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Unlocking synergy in bimetallic catalysts by core–shell design

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.

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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.

Data availability

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

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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.

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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.

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The authors declare no competing interests.

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

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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.

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

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