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In situ observation of self-assembled hydrocarbon Fischer–Tropsch products on a cobalt catalyst

Nature Chemistry volume 8, pages 929–934 (2016)Cite this article

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Abstract

Fischer–Tropsch synthesis is a heterogeneous catalytic reaction that creates approximately 2% of the world's fuel. It involves the synthesis of linear hydrocarbon molecules from a gaseous mixture of carbon monoxide and hydrogen at high pressures (from a few to tens of bars) and high temperatures (200–350 °C). To gain further insight into the fundamental mechanisms of this industrial process, we have used a purpose-built scanning tunnelling microscope to monitor a cobalt model catalyst under reaction conditions. We show that, after 30 minutes of reaction, the terraces of the cobalt catalyst are covered by parallel arrays of stripes. We propose that the stripes are formed by the self-assembly of linear hydrocarbon product molecules. Surprisingly, the width of the stripes corresponds to molecules that are 14 or 15 carbon atoms long. We introduce a simple model that explains the accumulation of such long molecules by describing their monomer-by-monomer synthesis and explicitly accounting for their thermal desorption.

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Figure 1: Scanning tunnelling topographic image of the clean single-crystal cobalt surface before exposure to the reactive gases but already at 221 °C and 4 bar total pressure.
Figure 2: Highly mobile cobalt surface under reaction conditions.
Figure 3: Image (and detail) of the cobalt surface fully covered by a striped pattern after 40 min of reaction.
Figure 4: Schematic scenario for the formation of the striped alkane phase during Fischer–Tropsch synthesis.
Figure 5: Terrace coverage of molecules of different lengths as a function of reaction time, and representation of the time required for the first molecular lengths to reach significant terrace coverages of 0.1 and 0.01, which condense to form the striped layer.

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Acknowledgements

V.N. acknowledges the Netherlands Organization for Scientific Research (NWO) and the Technology Foundation (STW) for the financial support as part of the research programme Veni (project no. 11920). The authors acknowledge scientific discussions with A.P. van Bavel, H. Oosterbeek and H.P.C.E. Kuipers from Shell Global Solutions International B.V.

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  1. Violeta Navarro, Matthijs A. van Spronsen & Joost W. M. Frenken

    Present address: Present addresses: TNO, Stieltjesweg 1, 2628 CK Delft, The Netherlands (V.N.). Department of Chemistry and Biological Chemistry, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, USA (M.A.v.S.). Advanced Research Center for Nanolithography (ARCNL), Science Park 110, Amsterdam 1098 XG, The Netherlands (J.W.M.F.),

Authors and Affiliations

  1. Kamerlingh Onnes Laboratory, Leiden University, Niels Bohrweg 2, Leiden, 2333 CA, The Netherlands

    Violeta Navarro, Matthijs A. van Spronsen & Joost W. M. Frenken

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Contributions

J.W.M.F. and V.N. conceived the experiment, developed the analytical model and wrote the paper. V.N. designed and performed the experiment and analysed the results. M.A.v.S. assisted with experiments and commented on the manuscript.

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Correspondence to Violeta Navarro.

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Navarro, V., van Spronsen, M. & Frenken, J. In situ observation of self-assembled hydrocarbon Fischer–Tropsch products on a cobalt catalyst. Nature Chem 8, 929–934 (2016). https://doi.org/10.1038/nchem.2613

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