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 d‐p Orbital Hybridization to Decipher the Essential Effects of Heteroatom Substitution on Redox Kinetics DOI
Jian Zhao, Yuxiao Zhang, Zechao Zhuang

et al.

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

Published: June 4, 2024

Abstract The heteroatom substitution is considered as a promising strategy for boosting the redox kinetics of transition metal compounds in hybrid supercapacitors (HSCs) although dissimilar identification and essential mechanism that dominate remain unclear. It presented d‐p orbital hybridization between electrolyte ions can be utilized descriptor understanding kinetics. Herein, series Co, Fe Cu heteroatoms are respectively introduced into Ni 3 Se 4 cathodes, among them, only moderate Co‐substituted hold optimal resulted from formed more unoccupied antibonding states π*. inevitably enhances interfacial charge transfer ensures balanced OH − adsorption‐desorption to accelerate validated by lowest reaction barrier (0.59 eV, matching well with theoretical calculations). Coupling lower diffusion energy barrier, prepared cathode delivers ultrahigh rate capability (~68.7 % capacity retention even current density increases 200 times), an assembled HSC also presents high energy/power density. This work establishes principles determining deciphers underlying effects on improving performance battery‐type electrodes novel perspective orbital‐scale manipulation.

Language: Английский

Citations

19
Disentangling the Activity‐Stability Trade‐Off of Pyrrolic N‐Coordinated Fe─N4 Catalytic Sites for Long‐Life Oxygen Reduction Reaction in Acidic Medium DOI

Dongping Xue,

Shuyan Zhao, Bang‐An Lu

et al.

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(12)

Published: Jan. 8, 2024

Abstract Fe─N─C materials with Fe─N 4 sites are considered as most promising non‐precious metal‐based electrocatalysts for low‐cost proton‐exchange‐membrane fuel cells (PEMFCs). Breaking the trade‐off between activity and stability has been a long‐standing challenge in field of acidic oxygen reduction reaction (ORR). Herein, “top‐down” thermally‐driven strategy is developed to achieve highly active pyrrolic N‐coordinated Fe high spin state atomic cluster (Fe n @Fe─N pyrr ─C) discover that neighboring can synergistically stabilize such vulnerable by inhibiting their protonation. Consequently, ─C catalysts exhibit much enhanced ORR stability, endowing PEMFCs power density 804.6 mW cm −2 (testing conditions: 80 °C, 100% RH, 2.0 bar) over 100 h durability (at 0.5 V). These findings open up opportunities exploration durable other applications.

Language: Английский

Citations

17
In-depth understanding and precise modulation of surface reconstruction during heterogeneous electrocatalysis: From model to practical catalyst DOI
Weidong Dai, Kaiwei Wan, Kanglei Pang

et al.

Chem, Journal Year: 2025, Volume and Issue: 11(1), P. 102345 - 102345

Published: Jan. 1, 2025

Language: Английский

Citations

5
Tuning the Bonding Behavior of d‐p Orbitals to Enhance Oxygen Reduction through Push–Pull Electronic Effects DOI Open Access
Qi Jing, Zhiyuan Mei,

Xuelin Sheng

et al.

Advanced Functional Materials, Journal Year: 2023, Volume and Issue: 34(3)

Published: Oct. 5, 2023

Abstract The regulation of electronic structure is intricately linked to the intrinsic activity oxygen reduction. Herein, a strategy for modulation induced by bimetallic push–pull effects in dual‐atom catalysts (Fe,Ni/N‐C@NG) developed. Experiments and theoretical analysis reveal that Fe sites exhibit favorable bonding behaviors (Fe–O: d xz ‐p, yz z 2 ‐p) spin configurations, which can enable rapid desorption *OH thus enhance In situ monitoring techniques Gibbs free energy diagram further demonstrate adjacent Ni could serve as second active center participate Fe,Ni/N‐C@NG exhibits enhanced reduction reaction excellent stability. Meanwhile, assembled Zn–air battery maintains stability over 300 h with small voltage gap. This study provides multiple insights into orbital scale laws

Language: Английский

Citations

40
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

Citations

37