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 Na 2 SiO 3 9H 2 O (SiO 2 of 20 wt.%, Tianjin Guangfu Chemical Reagent Co, Ltd.), Fumed silica (SiO 2 of 100 wt.%, Shenyang Chemical Reagent Co, Ltd.), Tetrapropylammonium bromide (TPABr, 98%, Tianjin Guangfu Chemical Reagent Co, Ltd.), NH 4 Cl (Tianjin Fuchen Chemical Reagent Co, Ltd.), Boehmite (Al 2 O 3 of 70 wt.%, Liaoning hydratight science and technology development Co., LTD), Fe(NO 3 ) 3 9H 2 O (Beijing Chemical Works), H 3 BO 3 (Beijing Chemical Works), Ga 2 O 3 (Beijing Chemical Works), CaCO 3 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), NaAlO 2 (Sinopharm Chemical Reagent Co, Ltd.), and SiO 2 2H 2 O (produced in our lab). Syntheses of samples S-Si-ZSM-5. 1.315 g of Na 2 SiO 3 9H 2 O, 0.30-0.36 g of fumed silica, 0.24 g of TPABr, and 0.40-0.46 g of NH 4 Cl 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 24-48 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 Na 2 SiO 3 9H 2 O, 0.30-0.36 g of fumed silica, 0.24 g of TPABr, 0.32-0.48 g of NH 4 Cl, 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(NO 3 ) 3 9H 2 O, 0.005-0.021 g of H 3 BO 3, or 0.008-0.07 g of Ga 2 O 3, 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 Na 2 SiO 3 9H 2 O, 0.30-0.36 g of fumed silica, 0.24 g of TPABr, 0.5-2.0 g of nano CaCO 3 and 0.40-0.46 g of NH 4 Cl 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 SiO 2, 1.35 g of Na 2 SiO 3 9H 2 O, 0.18 g of NH 4 Cl, 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 Na 2 SiO 3 9H 2 O were mixed with 1.18 g of NaAlO 2. After grinding for 15 min, the mixture was transferred to an autoclave and heated at 80 C for 4 h. S2
S-MOR zeolite. As a typical run, 2.67 g of SiO 2 2H 2 O were mixed with 0.363 g of NaAlO 2 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 SiO 2 3H 2 O were mixed with 1.09 g of NaAlO 2 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 SiO 2 3H 2 O were mixed with 1.64 g of NaAlO 2. 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 15 20 25 30 35 40 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. S4
a b Figure S2. SEM images of (a) S-B-ZSM-5 with a Si/B ratio of 33 and (b) S-Ga-ZSM- 5 with a Si/Ga ratio of 67. S5
Figure S3. SEM image of CaCO 3 nanocrystals, which were used as hard templates for synthesizing hierarchically porous S-Si-ZSM-5 zeolite. S6
Intensity/a.u. 5 10 15 20 25 30 35 40 2 Theta/degree Figure S4. XRD pattern of hierarchically porous calcined and acid-treated S-Si-ZSM- 5 zeolite synthesized from using CaCO 3 nanocrystals as hard templates [Calcination at 550 C for 6 h and acidic treating (HCl, 1M) for 24 h at room temperature]. S7
225 Volume adsorbed( cm 3 /g) 180 135 90 45 0 0.0 0.2 0.4 0.6 0.8 1.0 p/p 0 Figure S5. N 2 sorption isotherms of hierarchically porous calcined and acid-treated S- Si-ZSM-5 synthesized from using CaCO 3 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. S8
Cumulative Intrusion(mL/g) Log Differential Intrusion(mL/g) 1.2 1.0 a 0.4 0.3 b 0.8 0.6 intrusion extrusion 0.2 0.4 0.2 0.1 Intrusion Pore size 0.0 1 10 100 1000 10000 100000 Pressure/Pa 0.0 0 500 1000 1500 2000 Pore size/nm Figure S6. Mercury method characterization of hierarchically porous calcined and acid-treated S-Si-ZSM-5 synthesized from using CaCO 3 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 cm 3 /g. S9
Intensity/a.u. d c b a 5 10 15 20 25 30 35 40 2 Theta/degree Figure S7. XRD patterns of (a) Na 2 SiO 3 9H 2 O, (b) NH 4 Cl, (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 Na 2 SiO 3 9H 2 O with TPABr. S10
Volume adsorbed(cm 3 /g) dv/dlog(w) 60 50 40 30 20 10 0 a 0.0 0.2 0.4 0.6 0.8 1.0 P/P 0 0.005 b 0.004 0.003 0.002 0.001 0.000 0 1 2 3 4 5 Pore width/nm Figure S8. (a) N 2 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. S11
Crystallinity/% 100 80 60 40 a b 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. S12
Volume adsorbed (cm 3 /g) Volume adsorbed (cm 3 /g) Volume adsorbed (cm 3 /g) Volume adsorbed (cm 3 /g) 300 250 200 a 300 250 200 b 150 150 100 100 50 50 0 0 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 160 140 120 c p/p 0 250 200 d p/p 0 100 150 80 60 100 40 50 20 0 0 0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 p/p 0 p/p 0 Figure S10. N 2 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. S13
TG/% DTA/(uV/mg) 2.5 105 100 2.0 1.5 1.0 95 90 85 0.5 0.0-0.5-1.0-1.5 100 200 300 400 500 600 700 800 Temp/ C Figure S11. TG-DTA curves of as-synthesized S-Si-ZSM-5 zeolite. S14
Intensity/a.u. 5 10 15 20 25 30 35 40 2 Theta/degree Figure S12. XRD pattern and SEM image of as-synthesized S-ZSM-39 zeolite from solvent-free synthesis. S15
Intensity/a.u. 5 10 15 20 25 30 35 40 2 Theta/degree Figure S13. XRD pattern and SEM image of as-synthesized S-SOD zeolite from solvent-free synthesis. S16
Intensity/a.u. 5 10 15 20 25 30 35 40 2 Theta/degree Figure S14. XRD pattern and SEM image of as-synthesized S-MOR zeolite from solvent-free synthesis. S17
Intensity/a.u. 5 10 15 20 25 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. S18
Intensity/a.u. 5 10 15 20 25 30 35 40 2 Theta/degree Figure S16. XRD pattern and SEM image of as-synthesized S-FAU zeolite from solvent-free synthesis. S19
Table S1. The starting raw solids for synthesizing zeolites with MFI structure. Run Starting raw solids, g Crystallization time, h Si/M ratios in products (M=Al, Fe, Ga, or B) Sample name 1 1.315 Na 2 SiO 3 9H 2 O, 0.30-0.36 fumed silica, 0.24 TPABr, 0.40-0.46 of NH 4 Cl 2 1.315 Na 2 SiO 3 9H 2 O, 0.30-0.36 fumed silica, 0.24 TPABr, 0.009-0.026 boehmite, 0.40-0.48 NH 4 Cl 3 1.315 Na 2 SiO 3 9H 2 O, 0.30-0.36 g fumed silica, 0.24 TPABr, 0.36-0.44 NH 4 Cl, 0.024-0.157 Fe(NO 3 ) 3 9H 2 O 4 1.315 Na 2 SiO 3 9H 2 O, 0.30-0.36 g fumed silica, 0.24 TPABr, 0.42-0.48 NH 4 Cl, 0.008-0.07 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 Ga 2 O 3 5 1.315 Na 2 SiO 3 9H 2 O, 0.30-0.36 g fumed silica, 0.24 TPABr, 0.32-0.44 NH 4 Cl, 0.005-0.021 48-72 110-21 S-B-ZSM-5 H 3 BO 3 6 1.315 Na 2 SiO 3 9H 2 O, 0.30-0.36 g fumed silica, 0.24 TPABr, 0.40-0.46 NH 4 Cl, 0.5-2.0 48-72 Pure silica S-Si-ZSM-5 with macropore CaCO 3 S20