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: hychen@nwu.edu.cn

Phone: (+86) 150 2993 2016

Prof. Baoyu Liu

E-mail: baoyu.liu@gdut.edu.cn

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

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..

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.

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.

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.

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.

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

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.

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.