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The role of metal/oxide interfaces for long-range metal particle activation during CO oxidation

Nature Materials volume 17, pages 519–522 (2018)Cite this article

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The interaction of metal nanoparticles with oxide supports in heterogeneous catalysis has been intensely discussed for decades because the support may change the surface properties and electronic structure of the nanoparticles1,2,3,4,5. To understand support-induced phenomena is key for the design of advanced materials. Here we demonstrate a long-range effect of metal/oxide boundaries on the reactivity of Pd in CO oxidation. The effect was observed directly by photoemission electron microscopy (PEEM) and rationalized by density functional theory (DFT) calculations. We show that the higher CO tolerance of sites at the nanoscale perimeter of the metal/oxide interface makes entire micrometre-sized Pd particles more resistant to CO poisoning. This is attributed to the critical role of the perimeter sites for the initiation of deactivation and reactivation fronts, which were used to probe the metal/oxide interface effect. This finding should affect the quest for better CO oxidation catalysts, a hot topic for automotive stop–start systems and hybrid vehicles6,7.

The complexity of heterogeneous catalysts makes their research extremely challenging. However, this complexity provides various structural features that can be favourably tuned, for example, the choice of materials that support the catalytically active metal nanoparticles is crucial8,9,10. Supports affect not only the growth, size and shape of nanometre-sized particles, but also the catalytic activity: sites at metal/oxide interfaces are often considered to be the most active. Metal/support interactions are believed to be localized, that is, to affect only the reactivity of sites that are <1 nm away from the interface. Among such sites, the most affected should be those located in the immediate vicinity of the metal/support interface, that is, its perimeter sites.

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Fig. 1: Long-range effect of the metal/oxide interface on CO oxidation on Pd.
Fig. 2: Kinetic data for CO oxidation on Pd.
Fig. 3: Adsorption energies of O on Pd aggregates.

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Acknowledgements

This work was financially supported by the Austrian Science Fund (FWF) through project SFB FOXSI (F4504/02-N16) and by the Spanish MINECO/FEDER grant CTQ2015-64618-R and by grants 2017SGR13 and XRQTC of the Generalitat de Catalunya. The authors thank the Red Española de Supercomputación for the computer resources and technical support.

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Author notes

  1. These authors contributed equally: Yuri Suchorski, Sergey M. Kozlov.

Authors and Affiliations

  1. Institut für Materialchemie, Technische Universität Wien, Vienna, Austria

    Yuri Suchorski, Ivan Bespalov, Martin Datler, Diana Vogel, Zuzana Budinska & Günther Rupprechter

  2. Departament de Ciència dels Materials i Química Física and Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, Barcelona, Spain

    Sergey M. Kozlov & Konstantin M. Neyman

  3. ICREA (Institució Catalana de Recerca i Estudis Avançats), Barcelona, Spain

    Konstantin M. Neyman

Authors
  1. Yuri Suchorski
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Contributions

I.B., M.D., D.V. and Z.B. performed the PEEM experiments. Y.S. and G.R. supervised the experimental work and were involved in the analysis of the experimental data and the preparation of the manuscript. S.M.K. performed the DFT calculations and K.M.N. supervised the theoretical work. S.M.K. and K.M.N. analysed the calculated data and were involved in the preparation of the manuscript. All the authors contributed to the discussion and approved the manuscript. Y.S. and S.M.K. contributed equally to this work.

Corresponding authors

Correspondence to Konstantin M. Neyman or Günther Rupprechter.

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The authors declare no competing interests.

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Supplementary information

Supplementary Information

Supplementary Figures 1–8; Key calculated structures: CO molecule; O2 molecule; Pd119 particle; 2xO/Pd119 particle; 2xCO/Pd119 particle; Pd119/ZrO2(111) structure; 2xO/Pd119/ZrO2(111) structure; 2xCO/Pd119/ZrO2(111) structure; Pd119/MgO(100) structure; 2xO/Pd119/MgO(100) structure; 2xCO/Pd119/MgO(100) structure; Supplementary References 1–23

PEEM Video

PEEM video of CO oxidation on Pd-ZrO2

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Suchorski, Y., Kozlov, S.M., Bespalov, I. et al. The role of metal/oxide interfaces for long-range metal particle activation during CO oxidation. Nature Mater 17, 519–522 (2018). https://doi.org/10.1038/s41563-018-0080-y

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