Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN 4 Sites for Oxygen Reduction

Li, Jiazhan; Zhang, Hanguang; Samarakoon, Widitha; Shan, Weitao; Cullen, David A.; Karakalos, Stavros; Chen, Mengjie; Gu, Daming; More, Karren L.; Wang, Guofeng; Feng, Zhenxing; Wang, Zhenbo; Wu, Gang

doi:10.1002/ange.201909312

Title: Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN ₄ Sites for Oxygen Reduction

Journal Article · Mon Nov 11 00:00:00 EST 2019 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201909312· OSTI ID:1573874

Li, Jiazhan ^[1]; Zhang, Hanguang ^[2]; Samarakoon, Widitha ^[3]; Shan, Weitao ^[4]; Cullen, David A. ^[5]; Karakalos, Stavros ^[6]; Chen, Mengjie ^[2]; Gu, Daming ^[7]; More, Karren L. ^[5]; Wang, Guofeng ^[4]; Feng, Zhenxing ^[3]; Wang, Zhenbo ^[7];

^[2]

Department MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage School of Chemistry and Chemical Engineering Harbin Institute of Technology Harbin 150001 China, Department of Chemical and Biological Engineering University at Buffalo The State University of New York Buffalo NY 14260 USA
Department of Chemical and Biological Engineering University at Buffalo The State University of New York Buffalo NY 14260 USA
School of Chemical Biological, and Environmental Engineering Oregon State University Corvallis OR 97331 USA
Department of Mechanical Engineering and Materials Science University of Pittsburgh Pittsburgh PA 15261 USA
Center for Nanophase Materials Sciences Oak Ridge National Laboratory Oak Ridge TN 37831 USA
Department of Chemical Engineering University of South Carolina Columbia SC 29208 USA
Department MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage School of Chemistry and Chemical Engineering Harbin Institute of Technology Harbin 150001 China

Abstract FeN ₄ moieties embedded in partially graphitized carbon are the most efficient platinum group metal free active sites for the oxygen reduction reaction in acidic proton‐exchange membrane fuel cells. However, their formation mechanisms have remained elusive for decades because the Fe−N bond formation process always convolutes with uncontrolled carbonization and nitrogen doping during high‐temperature treatment. Here, we elucidate the FeN ₄ site formation mechanisms through hosting Fe ions into a nitrogen‐doped carbon followed by a controlled thermal activation. Among the studied hosts, the ZIF‐8‐derived nitrogen‐doped carbon is an ideal model with well‐defined nitrogen doping and porosity. This approach is able to deconvolute Fe−N bond formation from complex carbonization and nitrogen doping, which correlates Fe−N bond properties with the activity and stability of FeN ₄ sites as a function of the thermal activation temperature.

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Sponsoring Organization:: USDOE

OSTI ID:: 1573874

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 131 Journal Issue: 52; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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