SUPPORTING INFORMATION Hierarchical macroporous-mesoporous ...
Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2010
SUPPORTING INFORMATION
Hierarchical macroporous-mesoporous SBA-15 sulfonic acid catalysts for biodiesel synthesis
Jérémy Dhainaut, Jean-Philippe Dacquin, Adam F. Lee* and Karen Wilson* School of Chemistry, Cardiff University, Cardiff CF10 3AT
Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2010
1. Characterisation of PS beads SEM of the PS beads (Figure S1), reveals a narrow size distribution with an average diameter of ~320 nm (Figure S2). Thermal analysis shows that complete decomposition/combusion of the beads, and thus template removal, can be achieved at 550 °C (Figure S3).
Figure S1. SEM images of 320 nm polystyrene beads.
Figure S2. Particle size distribution of PS beads.
Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2010
Figure S3. TGA of PS beads.
Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2010
2. Characterisation of macroporous-mesporous silicas HRTEM images of as-prepared SBA-15 and MM-SBA15-4 are shown in Figure S4.
a
11.3 nm
b
10.1 nm
Figure S4. HRTEM micrographs of (a) SBA-15 and (b) MM-SBA15-4.
Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2010
3. Functionalization of macroporous-mesporous silicas Fitted S 2p1/2 (blue) and S 2p3/2 (red) XP spectra of sulfonic acid functionalized materials are shown in Figure S5.
Figure S5. S 2p XPS of sulfonic acid functionalised (a) SBA-15, (b) MM-SBA15-1, (c) MM-SBA15-2 and (d) MM-SBA15-4.
Table S1. Carbon content of pre- and post-sulfonic acid functionalized macroporous-mesoporous silicas
Sample
Fresh C contenta / wt%
Meso SBA-15
1.28
Functionalised Cb content / wt% 4.92
MM-SBA-15-1
2.11
4.32
MM-SBA-15 -2
2.73
3.69
MM-SBA-15-4
3.78
3.59
a
ICP analysis. bXPS analysis.
Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2010
Porosimetry (Figure S6a-b) and low angle XRD (Figure S7)of as-prepared and sulphonated macroporousmesoporous SBA-15 silicas shows preservation of mesopore structure.
800
800
RSO3H-SBA15 3 -1
SBA15 600 500 400 300 200
MM-SBA15-4 600 500 400 300 200 100
100 0 0.00
RSO3H-MM-SBA15-4
700
Volume adsorbed / cm g
Volume adsorbed / cm g
3 -1
700
0.20
0.40
0.60
0.80
0 0.00
1.00
0.20
0.40
0.60
0.80
1.00
P / Po
P / Po
Figure S6a. Adsorption-desorption isotherms of SBA-15 and MM-SBA15-4 before and after functionalisation with sulfonic acid groups.
Bare Support
dV(Log d)
+ SO3H
SBA15 MM-SBA15-4 2
4
6
8
10
12
14
Pore diameter (d) / nm
Figure S6b. BJH pore size distributions for SBA-15 and MM-SBA15-4 before and after functionalisation with sulfonic acid groups.
Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2010
Figure S7. Low angle XRD of mesoporous SBA-15 before (---) and after functionalization (___).
Table S2. Textural properties of sulfonic acid functionalized macroporous-mesoporous silicas
SBA-15
Mesopore diametera / nm 5.8
Mesopore volumea,b / cm3g-1 1.08 (1.18)
RSO3H-SBA-15
5.7
0.81 (0.91)
MM-SBA15-1
5.0
0.82 (1.07)
RSO3H-MM-SBA15-1
5.0
0.62 (0.71)
MM-SBA15-2
4.5
0.87 (0.99)
RSO3H-MM-SBA15-2
4.4
0.54 (0.65)
MM-SBA15-4
3.9
0.84 (1.15)
RSO3H-MM-SBA15-4
4.1
0.56 (0.67)
Sample
a
BJH mesopore volumes and diameters from the desorption isotherm. bTotal pore volume shown in brackets.
SUPPORTING INFORMATION
Hierarchical macroporous-mesoporous SBA-15 sulfonic acid catalysts for biodiesel synthesis
Jérémy Dhainaut, Jean-Philippe Dacquin, Adam F. Lee* and Karen Wilson* School of Chemistry, Cardiff University, Cardiff CF10 3AT
Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2010
1. Characterisation of PS beads SEM of the PS beads (Figure S1), reveals a narrow size distribution with an average diameter of ~320 nm (Figure S2). Thermal analysis shows that complete decomposition/combusion of the beads, and thus template removal, can be achieved at 550 °C (Figure S3).
Figure S1. SEM images of 320 nm polystyrene beads.
Figure S2. Particle size distribution of PS beads.
Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2010
Figure S3. TGA of PS beads.
Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2010
2. Characterisation of macroporous-mesporous silicas HRTEM images of as-prepared SBA-15 and MM-SBA15-4 are shown in Figure S4.
a
11.3 nm
b
10.1 nm
Figure S4. HRTEM micrographs of (a) SBA-15 and (b) MM-SBA15-4.
Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2010
3. Functionalization of macroporous-mesporous silicas Fitted S 2p1/2 (blue) and S 2p3/2 (red) XP spectra of sulfonic acid functionalized materials are shown in Figure S5.
Figure S5. S 2p XPS of sulfonic acid functionalised (a) SBA-15, (b) MM-SBA15-1, (c) MM-SBA15-2 and (d) MM-SBA15-4.
Table S1. Carbon content of pre- and post-sulfonic acid functionalized macroporous-mesoporous silicas
Sample
Fresh C contenta / wt%
Meso SBA-15
1.28
Functionalised Cb content / wt% 4.92
MM-SBA-15-1
2.11
4.32
MM-SBA-15 -2
2.73
3.69
MM-SBA-15-4
3.78
3.59
a
ICP analysis. bXPS analysis.
Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2010
Porosimetry (Figure S6a-b) and low angle XRD (Figure S7)of as-prepared and sulphonated macroporousmesoporous SBA-15 silicas shows preservation of mesopore structure.
800
800
RSO3H-SBA15 3 -1
SBA15 600 500 400 300 200
MM-SBA15-4 600 500 400 300 200 100
100 0 0.00
RSO3H-MM-SBA15-4
700
Volume adsorbed / cm g
Volume adsorbed / cm g
3 -1
700
0.20
0.40
0.60
0.80
0 0.00
1.00
0.20
0.40
0.60
0.80
1.00
P / Po
P / Po
Figure S6a. Adsorption-desorption isotherms of SBA-15 and MM-SBA15-4 before and after functionalisation with sulfonic acid groups.
Bare Support
dV(Log d)
+ SO3H
SBA15 MM-SBA15-4 2
4
6
8
10
12
14
Pore diameter (d) / nm
Figure S6b. BJH pore size distributions for SBA-15 and MM-SBA15-4 before and after functionalisation with sulfonic acid groups.
Supplementary Material (ESI) for Green Chemistry This journal is © The Royal Society of Chemistry 2010
Figure S7. Low angle XRD of mesoporous SBA-15 before (---) and after functionalization (___).
Table S2. Textural properties of sulfonic acid functionalized macroporous-mesoporous silicas
SBA-15
Mesopore diametera / nm 5.8
Mesopore volumea,b / cm3g-1 1.08 (1.18)
RSO3H-SBA-15
5.7
0.81 (0.91)
MM-SBA15-1
5.0
0.82 (1.07)
RSO3H-MM-SBA15-1
5.0
0.62 (0.71)
MM-SBA15-2
4.5
0.87 (0.99)
RSO3H-MM-SBA15-2
4.4
0.54 (0.65)
MM-SBA15-4
3.9
0.84 (1.15)
RSO3H-MM-SBA15-4
4.1
0.56 (0.67)
Sample
a
BJH mesopore volumes and diameters from the desorption isotherm. bTotal pore volume shown in brackets.
