Identifying the Active Site of N-Doped Graphene for Oxygen Reduction by Selective Chemical Modification

被引：128

作者：

Wang, Tao ^{[1
]}

Chen, Zhi-Xin ^{[1
]}

Chen, Yu-Gang ^{[2
,3
]}

Yang, Li-Jun ^{[2
,3
]}

Yang, Xiao-Dong ^{[4
]}

Ye, Jin-Yu ^{[1
]}

Xia, Hai-Ping ^{[1
]}

Zhou, Zhi-You ^{[1
]}

Sun, Shi-Gang ^{[1
]}

机构：

[1] Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Collaborat Innovat Ctr Chem Energy Mat, Xiamen 361005, Peoples R China

[2] Nanjing Univ, Sch Chem & Chem Engn, Key Lab Mesoscop Chem MOE, Nanjing 210023, Jiangsu, Peoples R China

[3] Nanjing Univ, Sch Chem & Chem Engn, Jiangsu Prov Lab Nanotechnol, Nanjing 210023, Jiangsu, Peoples R China

[4] Huaqiao Univ, Coll Mat Sci & Engn, Xiamen 361021, Fujian, Peoples R China

来源：

ACS ENERGY LETTERS | 2018年 / 3卷 / 04期

关键词：

METAL-FREE ELECTROCATALYSTS; DENSITY-FUNCTIONAL THEORY; ELECTROLYTE FUEL-CELLS; ALKALINE MEDIA; CATALYSTS; CARBON; PERFORMANCE; IRON; EXPLORATION; SULFUR;

D O I：

10.1021/acsenergylett.8b00258

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

N-doped carbon materials are promising electro-catalysts for oxygen reduction reaction (ORR). However, the lack of knowledge in the nature of active sites limits the rational design of this type of catalysts. Although pyridinic N species are proposed to be active for ORR, little experimental evidence is provided to reveal the reactive sites. Herein, we developed a surface modification method to identify the ortho-carbon atom of the pyridinic ring as the reactive site for ORR on N-doped graphene. The pyridinic ring of N-doped graphene was selectively grafted by an acetyl group at pyridinic N and ortho-C atoms by electrophilic and radical substitution, respectively. The former remained most of ORR catalytic activity, while the latter lost its activity completely. DFT calculations confirm that O-2 can get adsorbed and reduced favorably on the ortho-C atom of the pyridinic ring. This study provides new insight into the nature of active sites and the ORR mechanism for N-doped carbon materials.

引用

页码：986 / 991

页数：11

共 37 条

[1] ADDITION OF TRIMETHYLSILYL ENOL ETHERS TO ISOQUINOLINIUM SALTS - A FACILE SYNTHESIS OF 1-(2-OXOALKYL)-2-(ETHOXYCARBONYL)(OR ACETYL)-1,2-DIHYDROISOQUINOLINES AND THEIR CYCLIZATION FOR THE SYNTHESIS OF THE ISOQUINOLINE ALKALOID SKELETO [J].