Supporting Information

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1 S1 Supporting Information Synthesis of High-Silica LTA and UFI Zeolites and NH 3 -SCR Performance of Their Copper-Exchanged Form Donghui Jo, Taekyung Ryu, Gi Tae Park, Pyung Soon Kim, Chang Hwan Kim, In-Sik Nam, and Suk Bong Hong *, Center for Ordered Nanoporous Materials Synthesis, School of Environmental Science and Engineering, POSTECH, Pohang , Republic of Korea Advanced Catalysts and Emission-control Research Lab, Research and Development Division, Hyundai Motor Group, Hwaseong , Republic of Korea. *S.B.H: , sbhong@postech.ac.kr

2 S2 Experimental Details Organic Structure-Directing Agent (OSDA) Synthesis. A general procedure for the alkylation of 1,2-dimethylimidazole: a mixture of mol 1,2-dimethylimidazole (98%, Aldrich) and mol alkyl halide was stirred in 100 ml chloroform (99.8%, Merck) at room temperature (RT) for 2 days. 1 The solvent was removed using rotary evaporation at 90 C, and the product was recrystallized or washed by ether (99%, Samchun). 1-Benzyl-2,3-dimethylimidazolium (1B23DMI) chloride: benzyl chloride (99%, Aldrich) was used as an alkylation agent. 1 H NMR (300 MHz, D 2 O): , 5.19, 3.65, ,2-Dimethyl-3-(2-methylbenzyl)imidazolium (12DM3(2MB)I) chloride: 2-methylbenzyl chloride (98%, TCI) was used as an alkylation agent. 1 H NMR (300 MHz, D 2 O): , , , 5.20, 3.68, 2.46, ,2-Dimethyl-3-(3-methylbenzyl)imidazolium (12DM3(3MB)I) chloride: 3-methylbenzyl chloride (97%, TCI) was used as an alkylation agent. 1 H NMR (300 MHz, D 2 O): , , 5.13, 3.63, 2.43, ,2-Dimethyl-3-(4-methylbenzyl)imidazolium (12DM3(4MB)I) chloride: 4-methylbenzyl chloride (98%, TCI) was used as an alkylation agent. 1 H NMR (300 MHz, D 2 O): , 5.16, 3.64, 2.44, ,2-Dimethyl-3-(2-fluorobenzyl)imidazolium (12DM3(2FB)I) chloride: 2-fluorobenzyl chloride (98%, TCI) was used as an alkylation agent. 1 H NMR (300 MHz, D 2 O): , , 5.27, 3.68, ,2-Dimethyl-3-(3-fluorobenzyl)imidazolium (12DM3(3FB)I) chloride: 3-fluorobenzyl chloride (95%, TCI) was used as an alkylation agent. 1 H NMR (300 MHz, D 2 O): , , 5.27, 3.69, ,2-Dimethyl-3-(4-fluorobenzyl)imidazolium (12DM3(4FB)I) chloride: 4-fluorobenzyl chloride (98%, TCI) was used as an alkylation agent. 1 H NMR (300 MHz, D 2 O): , , 5.23, 3.69, (Cyclohexylmethyl)-2,3-dimethylimidazolium (1(CHM)23DMI) bromide: a mixture of mol 1,2-dimethylimidazole and mol cyclohexylmethyl bromide (99%, Aldrich) was refluxed in 20 ml acetonitrile (99.5%, Samchun) at 70 C for 4 days. After the reaction, the product was recrystallized by hexane (98.5%, Macron Fine Chemicals). 2 1 H NMR (300 MHz, D 2 O): , , 3.70, 2.51, , Benzyl-2-methyl-3-ethylimidazolium (1B2M3EI) iodide: a mixture of mol 1- benzyl-2-methylimidazole (90%, TCI) and mol iodoethane (98%, Kanto) was stirred in

3 S3 20 ml acetonitrile (99.5%, Samchun) at RT for 6 h. The product was obtained by the addition of excess ether followed by decantation, and the solvent was removed using rotary evaporation at 90 C. 3 1 H NMR (300 MHz, D 2 O): , 5.24, , 2.50, Benzyl-2-methyl-3-propylimidazolium (1B2M3PI) iodide: a mixture of mol 1- benzyl-2-methylimidazole (90%, TCI) and mol iodopropane (99%, Aldrich) was stirred in 20 ml acetonitrile at RT for 6 h. The product was obtained by the addition of excess ether followed by decantation, and the solvent was removed using rotary evaporation at 90 C. 1 H NMR (300 MHz, D 2 O): , 5.26, , 2.50, , Prior to their use as OSDAs, the halide salts of imidazolium-based cations obtained were converted to the hydroxide form by anion exchange in aqueous solution using Amberlite IRN- 78 anion-exchange resin (Aldrich). Each of the resulting solutions was concentrated by rotary evaporation at 80 C, and its final hydroxide concentration was determined by titration using phenolphthalein as an indicator. Zeolite Synthesis. The synthesis of zeolites in the presence of imidazolium-based OSDAs was performed using synthesis mixtures prepared by combining tetramethylammonium hydroxide pentahydrate (TMAOH 5H 2 O, 97%, Aldrich), HF (48%, J.T. Baker), tetraethylorthosilicate (TEOS, 98%, Aldrich), aluminum hydroxide (Al(OH) 3 H 2 O, Aldrich), and deionized water. The composition of the final synthesis mixture was xroh ytmaoh 0.49HF 1.0SiO 2 0.5yAl 2 O 3 5.0H 2 O, where R is the imidazolium-based OSDA prepared here and x and y are varied between 0.40 x 0.50 and 0 y 0.067, respectively, unless otherwise stated. When necessary, a small amount (4 wt % of the silica in the synthesis mixture) of calcined LTA with Si/Al = 23 or calcined PST-7 with Si/Al = 11 was added as seed crystals to the synthesis mixture and stirred for 24 h, before heating the resulting mixture at 80 C to remove the ethanol molecules generated by the hydrolysis of TEOS and some water for the desired composition. The final synthesis mixture was charged into Teflon-lined 23-mL autoclaves and heated under rotation (60 rpm) at 175 C for the desired time. The solid product was recovered by filtration or centrifugation, washed repeatedly with water, and dried overnight at RT. As-made LTA and PST-7 zeolites were calcined in air at 600 ºC for 8 h to remove the occluded OSDA molecules. The calcined samples were then refluxed twice in 1.0 M NH 4 NO 3 (2.0 g solid per 100 ml solution) for 6 h followed by calcination at 550 ºC for 8 h in order to ensure that the samples were completely in their proton form. Cu-LTA and Cu-PST-7 were

4 S4 prepared by ion exchange of their ammonium form three times with 0.01 M Cu(CH 3 CO 2 ) 2 H 2 O solutions at RT for 6 h followed by drying at 90 C overnight and calcining at 550 C in air for 8 h. 4 For catalytic comparison, Cu-SSZ-13 and Cu-ZSM-5 with similar Cu contents (2.9 and 3.2 wt %, respectively) were prepared according to the procedures similar to the Cu-LTA or Cu-PST-7 preparation. SSZ-13 (Si/Al = 16) was synthesized based on previously reported procedures, 5 and ZSM-5 (Si/Al = 14, HSZ-830 HNA) was obtained from Tosoh. Characterization. Powder X-ray diffraction (XRD) patterns were recorded on a PANalytical X Pert diffractometer (Cu K α radiation) with an X Celerator detector. Elemental analyses for Al, Si and Cu were carried out by a Shimadzu ICPE-9000 inductively coupled plasma spectrometer. Crystal morphology and average size were determined by a JEOL JSM-6510 scanning electron microscope (SEM). N 2 sorption experiments were preformed on a Mirae SI nanoporosity-xg analyzer. The fluorescence spectra were measured on a PTI QuantaMaster 300 spectrometer. During the measurements, diluted and concentrated OSDA solutions were placed within 1 cm and 100 µm pathway quartz cells, respectively, whereas the as-made zeolite was supported on a quartz slide by the solvent evaporation of dichloromethane suspension. 6 NH 3 temperature programmed-desorption (NH 3 -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. 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 750 C at a temperature ramp of 10 C min -1. H 2 temperature-programmed reduction (TPR) was measured on a Micromeritics AutoChem II 2920 analyzer. The sample pretreated at 500 ºC for 1 h with 5% O 2 in Ar flow was cooled to room temperature, and then heated to 800 ºC at a heating rate of 10 ºC min -1 with 5% H 2 in Ar flow. The 1 H- 13 C CP MAS NMR spectra at a spinning rate of 5.0 khz were recorded on a Bruker AVANCE II 500 spectrometer at a 13 C frequency of MHz with a π/2 rad pulse length of 6.3 µs, a contact time of 2.0 ms, a recycle delay of 5.0 s, and an acquisition of ca pulse transients. The 29 Si MAS spectra at a spinning rate of 5.0 khz were recorded at a 29 Si frequency of MHz with a π/2 rad pulse length of 4.0 µs, recycle delay of 20 s, and an acquisition of 500 pulse transients. The 13 C and 29 Si shifts are referenced relative to TMS. The 19 F MAS NMR spectra at a spinning rate of 25.0 khz were measured on a Varian

5 S5 Unity Inova 600 spectrometer at a 19 F frequency of MHz with a π/4 rad pulse length of 1.5 µs, a recycle delay of s, and acquisition of 4 pulse transients. The 19 F chemical shifts are referenced relative to CFCl 3. The 27 Al MAS NMR spectra at a spinning rate of 24.0 khz were recorded on a Bruker DRX500 spectrometer at a 27 Al frequency of MHz with a π/6 rad pulse length of 1.0 µs, a recycle delay of 2.0 s, and acquisition of ca. 100 pulse transients. The 27 Al chemical shifts are referenced relative to Al(H 2 O) 3+ 6 solution. Reaction System. The denox activity tests were conducted under atmospheric pressure in a fixed-bed flow reactor (3/8-in.-od Al tube). 7 Before each experiment, 0.6 g of catalyst in the 20/30 mesh size packed into the reactor were heated from room temperature to 500 C at a heating rate of 10 C min -1 under 21% O 2 /N 2 flow (2,000 ml min -1 ) and held at the final temperature for 2 h. A feed gas mixture containing 500 ppm NH 3, 500 ppm NO, 5% O 2, 10% H 2 O and N 2 balance was supplied through mass flow controllers, and the gas hourly space velocity (GHSV) was maintained at 100,000 h -1. The inlet and outlet concentrations of NO were determined by an online Nicolet 6700 FT-IR spectrometer. The hydrothermal aging was performed at 750 C for 24 h with flowing air containing 10% H 2 O. NH 3 oxidation was conducted under the identical reaction conditions described above except that the NO feed was stopped. Structural Analysis. The synchrotron powder X-ray diffraction (XRD) data of as-made puresilica LTA were recorded on the beamline 9B at the Pohang Acceleration Laboratory using monochromated radiation with λ = Å. The detector arm of the vertical scan diffractometer consists of seven sets of Soller slits, flat Ge(111) crystal analyzers, anti-scatter baffles, and scintillation detectors, with each set separated by 20. Data were collected at room temperature in flat plate mode, with a step size of 0.01 and overlaps of 2 to the next detector bank over the 2θ range The pattern of as-made pure-silica LTA was successfully indexed as cubic, with a = Å, using the program N-TREOR09, 8 as implemented in the program EXPO Attempts to solve the structure by direct method using the program EXPO2014 revealed the locations of framework atoms with the electron density maps generated in automatic Fourier recycling procedures. Powder XRD data for calcined PST-7 (UFI) were collected on a PANalytical MPD X'Pert Pro diffractometer with a flat-plate Bragg-Brentano theta-theta geometry using Cu-K α radiation (λ = Å). The pattern was collected at room temperature with a step size of and a time per step of 300 s over the 2θ range º. For the Rietveld refinement, the initial framework atom positions of calcined PST-7 were taken from the IZA Database of Zeolite Structures. 10 Using

6 S6 these data, the zeolite structures were refined via the Rietveld method using the GSAS suite of programs and EXPGUI graphical interface, 11 with soft restraints applied to T-O and O-O distances in the tetrahedral framework (1.62 and 2.65 Å, respectively). Peak shape was modeled using the pseudo-voigt profile function. 12 The highly disordered water molecules were located in the difference Fourier maps. The convergence was achieved by refining simultaneously all profile parameters, scale factor, lattice constants, 2θ zero-point, atomic positional and thermal displacement parameters, and occupancy factors for the framework atoms and water O atoms. References (1) Rojas, A.; Gómez-Hortigüela, L.; Camblor, M. A. Dalton Trans. 2013, 42, (2) Shirota, H.; Matsuzaki, H.; Ramati, S.; Wishart, J. F. J. Phys. Chem. B 2015, 119, (3) Dean, P. M.; Golding, J. J.; Pringle, J. M.; Forsyth, M.; Skelton, B. W.; Whitec, A. H.; MacFarlane, D. R. CrystEngComm 2009, 11, (4) Heo, I. J.; Lee, Y. M.; Nam, I.-S.; Choung, J. W.; Lee, J.-H.; Kim, H.-J. Microporous Mesoporous Mater. 2011, 141, (5) (a) Zones, S. I. U.S. Patent 4,544,538, (b) Zones, S. I. J. Chem. Soc., Faraday Trans. 1991, 87, (6) Gómez-Hortigüela, L.; López-Arbeloa, F.; Corá, F.; Pérez-Pariente, J. J. Am. Chem. Soc. 2008, 130, (7) Park, J. H.; Park, H. J.; Baik, H. J.; Nam, I.-S.; Shin, C. H.; Lee, J.-H.; Cho, B. K.; Oh, S. H. J. Catal. 2006, 240, (8) Altomare, A.; Campi, G.; Cuocci, C.; Eriksson, L.; Giacovazzo, C.; Moliterni, A.; Rizzi, R.; Werner, P.-E. J. Appl. Crystallogr. 2009, 42, (9) Altomare, A.; Cuocci, G.; Giacovazzo, C.; Rizzi, R.; Corriero, N.; Falcicchio, A. J. Appl. Crystallogr. 2013, 46, (10) Baerlocher, Ch.; McCusker, L. B. Database of Zeolite Structures. (11) (a) Rietveld, H. M. J. Appl. Crystallogr. 1969, 2, (b) Larson, A.; von Dreele, R. B. General Structure Analysis System GSAS; Los Alamos National Laboratory: Los Alamos, NM, (c) Toby, B. H. J. Appl. Crystallogr. 2001, 34, (12) Hastings, J. B.; Thomlinson, W.; Cox, D. E. J. Appl. Crystallogr. 1984, 17,

7 Figure S1. Powder XRD pattern of as-made pure-silica LTA zeolite synthesized using 12DM3(2FB)I as an OSDA in fluoride media. S7

8 Figure S2. Electron density map (yellow surface) of as-made pure-silica LTA synthesized using 12DM3(4MB)I generated by the automatic Fourier recycling procedures in the EXPO2014 program. The LTA framework (black, Si; red, O) was obtained using the direct method implemented by the EXPO2014 program. S8

9 Figure S3. Height-normalized fluorescence emission spectra of as-made pure-silica LTA zeolites synthesized using (a) 12DM3(4MB)I and (b) 12DM3(2FB)I, respectively, and diluted (10-3 M) and concentrated (1.0 M) aqueous solutions of hydroxide form of each OSDA. The excitation wavelength was 250 nm. A diluted aqueous solution (10-3 M) of 12DM3(4MB)I displays a prominent band around 290 nm due to its monomers and a weak one around 570 nm corresponding to the uncorrected second-order effects of the emission monochromator for the fluorescent emission from monomers. 6 Its concentrated solution (1.0 M) shows not only the monomer emission band at a slightly red-shifted position, but also a new weak band around 440 nm, assignable to the 12DM3(4MB)I dimers formed by π-π interactions. By contrast, the emission spectrum of as-made pure-silica LTA synthesized with the same OSDA exhibits no noticeable band in the similar region. Quite similar trends can also be observed for the 12DM3(2FB)I case. S9

10 Figure S4. SEM image of as-made LTA with Si/Al = 11 synthesized using 12DM3(4MB)I and TMA (TMA/(12DM3(4MB)I) = 0.11). For further details of the synthesis condition, see Table S1. S10

11 Figure S5. 27 Al MAS NMR spectra of an as-made PST-7 zeolite (UFI) with Si/Al = 11 and a series of as-made LTA zeolites with different Si/Al ratios. The Si/Al ratios given in parentheses were determined by elemental analysis. S11

12 Figure S6. 1 H- 13 C CP MAS NMR spectrum of as-made PST-7. S12

13 Figure S7. 29 Si MAS NMR spectrum of as-made PST-7 with Si/Al = 11: experimental (top); simulated (middle); deconvoluted components (bottom). S13

14 Figure S8. Rietveld plot for calcined PST-7: observed (crosses), calculated (solid line), and difference (lower trace) powder synchrotron diffraction patterns. The tick marks indicate the positions of allowed reflections. S14

15 Figure S9. 19 F MAS NMR spectra of as-made LTA and PST-7 zeolites synthesized using 12DM3(4MB)I and 12DM3(2FB)I, respectively, without or with TMA present. Spinning side bands are marked by asterisks. S15

16 Figure S10. NO conversion as a function of temperature in NH 3 -SCR reaction over H- LTA(16) ( ) and H-SSZ-13(16) ( ). The feed contains 500 ppm NH 3, 500 ppm NO, 5% O 2, 10% H 2 O balanced with N 2 at 100,000 h -1 GHSV. S16

17 Figure S11. Powder XRD patterns of Cu-LTA(16) zeolites before and after hydrothermal aging at different temperatures for 24 h. S17

18 Figure S12. NO conversion as a function of temperature in NH 3 -SCR reaction over (a) fresh and (b) 750 C-aged Cu-LTA(11) ( ), Cu-LTA(16) ( ), and Cu-SSZ-13(16) ( ) catalysts. The feed contains 500 ppm NH 3, 500 ppm NO, 5% O 2, 10% H 2 O balanced with N 2 at 100,000 h -1 GHSV. Hydrothermal aging was performed under flowing air containing 10% H 2 O at the desired temperature for 24 h. S18

19 Figure S13. NH 3 conversion as a function of temperature in NH 3 oxidation reaction over Cu- LTA(16) ( ), Cu-SSZ-13(16) ( ), and Cu-ZSM-5(14) ( ) catalysts. The feed contains 500 ppm NH 3, 5% O 2, and 10% H 2 O balanced with N 2 at 100,000 h -1 GHSV. S19

20 Figure S14. NH 3 -TPD profiles of fresh Cu-LTA(16) (black) and Cu-SSZ-13(16) (red). S20

21 S21 Table S1. Representative Products from Syntheses Using 12DM3(4MB)I as an OSDA gel composition Si/Al in the run a R/Si TMA/Si Si/Al time (h) product b product c LTA LTA LTA + AST AST + LTA LTA LTA 56 7 d amorphous LTA LTA e LTA amorphous + LTA + FER 12 d,e amorphous 13 e amorphous 14 e LTA e,f LTA e,g amorphous 17 e,g LTA + RUT a The composition of the synthesis mixture is xroh ytmaoh 0.49HF 1.0SiO 2 0.5yAl 2 O 3 5.0H 2 O, where R is 12DM3(4MB)I, unless otherwise stated. All syntheses were performed under rotation (60 rpm) at 175 C. b The product appearing first is the major phase. c Determined by elemental analysis. d TMA/Al = 0. e The product obtained using a small amount (4 wt % of the silica in the synthesis mixture) of calcined LTA with Si/Al = 23 as seed crystals. f TMA/Al = g TMA/Al = 0.60.

22 S22 Table S2. Representative Products from Syntheses Using 12DM3(2FB)I as an OSDA gel composition run a R/Si TMA/Si Si/Al time (h) product b LTA LTA LTA + ANA + amorphous 4 c amorphous LTA + UFI + RUT + amorphous UFI + amorphous + LTA + RUT 7 d UFI + LTA 8 e amorphous + UFI + RUT + LTA 9 d,e UFI + LTA + amorphous 10 c amorphous UFI a The composition of the synthesis mixture is xroh ytmaoh 0.49HF 1.0SiO 2 0.5yAl 2 O 3 5.0H 2 O, where R is 12DM3(2FB)I, unless otherwise stated. All syntheses were performed under rotation (60 rpm) at 175 C. b The product appearing first is the major phase. c TMA/Al = 0. d The product obtained using a small amount (4 wt % of the silica in the synthesis mixture) of calcined PST-7 (UFI) with Si/Al = 11 as seed crystals. e TMA/Al = 1.50.

23 S23 Table S3. Representative Products from Syntheses Using an Aluminosilicate Synthesis Mixture with Si/Al = 10 and Various Imidazolium-Based OSDAs product b run a R time = 1 day 3 days 7 days 14 days 1 1B23DMI UFI + (RUT) UFI + RUT UFI + RUT 2 12DM3(2MB)I amorphous amorphous amorphous RUT + amorphous 3 12DM3(3MB)I amorphous amorphous amorphous RUT + U 4 12DM3(4MB)I amorphous + LTA LTA + RUT + FER LTA + FER + RUT 5 12DM3(2FB)I UFI UFI + RUT UFI + RUT 6 12DM3(3FB)I amorphous amorphous amorphous amorphous 7 12DM3(4FB)I amorphous FER + amorphous FER + U 8 1(CHM)23DMI amorphous + FER FER + U FER + U 9 1B2M3EI amorphous amorphous amorphous RUT + FER + MWW 10 1B2M3PI amorphous amorphous MWW + RUT a The composition of the synthesis mixture is 0.50ROH 0.1TMAOH 0.49HF 0.5Al 2 O 3 1.0SiO 2 5.0H 2 O, where R is OSDA. All syntheses were performed under rotation (60 rpm) at 175 C. b The product appearing first is the major phase, and the product obtained in a trace amount is given in parentheses. U indicates an unknown phase.

24 S24 Table S4. Data Collection and Crystallographic Data for Calcined PST-7 refined structure (Si, Al) 64 O H 2 O symmetry tetragonal space group I4/mmm a (Å) (10) b (Å) (10) c (Å) (4) α ( ) 90 β ( ) 90 γ ( ) 90 unit cell volume (Å 3 ) (7) diffractometer PANalytical MPD X Pert Pro geometry Bragg-Brentano wavelength (Å) θ scan range ( ) No. of contributing reflections 1076 No. of refined parameters 82 No. of geometric restraints 38 R wp (%) 4.33 R p (%) 3.18 R 2 F (%) 9.69

25 Table S5. Atomic Coordinates and Thermal Parameters for Calcined PST-7 atom x y z occupancy U iso ( 100 Å 2 ) T (20) (8) (4) T (17) (16) (7) (4) T (22) (10) (4) O (22) (11) (8) O (40) (8) O (27) (27) (11) (8) O (23) (23) (8) O (24) (15) (7) (8) O (31) (16) (8) O (25) (25) (14) (8) O (21) (8) Ow (104) 0.372(9) 14.20(47) Ow (170) (170) (6) 14.20(47) Ow (67) 0.640(10) 14.20(47) Ow (10) 14.20(47) Ow (44) (44) (26) 0.772(4) 14.20(47) Ow (13) 14.20(47) Ow (127) 0.323(9) 14.20(47) Ow (170) (5) 14.20(47) Ow (142) (6) 14.20(47) S25

26 Table S6. Selected Bond Lengths and Angles for Calcined PST-7 bond length (Å) bond angle ( ) T1-O (4) O1-T1-O (26) T1-O (28) O1-T1-O (19) T1-O (21) O1-T1-O (19) T1-O (21) O2-T1-O (17) T2-O (20) O2-T1-O (17) T2-O (29) O3-T1-O (4) T2-O (27) O4-T2-O (25) T2-O (24) O4-T2-O (22) T3-O (4) O4-T2-O (17) T3-O (26) O7-T2-O (24) T3-O (26) O7-T2-O (22) T3-O (4) O6-T2-O (23) T-O (Avg.) O1-T3-O (16) O1-T3-O (16) O1-T3-O (29) O5-T3-O (24) O5-T3-O (19) O5-T3-O (19) O-T-O (Avg.) S26

27 S27 Table S7. Physical Properties of Cu 2+ -Exchanged Zeolite Catalysts Employed in This Work N 2 BET surface area (m 2 g -1 ) catalyst Cu (wt %) Si/Al Cu/Al fresh aged at 650 C aged at 750 C aged at 850 C Cu-LTA(11) Cu-LTA(16) Cu-SSZ-13(16) Cu-ZSM-5(14) Cu-PST-7(11)