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Eliminating dissolution of platinum-based electrocatalysts at the atomic scale

An Author Correction to this article was published on 28 July 2020

This article has been updated

Abstract

A remaining challenge for the deployment of proton-exchange membrane fuel cells is the limited durability of platinum (Pt) nanoscale materials that operate at high voltages during the cathodic oxygen reduction reaction. In this work, atomic-scale insight into well-defined single-crystalline, thin-film and nanoscale surfaces exposed Pt dissolution trends that governed the design and synthesis of durable materials. A newly defined metric, intrinsic dissolution, is essential to understanding the correlation between the measured Pt loss, surface structure, size and ratio of Pt nanoparticles in a carbon (C) support. It was found that the utilization of a gold (Au) underlayer promotes ordering of Pt surface atoms towards a (111) structure, whereas Au on the surface selectively protects low-coordinated Pt sites. This mitigation strategy was applied towards 3 nm Pt3Au/C nanoparticles and resulted in the elimination of Pt dissolution in the liquid electrolyte, which included a 30-fold durability improvement versus 3 nm Pt/C over an extended potential range up to 1.2 V.

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Fig. 1: Dissolution trends for Pt surfaces.
Fig. 2: The effect of subsurface Au on Pt dissolution rates.
Fig. 3: Effect of surface Au on Pt(111) dissolution and ORR rates.
Fig. 4: Pt3Au NPs.

Data availability

All the data are available in the main text and in the Supplementary Information, and are also available from corresponding author upon reasonable request. Source data for the bar graphs are provided with this paper.

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Acknowledgements

This work was done at the Argonne National Laboratory, which is operated for the US Department of Energy (DOE) Office of Science by the UCArgonne, LLC, under contract no. DE-AC02-06CH11357. The research efforts on single-crystalline systems, well-defined thin films and in situ dissolution measurements were supported by the Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division. Synthesis and characterization of the nanoscale materials was supported by the US DOE Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office. Transmission electron microscopy studies were accomplished at the Center for Nanoscale Materials at the Argonne National Laboratory, an Office of Science user facility supported by the US DOE Office of Science, Office of Basic Energy Sciences, under contract no. DE-AC02- 06CH11357, and at the Center for Nanophase Materials Sciences at Oak Ridge National Laboratory, an Office of Science user facility supported by the US DOE Office of Science, Office of Basic Energy Sciences, with work supported by the Hydrogen & Fuel Cell Technologies Office, Energy Efficiency and Renewable Energy, US Department of Energy. Computational modelling work at University of Wisconsin-Madison was supported by the Department of Energy, Basic Energy Sciences, Division of Chemical Sciences (grant DE-FG02-05ER15731), and was partially performed using supercomputer resources at the National Energy Research Scientific Computing Center (NERSC). NERSC is supported by the US DOE, Office of Science, under contract no. DE-AC02-05CH11231.

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P.P.L., H.D., C.W. and V.R.S. conceived the idea and designed the experiments. P.P.L. performed in situ dissolution measurements on all the systems. C.W., D.L. and J.S. developed and performed thin-film depositions. H.L., Y.K., N.B. and D.L. performed the synthesis and characterization of nanoscale materials. M.M. and R.S. designed and performed the theoretical modelling work. D.T. and Y.S. performed STM and AFM measurements. K.L.M. performed the HR-STEM and EDS characterizations. P.P.L., D.L., D.S., M.M., N.M.M. and V.R.S. analysed and discussed the results. C.W., P.P.L. and V.R.S. drafted the manuscript. V.R.S. supervised the research. All the authors approved the final version of the manuscript.

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Correspondence to Vojislav R. Stamenkovic.

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Supplementary Information

Supplementary Tables 1 and 2, Figs. 1–13, captions and notes for Tables 1 and 2 and Figs. 1–13 and references 1–6.

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Source Data Fig. 1

Numerical data used to generate bar graphs displayed in panels g, h, and i.

Source Data Fig. 2

Numerical data used to generate bar graph displayed in panel f.

Source Data Fig. 3

Numerical data used to generate graph displayed in panel c.

Source Data Fig. 4

Numerical data used to generate bar graph data displayed in panel h.

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Lopes, P.P., Li, D., Lv, H. et al. Eliminating dissolution of platinum-based electrocatalysts at the atomic scale. Nat. Mater. 19, 1207–1214 (2020). https://doi.org/10.1038/s41563-020-0735-3

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