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Tunable gold catalysts for selective hydrocarbon oxidation under mild conditions

Abstract

Oxidation is an important method for the synthesis of chemical intermediates in the manufacture of high-tonnage commodities, high-value fine chemicals, agrochemicals and pharmaceuticals: but oxidations are often inefficient1. The introduction of catalytic systems using oxygen from air is preferred for ‘green’ processing2. Gold catalysis is now showing potential in selective redox processes3,4,5,6, particularly for alcohol oxidation7,8,9,10 and the direct synthesis of hydrogen peroxide11,12. However, a major challenge that persists is the synthesis of an epoxide by the direct electrophilic addition of oxygen to an alkene13. Although ethene is epoxidized efficiently using molecular oxygen with silver catalysts in a large-scale industrial process14, this is unique because higher alkenes can only be effectively epoxidized using hydrogen peroxide15,16,17, hydroperoxides16 or stoichiometric oxygen donors. Here we show that nanocrystalline gold catalysts can provide tunable active catalysts for the oxidation of alkenes using air, with exceptionally high selectivity to partial oxidation products (98%) and significant conversions. Our finding significantly extends the discovery by Haruta18,19 that nanocrystalline gold can epoxidize alkenes when hydrogen is used to activate the molecular oxygen; in our case, no sacrificial reductant is needed. We anticipate that our finding will initiate attempts to understand more fully the mechanism of oxygen activation at gold surfaces, which might lead to commercial exploitation of the high redox activity of gold nanocrystals.

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Figure 1: Cyclic voltammograms of 0.5 wt% Au/carbon catalyst.

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Acknowledgements

We acknowledge the support of the Engineering and Physical Sciences Research Council (EPSRC) of the UK, Johnson Matthey plc (project ATHENA) and the European Union (project AURICAT). We also thank D. Bethell for discussions on the reaction mechanism. Author Contributions: M.D.H. and Y-J. X. prepared and tested the catalysts under the supervision of P.L., D.I.E. and P.M. C.J.K. made the TEM measurements and A.F.C. the XPS measurements. P. Jenkins prepared the Bi-doped catalysts and made the CV measurements under the supervision of G.A.A. G.J.H. directed the research and wrote the paper. E.H.S., F.K., P. Johnston and K.G. provided discussions and advice on catalyst synthesis.

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Correspondence to Graham J. Hutchings.

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Supplementary information

Supplementary Figure 1

Reaction of cyclohexene with O2 in 1,2,3,5-tetramethylbenzene at 80 °C. (DOC 55 kb)

Supplementary Figure 2

Au(4f) and Bi(4f) photoemission spectra obtained for (a) graphite support (b) as prepared Bi-doped 1 wt % Au-graphite catalyst, (c) catalyst after reaction, (d) catalyst in (c) after further reaction with a fresh reactant mixture. (DOC 145 kb)

Supplementary Figure 3

Transmission electron micrograph of a 1% Au/C catalyst. (DOC 51 kb)

Supplementary Table 1

Alkene oxidation with molecular oxygen using Au/C catalysts. (DOC 68 kb)

Supplementary Table 2

cis-Stilbene oxidation with molecular oxygen using a 1% Au/G catalyst. (DOC 46 kb)

Supplementary Table 3

Cyclohexene Oxidation Using Au/G or Sb, Sn and Pb modified gold/G catalyst. (DOC 39 kb)

Supplementary Table 4

cis-Cyclooctene oxidation using 1% Au/carbon catalysts in a glass reactor. (DOC 55 kb)

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Hughes, M., Xu, YJ., Jenkins, P. et al. Tunable gold catalysts for selective hydrocarbon oxidation under mild conditions. Nature 437, 1132–1135 (2005). https://doi.org/10.1038/nature04190

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  • DOI: https://doi.org/10.1038/nature04190

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