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Low-temperature non-equilibrium synthesis of anisotropic multimetallic nanosurface alloys for electrochemical CO2 reduction

Nature Synthesis volume 3, pages 47–57 (2024)Cite this article

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Abstract

Multimetallic nanoparticles are of interest as functional materials due to their highly tunable properties. However, synthesizing congruent mixtures of immiscible components is limited by the need for high-temperature procedures followed by rapid quenching that lack size and shape control. Here we report a low-temperature (≤80 °C) non-equilibrium synthesis of nanosurface alloys (NSAs) with tunable size, shape and composition regardless of miscibility. We show the generality of our method by producing both bulk miscible and immiscible monodisperse anisotropic Cu-based NSAs of up to three components. We demonstrate our synthesis as a screening platform to investigate the effects of crystal facet and elemental composition by testing tetrahedral, cubic and truncated-octahedral NSAs as catalysts in the electroreduction of CO2. The use of machine learning has enabled the prediction and informed synthesis of both multicarbon-product-selective and phase-stable Cu–Ag–Pd compositions. This combination of non-equilibrium synthesis and theory-guided candidate selection is expected to accelerate test–learn–repeat cycles of structure–performance optimization processes.

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Fig. 1: The conventional and non-equilibrium synthesis.
Fig. 2: Structural and compositional analysis of anisotropic Cu–Ag NSAs.
Fig. 3: XPS/XAS analysis of anisotropic Cu–Ag NSAs.
Fig. 4: Determination of the penetration depth of Ag in the NSAs.
Fig. 5: Electrocatalysis of (an)isotropic Cu–Ag NPs and NSAs.
Fig. 6: Phase segregation of Cu–Ag NSAs during the electrochemical CO2 reduction reaction (CO2RR).
Fig. 7: Theory-guided optimization of the ternary alloy system.

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Data availability

The data generated in this study are provided in supplementary information and source data. Source data are provided with this paper.

Code availability

DFT simulated atomic structures have been made freely available at https://nano.ku.dk/english/research/theoretical-electrocatalysis/katladb/co2-reduction-on-ag-cu-pd/.

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Acknowledgements

This research was supported by Swiss National Science Foundation (Ambizione Project PZ00P2_179989). M.L. acknowledges the financial support from China Scholarship Council (grant no. 201506060156). J.K.P. and J.R. acknowledge support from the Danish National Research Foundation Center for High Entropy Alloy Catalysis (CHEAC) DNRF-149. L. Menin and N. Gasilova of the Mass Spectrometry and Elemental Analysis Platform (MSEAP), Institute of Chemical Sciences and Engineering (ISIC), Basic Science Faculty (SB), École Polytechnique Fédérale de Lausanne (EPFL) Valais/Wallis, Energypolis, Sion, Switzerland, are acknowledged for their facilitation of the ICP–MS/OES measurements. S. Phadke is acknowledged for his assistance in the preparation of the capillaries.

Author information

Authors and Affiliations

  1. Laboratory of Materials for Renewable Energy (LMER), Institute of Chemical Sciences and Engineering (ISIC), Basic Science Faculty (SB), École Polytechnique Fédérale de Lausanne (EPFL) Valais/Wallis, Energypolis, Sion, Switzerland

    Cedric David Koolen, Jie Zhang, Mo Li & Andreas Züttel

  2. Empa Materials Science & Technology, Dübendorf, Switzerland

    Cedric David Koolen, Jie Zhang, Mo Li & Andreas Züttel

  3. SCIDENTIFY, Lausanne, Switzerland

    Cedric David Koolen

  4. Interdisciplinary Centre for Electron Microscopy (CIME), École Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland

    Emad Oveisi

  5. Paul Scherrer Institute, Villigen, Switzerland

    Olga V. Safonova

  6. Center for High Entropy Alloy Catalysis (CHEAC), Department of Chemistry, University of Copenhagen, Copenhagen, Denmark

    Jack K. Pedersen & Jan Rossmeisl

  7. School of Environmental and Chemical Engineering, Shanghai University, Shanghai, China

    Wen Luo

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  1. Cedric David Koolen
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Contributions

C.D.K., W.L. and A.Z. conceptualized the project. W.L. and A.Z. supervised the project. C.D.K. developed the synthesis of the catalysts and performed the electrochemical tests, catalyst characterizations and the related data processing. E.O. performed the high-resolution transmission electron microscopy characterizations and the related data processing. J.Z. performed the SEM characterizations and assisted with the electrochemical tests and product analysis. M.L. performed the XPS analysis. O.V.S. performed the XAS measurement and related data treatment. J.K.P. performed the DFT simulation with supervision from J.R. C.D.K. and W.L. co-wrote the manuscript. All the authors discussed the results and revised the manuscript.

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Correspondence to Wen Luo.

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Koolen, C.D., Oveisi, E., Zhang, J. et al. Low-temperature non-equilibrium synthesis of anisotropic multimetallic nanosurface alloys for electrochemical CO2 reduction. Nat. Synth 3, 47–57 (2024). https://doi.org/10.1038/s44160-023-00387-3

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