Atomically dispersed Fe/Co dual site electrocatalysts derived from covalent triazine frameworks for boosting oxygen reduction

Dun, Rongmin; He, Xiang; Huang, Jian; Wang, Wei; Liu, Yiwei; Li, Linghao; Lu, Bowen; Hua, Zile; Shi, Jianlin

doi:10.1039/d3ta00307h

“…3c). 39 The Koutecky-Levich (K-L) plot of CoFe 2 O 4 @NCNF derived from LSV curves suggests J − 1 keeps perfect linear relationship with ω −1/2 (Fig. 3d).…”

Section: Orr Activity Studymentioning

confidence: 89%

Structure preferred spinel ferrite on polypyrrole derived N-doped carbon nanofibers as bifunctional electrocatalyst for Zn-air battery

Shi,

Xu,

Chen

2024

Preprint

0

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The exploration of noble metal free bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) electrocatalysts is very important for Zn-air batteries (ZABs). Spinel ferrites are famous bifunctional ORR/OER electrocatalysts. Herein, to further improve their ORR and OER activities, we anchor CoFe2O4 on N-doped carbon nanofibers (NCNF) derived from polypyrrole (PPy) and obtain CoFe2O4 loaded NCNF (CoFe2O4@NCNF). In its structure, CoFe2O4 particles with small size distribute evenly on NCNF. The combination of CoFe2O4 and NCNF generates excellent ORR activity with typical four-electron character in both alkaline and neutral electrolyte. In OER, the activity of CoFe2O4@NCNF is also excellent. To explore the superior ORR and OER activities of CoFe2O4@NCNF over other spinel ferrites, theoretical calculation was employed. A rechargeable ZAB is constructed with CoFe2O4@NCNF as cathode material. The specific capacity and energy density of this ZAB reach 807.4 mA·h·g− 1 and 963.6 Wh·kg− 1 at 10 mA·cm− 2, respectively. ZAB can keep stable after continuous charge/discharge test for 120 h. This work not only provides an efficient and low cost cathode material for ZABs, but also clarifies the structure-activity relationship in ORR/OER for spinel ferrites.

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“…Moreover, the abundant nitrogen species within CTFs offer ideal binding sites for metal atoms, enabling the creation of welldefined and densely-packed MN x sites essential for catalytic reactions. [7] Currently, numerous studies focus on creating MN 4 sites within COFs or covalent organic polymers (COPs) for ORR. [8] And these investigations commonly employ organic network structures derived from metalporphyrin or metal-phthalocyanine structural units to generate planar and symmetric MN 4 sites.…”

Section: Introductionmentioning

confidence: 99%

Precisely Engineering Asymmetric Atomic CoN₄ by Electron Donating and Extracting for Oxygen Reduction Reaction

Lv,

Cui,

Huang

et al. 2024

Angew Chem Int Ed

0

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The development of nonpyrolytic catalysts featuring precisely defined active sites represents an effective strategy for investigating the fundamental relationship between the catalytic activity of oxygen reduction reaction (ORR) catalysts and their local coordination environments. In this study, we have synthesized a series of model electrocatalysts with well‐defined CoN4 centers and nonplanar symmetric coordination structures. These catalysts were prepared by a sequential process involving the chelation of cobalt salts and 1,10‐phenanthroline‐based ligands with various substituent groups (phen(X), where X = OH, CH3, H, Br, Cl) onto covalent triazine frameworks (CTFs). By modulating the electron‐donating or electron‐withdrawing properties of the substituent groups on the phen‐based ligands, we were able to effectively control the electron density surrounding the CoN4 centers. Our results demonstrated a direct correlation between the catalytic activity of the CoN4 centers and the electron‐donating ability of the substituent group on the phenanthroline ligands. Notably, the catalyst denoted as BCTF‐Co‐phen(OH), featuring the electron‐donating OH group, exhibited the highest ORR catalytic activity. This custom‐crafted catalyst achieved a remarkable half‐wave potential of up to 0.80 V vs. RHE and an impressive turnover frequency (TOF) value of 47.4×10‐3 Hz at 0.80 V vs. RHE in an alkaline environment.

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Precisely Engineering Asymmetric Atomic CoN₄ by Electron Donating and Extracting for Oxygen Reduction Reaction

Lv,

Cui,

Huang

et al. 2024

Angewandte Chemie

1

0

View full text Add to dashboard Cite

The development of nonpyrolytic catalysts featuring precisely defined active sites represents an effective strategy for investigating the fundamental relationship between the catalytic activity of oxygen reduction reaction (ORR) catalysts and their local coordination environments. In this study, we have synthesized a series of model electrocatalysts with well‐defined CoN4 centers and nonplanar symmetric coordination structures. These catalysts were prepared by a sequential process involving the chelation of cobalt salts and 1,10‐phenanthroline‐based ligands with various substituent groups (phen(X), where X = OH, CH3, H, Br, Cl) onto covalent triazine frameworks (CTFs). By modulating the electron‐donating or electron‐withdrawing properties of the substituent groups on the phen‐based ligands, we were able to effectively control the electron density surrounding the CoN4 centers. Our results demonstrated a direct correlation between the catalytic activity of the CoN4 centers and the electron‐donating ability of the substituent group on the phenanthroline ligands. Notably, the catalyst denoted as BCTF‐Co‐phen(OH), featuring the electron‐donating OH group, exhibited the highest ORR catalytic activity. This custom‐crafted catalyst achieved a remarkable half‐wave potential of up to 0.80 V vs. RHE and an impressive turnover frequency (TOF) value of 47.4×10‐3 Hz at 0.80 V vs. RHE in an alkaline environment.

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Atomically dispersed Fe/Co dual site electrocatalysts derived from covalent triazine frameworks for boosting oxygen reduction

Abstract: Single-atom catalysts (SACs), especially transition metal-nitrogen-carbon materials, show high catalytic activity for oxygen reduction reaction (ORR). Herein, we successfully construct covalent triazine frameworks (CTFs) derived Fe/Co binary metallic SACs by...

Cited by 12 publications

References 64 publications

Structure preferred spinel ferrite on polypyrrole derived N-doped carbon nanofibers as bifunctional electrocatalyst for Zn-air battery

Structure preferred spinel ferrite on polypyrrole derived N-doped carbon nanofibers as bifunctional electrocatalyst for Zn-air battery

Precisely Engineering Asymmetric Atomic CoN₄ by Electron Donating and Extracting for Oxygen Reduction Reaction

Precisely Engineering Asymmetric Atomic CoN₄ by Electron Donating and Extracting for Oxygen Reduction Reaction

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Atomically dispersed Fe/Co dual site electrocatalysts derived from covalent triazine frameworks for boosting oxygen reduction

Abstract: Single-atom catalysts (SACs), especially transition metal-nitrogen-carbon materials, show high catalytic activity for oxygen reduction reaction (ORR). Herein, we successfully construct covalent triazine frameworks (CTFs) derived Fe/Co binary metallic SACs by...

Cited by 12 publications

References 64 publications

Structure preferred spinel ferrite on polypyrrole derived N-doped carbon nanofibers as bifunctional electrocatalyst for Zn-air battery

Structure preferred spinel ferrite on polypyrrole derived N-doped carbon nanofibers as bifunctional electrocatalyst for Zn-air battery

Precisely Engineering Asymmetric Atomic CoN4 by Electron Donating and Extracting for Oxygen Reduction Reaction

Precisely Engineering Asymmetric Atomic CoN4 by Electron Donating and Extracting for Oxygen Reduction Reaction

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Product

Resources

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Precisely Engineering Asymmetric Atomic CoN₄ by Electron Donating and Extracting for Oxygen Reduction Reaction

Precisely Engineering Asymmetric Atomic CoN₄ by Electron Donating and Extracting for Oxygen Reduction Reaction