Tunable Gold Catalysts for Selective Hydrocarbon Oxidation under Mild Conditions

Mathew D. Hughes, Yi-Jun Xu, Patrick Jenkins, Paul McMorn, Philip Landon1, Dan I. Enache, Albert F. Carley, Gary A. Attard1, Graham J. Hutchings, Frank King, E. Hugh Stitt, Peter Johnston, Ken Griffin & Christopher J. Kiely

Nature. 2005, 437, 1132-1135

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Catalytic oxidations of organic molecules

Enzymatic oxidation

Free radical auto-oxidations initiated by transition metal cations

Metal ion oxidation of coordinated substrates such as PdII-catalyzed oxidations of olefins Oxygen transfer to the organic substrate mediated by metaloxo or peroxo complexes Oxidative dehydrogenation on metal surfaces
2 Gallezot, P. et. al. Catal. Today. 1997, 37, 405-418.

Epoxides
cytochrome P450 O2 epoxides O

3 http://www.cem.msu.edu/~reusch/VirtualText/addene2.htm

Selective oxidation of glycerol to glyceric acid using a gold catalyst

Table 1 Oxidation of glycerol using Au/carbon catalystsa

4 Hutchings, G. J. et. al. Chem. Commun. 2002, 37, 696-697.

Direct formation of hydrogen peroxide from H2/O2 using a gold catalyst

Scheme 2

Table 2 Formation of H2O2 using Au catalysts

5 Hutchings, G. J. et. al. Phys. Chem. Chem. Phys. 2003, 5, 1917-1923.

Synthesis of Gold Catalyst

O graphite + HAuCl4 4H2O refluxe 30min H H Au/C

Bi-doped catalyst

Au/C +

Bi(NO3)3

stirred for 3h

Au/C(ml Bi soln)

Effect of solvent on selective oxidation of cyclohexene using Au/C catalyst

+ Au/C polar solvent O2 products
+ Au/C O2, apolar solvent H2O2 or TBHP products

Styrene oxidation with molecular oxygen using Au/C catalysts

Alkene Solvent Initiator (mol%) Gold (wt%) Conversi on (%) Product Selectivity
O

Cn
CHO

Sel

Yield

Toluene

TBHP (5)

1.0

12.3

22.8

11.9

62.4

97.1

11.9

1,4Dimethylbenze ne 1,2,4,5TMB/1,4Dimethylbenze ne 1,4Difluorobenzen e

TBHP (5)

1.0

34.2

13.5

10.5

37.7

61.7

21.1

TBHP (5)

1.0

17.3

28.9

15

46.8

90.7

15.7

TBHP (5)

1.0

19.2

18.2

9.9

45.8

73.9

14.2 9

cis-Stilbene oxidation with molecular oxygen using a 1% Au/C catalyst

Solvent Conversion Selectivity (%) cis:trans ratio sel C6
a

yield C6 b

(%)

cis-Stilbene oxide

trans-Stilbene oxide

Toluene 1,4-Dimethylbenzene Durene/p-Xylene i-Propylbenzene

5.5 18.6 11.1 47.6

10.9 26.9 38.7 7.1

65.5 57.5 52.3 73.9

0.17 0.47 0.74 0.1

76.4 84.4 91.0 81.0

4.2 15.7 10.1 38.6

t-Butylbenzene
1,3,5-tri-iPropylbenzene

5.8
27.6

0
9.8

75.8
55.8

0
0.18

75.8
65.3

4.4
18.0

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Cyclohexene oxidation with molecular oxygen using unmodified and Bimodified Au/C catalysts

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XPS (X-ray photoelectron spectroscopic)

(a) graphite support (b) as prepared Bi-doped 1 wt % Au-graphite catalyst, (c) catalyst 12 after reaction, (d) catalyst in (c) after further reaction with a fresh reactant mixture

Cyclic voltammograms of 0.5 wt% Au/carbon catalyst

a, Changes in voltammetric response as a function of irreversibly adsorbed Bi. The feature at 0.40.5V is associated with Bi in the first monolayer. Multi-layers of Bi are associated with a stripping peak at 0.2V. Bi loading (mmol): solid line, 0; dot-dashed, 0.3; dashed, 1.48; dotted, 5.92. b, Loss of multi-layer Bi after reaction as demonstrated by the attenuation of the Bi stripping peak. The presence of the Bi monolayer feature suggests that some Bi remains on the 13 catalyst. Solid line, before reaction; dotted line, after reaction.

cis-Cyclooctene oxidation with molecular oxygen in the absence of a solvent

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Conclusions

The results show the gold catalyst to have significant potential for selective epoxide formation rather than the competing allylic oxidation. Author 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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