Pyrazine-nitrogen-rich exfoliated C4N nanosheets as efficient metal-free polymeric catalysts for oxygen reduction reaction

doi:10.1016/j.jechem.2020.02.046

能源化学(英文版) ›› 2020, Vol. 49 ›› Issue (10): 243-247.DOI: 10.1016/j.jechem.2020.02.046

Pyrazine-nitrogen-rich exfoliated C₄N nanosheets as efficient metal-free polymeric catalysts for oxygen reduction reaction

Yuan Li, Chunshao Mo, Jing Li, Dingshan Yu

Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education,Key Laboratory of High Performance Polymer-based Composites of Guangdong Province,School of Chemistry,Sun Yat-sen University,Guangzhou 510275,Guangdong,China

收稿日期:2020-02-15 修回日期:2020-02-25 出版日期:2020-10-15 发布日期:2020-12-18
通讯作者: Dingshan Yu
基金资助:
We gratefully acknowledge financial support from the National Natural Science Foundation of China(No.51973240),the Fundamental Research Funds for the Central Universities(Grant No.19lgzd19 and 19lgpy117),China Postdoctoral Science Foundation(No.2019M653176)and the Guangdong YangFan Innovative & Entepreneurial Research Team Program(Grant No.2016YT03C077).

Pyrazine-nitrogen-rich exfoliated C₄N nanosheets as efficient metal-free polymeric catalysts for oxygen reduction reaction

Yuan Li, Chunshao Mo, Jing Li, Dingshan Yu

Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education,Key Laboratory of High Performance Polymer-based Composites of Guangdong Province,School of Chemistry,Sun Yat-sen University,Guangzhou 510275,Guangdong,China

Received:2020-02-15 Revised:2020-02-25 Online:2020-10-15 Published:2020-12-18
Contact: Dingshan Yu
Supported by:
We gratefully acknowledge financial support from the National Natural Science Foundation of China(No.51973240),the Fundamental Research Funds for the Central Universities(Grant No.19lgzd19 and 19lgpy117),China Postdoctoral Science Foundation(No.2019M653176)and the Guangdong YangFan Innovative & Entepreneurial Research Team Program(Grant No.2016YT03C077).

摘要/Abstract

摘要： Herein,we for the first time demonstrate the synthesis of exfoliated C₄N nanosheets via a top-down approach and exploit their use as a new class of organic polymeric catalyst for the oxygen reduction reaction (ORR).The obtained C₄N nanosheets are semi-conductive with a small band gap of 1.41 eV and contain abundant pyrazine-nitrogen moieties uniformly distributed throughout C₄N.Density function theory calculations reveal that the intramolecular charge transfer induced by pyrazine-nitrogen in C₄N enables effective charge redistribution to activate the conjugated structure and facilitate the oxygen adsorption,while the exfoliated sheet-like C₄N formation renders improved electrochemical active surface area and results in high exposure of active sites.As a result,despite the bulk C₄N is not active,the sheet-like C₄N yield markedly improved ORR performance,even on a par with the commercial Pt/C catalyst.Our recent findings not only enrich the family members of two-dimensional conjugated polymer nanosheets but also open up new opportunity to explore new metal-free organic polymeric materials for efficient oxygen reduction catalysis and beyond.

关键词: Oxygen reduction reaction, Metal-free electrocatalyst, Polymeric electrocatalysts, C₄N nanosheets, Pyrazine-nitrogen

Abstract: Herein,we for the first time demonstrate the synthesis of exfoliated C₄N nanosheets via a top-down approach and exploit their use as a new class of organic polymeric catalyst for the oxygen reduction reaction (ORR).The obtained C₄N nanosheets are semi-conductive with a small band gap of 1.41 eV and contain abundant pyrazine-nitrogen moieties uniformly distributed throughout C₄N.Density function theory calculations reveal that the intramolecular charge transfer induced by pyrazine-nitrogen in C₄N enables effective charge redistribution to activate the conjugated structure and facilitate the oxygen adsorption,while the exfoliated sheet-like C₄N formation renders improved electrochemical active surface area and results in high exposure of active sites.As a result,despite the bulk C₄N is not active,the sheet-like C₄N yield markedly improved ORR performance,even on a par with the commercial Pt/C catalyst.Our recent findings not only enrich the family members of two-dimensional conjugated polymer nanosheets but also open up new opportunity to explore new metal-free organic polymeric materials for efficient oxygen reduction catalysis and beyond.

Key words: Oxygen reduction reaction, Metal-free electrocatalyst, Polymeric electrocatalysts, C₄N nanosheets, Pyrazine-nitrogen

Yuan Li, Chunshao Mo, Jing Li, Dingshan Yu. Pyrazine-nitrogen-rich exfoliated C₄N nanosheets as efficient metal-free polymeric catalysts for oxygen reduction reaction[J]. 能源化学(英文版), 2020, 49(10): 243-247.

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Pyrazine-nitrogen-rich exfoliated C₄N nanosheets as efficient metal-free polymeric catalysts for oxygen reduction reaction

Pyrazine-nitrogen-rich exfoliated C₄N nanosheets as efficient metal-free polymeric catalysts for oxygen reduction reaction

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