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Controlling the catalytic bond-breaking selectivity of Ni surfaces by step blocking

Nature Materials volume 4, pages 160–162 (2005)Cite this article

Abstract

The reactivity of catalytic surfaces is often dominated by very reactive low-coordinated atoms such as step-edge sites1,2,3,4,5,6,7,8,9,10,11. However, very little knowledge exists concerning the influence of step edges on the selectivity in reactions involving multiple reaction pathways. Such detailed information could be very valuable in rational design of new catalysts with improved selectivity. Here we show, from an interplay between scanning tunnelling microscopy experiments and density functional theory calculations, that the activation of ethylene on Ni(111) follows the trend of higher reactivity for decomposition at step edges as compared with the higher-coordinated terrace sites. The step-edge effect is considerably more pronounced for the C–C bond breaking than for the C–H bond breaking, and thus steps play an important role in the bond-breaking selectivity. Furthermore, we demonstrate how the number of reactive step sites can be controlled by blocking the steps with Ag. This approach to nanoscale design of catalysts is exploited in the synthesis of a new high-surface-area AgNi alloy catalyst, which is tested in hydrogenolysis experiments.

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Figure 1: Ethylene decomposition on Ni(111) and Ag/Ni(111).
Figure 2: Potential energy diagram for ethylene decomposition on Ni(111) and stepped Ni(211).
Figure 3: Arrhenius plot of the rate constant for ethane hydrogenolysis over Ni/MgAl2O4 and Ag/Ni/MgAl2O4.

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Acknowledgements

We acknowledge the financial support from the European Union through the contract HPRN-CT-2002-00170.

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Authors and Affiliations

  1. Interdisciplinary Nanoscience Center (iNANO), Center for Atomic-scale Materials Physics (CAMP),

    Ronnie T. Vang, Ebbe K. Vestergaard, Joachim Schnadt, Erik Lægsgaard, Jens K. Nørskov & Flemming Besenbacher

  2. Department of Physics and Astronomy, University of Aarhus, Aarhus C, DK-8000, Denmark

    Ronnie T. Vang, Ebbe K. Vestergaard, Joachim Schnadt, Erik Lægsgaard, Jens K. Nørskov & Flemming Besenbacher

  3. Center for Atomic-scale Materials Physics (CAMP), and Department of Physics, Technical University of Denmark, Lyngby, DK-2800, Denmark

    Karoliina Honkala & Jens K. Nørskov

  4. Haldor Topsøe A/S, Nymøllevej 55, Lyngby, DK-2800, Denmark

    Søren Dahl & Bjerne S. Clausen

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  1. Ronnie T. Vang
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  2. Karoliina Honkala
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Correspondence to Flemming Besenbacher.

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Vang, R., Honkala, K., Dahl, S. et al. Controlling the catalytic bond-breaking selectivity of Ni surfaces by step blocking. Nature Mater 4, 160–162 (2005). https://doi.org/10.1038/nmat1311

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