Supplementary Material (ESI) for Dalton Transactions

This journal is (c) The Royal Society of Chemistry 2011

Synthesis of glycerol carbonate from glycerol and urea with gold-based

catalysts
Supplementary Material
Ceri Hammond,a Jose A. Lopez-Sanchez,a,**Mohd Hasbi Ab Rahim,
Dimitratos,a Robert L. Jenkins,a Albert F. Carley,a Qian He,

Nikolaos

Christopher J. Kiely,b

David W. Knight,a and Graham J. Hutchingsa*

Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building,

Park Place, Cardiff, CF10 3AT, UK

b

Center for Advanced Materials and Nanotechnology, Lehigh University, 5 East Packer

Avenue, Bethlehem, PA 18015-3195, USA

** Co-corresponding author:
sacjal@cardiff.ac.uk
Tel: +44 29 2087 4061
Fax: +44 29 2087 4059
*Corresponding author:
hutch@cardiff.ac.uk
Tel: +44 29 2087 4059
Fax: +44 29 2087 4059

Supplementary Material (ESI) for Dalton Transactions

This journal is (c) The Royal Society of Chemistry 2011

Contents
Table S1 Reusability data with 2.5 wt% Au/MgO synthesized via an impregnation
methoda
Fig. S1 XRD diffractogram of 2.5 wt% Au supported on MgO. TiO2, carbon and ZnO.
Fig. S2 X-ray diffraction patterns for (a) MgO, calcined at 400 oC for 3 h in static air; (b)
2.5 wt. % Au/MgO prepared by impregnation and calcined at 400 oC for 3 h in
static air and (c) 2.5 wt. % Au/MgO prepared by impregnation and calcined at
400 oC for 3 h in static air after 9 catalytic cycles.
Fig. S3 TOL data in molar composition obtained with 2.5 wt% Au/MgO (Mol vs Time).
Fig. S4 Plot of glycerol carbonate converted from reaction of glycerol carbonate with
urea at 150oC under flow of nitrogen.
Fig. S5 TOL blank glycerol carbonate synthesis reaction performed with a ratio of 2:1
glycerol to urea.
Fig. S6 TOL of 2:1 glycerol to urea ratio with presence of 2.5 wt% Au/MgO
impregnation catalyst

Supplementary Material (ESI) for Dalton Transactions

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Table S1 Reusability data with 2.5 wt% Au/MgO synthesized via an impregnation
methoda
Entry

Catalyst

Selectivity (%)

Conv.
(%)

Glycerol
Carbonate
Glycerol

Yield (%)

carbonate
1

Blank

59

36

44

13

21

MgO

67

37

37

10

16

27

2.5wt%Au/MgO

81

68

16

12

56

79

71

16

10

56

78

65

19

11

51

80

63

20

11

51

90

63

12

19

57

87

81

70

80

69

17

10

55

Fresh

2.5wt%Au/MgO
After 1st used

2.5wt%Au/MgO
After 2nd used

2.5wt%Au/MgO
After 4th used

2.5wt%Au/MgO
After 6th used

2.5wt%Au/MgO
th

After 8 used
9

2.5wt%Au/MgO
th

After 10 used
a

Reaction conditions: Glycerol to Urea molar ratio: (1:1.5), Temperature: 150 oC,
Catalyst: 0.25 g, Reaction time: 4 hrs, N2 flow. Product (5): 2,3-dixydroxylpropyl
carbamate, Product (7): 4-(hydroxymethyl) oxazolidin-2-one, Product (9):(2-oxo-1,3dioxolan-4-yl) methyl carbamate.

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Intensity/ a.u

2.5wt%Au/ZnO

Au

Au

Au

2.5wt%Au/Carbon (G60)

2.5wt%Au/TiO2

2.5wt%Au/MgO
20

30

40

50

60

70

2/degree

Fig. S1 XRD diffractogram of 2.5 wt% Au supported on MgO. TiO2, carbon and
ZnO.

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(111)

(200)

(c)

(220)

(311)

Au/MgOimp
calcined
(used x 9)

(b)

Au/MgOimp
calcined
(fresh)

(a)

20

25

MgO
calcined
30

35

40

45

50

55

60

65

70

75

80

2 Theta

Fig. S2 X-ray diffraction patterns for (a) MgO, calcined at 400 oC for 3 h in static air; (b)
2.5 wt. % Au/MgO prepared by impregnation and calcined at 400 oC for 3 h in static air
and (c) 2.5 wt. % Au/MgO prepared by impregnation and calcined at 400 oC for 3 h in
static air after 9 catalytic cycles.

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80
70

Mol (%)

60
50
40
30
20
10
0
0

Reaction Time / h

Fig. S3 TOL data in molar composition obtained with 2.5 wt% Au/MgO (Mol vs Time).
Key: 4-(hydroymethyl)-1,3-dioxolan-2-one, 2,3-dihydroxyproyl carbamate, 4(hydroxymethyl) oxazolidin-2-one, (2-oxo-1,3-dioxolan-4-yl) methyl carbamate,
glycerol.

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Glycerol carbonate converted (%)

80
70
60
50
40
30
20
10
0
0

Reaction time

Fig. S4 Plot of glycerol carbonate converted from reaction of glycerol carbonate with
urea at 150oC under flow of nitrogen.

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4-(hydroxymethyl)-1,3-dioxolan-2-one
2,3-dihydroxypropyl carbamate
4-(hydroxymethyl) oxazolidin-2-one
(2-oxo-1,3-dioxolan-4-yl)methyl carbamate
Conversion (%)

50

80

40

60

30

40

20

20

10

0
0

Conversion (%)

Selectivity (%)

100

Reaction Time / h

Fig. S5 TOL blank glycerol carbonate synthesis reaction performed with a 2:1
glycerol: urea. Key: selectivity to 4-(hydroymethyl)-1,3-dioxolan-2-one, selectivity
to 2,3-dihydroxyproyl carbamate, selectivity to 4-(hydroxymethyl) oxazolidin-2-one,
selectivity to (2-oxo-1,3-dioxolan-4-yl) methyl carbamate and, glycerol conversion.

Supplementary Material (ESI) for Dalton Transactions

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4-(hydroxymethyl)-1,3-dioxolan-2-one
2,3-dihydroxypropyl carbamate
4-(hydroxymethyl) oxazolidin-2-one
(2-oxo-1,3-dioxolan-4-yl)methyl carbamate
Conversion (%)

Selectivity (%)

100

50

80

40

60

30

40

20

20

10

0
0

Reaction Time / h
Fig. S6 TOL of 2:1 glycerol to urea ratio with presence of 2.5 wt% Au/MgO
impregnation catalyst. Key: selectivity to 4-(hydroymethyl)-1,3-dioxolan-2-one,
selectivity to 2,3-dihydroxyproyl carbamate, selectivity to 4-(hydroxymethyl)
oxazolidin-2-one, selectivity to (2-oxo-1,3-dioxolan-4-yl) methyl carbamate and,
glycerol conversion.