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Title: Evolution of N-Coordinated Iron–Carbon (FeNC) Catalysts and Their Oxygen Reduction (ORR) Performance in Acidic Media at Various Stages of Catalyst Synthesis: An Attempt at Benchmarking

Abstract

The objective of this study was to understand the role of iron and the heat treatment steps involved in nitrogen-coordinated iron-carbon (FeNC) catalyst synthesis. We have studied the oxygen reduction reaction (ORR) performance of these catalysts as they evolve from their most crude and inactive form to their most active form. Electrochemical half-cell and fuel cell tests suggest that the presence of Fe was crucial in these samples. The high-temperature heat treatment (once in argon and then in ammonia) at temperatures ≥950 °C were also critical in imparting these catalysts with their highest activity; however, significant loss of activity was observed with cycling and potential hold at 0.5 V for 100 h. In addition, acid-washing after the first or the second pyrolysis steps produced a marked decrease in ORR activity relative to their unwashed counterparts. We also report findings from our efforts towards benchmarking FeNC catalysts for oxygen reduction reaction electrocatalysis. Specifically, we focus on correlating the specific kinetic current (iK) at 0.75 V to electrochemically accessible surface area (EASA) and roughness factor (RF) determined from electrochemical double layer capacitance measurements. 57Fe Mössbauer spectroscopy was employed to shed light into the nature of active sites in FeNC catalysts and providemore » insights into their deactivation behavior caused by acid-washing. The results suggest planar FeN 4 doublet (Fe 2+, low spin) as an active site in these materials, which may be leached away in acid, explaining their decreased activity after acid washing. Results for characterization experiments using X-ray photoelectron spectroscopy, temperature programmed oxidation and X-ray absorption spectroscopy, superconducting quantum interference device magnetometry are also presented.« less

Authors:
; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1329417
Resource Type:
Journal Article
Journal Name:
Catalysis Letters
Additional Journal Information:
Journal Volume: 146; Journal Issue: 9; Journal ID: ISSN 1011-372X
Publisher:
Springer
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Mamtani, Kuldeep, Singh, Deepika, Tian, Juan, Millet, Jean-Marc M., Miller, Jeffrey T., Co, Anne C., and Ozkan, Umit S. Evolution of N-Coordinated Iron–Carbon (FeNC) Catalysts and Their Oxygen Reduction (ORR) Performance in Acidic Media at Various Stages of Catalyst Synthesis: An Attempt at Benchmarking. United States: N. p., 2016. Web. doi:10.1007/s10562-016-1800-z.
Mamtani, Kuldeep, Singh, Deepika, Tian, Juan, Millet, Jean-Marc M., Miller, Jeffrey T., Co, Anne C., & Ozkan, Umit S. Evolution of N-Coordinated Iron–Carbon (FeNC) Catalysts and Their Oxygen Reduction (ORR) Performance in Acidic Media at Various Stages of Catalyst Synthesis: An Attempt at Benchmarking. United States. doi:10.1007/s10562-016-1800-z.
Mamtani, Kuldeep, Singh, Deepika, Tian, Juan, Millet, Jean-Marc M., Miller, Jeffrey T., Co, Anne C., and Ozkan, Umit S. Tue . "Evolution of N-Coordinated Iron–Carbon (FeNC) Catalysts and Their Oxygen Reduction (ORR) Performance in Acidic Media at Various Stages of Catalyst Synthesis: An Attempt at Benchmarking". United States. doi:10.1007/s10562-016-1800-z.
@article{osti_1329417,
title = {Evolution of N-Coordinated Iron–Carbon (FeNC) Catalysts and Their Oxygen Reduction (ORR) Performance in Acidic Media at Various Stages of Catalyst Synthesis: An Attempt at Benchmarking},
author = {Mamtani, Kuldeep and Singh, Deepika and Tian, Juan and Millet, Jean-Marc M. and Miller, Jeffrey T. and Co, Anne C. and Ozkan, Umit S.},
abstractNote = {The objective of this study was to understand the role of iron and the heat treatment steps involved in nitrogen-coordinated iron-carbon (FeNC) catalyst synthesis. We have studied the oxygen reduction reaction (ORR) performance of these catalysts as they evolve from their most crude and inactive form to their most active form. Electrochemical half-cell and fuel cell tests suggest that the presence of Fe was crucial in these samples. The high-temperature heat treatment (once in argon and then in ammonia) at temperatures ≥950 °C were also critical in imparting these catalysts with their highest activity; however, significant loss of activity was observed with cycling and potential hold at 0.5 V for 100 h. In addition, acid-washing after the first or the second pyrolysis steps produced a marked decrease in ORR activity relative to their unwashed counterparts. We also report findings from our efforts towards benchmarking FeNC catalysts for oxygen reduction reaction electrocatalysis. Specifically, we focus on correlating the specific kinetic current (iK) at 0.75 V to electrochemically accessible surface area (EASA) and roughness factor (RF) determined from electrochemical double layer capacitance measurements. 57Fe Mössbauer spectroscopy was employed to shed light into the nature of active sites in FeNC catalysts and provide insights into their deactivation behavior caused by acid-washing. The results suggest planar FeN4 doublet (Fe2+, low spin) as an active site in these materials, which may be leached away in acid, explaining their decreased activity after acid washing. Results for characterization experiments using X-ray photoelectron spectroscopy, temperature programmed oxidation and X-ray absorption spectroscopy, superconducting quantum interference device magnetometry are also presented.},
doi = {10.1007/s10562-016-1800-z},
journal = {Catalysis Letters},
issn = {1011-372X},
number = 9,
volume = 146,
place = {United States},
year = {2016},
month = {11}
}

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