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Engineering stable electrocatalysts by synergistic stabilization between carbide cores and Pt shells

Abstract

Core–shell particles with earth-abundant cores represent an effective design strategy for improving the performance of noble metal catalysts, while simultaneously reducing the content of expensive noble metals1,2,3,4. However, the structural and catalytic stabilities of these materials often suffer during the harsh conditions encountered in important reactions, such as the oxygen reduction reaction (ORR)3,4,5. Here, we demonstrate that atomically thin Pt shells stabilize titanium tungsten carbide cores, even at highly oxidizing potentials. In situ, time-resolved experiments showed how the Pt coating protects the normally labile core against oxidation and dissolution, and detailed microscopy studies revealed the dynamics of partially and fully coated core–shell nanoparticles during potential cycling. Particles with complete Pt coverage precisely maintained their core–shell structure and atomic composition during accelerated electrochemical ageing studies consisting of over 10,000 potential cycles. The exceptional durability of fully coated materials highlights the potential of core–shell architectures using earth-abundant transition metal carbide (TMC) and nitride (TMN) cores for future catalytic applications.

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Fig. 1: SFC–ICP–MS single potential cycle and galvanostatic measurements.
Fig. 2: Structural stability during potential cycling.
Fig. 3: Long-term durability in O2-sat electrolyte and at elevated temperature.
Fig. 4: ORR catalytic stability.

Data availability

Experimental data are available from the corresponding authors on reasonable request.

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Acknowledgements

This research was funded by the Federal Ministry for Economic Affairs and Energy (BMWi) of Germany in the framework of PtTM@HGS (project number 03ET6080A) and by the Toyota Research Institute through the Accelerated Materials Design and Discovery program. We acknowledge Z. Wang for his help in synthesis of materials, A. Mingers for her help at the ICP–MS and G. Fortunato for the TEM images of Pt NPs/bulk WC.

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D.G., A.G., Y.R.-L. and M.L. conceived this study. A.G. synthesized the materials and performed physicochemical characterization. D.G. conducted the electrochemical stability measurements via SFC–ICP–MS. P.P. carried out IL–STEM measurements accompanied with EDX elemental mapping. D.G. and A.G. conducted ORR activity measurements via RDE. The manuscript was written by A.G., Y.R.-L., D.G. and M.L. All authors discussed the manuscript and the results.

Corresponding authors

Correspondence to Yuriy Román-Leshkov or Marc Ledendecker.

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Supplementary Information

Supplementary Figs. 1–12, Table 1, discussion and ref. 1.

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Göhl, D., Garg, A., Paciok, P. et al. Engineering stable electrocatalysts by synergistic stabilization between carbide cores and Pt shells. Nat. Mater. 19, 287–291 (2020). https://doi.org/10.1038/s41563-019-0555-5

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