Redox chemistry of N4-Fe2+ in iron phthalocyanines for oxygen reduction reaction

被引：35
作者：
Kumar, Anuj [1 ,2 ]
Zhang, Ying [3 ]
Jia, Yin [1 ]
Liu, Wen [1 ]
Sun, Xiaoming [1 ]
机构：
[1] Beijing Univ Chem Technol, Coll Chem, Beijing Adv Innovat Ctr Soft Matter Sci & Engn, State Key Lab Chem Resource Engn, Beijing 100029, Peoples R China
[2] GLA Univ, Inst Humanities & Appl Sci, Dept Chem, Mathura 281406, India
[3] Monash Univ, Sch Chem, Wellington Rd, Clayton, Vic 3800, Australia
来源：
CHINESE JOURNAL OF CATALYSIS | 2021年 / 42卷 / 08期
基金：
中国国家自然科学基金;
关键词：
Iron phthalocyanines; Substitution effect; Oxygen reduction reaction; Carbon nanotubes; Activity descriptor;
D O I：
10.1016/S1872-2067(20)63731-7
中图分类号：
O69 [应用化学];
学科分类号：
081704 ;
摘要：
A precise understanding of the redox chemistry of N-m-Mn+ (like N-4-Fe2+) systems is essential for fundamental studies and rational design of N-m-Mn+-based electrocatalysts for the oxygen reduction reaction (ORR). Herein, three different iron phthalocyanines (FePcs) adsorbed on carbon nanotubes ((NH2)(4)FePc@CNTs, (t-Bu)(4)FePc@CNTs, and FePc@CNTs) were evaluated to demonstrate the effect of the electron donating power of the substituents on the Fe3+/Fe2+ redox potential of FePc@CNTs and the role of these composites as ORR mediators in alkaline media. The Fe3+/Fe2+ redox potential of the FePcs was found to shift towards the cathodic region upon substitution with electron-donating groups. This up-field shift in the eg-orbital leads to a lower overlap between the onset potential of the Fe3+/Fe2+ redox couple and that of the ORR, and thus, the ORR activity decreased in the following order based on the substitution of FePc:-H >-t-Bu >-NH2. (C) 2021, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.
引用
收藏
页码：1404 / 1412
页数：9
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