulation of Ligand Fields in a Single-Atom Site by the Molten Salt Strategy for Enhanced Oxygen Bifunctional Activity for Zinc-Air Batteries

ACS Nano, Год журнала: 2022, Номер 16(8), С. 11944 - 11956

Опубликована: Июль 26, 2022

Achieving full utilization of active sites and optimization the electronic structure metal centers is key to improving intrinsic activity single-atom catalysts (SACs) but still remains a challenge date. Herein, versatile molten salt-assisted pyrolysis strategy was developed construct ultrathin, porous carbon nanosheets supported Co SACs. Molten salts are capable inducing formation graphene-like carbon, which facilitates exposure center simultaneously endows SACs with abundant defective Co-N4 configurations. The reported deliver an excellent bifunctional good stability for oxygen reduction reaction (ORR) evolution (OER). Moreover, metal-air batteries (MABs) assembled as air electrode also performance high power densities 160 mW·cm-2, large capacities 760 mAh·g-1, superior long-term charge/discharge stability, outperforming those commercial Pt/C+RuO2. DFT theoretical calculation results show that defects in second coordination shell (CS) promote desorption OH* intermediate ORR facilitate deprotonation OER, can serve favorable site catalysts. Our work provides efficient preparation fully exposed optimized structures.

Язык: Английский

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Robust Electronic Correlation of Co‐CoN₄ Hybrid Active Sites for Durable Rechargeable Zn‐Air Batteries

Advanced Functional Materials, Год журнала: 2022, Номер 32(52)

Опубликована: Окт. 10, 2022

Abstract The rational design of bifunctional catalysts with excellent activity and stability toward the oxygen evolution reaction (OER) reduction (ORR) is essential for rechargeable Zn‐air batteries (ZABs). In this study, a facile coordination bridging strategy proposed to construct Co‐CoN 4 hybrid active sites embedded in porous N‐rich carbon nanolamellas (denoted as @NCNs) both ORR OER. Synchrotron X‐ray absorption spectroscopy density functional theory calculations reveal that increased intrinsic ORR/OER activities can be attributed efficient interfacial charge transfer between atomic CoN metallic Co due their robust electronic correlation. situ Raman confirms OER depends on CoOOH intermediates formed during reaction. @NCNs exhibits superior catalytic performance ( E 1/2 = 0.83 V) (η 310 mV at 10 mA cm −2 ) conducted alkaline media. assembled @NCNs‐based ZAB displays an open‐circuit voltage 1.47 V, peak power 118.8 mW , specific capacity 776.7 mAh g −1 outstanding cycling over 1500 cycles. regulation properties contribute electrocatalysts used metal‐air batteries.

Язык: Английский

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Modulating Coordination of Iron Atom Clusters on N,P,S Triply‐Doped Hollow Carbon Support towards Enhanced Electrocatalytic Oxygen Reduction

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(49)

Опубликована: Окт. 24, 2023

Constructing atom-clusters (ACs) with in situ modulation of coordination environment and simultaneously hollowing carbon support are critical yet challenging for improving electrocatalytic efficiency atomically dispersed catalysts (ADCs). Herein, a general diffusion-controlled strategy based on spatial confining Kirkendall effect is proposed to construct metallic ACs N,P,S triply-doped hollow matrix (MACs /NPS-HC, M=Mn, Fe, Co, Ni, Cu). Thereinto, FeACs /NPS-HC the best catalytic activity oxygen reduction reaction (ORR) thoroughly investigated. Unlike benchmark sample symmetrical N-surrounded iron single-atoms N-doped (FeSAs /N-C), comprises bi-/tri-atomic Fe centers engineered S/N coordination. Theoretical calculation reveals that proper gathering could mildly delocalize electron distribution optimize free energy pathways ORR. In addition, triple doping structure further regulate local allow sufficient exposure active sites, resulting more enhanced ORR kinetics /NPS-HC. The zinc-air battery assembled as cathodic catalyst exhibits all-round superiority Pt/C most Fe-based ADCs. This work provides an exemplary method establishing atomic-cluster S-dominated hollowed matrix, which paves new avenue fabrication optimization advanced

Язык: Английский

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Recent progress of transition metal-based bifunctional electrocatalysts for rechargeable zinc–air battery application

Current Opinion in Electrochemistry, Год журнала: 2023, Номер 38, С. 101229 - 101229

Опубликована: Фев. 4, 2023

Язык: Английский

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Electronic modulation induced by decorating single-atomic Fe-Co pairs with Fe-Co alloy clusters toward enhanced ORR/OER activity

Applied Catalysis B Environment and Energy, Год журнала: 2023, Номер 340, С. 123231 - 123231

Опубликована: Авг. 29, 2023

Язык: Английский

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