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Non-lattice surface oxygen species implicated in the catalytic partial oxidation of decane to oxygenated aromatics

Nature Chemistry volume 4, pages 134–139 (2012)Cite this article

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Abstract

The one-step transformation of C7–C12 linear alkanes into more valuable oxygenates provides heterogeneous catalysis with a major challenge. In evaluating the potential of a classic mixed-metal-oxide catalyst, we demonstrate new insights into the reactivity of adsorbed oxygen species. During the aerobic gas-phase conversion of n-decane over iron molybdate, the product distribution correlates with the condition of the catalyst. Selectivity to oxygenated aromatics peaks at 350 °C while the catalyst is in a fully oxidized state, whereas decene and aromatic hydrocarbons dominate at higher temperatures. The high-temperature performance is consistent with an underlying redox mechanism in which lattice oxide ions abstract hydrogen from decane. At lower temperatures, the formation of oxygenated aromatics competes with the formation of CO2, implying that electrophilic adsorbed oxygen is involved in both reactions. We suggest, therefore, that so-called non-selective oxygen is capable of insertion into carbon-rich surface intermediates to generate aromatic partial oxidation products.

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Figure 1: Crystalline phase composition.
Figure 2: Yields of major products of partial oxidation.
Figure 3: Surface analysis.
Figure 4: Yields of major products as a function of temperature and state of the catalyst.

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Acknowledgements

The authors thank X. Baucherel and M. Watson (Johnson Matthey) and J. Chetty and C. Dwyer (Sasol) for their support throughout this study, which was sponsored by Johnson Matthey and Sasol.

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Authors and Affiliations

  1. Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Cardiff CF10 3AT, UK

    Sivaram Pradhan, Jonathan K. Bartley, Donald Bethell, Albert F. Carley, Marco Conte, Stan Golunski, Matthew P. House, Robert L. Jenkins, Rhys Lloyd & Graham J. Hutchings

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  1. Sivaram Pradhan
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Contributions

G.J.H. directed the study. All authors contributed to the planning and interpretation of the experimental work, which was carried out by S.P., M.P.H., A.F.C., M.C., R.L.J. and R.L. The manuscript was drafted by S.P., J.K.B., D.B., A.F.C., S.G. and G.J.H., with input from all authors.

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Correspondence to Graham J. Hutchings.

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Pradhan, S., Bartley, J., Bethell, D. et al. Non-lattice surface oxygen species implicated in the catalytic partial oxidation of decane to oxygenated aromatics. Nature Chem 4, 134–139 (2012). https://doi.org/10.1038/nchem.1245

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