Axial Coordination Modulation of FeN4 Sites in Dioxin-Linked Covalent Organic Hybrid Catalysts for Enhanced ORR Activity and Zinc–Air Battery Application

Zhu, Danyang; Liu, Baolong; Mo, Yiping; Zhang, Qiao; Ma, Yuhan; Dai, Wenqi; Lu, Wangyang

doi:10.3390/catal16050462

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Axial Coordination Modulation of FeN₄ Sites in Dioxin-Linked Covalent Organic Hybrid Catalysts for Enhanced ORR Activity and Zinc–Air Battery Application

by

Danyang Zhu

,

Baolong Liu

,

Yiping Mo

^*

,

Qiao Zhang

,

Yuhan Ma

,

Wenqi Dai

and

Wangyang Lu

^*

National Engineering Lab for Textile Fiber Materials & Processing Technology (Zhejiang), Zhejiang Sci-Tech University, Hangzhou 310018, China

^*

Authors to whom correspondence should be addressed.

Catalysts 2026, 16(5), 462; https://doi.org/10.3390/catal16050462 (registering DOI)

Submission received: 17 April 2026 / Revised: 10 May 2026 / Accepted: 14 May 2026 / Published: 15 May 2026

(This article belongs to the Special Issue Catalysis and New Energy Materials)

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Abstract

Effective regulation of the adsorption strength of oxygen reduction reaction (ORR) intermediates on active sites is the key to enhancing their catalytic performance. This study proposes an axial coordination modulation strategy by successfully anchoring the dioxin-linked FePcF₁₆-based covalent organic frameworks (COFs) onto amino-functionalized multi-walled carbon nanotubes (NH₂-MWCNTs), constructing a FePcF₁₆-COF/NH₂-MWCNT hybrid catalyst. Experimental results demonstrate that the catalyst exhibits outstanding ORR activity (E_1/2 = 0.901 V; J_L = 5.133 mA cm⁻²), outperforming commercial 20% Pt/C and most reported Fe-based non-precious metal catalysts. Furthermore, the robust dioxin-linked COF skeleton endows the catalyst with excellent electrochemical stability. A zinc–air battery using this catalyst as the cathode also demonstrates superior power density and cycling performance. This work provides a new strategy for designing highly efficient ORR catalysts through axial coordination environment engineering.

Keywords: covalent organic frameworks; axial coordination; dioxin linkage; oxygen reduction reaction; zinc–air battery

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MDPI and ACS Style

Zhu, D.; Liu, B.; Mo, Y.; Zhang, Q.; Ma, Y.; Dai, W.; Lu, W. Axial Coordination Modulation of FeN₄ Sites in Dioxin-Linked Covalent Organic Hybrid Catalysts for Enhanced ORR Activity and Zinc–Air Battery Application. Catalysts 2026, 16, 462. https://doi.org/10.3390/catal16050462

AMA Style

Zhu D, Liu B, Mo Y, Zhang Q, Ma Y, Dai W, Lu W. Axial Coordination Modulation of FeN₄ Sites in Dioxin-Linked Covalent Organic Hybrid Catalysts for Enhanced ORR Activity and Zinc–Air Battery Application. Catalysts. 2026; 16(5):462. https://doi.org/10.3390/catal16050462

Chicago/Turabian Style

Zhu, Danyang, Baolong Liu, Yiping Mo, Qiao Zhang, Yuhan Ma, Wenqi Dai, and Wangyang Lu. 2026. "Axial Coordination Modulation of FeN₄ Sites in Dioxin-Linked Covalent Organic Hybrid Catalysts for Enhanced ORR Activity and Zinc–Air Battery Application" Catalysts 16, no. 5: 462. https://doi.org/10.3390/catal16050462

APA Style

Zhu, D., Liu, B., Mo, Y., Zhang, Q., Ma, Y., Dai, W., & Lu, W. (2026). Axial Coordination Modulation of FeN₄ Sites in Dioxin-Linked Covalent Organic Hybrid Catalysts for Enhanced ORR Activity and Zinc–Air Battery Application. Catalysts, 16(5), 462. https://doi.org/10.3390/catal16050462

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Axial Coordination Modulation of FeN₄ Sites in Dioxin-Linked Covalent Organic Hybrid Catalysts for Enhanced ORR Activity and Zinc–Air Battery Application

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