Nitric Oxide Probe Molecule Studies of Iron-Nitrogen-Carbon PEMFC Oxygen Reduction Reaction Electrocatalysts

The highest oxygen reduction reaction (ORR) activities in acidic environments for platinum group metal-free electrocatalysts have been achieved for materials derived from iron, nitrogen, and carbon-containing precursors such as iron-substituted zinc-based zeolitic imidazolate frameworks (ZIF).[1-3] These precursors are typically heat treated in an inert atmosphere at temperatures ranging from 900 to 1100°C to form the ORR-active material. In addition to their high intrinsic activity, under certain preparation conditions these catalysts are free of crystalline iron species, with iron atomically dispersed in a nitrogen-doped carbon matrix, as determined through characterization by high-resolution electron microscopy and X-ray absorption spectroscopy. While the exact nature of the active site in these materials is still a matter of debate, the probe molecule, nitric oxide, has been shown to bind to Fe, using nuclear resonance vibrational spectroscopy, and also to poison the ORR.[4-6] An in-depth study of the interaction of nitric oxide with a variety of Fe-N-C catalysts can thus provide insight into the nature of the ORR active site in this class of catalysts. This presentation will discuss the application of multiple characterization techniques to understand the interaction of nitric oxide with Fe-N-C catalysts, including nuclear resonance vibrational spectroscopy, temperature-programmed desorption, and in situ X-ray absorption spectroscopy as a function of potential in aqueous acidic electrolyte. The implications of the results of these studies on the nature of the ORR active site will be discussed. References 1. X.X. Wang, M.T. Swihart, and G. Wu, “Achievements, challenges, and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation”, Nature Catalysis, 2 (2019) 578-589. 2. M. Chen, Y. He, J.S. Spendelow, and G. Wu, ACS Energy Letters, 4 (2019) 1619-1633. 3. S.T. Thompson and D. Papageorgopoulos, Nature Catalysis, 2 (2019) 558-561. 4. J.L. Kneebone, et al., “A Combined Probe-Molecule, Mossbauer, Nuclear Resonance Vibrational Spectroscopy, and Density Functional Theory Approach for Evaluation of Potential Iron Active Sites in an Oxygen Reduction Reaction Catalyst”, J. Phys. Chem. C 121 (2017) 16283-16290. 5. D. Myers and P. Zelenay, “ElectroCat (Electrocatalysis Consortium)”, Department of Energy Hydrogen and Fuel Cells Program Annual Merit Review, 2019. https://www.hydrogen.energy.gov/pdfs/review19/fc160_myers_zelenay_2019_o.pdf 6. P. Boldrin, et al., “Deactivation, reactivation and super-activation of Fe-N/C oxygen reduction electrocatalysts: Gas sorption, physical and electrochemical investigation using NO and O2”, Appl. Cat. B: Environ., 292 (2021) 120169-120180. Acknowledgements This work was supported by the U.S. Department of Energy, Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office under the auspices of the Electrocatalysis Consortium (ElectroCat 2.0). This research used the resources of the Advanced Photon Source (APS), a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Argonne National Laboratory is managed for the U.S Department of Energy by the University of Chicago Argonne, LLC, also under contract DE-AC-02-06CH11357.