Design and Preparation of Fe-N5 Catalytic Sites in Single-Atom Catalysts for Enhancing the Oxygen Reduction Reaction in Fuel Cells

被引:102
作者
Zhao, Ye-Min [1 ]
Zhang, Peng-Cheng [2 ]
Xu, Chao [1 ]
Zhou, Xin-You [1 ]
Liao, Li-Mei [1 ]
Wei, Ping-Jie [1 ]
Liu, Ershuai [3 ]
Chen, Hengquan [2 ]
He, Qinggang [2 ]
Liu, Jin-Gang [1 ]
机构
[1] East China Univ Sci & Technol, Key Lab Adv Mat, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China
[2] Zhejiang Univ, Coll Chem & Biol Engn, Hangzhou 310027, Zhejiang, Peoples R China
[3] Northeastern Univ, Dept Chem & Chem Biol, 360 Huntington Ave, Boston, MA 02115 USA
关键词
oxygen reduction reaction; electrocatalyst; iron porphyrin; single-atom catalyst; FeN5 active site; fuel cells; METAL-FREE ELECTROCATALYSTS; N-C ELECTROCATALYST; DOPED POROUS CARBON; ELECTRONIC-STRUCTURE; EFFICIENT ELECTROCATALYSTS; ACTIVE-SITES; PERFORMANCE; IRON; IDENTIFICATION; NITROGEN;
D O I
10.1021/acsami.9b20711
中图分类号
TB3 [工程材料学];
学科分类号
0805 ; 080502 ;
摘要
There is an urgent need for developing nonprecious metal catalysts to replace Pt-based electrocatalysts for oxygen reduction reaction (ORR) in fuel cells. Atomically dispersed M-N-x/C catalysts have shown promising ORR activity; however, enhancing their performance through modulating their active site structure is still a challenge. In this study, a simple approach was proposed for preparing atomically dispersed iron catalysts embedded in nitrogen- and fluorine-doped porous carbon materials with five-coordinated Fe-N-5 sites. The C@PVI-(DFTPP)Fe-800 catalyst, obtained through pyrolysis of a bio-inspired iron porphyrin precursor coordinated with an axial imidazole from the surface of polyvinylimidazole-grafted carbon black at 800 degrees C under an Ar atmosphere, exhibited a high electrocatalytic activity with a half-wave potential of 0.88 V versus the reversible hydrogen electrode for ORR through a four-electron reduction pathway in alkaline media. In addition, an anion-exchange membrane electrode assembly (MEA) with C@PVI-(DFTPP)Fe-800 as the cathode electrocatalyst generated a maximum power density of 0.104 W cm(-2) and a current density of 0.317 mA cm(-2). X-ray absorption spectroscopy demonstrated that a single-atom catalyst (Fe-N-x/C) with an Fe-N-5 active site can selectively be obtained; furthermore, the catalyst ORR activity can be tuned using fluorine atom doping through appropriate pre-assembling of the molecular catalyst on a carbon support followed by pyrolysis. This provides an effective strategy to prepare structure-performance-correlated electrocatalysts at the molecular level with a large number of M-N-x active sites for ORR. This method can also be utilized for designing other catalysts.
引用
收藏
页码:17334 / 17342
页数:9
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