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Quantum size effects in ambient CO oxidation catalysed by ligand-protected gold clusters

Nature Chemistry volume 2, pages 329–334 (2010)Cite this article

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Abstract

Finely dispersed nanometre-scale gold particles are known to catalyse several oxidation reactions in aerobic, ambient conditions. The catalytic activity has been explained by various complementary mechanisms, including support effects, particle-size-dependent metal–insulator transition, charging effects, frontier orbital interactions and geometric fluxionality. We show, by considering a series of robust and structurally well-characterized ligand-protected gold clusters with diameters between 1.2 and 2.4 nm, that electronic quantum size effects, particularly the magnitude of the so-called HOMO–LUMO energy gap, has a decisive role in binding oxygen to the nano-catalyst in an activated form. This can lead to the oxidation reaction 2CO + O2 → 2CO2 with low activation barriers. Binding of dioxygen is significant only for the smallest particles with a metal core diameter clearly below 2 nm. Our results suggest a potentially viable route to practical applications using ligand-protected gold clusters for green chemistry.

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Figure 1: Correlation between the binding energy of O2 to partially protected clusters 1–5 and the HOMO–LUMO gap of the corresponding fully protected cluster.
Figure 2: Bonding and activation of O2 by the partially protected cluster 1.
Figure 3: The two LH steps for CO oxidation cycle 2CO + O2 → 2CO2 by cluster 1.
Figure 4: The first LH step of the complete CO oxidation cycle by cluster 2′, which originally has two metallic electrons over the HOMO–LUMO gap of the parent cluster.
Figure 5: Dynamics of the formation and release of CO2 at cluster 1.

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Acknowledgements

The authors thank H. Grönbeck for fruitful discussions. This research was supported by the Academy of Finland. Computer resources were provided by the CSC—Finnish IT Center for Science in Espoo.

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Authors and Affiliations

  1. Department of Physics, Nanoscience Center, University of Jyväskylä, Jyväskylä, FI-40014, Finland

    Olga Lopez-Acevedo, Katarzyna A. Kacprzak, Jaakko Akola & Hannu Häkkinen

  2. Department of Physics, Tampere University of Technology, Tampere, FI-33101, Finland

    Jaakko Akola

  3. Department of Chemistry, Nanoscience Center, University of Jyväskylä, Jyväskylä, FI-40014, Finland

    Hannu Häkkinen

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  1. Olga Lopez-Acevedo
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H.H. planned the research and wrote the manuscript draft. O.L.-A., K.K. and J.A. performed calculations and analysed the results. All authors contributed to editing the manuscript.

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Correspondence to Hannu Häkkinen.

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Lopez-Acevedo, O., Kacprzak, K., Akola, J. et al. Quantum size effects in ambient CO oxidation catalysed by ligand-protected gold clusters. Nature Chem 2, 329–334 (2010). https://doi.org/10.1038/nchem.589

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