Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Unlocking synergy in bimetallic catalysts by core–shell design

Nature Materials volume 20, pages 1216–1220 (2021)Cite this article

Subjects

Abstract

Extending the toolbox from mono- to bimetallic catalysts is key in realizing efficient chemical processes1. Traditionally, the performance of bimetallic catalysts featuring one active and one selective metal is optimized by varying the metal composition1,2,3, often resulting in a compromise between the catalytic properties of the two metals4,5,6. Here we show that by designing the atomic distribution of bimetallic Au–Pd nanocatalysts, we obtain a synergistic catalytic performance in the industrially relevant selective hydrogenation of butadiene. Our single-crystalline Au-core Pd-shell nanorods were up to 50 times more active than their alloyed and monometallic counterparts, while retaining high selectivity. We find a shell-thickness-dependent catalytic activity, indicating that not only the nature of the surface but also several subsurface layers play a crucial role in the catalytic performance, and rationalize this finding using density functional theory calculations. Our results open up an alternative avenue for the structural design of bimetallic catalysts.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Our model system of monodisperse Au@Pd@SiO2 NRs with controlled Pd content and shell thickness.
Fig. 2: Core–shell structured Au–Pd catalysts outperform their alloyed counterparts.
Fig. 3: The catalytic performance of Au-core Pd-shell catalysts is highly sensitive to the number of shell layers.
Fig. 4: Crystallographic orientation of the surface facets, Pd-shell thickness and lattice strain govern the reactant adsorption energies.

Similar content being viewed by others

Data availability

All raw data are available upon request by contacting the corresponding authors. Source data are provided with this paper.

References

  1. Zhang, L., Zhou, M., Wang, A. & Zhang, T. Selective hydrogenation over supported metal catalysts: from nanoparticles to single atoms. Chem. Rev. 120, 683–733 (2020).

    Article  CAS  Google Scholar 

  2. Wu, C. H. et al. Bimetallic synergy in cobalt–palladium nanocatalysts for CO oxidation. Nat. Catal. 2, 78–85 (2019).

    Article  CAS  Google Scholar 

  3. Studt, F. et al. Identification of non-precious metal alloy catalysts for selective hydrogenation of acetylene. Science 320, 1320–1322 (2008).

    Article  CAS  Google Scholar 

  4. Enache, D. I. et al. Solvent-free oxidation of primary alcohols to aldehydes using Au-Pd/TiO2 catalysts. Science 311, 362–365 (2006).

    Article  CAS  Google Scholar 

  5. Hugon, A., Delannoy, L., Krafft, J. M. & Louis, C. Selective hydrogenation of 1,3-butadiene in the presence of an excess of alkenes over supported bimetallic gold palladium catalysts. J. Phys. Chem. C 114, 10823–10835 (2010).

    Article  CAS  Google Scholar 

  6. Masoud, N., Delannoy, L., Calers, C. & Gallet, J. J. Silica-supported Au–Ag catalysts for the selective hydrogenation of butadiene. Chem. Cat. Chem. 9, 2418–2425 (2017).

    CAS  Google Scholar 

  7. Lucci, F. R. et al. Selective hydrogenation of 1,3-butadiene on platinum–copper alloys at the single-atom limit. Nat. Commun. 6, 8550 (2015).

    Article  Google Scholar 

  8. Wang, G. H. et al. Platinum–cobalt bimetallic nanoparticles in hollow carbon nanospheres for hydrogenolysis of 5-hydroxymethylfurfural. Nat. Mater. 13, 293–300 (2014).

    Article  Google Scholar 

  9. Bu, L. et al. Biaxially strained PtPb/Pt core/shell nanoplate boosts oxygen reduction catalysis. Science 354, 1410–1414 (2016).

    Article  CAS  Google Scholar 

  10. Wang, X. et al. Palladium–platinum core–shell icosahedra with substantially enhanced activity and durability towards oxygen reduction. Nat. Commun. 6, 7594 (2015).

    Article  Google Scholar 

  11. Strasser, P. et al. Lattice-strain control of the activity in dealloyed core–shell fuel cell catalysts. Nat. Chem. 2, 454–460 (2010).

    Article  CAS  Google Scholar 

  12. Zugic, B. et al. Dynamic restructuring drives catalytic activity on nanoporous gold–silver alloy catalysts. Nat. Mater. 16, 558–565 (2016).

    Article  Google Scholar 

  13. Ahmadi, M., Behafarid, F., Cui, C., Strasser, P. & Cuenya, B. R. Long-range segregation phenomena in shape-selected bimetallic nanoparticles: chemical state effects. ACS Nano 7, 9195–9204 (2013).

    Article  CAS  Google Scholar 

  14. Wrasman, C. J. et al. Synthesis of colloidal Pd/Au dilute alloy nanocrystals and their potential for selective catalytic oxidations. J. Am. Chem. Soc. 140, 12930–12939 (2018).

    Article  CAS  Google Scholar 

  15. Luneau, M. et al. Dilute Pd/Au alloy nanoparticles embedded in colloid-templated porous SiO2: stable Au-based oxidation catalysts. Chem. Mater. 31, 5759–5768 (2019).

    Article  CAS  Google Scholar 

  16. Lee, J. D. et al. Tuning the electrocatalytic oxygen reduction reaction activity of Pt–Co nanocrystals by cobalt concentration with atomic-scale understanding. ACS Appl. Mater. Interfaces 11, 26789–26797 (2019).

    Article  CAS  Google Scholar 

  17. Gilroy, K. D., Ruditskiy, A., Peng, H. C., Qin, D. & Xia, Y. Bimetallic nanocrystals: syntheses, properties, and applications. Chem. Rev. 116, 10414–10472 (2016).

    Article  CAS  Google Scholar 

  18. Deng, T. S. et al. Oxidative etching and metal overgrowth of gold nanorods within mesoporous silica shells. Chem. Mater. 27, 7196–7230 (2015).

    Article  CAS  Google Scholar 

  19. Zhang, Y. J. et al. Probing the electronic structure of heterogeneous metal interfaces by transition metal shelled gold nanoparticle-enhanced Raman spectroscopy. J. Phys. Chem. C 120, 20684–20691 (2016).

    Article  CAS  Google Scholar 

  20. van der Hoeven, J. E. S. et al. In situ observation of atomic redistribution in alloying gold–silver nanorods. ACS Nano 12, 8467–8476 (2018).

    Article  Google Scholar 

  21. Yu, W. Y., Mullen, G. M. & Mullins, C. B. Hydrogen adsorption and absorption with Pd–Au bimetallic surfaces. J. Phys. Chem. C 117, 19535–19543 (2013).

    Article  CAS  Google Scholar 

  22. Molnár, A., Sárkány, A. & Varga, M. Hydrogenation of carbon–carbon multiple bonds: chemo-, regio- and stereo-selectivity. J. Mol. Catal. A Chem. 173, 185–221 (2001).

    Article  Google Scholar 

  23. Silvestre-Albero, J., Rupprechter, G. & Freund, H. J. From Pd nanoparticles to single crystals: 1,3-butadiene hydrogenation on well-defined model catalysts. Chem. Commun. 80–82 (2006).

  24. Bachiller-Baeza, B. et al. Detecting the genesis of a high-performance carbon-supported Pd sulfide nanophase and its evolution in the hydrogenation of butadiene. ACS Catal. 5, 5235–5241 (2015).

    Article  CAS  Google Scholar 

  25. McEwan, L., Juliusa, M., Robertsa, S. & Fletchera, J. C. Q. A review of the use of gold catalysts in selective hydrogenation reactions. Gold. Bull. 43, 298–306 (2010).

    Article  CAS  Google Scholar 

  26. Hugon, A., Delannoy, L. & Louis, C. Supported gold catalysts for selective hydrogenation of 1,3-butadiene in the presence of an excess of alkenes. Gold. Bull. 41, 127–138 (2008).

    Article  CAS  Google Scholar 

  27. Masoud, N. et al. Superior stability of Au/SiO2 compared to Au/TiO2 catalysts for the selective hydrogenation of butadiene. ACS Catal. 7, 5594–5603 (2017).

    Article  CAS  Google Scholar 

  28. Kolli, N. E., Delannoy, L. & Louis, C. Bimetallic Au–Pd catalysts for selective hydrogenation of butadiene: influence of the preparation method on catalytic properties. J. Catal. 297, 79–92 (2013).

    Article  CAS  Google Scholar 

  29. Goris, B. et al. Atomic-scale determination of surface facets in gold nanorods. Nat. Mater. 11, 930–935 (2012).

    Article  CAS  Google Scholar 

  30. Pinheiro, A., Zei, M., Luo, M. & Ertl, G. The epitaxial growth of Pd electrodeposition on Au(100) studied by LEED and RHEED. Surf. Sci. 600, 641–650 (2006).

    Article  CAS  Google Scholar 

  31. Dolle, P. et al. Strained Pd films, by epitaxial growth on Au(110), to control catalytic properties. Surf. Sci. 518, 1–13 (2002).

    Article  CAS  Google Scholar 

  32. Bertolini, J. C. et al. Electronic properties of supported Pd aggregates in relation with their reactivity for 1,3-butadiene hydrogenation. Catal. Lett. 6, 215–223 (1990).

    Article  CAS  Google Scholar 

  33. Piccolo, L., Piednoir, A. & Bertolini, J. C. Pd-Au single-crystal surfaces: segregation properties and catalytic activity in the selective hydrogenation of 1,3-butadiene. Surf. Sci. 592, 169–181 (2005).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We thank R. Beerthuis and J.W. de Rijk for useful discussions and technical support. We thank N. Masoud for providing the gold catalyst reference data. We thank S. Dussi for critically reading the manuscript. We thank S. Zanoni for useful discussions regarding the carbon monoxide infrared spectroscopy measurements. This project received funding from the European Research Council under the European Union’s Horizon 2020 research and innovation programme (ERC-2014-CoG no. 648991) and the European Union’s Seventh Framework Programme (FP-2007-2013; European Research Council Advanced Grant Agreement #291667 HierarSACol). J.E.S.v.d.H. also acknowledges the graduate programme of the Debye Institute for Nanomaterials Science (Utrecht University), which is facilitated by grant 022.004.016 of the Netherlands Organisation for Scientific Research. J.J. and F.S. gratefully acknowledge support by the state of Baden-Württemberg through bwHPC (bwunicluster and JUSTUS, RV bw17D011) as well as financial support from the Helmholtz Association.

Author information

Authors and Affiliations

  1. Materials Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Utrecht, The Netherlands

    Jessi E. S. van der Hoeven, Liselotte A. Olthof, Giorgio Totarella & Petra E. de Jongh

  2. Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University, Utrecht, The Netherlands

    Jessi E. S. van der Hoeven, Liselotte A. Olthof, Relinde J. A. van Dijk-Moes & Alfons van Blaaderen

  3. Institute of Catalysis Research and Technology, Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen, Germany

    Jelena Jelic & Felix Studt

  4. Laboratoire de Réactivité de Surface, Sorbonne Université, CNRS, Paris, France

    Jean-Marc Krafft & Catherine Louis

  5. Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology, Karlsruhe, Germany

    Felix Studt

Authors
  1. Jessi E. S. van der Hoeven
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jelena Jelic
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Liselotte A. Olthof
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Giorgio Totarella
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Relinde J. A. van Dijk-Moes
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Jean-Marc Krafft
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Catherine Louis
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Felix Studt
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Alfons van Blaaderen
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Petra E. de Jongh
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

J.E.S.v.d.H. performed the experiments supervised by A.v.B. and P.E.d.J.; J.J. performed the calculations under the supervision of F.S.; L.A.O. synthesized the NRs supervised by J.E.S.v.d.H.; and G.T. assisted in the catalysis experiments. R.J.A.v.D.-M. performed the inductively coupled plasma atomic emission spectroscopy measurements. J.-M.K. and C.L. conducted and interpreted the CO-DRIFTS analysis. J.E.S.v.d.H. and P.E.d.J. wrote the paper with the contributions of all the authors.

Corresponding authors

Correspondence to Alfons van Blaaderen or Petra E. de Jongh.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature Materials thanks the anonymous reviewers for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Methods, Figs. 1–16 and Tables 1–4.

Computational Data 1

Cartesian coordinates used to compute the binding energies of butadiene (C4H6, Fig. 4a,b), propene (C3H6, Fig. 4b) and butene (C4H8, Fig. 4b) in the sigma and pi binding configuration, and for the hydrogen binding energy (2H) on the Au, 1Pd, 2Pd, 3Pd, 4Pd and 8Pd structures. The hydrogen and butadiene binding energies on an 8Pd structure with Au lattice spacing (Fig. 4c). The coordinates are given for a 111, 100 or 110 fcc surface structure.

Source data

Source Data Fig. 1

Source data for Fig. 1b.

Source Data Fig. 2

Source data for Fig. 2b–d.

Source Data Fig. 3

Source data for Fig. 3a–c.

Source Data Fig. 4

Source data for Fig. 4a–c.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

van der Hoeven, J.E.S., Jelic, J., Olthof, L.A. et al. Unlocking synergy in bimetallic catalysts by core–shell design. Nat. Mater. 20, 1216–1220 (2021). https://doi.org/10.1038/s41563-021-00996-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-021-00996-3

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing