Solvent-free Synthesis of Zeolites from Solid Raw Materials Limin Ren,† Qinming Wu, § Chengguang Yang,† Longfeng Zhu, † Caijin Li,† Pengling Zhang,† Haiyan Zhang,† Xiangju Meng,*,§ Feng-Shou Xiao*,§ §
Department of Chemistry, Zhejiang University, Hangzhou 310028, China.
†
Department of Chemistry, Jilin University, Changchun 130012, China.
Reagents Na2SiO3·9H2O (SiO2 of 20 wt.%, Tianjin Guangfu Chemical Reagent Co, Ltd.), Fumed silica (SiO2 of 100 wt.%, Shenyang Chemical Reagent Co, Ltd.), Tetrapropylammonium bromide (TPABr, 98%, Tianjin Guangfu Chemical Reagent Co, Ltd.), NH4Cl (Tianjin Fuchen Chemical Reagent Co, Ltd.), Boehmite (Al2O3 of 70 wt.%, Liaoning hydratight science and technology development Co., LTD), Fe(NO3)3·9H2O (Beijing Chemical Works), H3BO3 (Beijing Chemical Works), Ga2O3 (Beijing Chemical Works), CaCO3 nanocrystals with average size of 100 nm (Jilin University), HCl acid (37 wt.%, Beijing Chemical Works), N,N'-Diaminoguanidine monohydrochloride (purity of 90 wt.%, Qingdao Xinyu chemical science and technology Co., Ltd.), NaOH (Beijing Chemical Works), NaAlO2 (Sinopharm Chemical Reagent Co, Ltd.), and SiO22H2O (produced in our lab).
Syntheses of samples S-Si-ZSM-5. 1.315 g of Na2SiO3·9H2O, 0.30-0.36 g of fumed silica, 0.24 g of TPABr, and 0.40-0.46 g of NH4Cl were mixed together one by one. After grinding for S1
10-20 min, the mixture was transformed to an autoclave and heated at 180 C for 2448 h. After filtration at room temperature and drying at 80 C, a crystalline product of S-Si-ZSM-5 was obtained. S-M-ZSM-5 (M=Al, Fe, B, or Ga). 1.315 g of Na2SiO3·9H2O, 0.30-0.36 g of fumed silica, 0.24 g of TPABr, 0.32-0.48 g of NH4Cl, and a certain amount of heteroatom source were mixed together one by one. The heteroatom source could be 0.009-0.026 g of boehmite, 0.024-0.157 g of Fe(NO3)3·9H2O, 0.005-0.021 g of H3BO3, or 0.008-0.07 g of Ga2O3, respectively. After grinding for 10-20 min, the mixture was transformed to an autoclave and heated at 180 C for 24-72 h. After filtration at room temperature and drying at 80 C overnight, a crystalline product of S-M-ZSM-5 was obtained. Hierarchically porous S-Si-ZSM-5. 1.315 g of Na2SiO3·9H2O, 0.30-0.36 g of fumed silica, 0.24 g of TPABr, 0.5-2.0 g of nano CaCO3 and 0.40-0.46 g of NH4Cl were mixed together one by one. After grinding for 10-20 min, the mixture was transformed to an autoclave and heated at 180 C for 24-72 h. After filtration at room temperature and drying at 80 C, a crystalline product of S-Si-ZSM-5 was obtained. After treatment by 1M HCl acid solution, hierarchically porous S-Si-ZSM-5 with macroporosity was obtained. S-ZSM-39 zeolite. As a typical run, 0.27 g of SiO2, 1.35 g of Na2SiO39H2O, 0.18 g of NH4Cl, and 0.565 g of N,N'-Diaminoguanidine monohydrochloride were mixed together one by one. After grinding for 15 min, the mixture was transferred to an autoclave and heated at 180 C for 4 days. S-SOD zeolite. As a typical run, 3.045 g of Na2SiO39H2O were mixed with 1.18 g of NaAlO2. After grinding for 15 min, the mixture was transferred to an autoclave and heated at 80 C for 4 h.
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S-MOR zeolite. As a typical run, 2.67 g of SiO22H2O were mixed with 0.363 g of NaAlO2 and 0.125 g of NaOH one by one. After grinding for 15 min, the mixture was transferred to an autoclave and heated at 160 C for 84 h. S-Beta zeolite. As a typical run, 6.5 g of SiO23H2O were mixed with 1.09 g of NaAlO2 and 0.19 g of NaOH one by one. After grinding for 15 min and addition of 0.4 g of Beta zeolite as seeds, the mixture was transferred to an autoclave and heated at 140 C for 72 h. The S-Beta sample contains a small amount of MOR zeolite. S-FAU zeolite. As a typical run, 3.17 g of SiO23H2O were mixed with 1.64 g of NaAlO2. After grinding for 15 min, the mixture was transferred to an autoclave and heated at 100 C for 24 h.
Characterization X-ray diffraction (XRD) patterns were obtained with a Rigaku D/MAX 2550 diffractometer with Cu Kα radiation. Scanning electron microscopy (SEM) images were collected by JEOL electron microscopes (FE-JSM 6700, Japan). UV/Vis spectra were measured on a PERKIN ELMER Lambda 20 spectrophotometer. NMR spectra were recorded on a Varian Infinityplus-400 spectrometer. The sample composition was determined by inductively coupled plasma (ICP) with a Perkin-Elmer plasma 40 emission spectrometer. The power of the laser at the sample was about 3.0 mW. Mercury method was taken by an Autopore IV 9500 mercury porosimeter (Micromeritics Co.). A contact angle of 130 was assumed in the pore size calculation. The nitrogen isotherms at -196 °C were measured using a Micromeritics ASAP 2020M system. The samples were outgassed for 10 h at 200 C before the measurements. The pore-size distribution for micropores was calculated using HK model. UV Raman spectra were measured with a Jobin-Yvon T64000 triple-stage spectrometer with spectral resolution of 2 cm-1. The laser line at 325 nm was used as an exciting source with an output of 50 mW. S3
Intensity/a.u.
Supporting Figures
e d c b a 5
10
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2 Theta/degree
Figure S1. XRD patterns of (a) S-Si-ZSM-5, (b) S-Al-ZSM-5 with a Si/Al ratio of 109, (c) S-Fe-ZSM-5 with a Si/Fe ratio of 38, (d) S-B-ZSM-5 with a Si/B ratio of 53, and (e) S-Ga-ZSM-5 with a Si/Ga ratio of 23.
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a
b
Figure S2. SEM images of (a) S-B-ZSM-5 with a Si/B ratio of 33 and (b) S-Ga-ZSM5 with a Si/Ga ratio of 67.
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Figure S3. SEM image of CaCO3 nanocrystals, which were used as hard templates for synthesizing hierarchically porous S-Si-ZSM-5 zeolite.
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Intensity/a.u. 5
10
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2 Theta/degree
Figure S4. XRD pattern of hierarchically porous calcined and acid-treated S-Si-ZSM5 zeolite synthesized from using CaCO3 nanocrystals as hard templates [Calcination at 550 C for 6 h and acidic treating (HCl, 1M) for 24 h at room temperature].
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3
Volume adsorbed( cm /g)
225
180
135
90
45
0 0.0
0.2
0.4
0.6
0.8
1.0
p/p0
Figure S5. N2 sorption isotherms of hierarchically porous calcined and acid-treated SSi-ZSM-5 synthesized from using CaCO3 nanocrystals as hard templates. [Calcination at 550 C for 6 h and acidic treating (HCl, 1M) for 24 h at room temperature].The steep increase at relative pressure of 0.95-0.99 is attributed to the presence of macroporosity in the sample.
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Cumulative Intrusion(mL/g)
a
1.0 intrusion extrusion
0.8 0.6 0.4 0.2
Log Differential Intrusion(mL/g)
0.4 1.2
b
0.3
0.2
Intrusion Pore size
0.1
0.0
0.0 1
10
100
1000
10000
100000
0
500
Pressure/Pa
1000
1500
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Pore size/nm
Figure S6. Mercury method characterization of hierarchically porous calcined and acid-treated S-Si-ZSM-5 synthesized from using CaCO3 nanocrystals as hard templates. [Calcination at 550 C for 6 h and acidic treating (HCl, 1M) for 24 h at room temperature]. (a) cumulative intrusion and extrusion curves, and (b) intrusion pore size distribution. The macropore volume was 1.2 cm3/g.
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Intensity/a.u.
d c b a 5
10
15
20
25
30
35
40
2 Theta/degree
Figure S7. XRD patterns of (a) Na2SiO3·9H2O, (b) NH4Cl, (c) TPABr, and (d) the mixture of these raw solid materials. The appearance of about 31 associated with NaBr in Fig. S7d is due to the solid reaction between Na2SiO39H2O with TPABr.
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50
a
b
0.005 0.004
40
dV/dlog(w)
Volume adsorbed(cm3/g)
60
30
0.003 0.002
20
0.001 10
0.000 0 0.0
0.2
0.4
0.6 P/P
0.8
1.0
0
1
2 3 Pore width/nm
4
5
0
Figure S8. (a) N2 sorption isotherms and (b) HK pore size distribution of the sample crystallized at 2 h for synthesizing S-Si-ZSM-5 zeolite from solvent-free route.
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100
Crystallinity/%
80
a 60
b
40 20 0 0
5
10
15
20
25
Time/h
Figure S9. Crystallization curves of (a) S-Si-ZSM-5 zeolite synthesized from solvent-free route and (b) silicalite-1 zeolite synthesized from hydrothermal route.
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300
250
a
Volume adsorbed (cm3/g)
Volume adsorbed (cm3/g)
300
200 150 100 50
0.0
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c
Volume adsorbed (cm3/g)
Volume adsorbed (cm3/g)
b
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120 100 80 60 40 20
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d
150 100 50 0
0 0.0
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0.4 p/p
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0.8
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0
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0.2
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0.8
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0
Figure S10. N2 sorption isotherms of the samples crystallized at (a) 0.5, (b) 1.0, (c) 2.0, and (d) 2.5 h for synthesizing silicalite-1 zeolite from hydrothermal route.
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2.5 105
2.0 1.5 1.0 0.5
95 0.0 -0.5
90
DTA/(uV/mg)
TG/%
100
-1.0 85 100
200
300
400
500
600
700
-1.5 800
Temp/ C
Figure S11. TG-DTA curves of as-synthesized S-Si-ZSM-5 zeolite.
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Intensity/a.u. 5
10
15
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35
40
2 Theta/degree
Figure S12. XRD pattern and SEM image of as-synthesized S-ZSM-39 zeolite from solvent-free synthesis.
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Intensity/a.u. 5
10
15
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40
2 Theta/degree
Figure S13. XRD pattern and SEM image of as-synthesized S-SOD zeolite from solvent-free synthesis.
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Intensity/a.u. 5
10
15
20
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40
2 Theta/degree
Figure S14. XRD pattern and SEM image of as-synthesized S-MOR zeolite from solvent-free synthesis.
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Intensity/a.u. 5
10
15
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30
35
40
2 Theta/degree
Figure S15. XRD pattern and SEM image of as-synthesized S-Beta zeolite from solvent-free synthesis. The S-Beta sample contains a small amount of MOR zeolite.
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Intensity/a.u. 5
10
15
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2 Theta/degree
Figure S16. XRD pattern and SEM image of as-synthesized S-FAU zeolite from solvent-free synthesis.
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Table S1. The starting raw solids for synthesizing zeolites with MFI structure. Run
Starting raw solids, g
Crystallization Si/M ratios time, h
in products
Sample name
(M=Al, Fe, Ga, or B) 1
1.315 Na2SiO3·9H2O, 0.30-0.36
24-48
Pure silica
S-Si-ZSM-5
24-48
109-20
S-Al-ZSM-5
48-72
123-27
S-Fe-ZSM-5
24-72
213-39
S-Ga-ZSM-5
48-72
110-21
S-B-ZSM-5
48-72
Pure silica
S-Si-ZSM-5
fumed silica, 0.24 TPABr, 0.400.46 of NH4Cl 2
1.315 Na2SiO3·9H2O, 0.30-0.36 fumed silica, 0.24 TPABr, 0.009-0.026 boehmite, 0.400.48 NH4Cl
3
1.315 Na2SiO3·9H2O, 0.30-0.36 g fumed silica, 0.24 TPABr, 0.36-0.44 NH4Cl, 0.024-0.157 Fe(NO3)3·9H2O
4
1.315 Na2SiO3·9H2O, 0.30-0.36 g fumed silica, 0.24 TPABr, 0.42-0.48 NH4Cl, 0.008-0.07 Ga2O3
5
1.315 Na2SiO3·9H2O, 0.30-0.36 g fumed silica, 0.24 TPABr, 0.32-0.44 NH4Cl, 0.005-0.021 H3BO3
6
1.315 Na2SiO3·9H2O, 0.30-0.36 g fumed silica, 0.24 TPABr,
with
0.40-0.46 NH4Cl, 0.5-2.0
macropore
CaCO3
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