Characterizing Complex Gas-Solid Interfaces with in Situ Spectroscopy: Oxygen Adsorption Behavior on Fe-N-C Catalysts

Michael J. Dzara; Kateryna Artyushkova; Moulay Tahar Sougrati; Chilan Ngo; Margaret A. Fitzgerald; Alexey Serov; Barr Zulevi; Plamen Atanassov; Frédéric Jaouen; Svitlana Pylypenko

doi:10.1021/acs.jpcc.0c05244

Characterizing Complex Gas-Solid Interfaces with in Situ Spectroscopy: Oxygen Adsorption Behavior on Fe-N-C Catalysts

Michael J. Dzara, Kateryna Artyushkova, Moulay Tahar Sougrati, Chilan Ngo, Margaret A. Fitzgerald, Alexey Serov, Barr Zulevi, Plamen Atanassov, Frédéric Jaouen, Svitlana Pylypenko

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21 Scopus citations

Abstract

Electrocatalysts for the oxygen reduction reaction within polymer electrolyte membrane fuel cells based on iron, nitrogen, and carbon elements (Fe-N-C) have received significant research attention as they offer an inexpensive alternative to catalysts based on platinum-group metals. Although both the performance and the fundamental understanding of Fe-N-C catalysts have improved over the past decade, there remains a need to differentiate the relative activity of different active sites. Toward this goal, our study is focused on characterizing the interactions between O2 and a set of five structurally different Fe-N-C materials. Detailed characterization of the Fe speciation was performed with 57Fe Mössbauer spectroscopy and soft X-ray absorption spectroscopy of the Fe L3,2-edge, whereas nitrogen chemical states were investigated with X-ray photoelectron spectroscopy (XPS). In addition to initial sXAS and XPS measurements performed in ultra-high vacuum (UHV), measurements were also performed (at the identical location) in an atmosphere of 100 mTorr of O2 at 80 °C (O2-rich). XPS and sXAS results reveal the presence of several types of FeNxCy adsorption sites. FeNxCy sites that are proposed as the most active ones do not show significant change (based on the techniques used in this study) when their environment is changed from UHV to O2-rich. Correlation with Mössbauer and sXAS results suggests that this is most likely due to the persistence of strongly adsorbed O2 molecules from their previous exposure to air. However, other species do show spectroscopic changes from UHV conditions to O2-rich. This implies that these sites have a weaker interaction with O2 that results in their desorption in vacuum conditions and re-adsorption when exposed to the O2-rich environment. The nature of these weakly and strongly O2-adsorbing FeNxCy sites is discussed in the context of different synthetic and processing parameters employed to fabricate each of these five Fe-N-C materials.

Original language	English
Pages (from-to)	16529-16543
Number of pages	15
Journal	Journal of Physical Chemistry C
Volume	124
Issue number	30
DOIs	https://doi.org/10.1021/acs.jpcc.0c05244
State	Published - Jul 30 2020
Externally published	Yes

Funding

This work was supported by start-up funds from Colorado School of Mines and NSF award #1800585—Probing Catalyst-support Interactions via Experiment and Theory. This research used resources of the ALS, which is a DOE Office of Science User Facility under contract no. DE-AC02-05CH11231. We gratefully acknowledge Dr. Hendrik Bluhm for his assistance in collecting data at beamline 11.0.2 of the ALS. K.A. acknowledges NSF award # 1738386 RII Track-4: Operando Analysis of Fuel Cell Materials at ALS. A.S. and B.Z. gratefully acknowledge financial support from US DOE EERE (DE-EE0008419 “Active and Durable PGM-free Cathodic Electrocatalysts for Fuel Cell Application”).

Funders	Funder number
National Science Foundation	1800585
Office of Science	1738386 RII Track-4, DE-AC02-05CH11231
Office of Energy Efficiency and Renewable Energy	DE-EE0008419
Colorado School of Mines

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title = "Characterizing Complex Gas-Solid Interfaces with in Situ Spectroscopy: Oxygen Adsorption Behavior on Fe-N-C Catalysts",

abstract = "Electrocatalysts for the oxygen reduction reaction within polymer electrolyte membrane fuel cells based on iron, nitrogen, and carbon elements (Fe-N-C) have received significant research attention as they offer an inexpensive alternative to catalysts based on platinum-group metals. Although both the performance and the fundamental understanding of Fe-N-C catalysts have improved over the past decade, there remains a need to differentiate the relative activity of different active sites. Toward this goal, our study is focused on characterizing the interactions between O2 and a set of five structurally different Fe-N-C materials. Detailed characterization of the Fe speciation was performed with 57Fe M{\"o}ssbauer spectroscopy and soft X-ray absorption spectroscopy of the Fe L3,2-edge, whereas nitrogen chemical states were investigated with X-ray photoelectron spectroscopy (XPS). In addition to initial sXAS and XPS measurements performed in ultra-high vacuum (UHV), measurements were also performed (at the identical location) in an atmosphere of 100 mTorr of O2 at 80 °C (O2-rich). XPS and sXAS results reveal the presence of several types of FeNxCy adsorption sites. FeNxCy sites that are proposed as the most active ones do not show significant change (based on the techniques used in this study) when their environment is changed from UHV to O2-rich. Correlation with M{\"o}ssbauer and sXAS results suggests that this is most likely due to the persistence of strongly adsorbed O2 molecules from their previous exposure to air. However, other species do show spectroscopic changes from UHV conditions to O2-rich. This implies that these sites have a weaker interaction with O2 that results in their desorption in vacuum conditions and re-adsorption when exposed to the O2-rich environment. The nature of these weakly and strongly O2-adsorbing FeNxCy sites is discussed in the context of different synthetic and processing parameters employed to fabricate each of these five Fe-N-C materials.",

author = "Dzara, {Michael J.} and Kateryna Artyushkova and Sougrati, {Moulay Tahar} and Chilan Ngo and Fitzgerald, {Margaret A.} and Alexey Serov and Barr Zulevi and Plamen Atanassov and Fr{\'e}d{\'e}ric Jaouen and Svitlana Pylypenko",

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AU - Dzara, Michael J.

AU - Artyushkova, Kateryna

AU - Sougrati, Moulay Tahar

AU - Ngo, Chilan

AU - Fitzgerald, Margaret A.

AU - Serov, Alexey

AU - Zulevi, Barr

AU - Atanassov, Plamen

AU - Jaouen, Frédéric

AU - Pylypenko, Svitlana

PY - 2020/7/30

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AB - Electrocatalysts for the oxygen reduction reaction within polymer electrolyte membrane fuel cells based on iron, nitrogen, and carbon elements (Fe-N-C) have received significant research attention as they offer an inexpensive alternative to catalysts based on platinum-group metals. Although both the performance and the fundamental understanding of Fe-N-C catalysts have improved over the past decade, there remains a need to differentiate the relative activity of different active sites. Toward this goal, our study is focused on characterizing the interactions between O2 and a set of five structurally different Fe-N-C materials. Detailed characterization of the Fe speciation was performed with 57Fe Mössbauer spectroscopy and soft X-ray absorption spectroscopy of the Fe L3,2-edge, whereas nitrogen chemical states were investigated with X-ray photoelectron spectroscopy (XPS). In addition to initial sXAS and XPS measurements performed in ultra-high vacuum (UHV), measurements were also performed (at the identical location) in an atmosphere of 100 mTorr of O2 at 80 °C (O2-rich). XPS and sXAS results reveal the presence of several types of FeNxCy adsorption sites. FeNxCy sites that are proposed as the most active ones do not show significant change (based on the techniques used in this study) when their environment is changed from UHV to O2-rich. Correlation with Mössbauer and sXAS results suggests that this is most likely due to the persistence of strongly adsorbed O2 molecules from their previous exposure to air. However, other species do show spectroscopic changes from UHV conditions to O2-rich. This implies that these sites have a weaker interaction with O2 that results in their desorption in vacuum conditions and re-adsorption when exposed to the O2-rich environment. The nature of these weakly and strongly O2-adsorbing FeNxCy sites is discussed in the context of different synthetic and processing parameters employed to fabricate each of these five Fe-N-C materials.

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Characterizing Complex Gas-Solid Interfaces with in Situ Spectroscopy: Oxygen Adsorption Behavior on Fe-N-C Catalysts

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