catalytic epoxidation of bulky cyclic olefins bolaform ...na li, ‡a manyun wang, ‡ab qing you, a...
TRANSCRIPT
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Bolaform surfactant-directed synthesis of TS-1 zeolite nanosheets for
catalytic epoxidation of bulky cyclic olefins
Na Li, ‡a Manyun Wang, ‡ab Qing You, a Chenyao Bi, a Huiyong Chen, *acd Baoyu Liu, *e
Ming Sun, acd Qingqing Hao, acd Jianbo Zhang acd and Xiaoxun Ma acd
a School of Chemical Engineering, Northwest University, Xi'an, Shaanxi 710069, China
b Lanzhou Petrochemical Research Center, Petrochemical Research Institute, Petrochina,
Lanzhou, Gansu 730060, China
c Chemical Engineering Research Center of the Ministry of Education for Advanced Use
Technology of Shanbei Energy, Shaanxi Research Center of Engineering Technology for
Clean Coal Conversion, Northwest University, Xi'an, Shaanxi 710069, China
d International Science & Technology Cooperation Base of MOST for Clean Utilization of
Hydrocarbon Resources, Collaborative Innovation Center for Development of Energy and
Chemical Industry in Northern Shaanxi, Xi'an, Shaanxi 710069, China
e School of Chemical Engineering and Light Industry, Guangdong University of Technology,
Guangzhou, Guangdong 510006, China
* Corresponding authors:
Prof. Huiyong Chen
E-mail: [email protected]
Phone: (+86) 150 2993 2016
Prof. Baoyu Liu
E-mail: [email protected]
Phone: (+86) 159 2050 8537
‡ Na Li and Manyun Wang contributed equally to this work.
Electronic Supplementary Material (ESI) for Catalysis Science & Technology.This journal is © The Royal Society of Chemistry 2020
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1 2 3 4 5
AIn
tens
ity (a
.u.)
2 Theta (degree)
cba
def
5 10 15 20 25 30 35 40
B
50330
3
322 50
1
301
002
102
200
2 Theta (degree)
Inte
nsity
(a.u
.)
c
b
a
d
e
f
101
Figure S1. (A) Low-angle and (B) wide-angle X-ray diffraction patterns of (a) CTS-1, (b)
MTS-1, (c) HTS-1_25, (d) HTS-1_50, (e) HTS-1_75 and (f) HTS-1_100 after the removal of
organic structure-directing agents by calcination.
-
Figure S2. TEM images of (a) HTS-1_25, (b) HTS-1_75 and (c) HTS-1_100..
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1 10 1000.0
0.1
0.2
0.3
0.4
0.5
0.6
dV/d
log(
D)
Pore Width (nm)
c
b
a
d
e
f
Figure S3. BJH pore size distributions calculated from the adsorption branches of the
isotherms of (a) CTS-1, (b) MTS-1, (c) HTS-1_25, (d) HTS-1_50, (e) HTS-1_75 and (f)
HTS-1_100.
10 1 0.1 0.010
1
2
3
4
5a CTS-1
MTS-1 HTS-1_50
Pore Width (μm)
Hg
Cum
ulat
ive
Intru
sion
(cm
3 .g-1)
10 1 0.1 0.010
1
2
3
4
5
6
7b
Diff
ren.
Vol
dV
/dD
(cm
3 .g-1)
Pore Width (μm)
CTS-1 MTS-1 HTS-1_50
Figure S4. (a) Hg intrusion curves and (b) pore size distributions of CTS-1, MTS-1 and HTS-
1_50 derived from Hg intrusion measurements.
-
Figure S5. SEM images and EDS elemental distributions of various TS-1 samples.
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0
2
4
6
8
10
1Run Number
542
Cyc
looc
tene
Con
vers
ion
(%)
30
20
40
60
80
100a
Calcination
Acetone washing and dring
Epo
xide
Sel
ectiv
ity (%
)
0
5
10
15
20
25
30b
1Run Number
542
Cyc
looc
tene
Con
vers
ion
(%)
30
20
40
60
80
100CalcinationAcetone washing and dring
Epo
xide
Sel
ectiv
ity (%
)
0
5
10
15
20
25
30c
1Run Number
542
Cyc
looc
tene
Con
vers
ion
(%)
30
20
40
60
80
100CalcinationAcetone washing and dring
Epo
xide
Sel
ectiv
ity (%
)Figure S6. Changes of cyclooctene conversion and epoxide selectivity with the reaction run
numbers over (a) CTS-1, (b) MTS-1 and (c) HTS-1. Reaction conditions: 10 mmol cyclic
olefins, 0.05 g catalyst, 10 ml CH3CN, 10 mmol H2O2 (30 wt%), 60oC, 2 h. Because 5-10 wt%
weight loss of catalysts happened in every catalytic run during collection, the next catalytic
run proceeded in a reduced system with a constant ratio of catalyst-reactant-oxidant-solvent.
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5 10 15 20 25 30 35 40
Regenerated
2 Theta (degree)
Inte
nsity
(a.u
.)
Fresh
Figure S7. X-ray diffraction patterns of the fresh and regenerated HTS-1_50 catalyst.
Figure S8. The SEM image of the regenerated HTS-1_50 catalyst by calcination.
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0 1 2 3 4 5 60
5
10
15
20
25
Cyclo
octe
ne C
onve
rsio
n (%
)
Time on Stream (h)
HTS-1_50 HTS-1_50 (Filter out)
Figure S9. The leaching test of HTS-1_50. It was found that the conversion of cyclooctene
almost stopped after the catalyst was filtered out at 2 hours, and the Ti content of the sample
after leaching was 238 μmol.g-1 determined by ICP-OES, closed to the value (238 μmol.g-1)
of the fresh sample, indicating that the leaching of Ti active sites in HTS-1_50 was
effectively suppressed.
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10 20 30 40 50
F-HTS-1_50
2 Theta (degree)
Inte
nsity
(a.u
.)
HTS-1_50
4000 3000 2000 1000
F-HTS-1_50
Wavenumber (cm-1)
Inte
nsity
(a.u
.) HTS-1_50
3450 cm-1
200 300 400 500
F-HTS-1_50
Inte
nsity
(a.u
.)
Wavelength (nm)
HTS-1_50
(a) (b)
(c) (d)
-90 -100 -110 -120 -130
-116
-113
-102 -105
Q3
Q4
Chemical shift (ppm)
F-HTS-1_50
Inte
nsity
(a.u
.) HTS-1_50
Figure S10. (a) X-ray diffraction patterns, (b) FTIR spectra, (c) UV-visible spectra and (d)
29Si MAS NMR spectra of HTS-1_50 before and after the fluoride treatment
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Table S1. Textural properties of the CTS-1, MTS-1 and HTS-1_50 zeolites from Hg intrusion
measurements.
Samples Vtotal
[cm3.g-1]
Stotal
[m².g-1]
DBulk
[g.cm-3]
DSkeletal
[g.cm-3] Porosity [%]
CTS-1 0.51 11.45 0.90 1.65 45.69
MTS-1 0.89 22.52 0.70 1.83 61.87
HTS-1_50 4.68 123.41 0.17 0.91 81.00
Vtotal:total intrusion volume, Stotal:total pore area, DBulk: bulk density, DSkeletal: skeletal density.
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Table S2. Recyclability of the CTS-1, MTS-1 and HTS-1_50 catalysts in the epoxidation of
cyclooctene a
Product selectivity [%] d
Samples Run Number bConversion
[%]
Recyclability c
[%] Epoxide Diol
1st run 2.2 100.0 98.2 1.8
2nd run 2.2 100.0 98.4 1.6
3rd run 2.0 90.9 98.3 1.7
4th run 2.0 90.9 98.1 1.9
CTS-1
5th run 1.8 81.8 98.1 1.9
1st run 12.9 100.0 92.3 7.7
2nd run 12.4 96.1 92.6 7.4
3rd run 12.5 96.9 92.1 7.9
4th run 11.2 86.8 91.5 8.5
MTS-1
5th run 9.4 72.9 91.1 8.9
1st run 18.0 100.0 96.9 3.1
2nd run 18.1 100.0 96.8 3.2
3rd run 17.7 98.3 95.2 4.8
4th run 17.4 96.7 96.1 3.9
HTS-1_50
5th run 16.9 93.9 96.6 3.4
a Reaction conditions: 10 mmol cyclic olefins, 0.05 g catalyst, 10 ml CH3CN, 10 mmol H2O2 (30 wt%),
60oC, 2 h. Because 5-10 wt% weight loss of catalysts happened in every catalytic run during collection, the
next catalytic run proceeded in a reduced system with a constant ratio of catalyst-reactant-oxidant-solvent.
b After the first three runs, the used catalysts were collected by simple filtration, washed by acetone and
then carried on the next run of reaction. After the fourth run, the used catalysts were calcined in air at 773
K for 6 h.
c Recyclability is defined as the percentage retention of conversion ( ).
Conv.current runConv.1st run
× 100%
d Epoxide: cyclooctene oxide; Diol: 1, 2-cyclooctenediol.