High Flux and Stability of Cationic Intercalation in Transition-Metal Oxides: Unleashing the Potential of Mn t2g Orbital via Enhanced π-Donation DOI

Shuyun Yao,

Shiyu Wang, Yuanming Liu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(49), P. 26699 - 26710

Published: Dec. 1, 2023

Transition-metal oxides (TMOs) often struggle with challenges related to low electronic conductivity and unsatisfactory cyclic stability toward cationic intercalation. In this work, we tackle these issues by exploring an innovative strategy: leveraging heightened π-donation activate the t2g orbital, thereby enhancing both electron/ion structural of TMOs. We engineered Ni-doped layered manganese dioxide (Ni–MnO2), which is characterized a distinctive Ni–O–Mn bridging configuration. Remarkably, Ni–MnO2 presents impressive capacitance 317 F g–1 exhibits robust stability, maintaining 81.58% its original capacity even after 20,000 cycles. Mechanism investigations reveal that incorporation configurations stimulates effect, beneficial π-type orbital hybridization involving O 2p Mn, accelerating charge-transfer kinetics activating redox orbital. Additionally, charge redistribution from Ni Mn effectively elevates low-energy level thus mitigating undesirable Jahn–Teller distortion. This results in subsequent decrease electron occupancy π*-antibonding promotes overall enhancement stability. Our findings pave way for paradigm development fast stable electrode materials intercalation energy storage orbitals TM center molecular perspective.

Language: Английский

Tailoring Oxygen Reduction Reaction Kinetics of Fe−N−C Catalyst via Spin Manipulation for Efficient Zinc–Air Batteries DOI
Huiwen Zhang, Hsiao‐Chien Chen,

Solmaz Feizpoor

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(25)

Published: April 9, 2024

The interaction between oxygen species and metal sites of various orbitals exhibits intimate correlation with the reduction reaction (ORR) kinetics. Herein, a new approach for boosting inherent ORR activity atomically dispersed Fe-N-C matrix is represented by implanting Fe atomic clusters nearby. as-prepared catalyst delivers excellent half-wave potentials 0.78 0.90 V in acidic alkaline solutions, respectively. decent can also be validated from high-performance rechargeable Zn-air battery. experiments density functional theory calculations reveal that electron spin-state monodispersed active transferred low spin (LS, t

Language: Английский

Citations

102
High-coordination Fe–N4SP single-atom catalysts via the multi-shell synergistic effect for the enhanced oxygen reduction reaction of rechargeable Zn–air battery cathodes DOI
Jiaqi Liu,

Weibin Chen,

Shuang Yuan

et al.

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 17(1), P. 249 - 259

Published: Nov. 16, 2023

Novel Fe single-atom catalysts with highly coordinated Fe–N 4 SP structures were designed via the multi-coordination-shell synergistic effect. The optimization of enhances their ORR activity in alkaline/acidic media towards rechargeable Zn–air batteries.

Language: Английский

Citations

73
Regulation of Atomic Fe‐Spin State by Crystal Field and Magnetic Field for Enhanced Oxygen Electrocatalysis in Rechargeable Zinc‐Air Batteries DOI Open Access
Yibo Wang,

Pengyu Meng,

Zhaohui Yang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(28)

Published: May 4, 2023

Highly-active and low-cost bifunctional electrocatalysts for oxygen reduction evolution are essential in rechargeable metal-air batteries, single atom catalysts with Fe-N-C promising candidates. However, the activity still needs to be boosted, origination of spin-related catalytic performance is uncertain. Herein, an effective strategy regulate local spin state through manipulating crystal field magnetic proposed. The atomic Fe can regulated from low intermediate high spin. cavitation dxz dyz orbitals FeIII optimize O2 adsorption promote rate-determining step (*O2 *OOH). Benefiting these merits, electrocatalyst displays highest electrocatalytic activities. Furthermore, Fe-N-C-based zinc-air battery a power density 170 mW cm-2 good stability.

Language: Английский

Citations

64
Insights on rational design and regulation strategies of Prussian blue analogues and their derivatives towards high-performance electrocatalysts DOI

Yu-Rui Ji,

Yafei Guo, Xu Liu

et al.

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 471, P. 144743 - 144743

Published: July 13, 2023

Language: Английский

Citations

56
Strengthened d‐p Orbital‐Hybridization of Single Atoms with Sulfur Species Induced Bidirectional Catalysis for Lithium–Sulfur Batteries DOI
Tingting Sun,

Fangduo Huang,

Junliang Liu

et al.

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 33(51)

Published: Aug. 17, 2023

Abstract Single‐atom catalysts (SACs) have been widely explored as additives to improve the performance of lithium–sulfur (Li–S) batteries, however, design highly catalytic and in‐depth knowledge structure–activity relationship SACs remains a huge challenge. Herein, electron redistribution Co site by introducing S atom replace N in first coordination shell is theoretically predicted enhance anchoring capability lithium polysulfides (LiPSs) simultaneously facilitate redox process Li–S due strengthened d‐p orbital hybridization between sulfur species compared with traditional CoN 4 architecture. Enlightened theoretical analysis, asymmetric (N, S) coordinated single atoms embedded on N, S‐doped hierarchically porous carbon (S‐Co‐SACs/NSC) precisely designed constructed high‐efficiency fixity catalyst for batteries. Therefore, battery S@S‐Co‐SACs/NSC cathode exhibits high areal capacity cycling stability. This work highlights vital function electronic structures promoting practical application

Language: Английский

Citations

55
Modulating Electronic Structures of Iron Clusters through Orbital Rehybridization by Adjacent Single Copper Sites for Efficient Oxygen Reduction DOI Open Access

Chunhong Qi,

Haoyu Yang, Ziqi Sun

et al.

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

Citations

53
Advances on Axial Coordination Design of Single-Atom Catalysts for Energy Electrocatalysis: A Review DOI Creative Commons
Linjie Zhang,

Na Jin,

Yi‐Bing Yang

et al.

Nano-Micro Letters, Journal Year: 2023, Volume and Issue: 15(1)

Published: Oct. 13, 2023

Abstract Single-atom catalysts (SACs) have garnered increasingly growing attention in renewable energy scenarios, especially electrocatalysis due to their unique high efficiency of atom utilization and flexible electronic structure adjustability. The intensive efforts towards the rational design synthesis SACs with versatile local configurations significantly accelerated development efficient sustainable electrocatalysts for a wide range electrochemical applications. As an emergent coordination avenue, intentionally breaking planar symmetry by adding ligands axial direction metal single atoms offers novel approach tuning both geometric structures, thereby enhancing electrocatalytic performance at active sites. In this review, we briefly outline burgeoning research topic axially coordinated provide comprehensive summary recent advances synthetic strategies Besides, challenges outlooks field also been emphasized. present review provides in-depth understanding SACs, which could bring new perspectives solutions fine regulation structures catering high-performing electrocatalysis.

Language: Английский

Citations

53
Active site engineering toward atomically dispersed M−N−C catalysts for oxygen reduction reaction DOI
Xiangyu Lu, Peixia Yang, Yongbiao Wan

et al.

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

Published: Aug. 21, 2023

Language: Английский

Citations

48
Redistribution of d-orbital in Fe-N4 active sites optimizing redox kinetics of the sulfur cathode DOI

Guiqiang Cao,

Xifei Li,

Ruixian Duan

et al.

Nano Energy, Journal Year: 2023, Volume and Issue: 116, P. 108755 - 108755

Published: Aug. 2, 2023

Language: Английский

Citations

43
Tailoring atomic strain environment for high-performance acidic oxygen reduction by Fe-Ru dual atoms communicative effect DOI
Lingfeng Li, Jiaming Zhu, Fanpeng Kong

et al.

Matter, Journal Year: 2024, Volume and Issue: 7(4), P. 1517 - 1532

Published: Feb. 8, 2024

Language: Английский

Citations

41