1
Prominent role of mesopore surface area and external acid sites for the synthesis
of polyoxymethylene dimethyl ethers (OME) on a hierarchical H-ZSM-5 zeolite
Supplementary information
Christophe J. Baranowski a, Ali M. Bahmanpour a, Florent Héroguel a, Jeremy S. Luterbacher a, Oli-
ver Kröcher *a, b
[a] Institute of Chemical Sciences and Engineering, École polytechnique fédérale de Lausanne (EPFL), 1015 Lau-
sanne, Switzerland [b] Paul Scherrer Institut, Bioenergy and Catalysis Laboratory, 5232 Villigen PSI, Switzerland.
* Corresponding author: [email protected]; Fax: +41 (0)56 310 21 99; Tel: +41 (0)56 310 20 66
1. Equilibrium constant calculation
Figure S1. Van 't Hoff plot of the experimental values of K*OME. The model is indicated by a dashed line. The OME syn-thesis process was performed with an OME1/TRI ratio of 3.3 and 0.5 wt % of catalyst. Reaction was stopped after 90,
180 and 360 min respectively for the synthesis at 90, 80 and 70 °C.
2.75 2.80 2.85 2.90
-0.21
-0.20
-0.19
-0.18
-0.17
Ln(K* OME)
(/)
1000/T (K-1)
y = 0.2404x - 0.8728R2 = 0.9995
Electronic Supplementary Material (ESI) for Catalysis Science & Technology.This journal is © The Royal Society of Chemistry 2018
2
2. XRD pattern
Figure S2. XRD diffractogram of H-ZSM-5 zeolites.
3. 27Al NMR of mesoporous and untreated zeolites
Figure S3. 27Al NMR of untreated and mesoporous H-ZSM-5.
5 10 15 20 25 30 35 40 45 50
H-ZSM-5@S-1
H-ZSM-5-AT30
H-ZSM-5
Inte
nsity
(a.u
.)
2q (°)
H-ZSM-5@SiO2
-40-20020406080100
H-ZSM-5 H-ZSM-5-AT30 H-ZSM-5-AT30-AW
Inte
nsity
(a.u
.)
d(27Al) (ppm)
AlVIAlV
AlIV
3
4. FTIR of the silanol region
Figure S4. DRIFT spectra in the silanol region of untreated and mesoporous H-ZSM-5.
5. ICP-OES Table S1. ICP results of untreated, mesoporous and passivated H-ZSM-5 zeolites.
Sample Si (wt %) Al (wt %) Si/Al (mol/mol)
H-ZSM5 39 3.3 11.3 H-ZSM-5-AT30 39.6 3.5 10.9
H-ZSM-5-AT30-AW 39.5 3.12 12.7 H-ZSM-5@SiO2 39.2 2.6 14.3 H-ZSM-5@S-1 40.3 3.3 11.7
6. Textural properties Table S2. Textural parameters of untreated, mesoporous and passivated H-ZSM-5 zeolites.
Sample SBET (m2.g-1)
Smicroa (m2.g-1)
Smesob (m2.g-1)
Sext (m2.g-1)
Vmicroa (cm3.g-1)
Vmesob (cm3.g-1)
H-ZSM-5 379 294 54 85 0.124 0.052 H-ZSM-5-AT30 388 280 80 108 0.116 0.110
H-ZSM-5-AT300.4M 389 273 94 116 0.118 0.168 H-ZSM-5-AT300.6M 329 177 131 152 0.076 0.512 H-ZSM-5-AT300.8M 376 173 179 203 0.075 0.545 H-ZSM-5-AT301.0M 43 25 14 17 0.011 0.032
H-ZSM-5-AT30-AW 414 287 99 127 0.122 0.127 H-ZSM-5-AT300.4M-AW 445 311 104 134 0.129 0.165 H-ZSM-5-AT300.5M-AW 468 320 111 147 0.136 0.208 H-ZSM-5-AT300.6M-AW 450 294 119 156 0.125 0.237
H-ZSM-5@SiO2 336 272 47 64 0.116 0.050 H-ZSM-5@S1 414 345 43 69 0.144 0.060
a microporous surface and volume are determined by the t-plot method, b Mesoporous volume and surface are deter-mined BJH method on the adsorption branch.
330034003500360037003800
H-ZSM-5-AT30
H-ZSM-5-AT30-AW
Si-OHintAl-OH Si-OH-Al
K-M
(a. u
.)
Wavenumber (cm-1)
Si-OHext
H-ZSM-5
4
7. 29Si NMR of untreated and passivated zeolites
Figure S5. 29Si ssNMR of untreated and passivated H-ZSM-5. A smoothing of the signal (adjacent-averaging, 20 points)
is displayed for clarity.
8. NH3-TPD
Figure S6. Weak and strong acidity concentrations resulting from the deconvolution of desorption peaks in NH3-TPD
with the H-ZSM-5 zeolites.
Table S3. NH3-TPD of untreated, mesoporous and passivated H-ZSM-5 zeolites.
Sample Total acidity (mmol/g)
Weak (100-200 °C) (mmol/g)
Strong (200-500 °C) (mmol/g)
H-ZSM-5 0.98 0.48 0.50 H-ZSM-5-AT30 1.07 0.53 0.54
H-ZSM-5-AT30-AW 0.94 0.50 0.44 H-ZSM-5-AT300.4M-AW 0.95 0.56 0.39 H-ZSM-5-AT300.6M-AW 0.82 0.41 0.41
H-ZSM-5@SiO2 0.86 0.35 0.50 H-ZSM-5@S-1 0.86 0.51 0.35
-130-120-110-100-90-80
H-ZSM-5@S-1
H-ZSM-5@SiO2
Q3 Q4
Inte
nsity
(a.u
.)
d29Si (ppm)
Q4(1Al)
H-ZSM-5
0.48
0.53
0.5
0.56
0.41
0.35
0.51
0.5
0.54
0.44
0.39
0.41
0.5
0.35
H-ZSM-5
H-ZSM-5-AT30
H-ZSM-5-AT30-AW
H-ZSM-5-AT300.4M-AW
H-ZSM-5-AT300.6M-AW
H-ZSM-5@SiO2
H-ZSM-5@S-1
0.0 0.5 1.0Acidity (mmol/g)
Weak Strong
5
9. DTBPy-TPD
Figure S7. DTBPy-TPD for untreated, mesoporous and passivated zeolites.
10. MF production for the untreated, mesoporous and passivated H-ZSM-5 zeolites
Figure S8. Production of methyl formate (MF) versus time in the batch reactor (OME1/TRI: 3.3; 0.5 wt % catalyst; 70
°C) obtained with untreated, mesoporous and passivated H-ZSM-5 zeolites.
0 20 40 60
H-ZSM-5@S-1
H-ZSM-5@SiO2
H-ZSM-5-AT30-AW
H-ZSM-5-AT30
Des
orbe
d D
TBPy
(a.u
.)
Time (min)
H-ZSM-5
0 50 100 150 200 250 3000.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
MF
(mol
/l)
Time (min)
H-ZSM-5 H-ZSM-5-AT30 H-ZSM-5-AT30-AW H-ZSM-5@SiO2
H-ZSM-5@S-1
6
11. Performance of the alkaline-treated and acid-washed samples
Figure S9. Performance comparison of untreated, mesoporous and passivated H-ZSM-5 zeolites with (a) TRI conversion
and (b) S(OME3-5) (OME1/TRI: 3.3; 0.5 wt % catalyst; 70 °C).
Figure S10. Influence of pre-treatment of H-ZSM-5 on the catalytic performance during OME synthesis (OME1/TRI:
3.3; 0.5 wt % catalyst; 70 °C). (a) initial reaction rate, (b) maximum selectivity S(OME3-5, max) reached during the run and (c) growth probability after 250 min.
0 50 100 150 200 2500.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
0 100 2000.0
0.1
0.2
0.3
0.4
0.5 H-ZSM-5 HZSM5-AT30-AW HZSM5-AT300.4M-AW HZSM5-AT300.5M-AW HZSM5-AT300.6M-AW
X TRI(/
)
Time (min)
S(O
ME 3
-5) (
/)
Time (min)
0.01
0.02
0.03
0.40
0.42
0.44
0.46
0.0 0.2 0.4 0.6
0.48
0.49
0.50
AWAT+AW
initi
al re
actio
n ra
te (m
ol.m
in.-1
g cat-1
)
AT
(a)
(b)
Untreated AT AT + AW
AWAT+AW
S OME3-5,max
(/)
AT
(c)
AWAT+AW
a250 (
/)
NaOH (mol/l)
AT
7
12. Kinetic study results and model outputs Table S4. Results of the kinetic model for the kinetic study on the various catalysts.
Number Catalyst Temperature (°C) RMSE (/) kOME,f (L.mol-1.min-1) K1 H-ZSM-5 70 0.60 0.0304 K2 H-ZSM-5 80 0.65 0.110 K3 H-ZSM-5 90 0.64 0.292 K4 H-ZSM-5@S-1 70 0.57 0.00695 K5 H-ZSM-5@S-1 80 0.58 0.0148 K6 H-ZSM-5@S-1 90 0.62 0.0318 K7 H-ZSM-5-AT300.4M-AW 70 0.65 0.0659 K8 H-ZSM-5-AT300.4M-AW 80 0.61 0.142 K9 H-ZSM-5-AT300.4M-AW 90 0.51 0.424
Figure S11. Concentration of the various components versus time for experiment K1 (OME1/TRI: 3.3; 0.5 wt % H-
ZSM-5; 70 °C). The model output is given by the solid lines.
0 50 100 150 200 250Time (min)0
2
4
6
8
Concentration (mol/l)
OME1
TRI
OME2
OME3
OME4
OME5
OME6
OME7
OME8
8
Figure S12. Concentration of the various components versus time for experiment K2 (OME1/TRI: 3.3; 0.5 wt % H-
ZSM-5; 80 °C). The model output is given by the solid lines.
Figure S13. Concentration of the various components versus time for experiment K3 (OME1/TRI: 3.3; 0.5 wt % H-
ZSM-5; 90 °C). The model output is given by the solid lines.
0 20 40 60 80 100 120Time (min)0
2
4
6
8
Concentration (mol/l)
OME1
TRI
OME2
OME3
OME4
OME5
OME6
OME7
OME8
0 10 20 30 40 50 60 70Time (min)0
2
4
6
8
Concentration (mol/l)
OME1
TRI
OME2
OME3
OME4
OME5
OME6
OME7
OME8
9
Figure S14. Concentration of the various components versus time for experiment K4 (OME1/TRI: 3.3; 0.5 wt % H-
ZSM-5-AT300.4M-AW; 70 °C). The model output is given by the solid lines.
Figure S15. Concentration of the various components versus time for experiment K5 (OME1/TRI: 3.3; 0.5 wt % H-
ZSM-5-AT300.4M-AW; 80 °C). The model output is given by the solid lines.
0 50 100 150 200 250Time (min)0
2
4
6
8
Concentration (mol/l)
OME1
TRI
OME2
OME3
OME4
OME5
OME6
OME7
OME8
0 20 40 60 80 100 120Time (min)0
2
4
6
8
Concentration (mol/l)
OME1
TRI
OME2
OME3
OME4
OME5
OME6
OME7
OME8
10
Figure S16. Concentration of the various components versus time for experiment K6 (OME1/TRI: 3.3; 0.5 wt % H-
ZSM-5-AT300.4M-AW; 90 °C). The model output is given by the solid lines.
Figure S17. Concentration of the various components versus time for experiment K7 (OME1/TRI: 3.3; 0.5 wt % H-
ZSM-5@S-1; 70 °C). The model output is given by the solid lines.
0 10 20 30 40 50 60 70Time (min)0
2
4
6
8
Concentration (mol/l)
OME1
TRI
OME2
OME3
OME4
OME5
OME6
OME7
OME8
0 50 100 150 200 250 300Time (min)0
2
4
6
8
Concentration (mol/l)
OME1
TRI
OME2
OME3
OME4
OME5
OME6
OME7
OME8
11
Figure S18. Concentration of the various components versus time for experiment K8 (OME1/TRI: 3.3; 0.5 wt % H-
ZSM-5@S-1; 80 °C). The model output is given by the solid lines.
Figure S19. Concentration of the various components versus time for experiment K9 (OME1/TRI: 3.3; 0.5 wt % H-
ZSM-5@S-1; 90 °C). The model output is given by the solid lines.
0 50 100 150Time (min)0
2
4
6
8
Concentration (mol/l)
OME1
TRI
OME2
OME3
OME4
OME5
OME6
OME7
OME8
0 20 40 60 80Time (min)0
2
4
6
8
Concentration (mol/l)
OME1
TRI
OME2
OME3
OME4
OME5
OME6
OME7
OME8