S1

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)3·1.0H2O, 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)3·1.0H2O 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·xAl2O3·5SiO2·150H2O, 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.

S2

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 NH4NO3 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 Kα 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 N2 sorption experiments were

performed on a Mirae SI nanoPorosity-XG analyzer.

1H-

13C CP and

27Al MAS NMR measurements were performed on a Varian Inova 300

spectrometer at a spinning rate of 6.0 kHz. The 1H-

13C CP MAS NMR spectra were recorded at a

13C 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

13C chemical shifts are reported relative to TMS. The

27Al MAS NMR were measured at a

27Al

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(H2O)63+

solution. 29

Si, 1H-

29Si CP MAS, and

27Al 3QMAS NMR

S3

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 1H-

29Si 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.

NH3 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% NH3 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

NH3. 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

. NH3 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 CaF2 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 K2CO3. The organic species from the resulting solution were extracted

by CH2Cl2 (Aldrich, 99.9%), and residual water in the organic phase was removed by adding a

small amount of Na2SO4 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

.

S4

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 N2 (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 N2/1-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/.

S5

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.

S6

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

N2 desorption branch isotherm, the inset of which shows the N2 adsorption-desorption isotherms.

S7

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 D2O solution of choline chloride, and the top one

is the 1H-

13C 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.

S8

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.

S9

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 Q3 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 1H-

29Si CP MAS NMR spectrum, which is not the case of H-FER(c).

S10

Figure S6. 27

Al 3QMAS NMR spectra of (a) H-FER(n) and (b) H-FER(c).

S11

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.

S12

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.

S13

Figure S9. GC-MS total ion chromatograms of the CH2Cl2 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 C2Cl6 used as an internal standard.

S14

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.