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Tunable gold catalysts for selective hydrocarbon oxidation under mild conditions


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.


  1. Sheldon, R. A. Heterogeneous catalytic oxidation and fine chemicals. Stud. Surf. Sci. Catal. 66, 33–54 (1991)

    Article  Google Scholar 

  2. Gallezot, P. Selective oxidation with air on metal catalysts. Catal. Today 37, 405–418 (1997)

    CAS  Article  Google Scholar 

  3. Bond, G. C. & Thompson, D. T. Catalysis by gold. Catal. Rev. Sci. Eng. 41, 319–388 (1999)

    CAS  Article  Google Scholar 

  4. Fu, Q., Saltsburg, H. & Flytzani-Stephanopoulos, M. Active non-metallic Au and Pt species on ceria-based water-gas shift catalysts. Science 301, 935–938 (2003)

    ADS  CAS  Article  Google Scholar 

  5. Bailie, J. E. & Hutchings, G. J. Promotion by sulfur of gold catalysts for crotyl alcohol formation from crotonaldehyde hydrogenation. Chem. Commun. 2152 (1999)

  6. Mohr, C., Hofmeister, H., Lucas, M. & Claus, P. Gold catalysts for the partial hydrogenation of acrolein. Chemie-Ingenieur-Technik 71, 869–873 (1999)

    CAS  Article  Google Scholar 

  7. Biella, S., Prati, L. & Rossi, M. Selectivity control in the oxidation of phenylethane-1,2-diol with gold catalyst. Inorg. Chim. Acta 349, 253–257 (2003)

    CAS  Article  Google Scholar 

  8. Biella, S., Prati, L. & Rossi, M. Selective oxidation of D-glucose on gold catalyst. J. Catal. 206, 242–247 (2002)

    CAS  Article  Google Scholar 

  9. Carrettin, S., McMorn, P., Johnston, P., Griffin, K. & Hutchings, G. J. Selective oxidation of glycerol to glyceric acid using a gold catalyst in aqueous sodium hydroxide. Chem. Commun. 696–697 (2002)

  10. Carrettin, S. et al. Oxidation of glycerol using supported Pt, Pd and Au catalysts. Phys. Chem. Chem. Phys. 5, 1329–1336 (2003)

    CAS  Article  Google Scholar 

  11. Landon, P., Collier, P. J., Papworth, A. J., Kiely, C. J. & Hutchings, G. J. Direct synthesis of hydrogen peroxide from H2/O2 using a gold catalyst. Chem. Commun. 2058–2059 (2002)

  12. Landon, P. et al. Direct synthesis of hydrogen peroxide from H2 and O2 using Pd and Au catalysts. Phys. Chem. Chem. Phys. 5, 1917–1923 (2003)

    CAS  Article  Google Scholar 

  13. Monnier, J. R. The direct epoxidation of higher olefins using molecular oxygen. Appl. Catal. A 221, 73–91 (2001)

    CAS  Article  Google Scholar 

  14. Boxhoorn, G. Process for the manufacture of silver-containing epoxidation catalysts. European Patent Application (Shell Internationale Research Maatschappij B.V., Neth., Appl. EP 87–201439, 19870727, 1988).

  15. Grigoropoulou, G. & Elings, J. A. Recent developments on the epoxidation of alkenes using hydrogen peroxide as oxidant. Green Chem. 5, 1–7 (2003)

    CAS  Article  Google Scholar 

  16. Sheldon, R. A. & Van Vliet, M. C. A. in Fine Chemicals through Heterogeneous Catalysis (eds Sheldon, R. A. & Van Bekkum, H.) (Wiley-VCH, Weinheim, 2001)

    Google Scholar 

  17. Lee, S. et al. Mechanistic insights into the conversion of cyclohexene to adipic acid by H2O2 in the presence of a TAPO-5 catalysts. Angew. Chem. Int. Edn Engl. 42, 1520–1523 (2003)

    CAS  Article  Google Scholar 

  18. Sinha, A. K., Seelan, S., Tsubota, S. & Haruta, M. A three-dimensional mesoporous titanosilicate support for gold nanoparticles: vapor-phase epoxidation of propene with high conversion. Angew. Chem. Int. Edn Engl. 43, 1546–1548 (2004)

    CAS  Article  Google Scholar 

  19. Sinha, A. K., Seelan, S., Tsubota, S. & Haruta, M. Catalysis by gold nanoparticles: epoxidation of propene. Top. Catal. 29, 95–102 (2004)

    CAS  Article  Google Scholar 

  20. Xu, Y.-J. et al. Selective conversion of cyclohexane to cyclohexanol and cyclohexanone using a gold catalyst under mild conditions. Catal. Lett. 101, 175–179 (2005)

    CAS  Article  Google Scholar 

  21. Clavilier, J., Feliu, J. M. & Aldaz, A. An irreversible structure sensitive adsorption step in bismuth underpotential deposition at platinum electrodes. J. Electroanal. Chem. 243, 419–433 (1988)

    CAS  Article  Google Scholar 

  22. Fordham, P., Besson, M. & Gallezot, P. Selective oxidation with air of glyceric to hydroxypyruvic acid and tartronic to mesoxalic acid on PtBi/C catalysts. Stud. Surf. Sci. Catal. 108, 429–436 (1997)

    CAS  Article  Google Scholar 

  23. Brust, M., Kiely, J. K., Bethell, D. & Schriffrin, D. J. C60 mediated aggregation of gold nanoparticles. J. Am. Chem. Soc. 120, 12367–12368 (1998)

    CAS  Article  Google Scholar 

  24. Attard, G. A. et al. Electrochemical evaluation of the morphology and enantioselectivity of Pt/graphite. Appl. Catal. A 222, 393–405 (2001)

    CAS  Article  Google Scholar 

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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).

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