Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN4 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/anie.201909312

Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN₄ Sites for Oxygen Reduction

Journal Article · Mon Oct 21 00:00:00 EDT 2019 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201909312· OSTI ID:1720213

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]

Harbin Inst. of Technology (China); State Univ. of New York (SUNY), Buffalo, NY (United States)
State Univ. of New York (SUNY), Buffalo, NY (United States)
Oregon State Univ., Corvallis, OR (United States)
Univ. of Pittsburgh, PA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Univ. of South Carolina, Columbia, SC (United States)
Harbin Inst. of Technology (China)

FeN₄ 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. In this study, we elucidate the FeN₄ 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 FeN₄ sites as a function of the thermal activation temperature.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)

Sponsoring Organization:: National Natural Science Foundation of China (NNSFC); National Science Foundation (NSF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office

Grant/Contract Number:: AC02-06CH11357; AC05-00OR22725; EE0008076

OSTI ID:: 1720213

Alternate ID(s):: OSTI ID: 1573855
OSTI ID: 1599437

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 52 Vol. 58; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
atomically dispersed active site
formation mechanism
iron
oxygen reduction reaction
proton exchange membrane fuel cell