Covalent organic framework-derived fluorine, nitrogen dual-doped carbon as metal-free bifunctional oxygen electrocatalysts

Wei Li; Jingyun Wang; Chunguang Jia; Junxiang Chen; Zhenhai Wen; Aisheng Huang

doi:10.1016/j.jcis.2023.06.210

Covalent organic framework-derived fluorine, nitrogen dual-doped carbon as metal-free bifunctional oxygen electrocatalysts

J Colloid Interface Sci. 2023 Nov 15;650(Pt A):275-283. doi: 10.1016/j.jcis.2023.06.210. Epub 2023 Jul 1.

Authors

Wei Li¹, Jingyun Wang¹, Chunguang Jia², Junxiang Chen³, Zhenhai Wen⁴, Aisheng Huang⁵

Affiliations

¹ State Key Laboratory of Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Dongchuan Road 500, Shanghai 200241, China.
² CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, CAS, Fuzhou 350002, China.
³ CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, CAS, Fuzhou 350002, China. Electronic address: cjxxjc729@fjirsm.ac.cn.
⁴ CAS Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, CAS, Fuzhou 350002, China. Electronic address: wen@fjirsm.ac.cn.
⁵ State Key Laboratory of Molecular & Process Engineering, Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Dongchuan Road 500, Shanghai 200241, China; Institute of Eco-Chongming, 20 Cuiniao Road, Chongming District, Shanghai 202162, China. Electronic address: huangash@chem.ecnu.edu.cn.

PMID: 37413861
DOI: 10.1016/j.jcis.2023.06.210

Abstract

The construction of heteroatom-doped metal-free carbon catalysts with bifunctional catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is highly desired for Zn-air batteries, but remains a great challenge owing to the sluggish kinetics of OER and ORR. Herein, a self-sacrificing template engineering strategy was employed to fabricate fluorine (F), nitrogen (N) co-doped porous carbon (F-NPC) catalyst by direct pyrolysis of F, N containing covalent organic framework (F-COF). The predesigned F and N elements were integrated into the skeletons of COF precursor, thus achieving uniformly distributed heteroatom active sites. The introduction of F is beneficial for the formation of edge-defects, contributing to the enhancement of the electrocatalytic activity. Attributing to the porous feature, abundant defect sites induced by F doping, as well as the strong synergistic effect between N and F atoms to afford a high intrinsic catalytic activity, the resulting F-NPC catalyst exhibits excellent bifunctional catalytic activities for both ORR and OER in alkaline mediums. Furthermore, the assembled Zn-air battery with F-NPC catalyst shows a high peak power density of 206.3 mW cm^-2 and great stability, surpassing the commercial Pt/C + RuO₂ catalysts.

Keywords: Bifunctional electrocatalysts; Covalent organic frameworks; Heteroatom-doping; Metal-free catalysts; Zn-air batteries.