Extending the limits of Pt/C catalysts with passivation-gas-incorporated atomic layer deposition

Abstract

Controlling the morphology of noble metal nanoparticles during surface depositions is strongly influenced by precursor–substrate and precursor–deposit interactions. Depositions can be improved through a variety of means, including tailoring the surface energy of a substrate to improve precursor wettability, or by modifying the surface energy of the deposits themselves. Here, we show that carbon monoxide can be used as a passivation gas during atomic layer deposition to modify the surface energy of already deposited Pt nanoparticles to assist direct deposition onto a carbon catalyst support. The passivation process promotes two-dimensional growth leading to Pt nanoparticles with suppressed thicknesses and a more than 40% improvement in Pt surface-to-volume ratio. This approach to synthesizing nanoparticulate Pt/C catalysts achieved high Pt mass activities for the oxygen reduction reaction, along with excellent stability likely facilitated by strong catalyst–support interactions afforded by this synthetic technique.

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Fig. 1: Pt nanoparticle growth with ALD and PALD.
Fig. 2: Comparing ORR activities of PALD and ALD Pt nanoparticles.
Fig. 3: Morphological difference between best-performing ALD and PALD Pt nanoparticles.
Fig. 4: Activity and stability of Pt/C catalysts synthesized with PALD.

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Acknowledgements

This work was supported financially by the Volkswagen Group of America. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-1542152. S.X. thanks support from and discussions with L. Johal, G. Li, Z. Lu and Y. Liu. D.H. acknowledges support from the Banting Postdoctoral Fellowship, administered by the government of Canada. J.T. acknowledges funding from the Austrian Science Fund (FWF) under contract J3505-N20. P.S. acknowledges financial support from the Austrian Science Fund (FWF) under contract J3980-N27.

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S.X. conceived the PALD process and conducted the initial feasibility tests with P.S., D.T., J.Pr. and J.T. under the supervision of F.B.P.; S.X., Y.K. and D.H. tested catalytic performance of PALD-deposited Pt under the supervision of F.B.P. and T.F.J.; S.X., J.Pa., D.T., S.S. and B.H.L. performed material characterizations and analysed the data; S.X., D.H., M.O., J.Pr., Y.K., T.G., T.D.S., T.F.J. and F.B.P. wrote the manuscript.

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Correspondence to Fritz B. Prinz.

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Xu, S., Kim, Y., Park, J. et al. Extending the limits of Pt/C catalysts with passivation-gas-incorporated atomic layer deposition. Nat Catal 1, 624–630 (2018). https://doi.org/10.1038/s41929-018-0118-1

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