Issue

Vol. 15 (2023)

Quasi-Three-Dimensional Cyclotriphosphazene-Based Covalent Organic Framework Nanosheet for Efficient Oxygen Reduction

https://doi.org/10.1007/s40820-023-01111-8
Jianhong Chang
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, People’s Republic of China
Cuiyan Li
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, People’s Republic of China
Xiaoxia Wang
State Key Laboratory of Bio‑Fibers and Eco‑Textiles, College of Materials Science and Engineering, Qingdao University, Qingdao 266071, People’s Republic of China
Daohao Li
State Key Laboratory of Bio‑Fibers and Eco‑Textiles, College of Materials Science and Engineering, Qingdao University, Qingdao 266071, People’s Republic of China
Jie Zhang
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, People’s Republic of China
Xiaoming Yu
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, People’s Republic of China
Hui Li
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, People’s Republic of China
Xiangdong Yao
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, People’s Republic of China
Valentin Valtchev
Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, 189 Song Ling Rd, Qingdao 266101, Shandong, People’s Republic of China
Shilun Qiu
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, People’s Republic of China
Qianrong Fang
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, People’s Republic of China

Corresponding Author: Qianrong Fang

qrfang@jlu.edu.cn

Nano-Micro Letters, Vol. 15 (2023), Article Number: 159

Abstract

Metal-free carbon-based materials are considered as promising oxygen reduction reaction (ORR) electrocatalysts for clean energy conversion, and their highly dense and exposed carbon active sites are crucial for efficient ORR. In this work, two unique quasi-three-dimensional cyclotriphosphazene-based covalent organic frameworks (Q3CTP-COFs) and their nanosheets were successfully synthesized and applied as ORR electrocatalysts. The abundant electrophilic structure in Q3CTP-COFs induces a high density of carbon active sites, and the unique bilayer stacking of [6 + 3] imine-linked backbone facilitates the exposure of active carbon sites and accelerates mass diffusion during ORR. In particular, bulk Q3CTP-COFs can be easily exfoliated into thin COF nanosheets (NSs) due to the weak interlayer π–π interactions. Q3CTP-COF NSs exhibit highly efficient ORR catalytic activity (half-wave potential of 0.72 V vs. RHE in alkaline electrolyte), which is one of the best COF-based ORR electrocatalysts reported so far. Furthermore, Q3CTP-COF NSs can serve as a promising cathode for Zn-air batteries (delivered power density of 156 mW cm–2 at 300 mA cm–2). This judicious design and accurate synthesis of such COFs with highly dense and exposed active sites and their nanosheets will promote the development of metal-free carbon-based electrocatalysts.


Highlights:


1 JUC-610-nanosheet exhibits highly efficient oxygen reduction reaction (ORR) catalytic activity in alkaline electrolyte with half-wave potential of 0.72 V versus reversible hydrogen electrode, which is one of the best covalent organic frameworks (COF)-based ORR electrocatalysts reported so far.
2 It has been confirmed by experiments and density functional theory calculations that the abundant electrophilic structure in Q3CTP-COFs induces a highly density of carbon active sites, and the unique bilayer stacking facilitates the exposure of active carbon sites and accelerates the mass diffusion during ORR.
3 JUC-610-nanosheet can also serve as a promising cathode for Zn-air batteries (power density of 156 mW cm–2 at 300 mA cm–2), which promotes the development of metal-free carbon-based electrocatalysts.

Keywords

Covalent organic framework Quasi-three-dimensional structures Oxygen reduction reaction Metal-free electrocatalyst
Chang, Jianhong, Cuiyan Li, Xiaoxia Wang, Daohao Li, Jie Zhang, Xiaoming Yu, Hui Li, Xiangdong Yao, Valentin Valtchev, Shilun Qiu, and Qianrong Fang. 2023. “Quasi-Three-Dimensional Cyclotriphosphazene-Based Covalent Organic Framework Nanosheet for Efficient Oxygen Reduction”. Nano-Micro Letters 15 (June):159. https://doi.org/10.1007/s40820-023-01111-8.
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