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

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

doi:10.1002/anie.201909312

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

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

Research output: Contribution to journal › Article › peer-review

427 Scopus citations

Abstract

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. Here, 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.

Original language	English
Pages (from-to)	18971-18980
Number of pages	10
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	52
DOIs	https://doi.org/10.1002/anie.201909312
State	Published - Dec 19 2019

Funding

G. Wu thanks the National Science Foundation (NSF) (CBET-1604392, 1804326) and U.S. Department of Energy, Fuel Cell Technologies Office (DE-EE0008076) for financial support. G. Wang acknowledges the support from NSF CBET-804534. Electron microscopy research was conducted at Oak Ridge National Laboratory's Center for Nanophase Materials Sciences of (D.A.C. and K.L.M.), which is a U.S. DOE Office of Science User Facility. XAS measurements were performed at beamline 5-BM-D of DND-CAT and 9-BM-C at the Advanced Photon Source, a User Facility operated by Argonne National Laboratory under Contract No. DE-AC02-06CH11357 (Z.F.). DND-CAT is supported through E. I. duPont de Nemours & Co., Northwestern University, and The Dow Chemical Company. Z. Wang acknowledges support from National Natural Science Foundation of China (21273058 and 21673064). G. Wang also acknowledges the computational resources provided by the University of Pittsburgh Center for Research Computing as well as the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by NSF ACI-1053575.

Keywords

electrode materials
iron
nanomaterials
oxygen reduction reaction
proton-exchange membrane fuel cells

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1002/anie.201909312

Cite this

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title = "Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN4 Sites for Oxygen Reduction",

abstract = "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. Here, 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.",

keywords = "electrode materials, iron, nanomaterials, oxygen reduction reaction, proton-exchange membrane fuel cells",

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

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T1 - Thermally Driven Structure and Performance Evolution of Atomically Dispersed FeN4 Sites for Oxygen Reduction

AU - Li, Jiazhan

AU - Zhang, Hanguang

AU - Samarakoon, Widitha

AU - Shan, Weitao

AU - Cullen, David A.

AU - Karakalos, Stavros

AU - Chen, Mengjie

AU - Gu, Daming

AU - More, Karren L.

AU - Wang, Guofeng

AU - Feng, Zhenxing

AU - Wang, Zhenbo

AU - Wu, Gang

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N2 - 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. Here, 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.

AB - 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. Here, 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.

KW - electrode materials

KW - iron

KW - nanomaterials

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KW - proton-exchange membrane fuel cells

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