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Minimizing Operando Demetallation of Fe–N–C Electrocatalysts in Acidic Medium

MPS-Authors
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Choi,  Chang Hyuck
Electrocatalysis, Interface Chemistry and Surface Engineering, Max-Planck-Institut für Eisenforschung GmbH, Max Planck Society;

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Baldizzone,  Claudio
Electrocatalysis, Interface Chemistry and Surface Engineering, Max-Planck-Institut für Eisenforschung GmbH, Max Planck Society;
Forschungszentrum Jülich GmbH, Helmholtz Institute Erlangen-Nürnberg for Renewable Energy (IEK-11), Egerlandstraße 3, 91058 Erlangen, Germany;

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Polymeros,  George
Electrocatalysis, Interface Chemistry and Surface Engineering, Max-Planck-Institut für Eisenforschung GmbH, Max Planck Society;

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Pizzutilo,  Enrico
Electrocatalysis, Interface Chemistry and Surface Engineering, Max-Planck-Institut für Eisenforschung GmbH, Max Planck Society;

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Kasian,  Olga
Electrocatalysis, Interface Chemistry and Surface Engineering, Max-Planck-Institut für Eisenforschung GmbH, Max Planck Society;

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Mayrhofer,  Karl J. J.
Helmholtz-Institute Erlangen-Nuremberg for Renewable Energy (IEK-11), Forschungszentrum Jülich, Egerlandstrasse 3, 91058 Erlangen, Germany;
Department of Chemical and Biological Engineering, Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058 Erlangen, Germany ;
Electrocatalysis, Interface Chemistry and Surface Engineering, Max-Planck-Institut für Eisenforschung GmbH, Max Planck Society;

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Citation

Choi, C. H., Baldizzone, C., Polymeros, G., Pizzutilo, E., Kasian, O., Schuppert, A. K., et al. (2016). Minimizing Operando Demetallation of Fe–N–C Electrocatalysts in Acidic Medium. ACS Catalysis, 6(5), 3136-3146. doi:10.1021/acscatal.6b00643.


Cite as: http://hdl.handle.net/11858/00-001M-0000-002D-2800-7
Abstract
For a successful replacement of Pt, tremendous efforts have hitherto been made to develop high-performing Fe-N-C catalysts for the oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs). In comparison to the remarkable progress in activity, the stability of Fe-N-C catalysts still remains critical, however. Fe demetallation in acidic medium is hypothesized to be one critical factor for the overall lifetime. In contrast to the general belief, we herein demonstrate using an operando spectroscopic analysis that catalytically inactive Fe particles exposed to acid electrolytes cannot be fully removed by acid washing due to a relatively high open circuit potential (ca. 0.9 V-RHE) leading to the formation of insoluble ferric species, whereas these particles dissolve under PEMFC operating conditions (E-cathode < 0.7 V-RHE) due to operando reduction to soluble ferrous cations. To overcome this issue, we demonstrate two approaches: (i) synthesis of Fe-N-C catalysts free of Fe particles and (ii) postsynthesis removal of exposed Fe particles through the control of potential using an external potentiostat or an internal reducing agent (i.e., SnCl2). Operando spectroscopic analyses verified that Fe demetallation during a given voltammetric protocol was dramatically decreased for both synthetically and postsynthetically modified Fe-N-C catalysts, while the initial ORR activity did not significantly change. However, all of these catalysts showed similar performance decay over short-term PEMFC durability tests, demonstrating the lack of a role played by ferrous cations leached from inactive Fe particles on catalyst deactivation. This supports the view that the activity is mainly imparted by FeNxCy moieties. Nevertheless, the presented guidelines are generally applicable to the whole class of Fe-N-C catalysts in order to minimize Fe demetallation in PEMFCs, which provides important advances for the future design of stable electrocatalytic systems for long-term operation.