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Title: Atomically Dispersed Iron Cathode Catalysts Derived from Binary Ligand-Based Zeolitic Imidazolate Frameworks with Enhanced Stability for PEM Fuel Cells

Abstract

Iron-nitrogen-carbon (Fe-N-C) catalysts for oxygen reduction reaction (ORR) have exhibited a great promise to replace current platinum-based catalysts for proton exchange membrane fuel cells (PEMFCs). However, insufficient stability is the major hurdle to prohibit their practical applications. Here, we report a binary ligand strategy to synthesize Fe-doped zeolitic imidazolate framework-8 (ZIF-8) catalyst precursors through combining traditional 2-methyimidazole (mIm) and the secondary imidazolate or triazole-containing ligands. Compared to triazole-based secondary ligands, imidazolate-based ones are able to retain the shape and size of crystal particles from precursors to catalysts during thermal activation, providing great feasibility to control catalyst morphologies. Among studied ligands, integrating 2-undecylimidazole (uIm) as the secondary ligand with mIm enabled atomically dispersed Fe-N-C catalysts with high ORR activity and obviously enhanced durability in acidic electrolytes. Unlike single mIm systems, using the mIm+uIm binary ligand synthesis, increasing Fe doping content does not result in the formation of Fe-rich aggregates. The unique hollow carbon particle morphology observed with the mIm+uIm-derived catalyst leads to increased surface area allowing to accommodate more atomic FeN4 active sites. The increased order of carbon structures in the mIm+uIm-derived catalyst is likely beneficial for enhancement of catalyst stability.

Authors:
; ; ; ORCiD logo; ; ; ORCiD logo; ORCiD logo
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1505884
Alternate Identifier(s):
OSTI ID: 1508744
Report Number(s):
BNL-211576-2019-JAAM
Journal ID: ISSN 0013-4651; /jes/166/7/F3116.atom
Grant/Contract Number:  
EE0008075; SC0012704
Resource Type:
Published Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Name: Journal of the Electrochemical Society Journal Volume: 166 Journal Issue: 7; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; PGM-free catalysts; metal-organic frameworks; ligands; oxygen reduction; PEM fuel cells

Citation Formats

Zhang, Hanguang, Ding, Shuo, Hwang, Sooyeon, Zhao, Xiaolin, Su, Dong, Xu, Hui, Yang, Haipeng, and Wu, Gang. Atomically Dispersed Iron Cathode Catalysts Derived from Binary Ligand-Based Zeolitic Imidazolate Frameworks with Enhanced Stability for PEM Fuel Cells. United States: N. p., 2019. Web. doi:10.1149/2.0141907jes.
Zhang, Hanguang, Ding, Shuo, Hwang, Sooyeon, Zhao, Xiaolin, Su, Dong, Xu, Hui, Yang, Haipeng, & Wu, Gang. Atomically Dispersed Iron Cathode Catalysts Derived from Binary Ligand-Based Zeolitic Imidazolate Frameworks with Enhanced Stability for PEM Fuel Cells. United States. doi:10.1149/2.0141907jes.
Zhang, Hanguang, Ding, Shuo, Hwang, Sooyeon, Zhao, Xiaolin, Su, Dong, Xu, Hui, Yang, Haipeng, and Wu, Gang. Tue . "Atomically Dispersed Iron Cathode Catalysts Derived from Binary Ligand-Based Zeolitic Imidazolate Frameworks with Enhanced Stability for PEM Fuel Cells". United States. doi:10.1149/2.0141907jes.
@article{osti_1505884,
title = {Atomically Dispersed Iron Cathode Catalysts Derived from Binary Ligand-Based Zeolitic Imidazolate Frameworks with Enhanced Stability for PEM Fuel Cells},
author = {Zhang, Hanguang and Ding, Shuo and Hwang, Sooyeon and Zhao, Xiaolin and Su, Dong and Xu, Hui and Yang, Haipeng and Wu, Gang},
abstractNote = {Iron-nitrogen-carbon (Fe-N-C) catalysts for oxygen reduction reaction (ORR) have exhibited a great promise to replace current platinum-based catalysts for proton exchange membrane fuel cells (PEMFCs). However, insufficient stability is the major hurdle to prohibit their practical applications. Here, we report a binary ligand strategy to synthesize Fe-doped zeolitic imidazolate framework-8 (ZIF-8) catalyst precursors through combining traditional 2-methyimidazole (mIm) and the secondary imidazolate or triazole-containing ligands. Compared to triazole-based secondary ligands, imidazolate-based ones are able to retain the shape and size of crystal particles from precursors to catalysts during thermal activation, providing great feasibility to control catalyst morphologies. Among studied ligands, integrating 2-undecylimidazole (uIm) as the secondary ligand with mIm enabled atomically dispersed Fe-N-C catalysts with high ORR activity and obviously enhanced durability in acidic electrolytes. Unlike single mIm systems, using the mIm+uIm binary ligand synthesis, increasing Fe doping content does not result in the formation of Fe-rich aggregates. The unique hollow carbon particle morphology observed with the mIm+uIm-derived catalyst leads to increased surface area allowing to accommodate more atomic FeN4 active sites. The increased order of carbon structures in the mIm+uIm-derived catalyst is likely beneficial for enhancement of catalyst stability.},
doi = {10.1149/2.0141907jes},
journal = {Journal of the Electrochemical Society},
number = 7,
volume = 166,
place = {United States},
year = {2019},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1149/2.0141907jes

Citation Metrics:
Cited by: 3 works
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Figures / Tables:

Figure 1 Figure 1: Schematic illustration of the binary ligand strategy for the preparation of Fe-N-C catalysts. The secondary ligands include 2-methylimidazole (mIm), 2-undecylimidazole (uIm), benzimidazole (bIm), and 1,2,4-triazole (tria).

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