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P-block single-metal-site tin/nitrogen-doped carbon fuel cell cathode catalyst for oxygen reduction reaction

Abstract

This contribution reports the discovery and analysis of a p-block Sn-based catalyst for the electroreduction of molecular oxygen in acidic conditions at fuel cell cathodes; the catalyst is free of platinum-group metals and contains single-metal-atom actives sites coordinated by nitrogen. The prepared SnNC catalysts meet and exceed state-of-the-art FeNC catalysts in terms of intrinsic catalytic turn-over frequency and hydrogen–air fuel cell power density. The SnNC-NH3 catalysts displayed a 40–50% higher current density than FeNC-NH3 at cell voltages below 0.7 V. Additional benefits include a highly favourable selectivity for the four-electron reduction pathway and a Fenton-inactive character of Sn. A range of analytical techniques combined with density functional theory calculations indicate that stannic Sn(iv)Nx single-metal sites with moderate oxygen chemisorption properties and low pyridinic N coordination numbers act as catalytically active moieties. The superior proton-exchange membrane fuel cell performance of SnNC cathode catalysts under realistic, hydrogen–air fuel cell conditions, particularly after NH3 activation treatment, makes them a promising alternative to today’s state-of-the-art Fe-based catalysts.

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Fig. 1: Chemical and structural characterization of atomically dispersed Sn atoms in SnNC.
Fig. 2: Electrochemical ORR activity, selectivity, active site density and TOF for selected MNC catalysts and for NC.
Fig. 3: Activity relationship, chemisorption relations and Sn motifs.
Fig. 4: The 119Sn Mössbauer spectroscopy characterization.
Fig. 5: Fuel cell measurements.

Data availability

The data supporting the findings of this study are available within this article and its Supplementary Information files, or from the corresponding author upon reasonable request.

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Acknowledgements

We thank S. Dresp, J. Li, H. Tian, S. Li, A. Thomas and T. Reier for assistance with RRDE, XPS and CO-pulse chemisorption experiments; S. Kühl for help with the TEM experiment; and R. Krähnert, H. Wang and D. Bernsmeier for help with the nitrogen physisorption experiments. We also thank Helmholtz-Zentrum Berlin (Bessy II) for allocation of synchrotron radiation beamtime. Aberration-corrected STEM-EELS was conducted at the Center for Nanophase Materials Sciences, which is a US Department of Energy Office of Science User Facility. L.S. and J.R. thank the Danish National Research Foundation for support via grant DNRF 149 and Innovation Fund Denmark for funding through the ProActivE Project no. 5160-00003B. This project received financial support from the BMBF via contract 05K16RD1 and by the Graduate School of Excellence Energy Science and Engineering (GRC1070). Research leading to some of these results has received funding from the Fuel Cells and Hydrogen 2 Joint Undertaking under grant agreement no. 779366, CRESCENDO. This Joint Undertaking receives support from the European Union’s Horizon 2020 research and innovation programme, Hydrogen Europe and Hydrogen Europe Research. F.L. and P.S. acknowledge partial funding by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy—EXC 2008/1—390540038 (zum Teil gefördert durch die DFG im Rahmen der Exzellenzstrategie des Bundes und der Länder—EXC 2008/1—390540038). F.L. also thanks the China Scholarship Council (CSC) for financial support.

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F.L., P.S. and F.J. conceived, designed and coordinated the study. F.L. carried out the materials synthesis, characterization and electrochemical evaluations. A.R. performed the membrane electrode assembly, D.A.C. performed STEM/EELS, A.Z. performed Sn K-edge EXAFS/XANES, M.T.S., I.C.O., T.M., S.W. and U.I.K. performed Mössbauer spectroscopy, and D.T. performed XPS and Fe L-edge XAS experimental work. L.S. and J.R. performed the DFT computational study. J.W. and F. D. participated in the discussion of the electrochemical results section. All authors discussed the results and commented on the manuscript. F.L. wrote the manuscript with the contribution of all co-authors.

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Correspondence to Jan Rossmeisl, Frédéric Jaouen or Peter Strasser.

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Supplementary methods, Notes 0–2, Figs. 1–15 and Tables 1–15.

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Luo, F., Roy, A., Silvioli, L. et al. P-block single-metal-site tin/nitrogen-doped carbon fuel cell cathode catalyst for oxygen reduction reaction. Nat. Mater. 19, 1215–1223 (2020). https://doi.org/10.1038/s41563-020-0717-5

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