Supporting Information for Synthesis and Catalytic Behavior of Ferrierite Zeolite Nanoneedles Yoorim Lee, Min Bum Park, Pyung Soon Kim, Aurélie Vicente, Christian Fernandez, In-Sik Nam, and Suk Bong Hong,* Department of Chemical Engineering and School of Environmental Science and Engineering, POSTECH, Pohang 790-784, Korea Laboratoire Catalyse et Spectrochimie, ENSICAEN, Université de CAEN, CNRS, 6 Bd. Maréchal Juin, 14050 CAEN, France *To whom correspondence should be addressed. Phone: +82-54-279-2284. Fax: +82-54-279-8299. E-mail: sbhong@postech.ac.kr. Zeolite Synthesis. The reagents used for zeolite syntheses included choline hydroxide (ChOH, 20% aqueous solution, Aldrich), aluminum hydroxide (Al(OH) 3 1.0H 2 O, Aldrich), and tetraethylorthosilicate (TEOS, 98%, Aldrich). The chlorides of alkali metal (M + = Li +, Na +, K +, Rb +, or Cs + ) cations were also used for zeolite syntheses. In a typical synthesis, 0-0.32 g of Al(OH) 3 1.0H 2 O were mixed with 8.08 g of ChOH in 2.46 g of water and stirred at room temperature for 2 h. Into this solution 3.53 g of TEOS was dropwisely added. After being aged at 95 C for 1 day, an appropriate amount of MCl was then dissolved. The final composition of the synthesis mixture was 4ChOH MCl xal 2 O 3 5SiO 2 150H 2 O, where x is varied between 0 x 0.5. After being stirred at room temperature for 1 day, the final synthesis mixture was charged into Teflon-lined 23-mL autoclaves and heated at 150 C under rotation (60 rpm) for 14-28 days. The solid product was recovered by filtration or centrifugation, washed repeatedly with distilled water, and dried overnight at room temperature. S1
As-made nanocrystalline ferrierite zeolite was heated in flowing air (50 ml min -1 ) from room temperature to 550 C at a ramping rate of 10 C min -1 and kept at this temperature for 8 h in order to remove the organic structure-directing agents (SDAs) occluded. The calcined sample was then refluxed twice in 1.0 M NH 4 NO 3 solutions for 6 h followed by calcinations at 550 C for 2 h to obtain its proton form. For comparison, the mixed NaK form of ferrierite zeolite with a Si/Al ratio of 8.9 and a platelike morphology of ca. 0.7 µm in base and 0.1 µm in thickness was obtained from Tosoh and converted into the proton form according to the procedure given above. Here we refer to these nano- and submicrocrystalline ferrierite zeolites as H-FER(n) and H- FER(c), respectively. Analytical Methods. Powder X-ray diffraction (XRD) patterns were recorded on a PANalytical X Pert diffractometer (Cu K α radiation) with an X Celerator detector. Elemental analysis was carried out by a Jarrell-Ash Polyscan 61E inductively coupled plasma spectrometer in combination with a Perkin Elmer 5000 atomic absorption spectrophotometer. The C, H, and N contents of the samples were analyzed by using a Vario EL III elemental organic analyzer. Thermogravimetric analyses (TGA) were performed in flowing air (100 ml min -1 ) on an SII EXSTAR 6000 thermal analyzer, where the weight losses related to the combustion of organic SDAs or coke deposits formed during 1-butene skeletal isomerization were further confirmed by differential analyses (DTA) using the same analyzer. Approximately 15 mg of sample was used at a heating rate of 10 C min -1. Crystal morphology and average size were determined by a JEOL JSM-6510 scanning electron microscope (SEM), a Hitachi S-4800 field emission scanning electron microscope (FE-SEM), and/or a JEOL JEM-2010 transmission electron microscope (TEM) operating with an acceleration voltage of 200 kv. The N 2 sorption experiments were performed on a Mirae SI nanoporosity-xg analyzer. 1 H- 13 C CP and 27 Al MAS NMR measurements were performed on a Varian Inova 300 spectrometer at a spinning rate of 6.0 khz. The 1 H- 13 C CP MAS NMR spectra were recorded at a 13 C frequency of 75.43 MHz using a pulse length of 7.0 µs, a recycle delay of 3 s, and an acquisition of ca. 5000 pulse transients, which was repeated with a contact time of 2.5 ms. The 13 C chemical shifts are reported relative to TMS. The 27 Al MAS NMR were measured at a 27 Al frequency of 78.16 MHz using a pulse length of 1.8 µs and a recycle delay of 0.5 s. Approximately 3000 pulse transients were accumulated, and the 27 Al chemical shifts were reported relative to an Al(H 2 O) 3+ 6 solution. 29 Si, 1 H- 29 Si CP MAS, and 27 Al 3QMAS NMR S2
measurements were carried out on a Bruker Avance 400 spectrometer. The 29 Si MAS NMR spectra were measured at a 29 Si frequency of 79.46 MHz at a spinning rate of 12.0 khz with a pulse length of 12.0 µs, a recycle delay of 50 s, and an acquisition of ca. 1000 pulse transients. The 1 H- 29 Si CP MAS NMR spectra were recorded with an acquisition of ca. 1000 pulse transients, which was repeated with a contact time of 4.0 ms and a recycle delay of 1 s. The 29 Si chemical shifts are reported relative to TMS. The 27 Al 3QMAS NMR spectra were obtained at a 27 Al frequency of 104.26 MHz using the multiplex spam z-filter pulse method at a spinning rate of 14.5 khz and a recycle delay of 0.2 s. The detailed procedure used in this method was described elsewhere. S1,S2 The initial excitation and conversion hard pulse lengths were 2.0 and 0.8 µs with an rf field of 160 khz, respectively. The soft pulse was 9 µs with an rf field of 30 khz. NH 3 temperature programmed-desorption (TPD) was carried out on a fixed bed, flow-type apparatus linked to a Hewlett-Packard 5890 series II gas chromatograph with a thermal conductivity detector (TCD). A sample of ca. 0.1 g was activated in flowing He (50 ml min -1 ) at 550 C for 2 h. Then, 10 wt% NH 3 was passed over the sample at 150 C for 0.5 h. The treated sample was subsequently purged with He at the same temperature for 1 h to remove physisorbed NH 3. Finally, the TPD was performed in flowing He (30 ml min -1 ) from 150 to 700 C at a temperature ramp of 10 C min -1. NH 3 TPD curve deconvolution was performed using the PeakFit curve-fitting program. The IR spectra in the OH region were measured on an ABB Bomen MB 104 FT-IR spectrometer using self-supporting zeolite wafers of approximately 12 mg (1.3 cm diameter). Prior to IR measurements, the zeolite wafers were pretreated under vacuum at 500 C for 2 h inside a home-built IR cell with CaF 2 windows. The coke species formed on the zeolite catalysts after 1-butene isomerization at 400 C for 24 h on stream were extracted by a modification of the procedure originally developed by Guisnet group. S3 In a typical GC-MS analysis, 50 mg of the used catalyst were dissolved in 3 ml of 10% HF and neutralized with K 2 CO 3. The organic species from the resulting solution were extracted by CH 2 Cl 2 (Aldrich, 99.9%), and residual water in the organic phase was removed by adding a small amount of Na 2 SO 4 that was subsequently recovered using an Advantec DISMIC-13JP syringe filter. The GC-MS total ion chromatograms were recorded on a Varian CP 3800 gas chromatograph equipped with a Varian 320-MSD mass selective detector. The split ratio was 100:1, and the column used was a VF-5 capillary column (30 m 0.25 mm) with flowing He (0.3 ml min -1 ). The temperature program ramps the column from 70 to 280 C at a rate of 4 C min -1. S3
The organic compounds extracted were identified in comparison with the NIST database. S4 Catalysis. All the catalytic experiments of this study were carried out under atmospheric pressure in a continuous-flow apparatus with a fixed-bed microreactor. In the skeletal isomerization of 1-butene, the catalyst was routinely activated under flowing N 2 (50 ml min -1 ) at 550 C for 2 h and kept at 400 C to establish a standard operating procedure, allowing time for the reactant/carrier gas distribution to be stabilized. Then, a reactant stream with N 2 /1-butene molar ratio of 9.0 was fed into a quartz reactor containing 0.1 g of zeolite catalyst at the same temperature. The total gas flow at the reactor inlet was kept constant at 50 ml min -1. The reaction products were analyzed online in a Varian CP-3800 gas chromatograph equipped with a CP- PoraPLOT Q capillary column (25 m 0.25 mm) and a flame ionization detector, with the first analysis carried out after 5 min on stream. Conversion was calculated by dividing the isobutene yield by the 1-butene conversion. After 24 h on stream at 400 C, if required, the used catalyst was regenerated under flowing air (100 ml min -1 ) at 550 C for 4 h and then employed for the reusability test under the reactions condition described above. (S1) Amoureux, J.-P.; Fernandez, C; Steuernagel, S. J. Magn. Reson. A 1996, 123, 116. (S2) Malicki, N.; Mafra, L.; Quoineaud, A.-A.; Rocha, J.; Thibault-Starzyk, F.; Fernandez, C. Solid State Nucl. Magn. Reson. 2005, 28, 13. (S3) Guisnet, M.; Magnoux, P. Appl. Catal. 1989, 54, 1. (S4) NIST Chemistry Web Book, http://webbook.nist.gov/chemistry/. S4
Figure S1. Powder XRD patterns of the as-made (left) and calcined (right) forms of (a) ZSM-34, (b) UZM-12, and (c) PST-8 obtained from the synthesis runs 3, 13, and 17 in Table 1, respectively. S5
Figure S2. (a) Powder XRD pattern and SEM image of the proton form (H-FER(c)) of submicrocrystalline ferrierite with a bulk Si/Al ratio of 8.9 and a platelike morphology obtained from Tosoh and (b) its pore size distribution curve calculated using the BJH formalism from the N 2 desorption branch isotherm, the inset of which shows the N 2 adsorption-desorption isotherms. S6
Figure S3. 13 C NMR spectra of organic SDA, choline, showing the assignment of each resonance. The bottom trace is the 13 C NMR spectrum of a D 2 O solution of choline chloride, and the top one is the 1 H- 13 C CP MAS NMR spectrum of the as-made form (FER(n)) of nanocrystalline ferrierite with a needlelike morphology. A small peak appearing around 48 ppm, assignable to trimethylamine, a choline decomposition product, is marked by an asterisk. S7
Figure S4. 27 Al MAS NMR spectra of (a) as-made FER(n) and (b) NaK-FER(c). Spinning side bands are marked by asterisks. S8
Figure S5. 29 Si MAS NMR spectra of (a) H-FER(n) and (b) H-FER(c): experimental (top), simulated (middle), and decomposed components (bottom). The Q 3 defect site has been introduced into the deconvolution of H-FER(n) because of the existence of one broad resonance around -105 ppm in its 1 H- 29 Si CP MAS NMR spectrum, which is not the case of H-FER(c). S9
Figure S6. 27 Al 3QMAS NMR spectra of (a) H-FER(n) and (b) H-FER(c). S10
Figure S7. (a) FER structure and its 10- and 8-ring channels and schematic illustrations of (b) FER(n) crystals with a needlelike morphology and (c) FER(c) crystals with a platelike morphology, showing their average crystal sizes. S11
Figure S8. TGA/DTA curves of (a) H-FER(n) and (b) H-FER(c) after 1-butene isomerization at 400 C and 10.1 kpa 1-butene pressure for 24 h on stream. S12
Figure S9. GC-MS total ion chromatograms of the CH 2 Cl 2 extracts obtained by dissolving (a) H- FER(n) and (b) H-FER(c) in HF solutions after 1-butene isomerization at 400 C and 10.1 kpa 1- butene pressure for 24 h on stream. The structures annotated onto the chromatograms are peak identifications having compared the mass spectra to those in the NIST database. S4 The peak indicated by an asterisk is the mass signal of C 2 Cl 6 used as an internal standard. S13
Figure S10. 1-Butene conversion and selectivity to isobutene at 12 h on time over H-FER(n) (, ) and H-FER(c) (, ) in the four successive runs carried out at 400 C for 24 h on stream, where the used catalyst was treated in flowing air (100 ml min -1 ) at 550 C for 4 h before its reuse. S14