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Real-time single-molecule imaging of oxidation catalysis at a liquid–solid interface

Nature Nanotechnology volume 2, pages 285–289 (2007)Cite this article

Abstract

Many chemical reactions are catalysed by metal complexes, and insight into their mechanisms is essential for the design of future catalysts. A variety of conventional spectroscopic techniques are available for the study of reaction mechanisms at the ensemble level, and, only recently, fluorescence microscopy techniques have been applied to monitor single chemical reactions carried out on crystal faces1 and by enzymes2,3,4. With scanning tunnelling microscopy (STM) it has become possible to obtain, during chemical reactions, spatial information at the atomic level5,6,7,8,9. The majority of these STM studies have been carried out under ultrahigh vacuum, far removed from conditions encountered in laboratory processes. Here we report the single-molecule imaging of oxidation catalysis by monitoring, with STM, individual manganese porphyrin catalysts, in real time, at a liquid–solid interface. It is found that the oxygen atoms from an O2 molecule are bound to adjacent porphyrin catalysts on the surface before their incorporation into an alkene substrate.

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Figure 1: STM studies of manganese porphyrin catalysts.
Figure 2: Oxidation of manganese porphyrins at a liquid–solid interface.
Figure 3: Proposed catalytic cycle of the epoxidation reaction carried out in the liquid-cell STM.
Figure 4: Following the separate steps of a chemical reaction with STM.

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Acknowledgements

M. Heijna is acknowledged for assistance with the UV-vis reflectance measurements, and M. C. Feiters for stimulating discussions. The National Research School Combination Catalysis (NRSC-C) (support to R.v.H.) and NanoNed (the Dutch nanotechnology initiative by the Ministry of Economic Affairs) are acknowledged, and the Council for the Chemical Sciences of the Netherlands Organization for Scientific Research (CW-NWO) for financing this research through a Veni innovative research grant to J.A.A.W.E.

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Authors and Affiliations

  1. Scanning Probe Microscopy, Institute for Molecules and Materials, Radboud University Nijmegen, Toernooiveld 1, 6525 ED, Nijmegen, The Netherlands

    Bas Hulsken, Jan W. Gerritsen, Johannes A. A. W. Elemans & Sylvia Speller

  2. Physical Organic and Supramolecular Chemistry, Institute for Molecules and Materials, Radboud University Nijmegen, Toernooiveld 1, 6525 ED, Nijmegen, The Netherlands

    Richard Van Hameren, Pall Thordarson, Roeland J. M. Nolte & Johannes A. A. W. Elemans

  3. School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia

    Tony Khoury, Pall Thordarson & Maxwell J. Crossley

  4. Molecular Materials, Institute for Molecules and Materials, Radboud University Nijmegen, Toernooiveld 1, 6525 ED, Nijmegen, The Netherlands

    Alan E. Rowan

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  1. Bas Hulsken
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  9. Johannes A. A. W. Elemans
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Contributions

J.A.A.W.E., A.E.R. and R.J.M.N. conceived and designed the epoxidation experiment. S.S. and J.A.A.W.E. were responsible for the STM experiment. B.H. and R.v.H. carried out the experiments. J.W.G. supplied technical support. T.K., P.T. and M.J.C. designed and synthesized the particular porphyrin catalyst. All authors discussed the results and commented on the manuscript.

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Correspondence to Johannes A. A. W. Elemans or Sylvia Speller.

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The authors declare no competing financial interests.

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Hulsken, B., Van Hameren, R., Gerritsen, J. et al. Real-time single-molecule imaging of oxidation catalysis at a liquid–solid interface. Nature Nanotech 2, 285–289 (2007). https://doi.org/10.1038/nnano.2007.106

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