Synthesis and Monte Carlo Structure Determination of SSZ-77: A New Zeolite Topology

Transcription

1 J. Phys. Chem. C XXXX, xxx, 000 A Synthesis and Monte Carlo Structure Determination of SSZ-77: A New Zeolite Topology David J. Earl, Allen W. Burton, Thomas Rea, Kenneth Ong, Michael W. Deem,*, Son-Jong Hwang, and Stacey I. Zones Department of Chemistry and Center for Molecular & Materials Simulations, UniVersity of Pittsburgh, 219 Parkman AVenue, Pittsburgh, PennsylVania 15260, CheVron Energy Technology Company, Richmond, California 94802, Departments of Bioengineering and Physics & Astronomy, Rice UniVersity, 6100 Main Street - MS142, Houston, Texas 77005, and The DiVision of Chemistry and Chemical Engineering, MC , California Institute of Technology, Pasadena, California ReceiVed: December 12, 2007; ReVised Manuscript ReceiVed: March 25, A new molecular sieve topology has been determined from a multistage Monte Carlo computer simulation procedure using the program ZEFSAII. The material, SSZ-77, consists of alternating layers present in the RUT and AST topologies, and intergrowths may be possible in the way that this material grows. The product first arose from a synthesis where it appears that the degradation of the quaternary ammonium structure directing agent (SDA) produced the viable organo-guest molecule in the structure formation. The synthesis requires the use of Ge as well as Si as lattice components. In the absence of Ge, only RUT forms. An additional study was carried out to determine the suitable size of guest molecules in a series spanning trimethylamine to tetraethylammonium in the presence of benzyltrimethylammonium. It is found from NMR investigations that none of the larger molecules are occluded within the cages of the SSZ-77 structure and that the primary occluded species is trimethylamine or tetramethylammonium Introduction Zeolites are crystalline porous solids and are one of the most important and valuable classes of materials in industry and society in general. 1 They are used as catalysts, adsorbents, molecular sieves, and ion exchangers, and are expected to be of importance in a range of emerging nanoscale applications. 2,3 Zeolites have structures composed of 4-coordinated tetrahedral atoms (for example silicon, aluminum, or germanium) linked to one another by 2-coordinated oxygen atoms. The International Zeolite Association currently recognizes the existence of 176 unique zeolite topologies. 4 The synthesis of new zeolite topologies remains an area of high interest due to the range of applications in which new materials can be utililized. Such examples would include new technology in the petroleum refining and petrochemicals sector. 5 Over the last two decades, the development and use of computational methods have led to the elucidation of a number of new zeolite structures In many cases, the resultant structure was not anticipated during the synthetic procedure and was not amenable to conventional structure solution methods. In this way, computer simulation can be seen as a valuable tool in understanding how synthetic conditions can influence the formation of different crystalline materials and in the development of structure-property relationships. Computational methods are also being applied to the generation of hypothetical zeolite topologies, many of which may be accessible to synthetic scientists in the future The inclusion of germanium in silicate gel systems (in both hydroxide and fluoride media) has led to the discovery of several * To whom correspondence should be addressed. mwdeem@ rice.edu. University of Pittsburgh. Chevron Energy Technology Company. Rice University. California Institute of Technology. new zeolite structures. Because germanium is tetravalent, it can be isomorphously substituted for silicon without introducing charge into the zeolite framework. The double four-ring unit (D4R) is a common subunit in most of these germanosilicates. Average Ge-O distances (1.74 Å) are longer than average Si-O distances (1.60 Å), and T-O-T angles for germanium ( ) are typically narrower than those measured in crystalline silica (>140 ). 17 These smaller angles may favor the formation of D4R units, which have not been observed in allsilica zeolites except in the presence of fluoride. Since 2000, several germanosilicates have been discovered: IM-10 (UOZ), 18 ITQ-17 (BEC), IM and ITQ (UTL), ITQ-21, 21 ITQ-22 (IWW), 22 ITQ-24 (IWR), 23 and ITQ ITQ-17 and ITQ-21 possess three-dimensional 12-ring channel systems, IM-12 possesses an intersecting 14- and 12-ring channel system, ITQ-22 and ITQ-24 possess three-dimensional systems of intersecting 12 and 10 rings, and ITQ-33 possesses intersecting 18- and 10-ring channel systems. Crystallographic studies indicate that germanium prefers to reside in the D4R units of all these materials. The layout of this paper is as follows: in section 2, the experimental methods used to synthesize and characterize SSZ- 77 are described; in section 3, we present the results of the Monte Carlo structure solution, provide details of the structure of SSZ-77, and describe further synthetic and experimental studies that we performed; in section 4, we discuss our results; and in section 5, we conclude. 2. Experimental Methods A. Synthesis. The material SSZ-77 was synthesized as follows. In the tared Teflon cup for a Parr 4545 (23 ml) reactor, we mixed 5 mmol of an 0.74 M solution of benzyltrimethylammonium hydroxide (see Table 3), 8 mmol of TEOS (tetraethyl orthosilicate, 1.68 g), and 1.5 mmol of germanium ethoxide (0.30 g). The mixture was allowed to hydrolyze with /jp CCC: $40.75 XXXX American Chemical Society PAGE EST: 6.4

2 B J. Phys. Chem. C, Vol. xxx, No. xx, XXXX Earl et al. JSM-6700F instrument. Electron diffraction data were obtained with a JEOL 2010 instrument operating at an accelerating voltage of 200 kv. Samples were prepared by dispersing the crystallites on a continuous carbon film. The electron diffraction patterns are shown in Figures S1 and S2 in the Supporting Information. A calcined sample for detailed structural analysis was examined at Beamline X16C at Brookhaven National Laboratory. The organic structure directing agent was removed by calcination to 595 C in an atmosphere of nitrogen containing 2% oxygen. The X16C sample was packed in an 1.5 mm outer diameter glass capillary that was sealed after being evacuated and heated overnight at 350 C. Data were collected at ambient temperature with a scintillation detector from 4 to 60 2Θ in steps of Θ and a wavelength of Å. Nitrogen adsorption experiments were performed with a Micromeritics 2100 instrument. C. Elemental Analysis. Elemental analyses were carried out at Galbraith Analytical in Knoxville, Tennessee. The elements were determined by use of ICP methods Figure 1. Sanning electron micrograph of the novel material SSZ-77. Figure 2. Figure 1. X-ray diffraction pattern of the same material shown in the cup placed in a hood so that ethanol (from hydrolysis of the Si and Ge compounds) and some water could evaporate. After a few days, the cup was weighed and deionized water was added to adjust the molar water/sio 2 ratio to 3.5. The cup was then closed, placed in the stainless steel jacketing for this reactor, placed on a rotating spit within a convection heating oven and rotated at 43 rpm while heating at 170 C. The reaction was cooled to room temperature and a sample taken for analysis by scanning electron microscope (SEM) after 6 days of heating. No indication of any crystallization could be seen. The reactor was heated for another 4 days and the process of analysis repeated. The nicely formed crystals seen in Figure 1 indicated a product had formed. The contents of the reactor were poured into a glass fritted filter and washed with 500 cc of water. The filter was then air-dried, and the sample taken for X-ray diffraction analysis. The pattern obtained is shown in Figure 2. We have recently described 25 the use of this synthetic approach for the equipment described and the use of SEM screening, using very small samples from reactors to first see if there is any crystalline material observable by SEM, before taking a larger sample for XRD analysis. B. Characterization. Preliminary powder X-ray diffraction (XRD) patterns were recorded on a Siemens D- 500 instrument. Diffraction peaks from the in-house diffraction data were profilefitted and indexed with the MDI JADE software package. Scanning electron micrographs (SEM) were recorded on a JEOL 3. Results A. Monte Carlo Structure Solution and Refinement. Powder diffraction data from our in-house Cu KR diffractometer were used for indexing. The powder diffraction peaks were fitted with the JADE suite of programs. The peak positions were then used as input to the TREOR 26 program. The XRD pattern of the synthesized material was indexed in a monoclinic unit cell: a ) Å, b ) Å, c ) Å, R)90.0, β ) , γ ) 90.0, with space group symmetry C2/m. The figures of merit were M(25) 27 ) 11 and F(25) 28 ) 32. The figures of merit are lower than those normally expected for a successful indexing, but this is mainly due to the abundance of broad, overlapping peaks (vide infra) in the powder pattern. The largest differences in the calculated and predicted peak positions (0.02 ) were for reflections located within a cluster of other peaks. The proposed unit cell is supported by electron diffraction images along selected zone axes. Figures 1 and 2 in the Supporting Information show electron diffraction patterns along the [011] and [-110] zone axes. Along the [011] zone axis, the major d spacings measured are 9.3 Å (11-1) and 6.9 Å (1-11). Along the [-110] zone axis, the major d spacings measured are 17.2 Å (001), 9.2 Å (11-1), and 8.4 Å (110). These d spacings are all within experimental error of those expected for the proposed monoclinic cell. To solve the structure of SSZ-77, a multistage Monte Carlo computer simulation procedure, with the ZEFSAII program, 7 was performed. This is a real space method that requires as input the powder diffraction data, and the symmetry and unit cell dimensions. The Monte Carlo method effectively minimizes a zeolite figure of merit, which contains contributions from geometric terms such as T-T distances and T-T-T angles (where T is a tetrahedrally coordinated atom such as silicon), density terms, and the match of simulated diffraction data to that of the experimental powder data. The figure of merit is a function of the simulation parameters and the positions of the unique T atoms. Further details regarding the zeolite figure of merit can be found in ref 8. In the first stage of the structure solution, 126 different parameter sets were constructed that covered the range of T atom densities for known zeolite topologies, from 12 to 20 T atoms per 1000 Å 3, and the possible number of crystallographically unique T atoms, from 4 to 14 unique T atoms. For each of these parameter sets, 100 Monte Carlo simulated annealing simulations were performed, 6 8 each with different initial

3 SSZ-77: A New Zeolite Topology J. Phys. Chem. C, Vol. xxx, No. xx, XXXX C TABLE 1: Refined Crystallographic Data space group C2/m a (5) Å b (4) Å c (7) Å R 90.0 β γ 90.0 R wp 7.15% R p 5.98% χ R(F 2 ) TABLE 2: Refined Atomic Position Parameters for SSZ-77 atom x y z occupancy U iso (Å 2 ) Si (7) (5) (4) Si (9) (6) (5) Si (7) (5) (4) Si (7) (5) (5) Si (8) (7) (4) Si (6) (5) (4) Si (6) (5) (4) Ge (0) (0) (0) Ge (0) (0) (0) Ge (6) (5) (4) Ge (6) (5) (4) O (16) (10) O (13) (9) O (10) (11) (4) O (8) (8) (8) O (11) (8) (6) O (8) (21) (17) O (26) (7) (6) O (8) (8) (6) O (8) (13) (8) O (18) (0) (10) O (13) (8) (9) O (19) (0) (11) O (16) (0) (11) O (12) (11) (5) O (9) (11) (6) O (0) (17) (0) O (14) (11) (5) configurations and seed random numbers, but otherwise identical annealing conditions. These simulations identified 17 potential structures that had zeolite figures of merit in the range of known zeolite topologies. The parameter sets that produced these structures had between 6 and 9 crystallographically unique T atoms and a T atom density of between 15 and 18.7 T atoms per 1000 Å 3. In the second stage of the structure solution, parallel tempering simulations, 8,29 that are more computationally intensive and effective at minimizing the zeolite figure of merit, were performed on each of the parameter sets that had produced viable structures from the first set of simulations. Following the parallel tempering simulations, the original 17 possible structures were narrowed down to two feasible topologies for SSZ-77, one with 7 unique T atoms and one with 8. These two visually similar structures were found to have the best zeolite figures of merit from the simulated annealing simulations and were the only two structures that optimization using parallel tempering simulations produced (it should be noted that the parallel tempering simulations did not produce any additional topologies that were not found through simulated annealing, but they did refine the positions of the T atoms in the structure). We will now term these two viable topologies as structures A and B. In the final stage of the structure solution, preliminary Rietveld refinements of the two feasible topologies found from the parallel tempering simulations were performed using the general structure analysis system (GSAS) package. 29 The 2θ range of the preliminary refinements was limited to 30. Asthe ZEFSAII computational procedure includes only T atoms in the structure solution, oxygen atoms were added to each structure, and their positions were optimized using energy minimization methods with a fixed unit cell size. Si-O bond restraints (1.60 ( 0.03) Å, Ge-O bond restraints (1.76 ( 0.03) Å, and the tetrahedral oxygen-oxygen distance restraints (2.61 ( 0.05) Å were used during the refinement. The tetrahedral atoms were constrained to have equivalent isotropic thermal displacement parameters, and the oxygen atoms were constrained to have equivalent isotropic thermal displacement paratmeters. Rietveld refinement with GSAS yielded final agreement values, with the background contribution to the profile subtracted, of R wp ) 6.68% and R p ) 5.69% for structure A and R wp ) 12.65% and R p ) 10.14% for structure B. In the final refinement for structure A, the full profile (5-60 2θ) was used. The R wp, R p, R(F 2 ), and χ 2 were 7.15%, 5.98%, 0.079, and 2.04 respectively. Refinement of the unit cell for structure A resulted in the parameters listed in Table 1. The agreement values for structure A give high confidence that it is indeed the correct topology for SSZ-77, and structure A also had a better zeolite figure of merit, from the simulated annealing and parallel tempering simulations, than structure B. The atomic parameters for SSZ- 77 are shown in Table 2. The bond lengths and angles are summarized in Tables 1 and 2 IN THE Supporting Information. The profiles from the GSAS refinement of SSZ-77 are shown in Figure 3. B. Structure of SSZ-77. A representation of the structure SSZ-77 is given in Figure 4. With color coding of the regions, we highlight that the material is composed of a strictly alternating sequence of layers present in the AST and RUT framework topologies. The term clathrate implies that there are no zeolitic portals for passage of hydrocarbon components. Materials with the RUT topology have previously been reported by Gies 30 and co-workers and by Broach et al. 31 In both instances, the samples were prepared from syntheses using a tetramethyl ammonium cation. AST-type phases have been found to be increasingly favored in syntheses by two factors that promote the formation of double 4-rings as subunit components. The presence of fluoride can promote their formation in all-silica systems, 32 and the addition of germanium can also lead to their formation in both hydroxide- and fluoridemediated syntheses. 33 C. Further Synthesis and NMR Studies. As we could not match the phase with any known material, subsequent reactions were set up to reproduce it and to understand the synthesis boundaries. Further runs did not reproduce the novel phase. Instead we observed either no crystallization or the crystallization of unrelated phases. An analysis of the first product showed that the C/N+ ratio was approximately 5.5, whereas the original SDA had a ratio of 10. So something seemed amiss. An EDX analysis (Figure 5) confirmed that both silicon and germanium were found in crystals. Once a structure solution had been proposed from the ZEFSAII program (see Results, section A), it was apparent that the original SDA would not fit into the cages of the proposed structure. It became clear why our attempts to reproduce the material were unsuccessful. The computational work suggested that, through serendipity, the SSZ-77 product may have been made from a fragment of the original SDA. Likely fragments

4 D J. Phys. Chem. C, Vol. xxx, No. xx, XXXX Earl et al. Figure 3. Experimental (top), simulated (middle), and difference (bottom) profiles for the synchrotron X-ray diffraction pattern (λ ) Å) of SSZ-77. Figure 4. Model of SSZ-77 showing the different cages found in AST (green) and RUT (red) topologies for the base-promoted decomposition of this SDA could be a free trimethyl amine and possibly a benzyl alcohol. We reran the synthesis, using all the same reagents as before but adding in 2 mmol of trimethylamine hydrochloride salt. The original product was once again made! Elemental analyses showed that the product contained 27 weight % Si and 15.9 for Ge. The 13 C and 1 H solid-state NMR spectra of sample of the newer reproduced material, SSZ-77, are shown in Figure 6. From the proton spectra it is clear that there is no indication of aromatic protons. For the 13 C, there is a single line that is quite sharp. The narrow lines can indicate that there is some mobility for the SDA in its environment, as though it is free to rotate at room temperature and is not tightly trapped in the host space. The single line also indicates that there is only one type of carbon and that the methyl is on the trimethylamine. Also the chemical shift position is consistent with the carbon being adjacent to a positively charged nitrogen. If the product could be made with just the trimethyl ammonium group, and the NMR indicated it might not be tightly bound, and then one can ask, what larger molecules might also work? Table 3 shows other SDA which go up in size as far as adding a fourth methyl group, then using triethylamine and subsequently adding a fourth bond of either methyl or ethyl. The triethylamine also works quite well to make the product, and its X-ray diffraction pattern is compared to the original in Figure 7. Table 4 shows the outcomes of using other SDAs in the synthesis. The largest in the series, tetraethyl ammonium, produces an AST-type phase only. AST cages are a primary component of the SSZ-77 structure. The SEM images of the AST phase are shown in Figure 8. If we consider the various Figure 5. Localized energy-dispersive X-ray (EDX) analysis of a field of SSZ-77 crystals. The data show the presence of Ge and an approximate molar ratio of 4 for Si and Ge. Follow-up elemental analyses showed a ratio for Si/Ge of 4.5 in the product. The C/N ratio (from combustion analysis) was also close to 4. competing forces in the synthesis, it is well-known that the presence of Ge can contribute at the subunit level, making both single and double 4-ring components. 35 The AST framework is composed primarily from the assembly of double 4-rings. If the tetraethyl amine cannot fit well into the RUT cage, then it is possible that the reaction will move right on to AST. We also looked at the compositional selectivity in this synthesis for changing the Si/Ge ratio, knowing that more Ge might favor an AST-type phase. The results of a series are also shown in Table 4. We find that SSZ-77 can be made at more than one ratio. Interestingly, if the Ge level is too low, then instead of getting a pure RUT-type phase as might have been expected the product is another clathrasil, MTN, which does form very nicely from trimethylamine (the ostensible fragment from the decomposition of the benzyl trimethyl SDA use in

5 SSZ-77: A New Zeolite Topology J. Phys. Chem. C, Vol. xxx, No. xx, XXXX E Figure 6. MASNMR spectra for the SSZ-77 sample after the reaction was rerun with trimethylamine addition. 1 H spectra (a) and 13 C (b) with both cross-polarization and bloch decay data shown. Panel c shows the 29 Si spectra and there are both Q3 and Q4 silicon atoms detected. SDA1 SDA2 a TABLE 4: Synthesis Results for Dual SDA Runs reaction result Si/Ge in B ZN + Me 3 A 9 SSZ-77 B ZN + Me 3 B 9 some SSZ-77 B alone 9 SSZ-77/RUT B ZN + Me 3 C 9 SSZ-77 B ZN + Me 3 D 9 SSZ-77 D alone 9 unknown B ZN + Me 3 E 9 AST E alone 9 MFI B ZN + Me 3 C 6 SSZ-77 B ZN + Me 3 C 4 SSZ-77 B ZN + Me 3 C 2 mix of phases * SSZ-77 Figure 7. XRD pattern for the SSZ-77 product made from the addition of SDA C to the synthesis (see Tables 3 and 4). The intensities of lines are different from those in the original pattern in Figure 2). a See Table 3 for structures TABLE 3: Structure-Directing Co-components a Used in SSZ-77 Synthesis A. (CH 3) 3N B. (CH 3) 4N + C. (CH 3 CH 2) 3N D (CH 3 CH 2) 3N + CH 3 E. (CH 3CH 2) 4N + a All reactions already have B ZN + Me 3. the synthesis). At a high level of Ge, the SSZ-77 no longer forms, and a mix of crystalline products is observed that does not contain AST. 4. Discussion SSZ-77 is an unusual structure that requires the presence of Ge to form. Too much Ge is not helpful though, as the results in Table 4 demonstrate. There are two cage types in the material, one previously described as an AST type and the other RUT. With the exception of the effects of the germanium, the chemistry at work here suggests that the guest molecules are possibly more focused on the RUT part of the structure. Once we learned that the ability to reproduce the crystallization hinged on using the decomposition fragment from the original synthesis (determined by MAS NMR), trimethylamine and possibly its protonated form, we then became interested in the influence of the size of related SDA molecules on the phase selectivity. So we reran the synthesis using the other secondary components listed in Table 3. The concept was to see what else might fit in the structure. Consistent with this view of the situation, trimethyl, tetramethyl, triethyl, and triethyl methyl SDA all yielded SSZ-77. The largest molecule, tetraethyl ammonium did not yield SSZ-77 and made AST only. The next question was, if the triethyl

6 F J. Phys. Chem. C, Vol. xxx, No. xx, XXXX Earl et al Figure 8. View of the bipyramidal morphology of AST crystals formed from the use of Tetra ethylammonium (SDA E) in the synthesis. methyl cation might be the largest to fit into the structure (RUT cage), would the behavior of the cation be changed in the clathrate cage? When there is considerable room for an organocation guest, the MAS NMR shows that there is line narrowing (as observed in Figure 6). As the SDA becomes more tightly trapped into a configuration, line broadening occurs. To our surprise in this study, when the 13 C NMR of the various additional SDA (A-E) were examined, the ethyl group presence in C, D, and E was not sufficient to indicate that these SDA were the main ones incorporated. Mainly the line-narrowed methyl (bonded to N) species were observed. We then went back and removed the benzytrimethyl ammonium cations from the reaction system but increased the contributions of B, D, and E as hydroxide sources to keep the basicity of the reaction systems constant. To our surprise, only B (tetramethyl ammonium) produced any product and it was not pure. The other reactions, lacking the ability to produce any trimethylamine (or ammonium) fragment, failed to yield any SSZ-77. Results are shown in Table 4. So the apparent role of the extra SDA added, all as bases, was to help accelerate the decomposition of the benzytrimethyl SDA, yielding the necessary fragment that can direct growth of SSZ-77 when some Ge is present. This perspective is consistent with the NMR results where the ethyl groups are minor compared with the dominant methyl groups in the host lattice as seen from 13 C MAS NMR. In addition, for some samples there is evidence of the presence of the aromatic fragment as well. In their description of the crystal structure and chemistry for the borosilicate RUB-10 (RUT topology) Gies and Rius note that NMR data indicate that there is considerable motion occurring for the tetramethyl ammonium SDA. 31 This result would be consistent with what we observe here in the SSZ-77 studies. The other description of the RUT material was a study of an aluminosilicate sample and was described as TMA silicate. 32 Here again, the synthesis used the tetramethyl ammonium cation. The framework of the RUT material has two types of cages (it is not unusual for some known clathrates to have more than one cage type in their structure as discussed in ref 34). The tetramethyl ammonium cation must reside in the larger cage. The study of the aluminosilicate also mentions that the material has a relationship to a previously described material in the zeolite literature, NU This material has been studied in catalysis and showed the ability to isomerize xylenes. 36 However, the same reference also shows almost no uptake of p-xylene in adsorption tests. Another study from the same ICI research group shows that aromatics are formed from catalytic conversion of methanol. 37 The study was carried out at 450 C which is quite high for this reaction. The structure of NU-1 was unknown at the time and the literature described it as a likely 10-ring, in response to these indirect methods. There are no micropores in this structure; it has only 8-rings within the larger cage (of the two) in the RUT structure. So, one wonders if the behavior of the NU-1 was more of a surface effect in terms of analysis of the behavior of the zeolite under dynamic conditions. We find here that, for the study of the SSZ-77 after calcination, we do not get a good analysis of gas uptake because the system has difficulty coming to equilibrium and that may indicate that there is still a slow desorption of calcination fragments under the high vacuum the experiment requires. The AST contribution to the SSZ-77 structure is not expected to enhance any micropore capacity as it is made up of linked double 4-rings to provide isolated cavities with the surface polyhedra no greater than 6-rings. 5. Conclusions We have described the structure of germanosilicate SSZ-77, a germanosilicate with a novel topology of alternating layers of RUT and AST cages. The structure forms under a range of Si/Ge compositions in the synthesis mixture and with a number of structure-directing agents, though it appears it is mainly the trimethyl amine fragment coming from the benzyltrimethyl SDA which is stabilizing the crystal growth. From the experimental XRD and TEM data, the Monte Carlo structure solution method ZEFSAII identified the structure as containing 7 unique T atoms sites. Interestingly, identification of the structure allowed a sufficiently good understanding of the required synthesis conditions that the material was able to be made reproduceably, and we were able to rationalize how the original SDA decomposed to form the SDA that actively formed the structure. The topology of SSZ-77 is essentially an ordered intergrowth of the zeolite topologies AST and RUT. SSZ-77 is a germanosilicate clathrate that possesses two different kinds of large cages. One cage is found in the RUT topology, and the other cage is found in the AST framework. Like other recently discovered germanosilicates, SSZ-77 possesses a double four-ring as a subunit Acknowledgment. This research was supported by the U. S. Department of Energy (M.W.D.) and the University of Pittsburgh Central Research Development Fund (D.J.E.). Research was carried out in part at the National Synchrotron Light Source, Brookhaven National Laboratory, which is supported by the U. S. Department of Energy, Division of Materials Sciences and Division of Chemical Sciences. Dr. Chul Kim (Caltech) is thanked for additional NMR experiments carried out to understand the behavior of additional SDA used in the study. We appreciated Tiffany Downey s contribution to the nitrogen adsorption work. Supporting Information Available: Additional experimental data found in Figures S1-S3 and Tables S1 and S2. This material is available free of charge via the Internet at pubs.acs.org. References and Notes (1) Breck, D. W. Zeolite Molecular SieVes: Structure, Chemistry, and Use; Wiley: London,

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