Long-Range Electron Transfer over Graphene-Based Catalyst for High-Performing Oxygen Reduction Reactions: Importance of Size, N-doping, and Metallic Impurities

被引:228
作者
Choi, Chang Hyuck [1 ]
Lim, Hyung-Kyu [2 ]
Chung, Min Wook [2 ]
Park, Jong Cheol [1 ,3 ]
Shin, Hyeyoung [2 ]
Kim, Hyungjun [2 ]
Woo, Seong Ihl [1 ,2 ]
机构
[1] Korea Adv Inst Sci & Technol, Dept Chem & Biomol Engn, Taejon 305701, South Korea
[2] Korea Adv Inst Sci & Technol, Grad Sch EEWS, Taejon 305701, South Korea
[3] GS Caltex, Connect & Dev Team 1, Taejon 305380, South Korea
基金
新加坡国家研究基金会;
关键词
PEM FUEL-CELLS; NITROGEN-DOPED GRAPHENE; CATHODE CATALYSTS; CARBON; ELECTROCATALYSTS; IRON; POLYANILINE; MECHANISM; PLATINUM; SITES;
D O I
10.1021/ja5033474
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
N-doped carbon materials are considered as next-generation oxygen reduction reaction (ORR) catalysts for fuel cells due to their prolonged stability and low cost. However, the underlying mechanism of these catalysts has been only insufficiently identified, preventing the rational design of high-performing catalysts. Here, we show that the first electron is transferred into O-2 molecules at the outer Helmholtz plane (ET-OHP) over a long range. This is in sharp contrast to the conventional belief that O-2 adsorption must precede the ET step and thus that the active site must possess as good an O-2 binding character as that which occurs on metallic catalysts. Based on the ET-OHP mechanism, the location of the electrode potential dominantly characterizes the ORR activity. Accordingly, we demonstrate that the electrode potential can be elevated by reducing the graphene size and/or including metal impurities, thereby enhancing the ORR activity, which can be transferred into single-cell operations with superior stability.
引用
收藏
页码:9070 / 9077
页数:8
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