Supporting Information © Wiley-VCH 2006

69451 Weinheim, Germany

- 1 -

Hierarchical Mesoporous Zeolites Templated from a Mixture of Small Organic

Ammonium and Mesoscale Cationic Polymer and Their Excellent Catalytic

Properties

Feng-Shou Xiao*, Lifeng Wang, Chengyang Yin, Kaifeng Lin, Yan Di, Jixue Li, Ruren Xu, Dang

Sheng Su, Robert Schlögl, Toshiyuki Yokoi, and Takashi Tatsumi

Supporting Figure 1. SEM images of calcined Beta-H.

c d

b a

- 2 -

5 10 15 20 25 30 35 40

In

tens

ity

2 theta

Supporting Figure 2. SEM image and XRD pattern of calcined Beta.

- 3 -

Supporting Figure 3. TEM images of calcined Beta-H.

a

b

- 4 -

Supporting Figure 4. Thermogravimetric (TG) and Differential

thermal analysis (DTA) curves of as-synthesized Beta-H.

0 100 200 300 400 500 600 700 800 900

65

70

75

80

85

90

95

100

105

M a

s s (

%)

Temperature oC

-1.0

-0.5

0.0

0.5

1.0

1.5

DTA

/ (uV/m

g)

- 5 -

5 10 15 20 25 30 35 40

0

100

200

300

400

Inte

nsity

2 theta

Supporting Figure 5. XRD pattern of calcined ZSM-5-H.

- 6 -

Supporting Figure 6. a) N2 adsorption/desorption isotherms and b, c) pore

size distribution curves of calcined ZSM-5-H.

0.0 0.2 0.4 0.6 0.8 1.0

80

100

120

140 a

Relative pressure (P/P0)

Volu

me

adso

rbed

(cm

3/g

STP)

10 20 30 40

cPore Size (nm)

0 1 2 3 4 5

b

Pore Size (nm)

- 7 -

Supporting Figure 7. SEM images of calcined ZSM-5-H in a) low

and b) high magnification.

b

a

- 8 -

b

a

Supporting Figure 8. TEM images of calcined ZSM-5-H.

- 9 -

Supporting Figure 9. SEM images of calcined Beta-H.

- 10 -

Supporting Figure 10 a) N2 adsorption/desorption isotherms and b, c) pore

size distribution curves of calcined Beta-H.

10 20 30 40

c

Pore Size (nm)

0.0 0.2 0.4 0.6 0.8 1.0

100

150

200 a

Volu

me

adso

rbed

(cm

3/g

STP)

Partial pressure (P/P0)

0 2 4 6 8

b

Pore Size (nm)

- 11 -

0.0 0.2 0.4 0.6 0.8 1.0

0

50

100

150

200

250

300

350

400

a

Partial pressure (P/P0)

Vol

ume

adso

rbed

(cm

3/g

STP

)

0 1 2 3 4 5 6 7 8 9

b

Pore Size (nm)

Supporting Figure 11 a) N2 adsorption/desorption isotherms and b) pore size

distribution curve of calcined Beta.

- 12 -

5 10 15 20 25 30 35 40

0

200

400

600

800

1000

a

Inte

nsity

2 theta

Supporting Figure 12. XRD patterns of calcined a) ZSM-5 and b) ZSM-5-F.

5 10 15 20 25 30 35 40

0

200

400

600

800

1000

1200

1400

b

2 theta

Inte

nsity

- 13 -

Supporting Figure 13. SEM images of calcined a) ZSM-5 and b) ZSM-5-F.

b a

- 14 -

0.0 0.2 0.4 0.6 0.8 1.0

0

20

40

60

80

100

120

140

160

180

a

Relative pressure (P/P0)

Volu

me

adso

rbed

(cm

3/g

STP)

Supporting Figure 14. a) N2 adsorption/desorption isotherms and b) pore size

distribution curve of calcined ZSM-5.

0 1 2 3 4 5

b

Pore Size (nm)

- 15 -

Supporting Figure 15. Catalytic conversions in the alkylation of benzene

with isopropanol over Beta-H, Beta, and Al-SBA-15.

1 2 3 4 5 60

10

20

30

40

50

60

70

80

90

100

Time on Stream (h)

Con

vers

ion

of Is

opro

pano

l (w

t %)

Beta-H Beta Al-SBA-15

- 16 -

Supporting Table 1 Pore structural parameters and catalytic activities in cracking of 1,3,5-tri-

isopropylbenzene@ over a) Hierarchical porous ZSM-5-H; b) ZSM-5; c) ZSM-5-F.

Sample@#

Mesopore Size (nm)

Micropore Size (nm)

BET Surface

Area (m2/g)

Si/Al Ratio

Particle Size (µm)

Conversion of 1,3,5-

triisopropylbenzene (%)

ZSM-5-H 12.5 0.55 371 31.7 0.4-0.6 90.5

ZSM-5 - 0.55 385 31.3 0.4-0.7 45.7

ZSM-5-F - 0.55 362 32.0 20 <5

@: Catalytic reactions were performed at 300 °C by pulse injections. In each run, 50 mg of catalyst was

used, the pulse injection of the reactant was 0.4 µml, and the reaction flow rate was 53.7 ml/min.

#: ZSM-5-H stands for hierarchical porous ZSM-5 zeolite; ZSM-5-F stands for larger ZSM-5 crystal.