Supporting Information

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Template–Framework Interactions in Tetraethylammonium-Directed .... BEA was prepared in fluoride media by dissolving 3.06 g of tetraethylammonium fluoride.
Supporting Information

Template–Framework Interactions in Tetraethylammonium-Directed Zeolite Synthesis Joel E. Schmidt, Donglong Fu, Michael W. Deem, and Bert M. Weckhuysen* anie_201609053_sm_miscellaneous_information.pdf

S1. Microporous materials Table S1. Framework properties, calculated stabilization energies, conformer distribution and goodness of fit for Raman spectral deconvolution for the 20 samples examined.

Framework AEI

Channel systema 3-D 8MR

Dmaxb 7.33 Å

∆Etg.tg-tt.tt (kJ/mol TEA+)c 3.2

AFI

1-D 12 MR

8.30 Å

0.0

Sample 1 2 3 4 5 6 7

BEA

3-D 12MR

6.68 Å

8.7 8 9 10

CHA

LTA MFI

3-D 8MR

7.37 Å

3.4

11 12 13 14 15 16 17 18 19

Material AlPO4-18 AlPO4-5 SAPO-5 e AlSi (OH ) AlSi (OH ) Borosilicate (OH ) Pure-silica (F ) Ti-AlSi (OH ) Titanosilicate (F-) Zincosilicate (OH ) AlSi CoAPO-34 MnAPO-34 SAPO-34 SAPO-34 ZnAPO-34 UZM-9 (AlSi) AlSi

Percent tg.tg conformer (%)d 20 17 12 0 0 0 0 0 0 0 23 22 29 25 16 79 0 100

Deconvolution R2 0.99 0.99 0.92 0.97 0.98 0.99 0.89 0.94 0.95 0.84 0.95 0.97 0.95 0.99 0.98 0.97 0.98 0.98 0.93

3-D 8 MR 11.05 Å 17.3 3-D 10 MR 6.36 Å -9.8 1-D 12MR, MOR 6.70 Å 2.1 AlSi 12 8MR UFI 2-D 8MR 10.09 Å 1.9 20 UZM-5 (AlSi) 0 0.95 a The channel system is defined by the dimensionality of the pores (1-D, 2-D or 3-D) as well as the pore size, defined b [1] by the number of tetrahedral atoms that encircle the pore (defined as membered ring, MR). From the IZA website c d Calculated using molecular modelling, complete results are in the Supporting Information. From Raman e spectroscopy, complete specta and explanation of deconvolution can be found in section S3. AlSi=aluminosilicate composition.

All microporous materials were synthesized according to well-established protocols. Detailed procedures are given for each material, and a list of all materials synthesized can be found in Table 1 and S1. Reactions were quickly quenched by immersing the reactors in cold water. After cooling, the reactors were opened and enough material was removed for powder X-ray diffraction analysis (PXRD). The materials were washed with water, and then recovered by centrifugation. This procedure was repeated a minimum of three times to ensure a clean product. A final wash was performed using acetone and then the collected solid was dried in air at 95°C. AlPO4-18 (AEI, sample 1) AlPO4-18 was synthesized by combining 1.53 g of phosphoric acid (Aldrich, 85%) with 1.98 g of distilled water. Then 1.00 g of aluminum hydroxide hydrate (Aldrich) was added with stirring, and stirred for 10 min at room temperature. Finally, 2.97 g of TEAOH (Alfa Aesar, 35%) was added with mechanical stirring. Then the entire mixture was stirred at room temperature for 2 h. Final molar ratios were: 1Al(OH)3:1.5H3PO4:0.8TEAOH:26 H2O. The solution was then charged in a Teflon lined Parr reactor and placed in a tumbling oven at 140°C and allowed to react for 24 h.

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AlPO4-5 (AFI, sample 2) AlPO4-5 was synthesized by slurring 1.00 g of Catapal B alumina in 2.40 g of water. Then 1.76 g of phosphoric acid (Aldrich, 85 wt %) was added and the mixture was stirred for 1 h. Next 3.21 g of TEAOH (Alfa Aesar, 35 wt %) was added and the mixture was stirred for 2 h. Final molar ratios were: 0.9Al2O3:1P2O5:1TEAOH:40 H2O. The solution was then charged in a Teflon lined Parr reactor and placed in an oven at 180°C and allowed to react for 12 h. SAPO-5 (AFI, sample 3) SAPO-5 was synthesized using the method reported in reference [2]. In a typical synthesis 2.54 g of phosphoric acid (Aldrich, 85 wt %) was mixed with 4.64 g of TEAOH (Alfa Aesar, 35 wt %) and 3.2 g of distilled water. Then 0.25 g of Ludox AS-40 was added with stirring at room temperature. Finally, 1.50 g of Plural SB Alumina was added and the resulting mixture was stirred for 2 h at room temperature. Final molar ratios were: 1Al2O3:0.15SiO2:1H3PO4:1TEAOH:35H2O. The solution was then charged in a Teflon lined Parr reactor and placed in a tumbling oven at 165°C and allowed to react for 66 h. Aluminosilicate BEA (Na+, sample 4) Aluminosilicate BEA was prepared by combining 4.00 g of TEAOH (Alfa Aesar, 35 wt %) with 0.37 g of NaOH and 0.88 g of water and stirring until the NaOH dissolved. Then 3.74 g of CBV-720 zeolite Y (Zeolyst, lot #72000N00989) was added and stirred until a thick paste was achieved. Final molar ratios were: 1SiO2:0.047Al2O3:0.2TEAOH:0.2NaOH:5H2O. The solution was charged in a Teflon lined Parr reactor and placed in an oven at 140°C and allowed to react for 3 days. Aluminosilicate BEA (no Na+, sample 5) Aluminosilicate BEA was prepared by combining 5.62 g of TEAOH (Alfa Aesar, 35 wt %) with 3.70 g of distilled water and 0.098 g of finely ground aluminum isopropoxide (Aldrich) and stirred until a homogeneous suspension was obtained. Then 5.00 g of tetraethylorthosilicate (Aldrich) was added with stirring. Final molar ratios were: 1SiO2:0.04Al2O3:0.55TEAOH:15H2O. Seeds of pure-silica zeolite BEA were added and the solution was charged in a Teflon lined Parr reactor and placed in a tumbling oven at 150 °C and allowed to react for 18 days. Borosilicate BEA (sample 6) Borosilicate BEA was prepared by combining 5.62 g of TEAOH (Alfa Aesar, 35 wt %) with 3.70 g of distilled water and 0.074 g of boric acid and stirred until a clear solution was obtained. Then 5.00 g of tetraethylorthosilicate (Aldrich) was added with stirring. Final molar ratios were: 1SiO2:0.04H3BO3:0.55TEAOH:15H2O. Seeds of pure-silica zeolite BEA were added and the solution was charged in a Teflon lined Parr reactor and placed in a tumbling oven at 150 °C and allowed to react for 8 days. Pure-silica BEA (sample 7) Pure-silica BEA was prepared in fluoride media by dissolving 3.06 g of tetraethylammonium fluoride dihydrate (Acros Organics) in ~ 8 g of water and then adding 5.00 g of tetraethylorthosilicate (Aldrich). The mixture was stirred at room temperature, covered, overnight. The lid was then removed and ethanol and water were allowed to evaporate until the correct final mass was reached. Final molar ratios were: 1SiO2:0.55TEAF:6H2O. The solid was charged in a Teflon lined Parr reactor and placed in an oven at 150°C and allowed to react for 7 days. Titanoaluminosilicate BEA (sample 8) Titanoaluminosilicate BEA was prepared by combining 4.5 g of TEAOH (Alfa Aesar, 35 wt %) with 3.20 g of distilled water and 0.43 g of titanium(IV)butoxide (Aldrich) and stirred vigorously for 1 h. Then 1.50 g of Cabosil M-5 was added and the mixture was stirred for 1 h. Separately, 0.08 g of aluminum nitrate nonahydrate (Aldrich) was dissolved in 1.42 g of TEAOH (Alfa Aesar, 35 %). The solutions were combined and an additional 0.75 g of water was used to rinse the jar of the aluminum solution. The combined solutions were stirred for 1 h, then the solution was charged in a Teflon lined Parr reactor and placed in a tumbling oven at 140 °C and allowed to react for 5 days.

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Titanosilicate BEA (sample 9) Titanosilicate BEA was prepared in fluoride media by dissolving 1.22 g of tetraethylammonium fluoride dihydrate (Acros Organics) in ~3 g of water and then adding 2.00 g of tetraethylorthosilicate and 0.033 g of titanium(IV) butoxide (Aldrich). The mixture was stirred at room temperature, covered, overnight. The lid was then removed and ethanol and water were allowed to evaporate until the final mass of 2.67 g was reached. Final molar ratios were: 1SiO2:0.01Ti:0.55TEAF:5H2O. The solid was charged in a Teflon lined Parr reactor and placed in an oven at 150 °C and allowed to react for 22 days. Zincosilicate BEA (sample 10) Zincosilicate BEA (CIT-6) was synthesized according to the method of references [3,4]. In a typical synthesis 3.64 g of TEAOH (Alfa Aesar, 35 wt %) was combined with 0.11 g of zinc acetate dihydrate (Aldrich) and 0.028 g of LiOH and 3.60 g of water and stirred until the salts dissolved. Then 2.00 g of Ludox AS-40 was added and the mixture was stirred for 2 h. The solution was charged in a Teflon lined Parr reactor and placed in an oven at 140 °C and allowed to react for approximately 1 week. The synthesis was carefully monitored to avoid the formation of VPI-8. Aluminosilicate CHA (sample 11) Aluminosilicate CHA was prepared according to a modified version of the method reported in reference [5]. First 5.34 g of TEAOH (Alfa Aesar, 35 wt %) was combined with 0.51 g of 50% NaOH and 1.80 g of water and stirred until the NaOH dissolved. Then 2.00 g of CBV-720 zeolite Y (Zeolyst, lot #72000N00989) was added and stirred until a thick, homogeneous paste was obtained. Final molar ratios were calculated to be: 1SiO2:0.028Al2O3:0.4TEAOH:0.2NaOH:5H2O. The solution was charged in a Teflon lined Parr reactor and placed in an oven at 140 °C and allowed to react for 3 days. Trace unreacted FAU was found by PXRD. CoAPO-34 (sample 12) CoAPO-34 was prepared in a similar manner as ZnAPO-34 (sample 17) except that cobalt acetate tetrahydrate was substituted for zinc acetate dihydrate. The final solution was charged in a Teflon lined Parr reactor and placed in an oven at 120 °C and allowed to react for 24 h. MnAPO-34 (sample 13) MnAPO-34 was prepared in a similar manner as ZnAPO-34 (sample 17) except that manganese acetate tetrahydrate was substituted for zinc acetate dihydrate. The final solution was charged in a Teflon lined Parr reactor and placed in an oven at 120 °C and allowed to react for 24 h. SAPO-34 (TEAOH and dipropylamine, sample 14) SAPO-34 was prepared by dissolving 1.64 g of phosphoric acid (Aldrich, 85 wt %) in 0.66 g of distilled water. Separately 0.98 g of Catapal B alumina was slurried in 2.44 g of distilled water. The phosphoric acid solution was then added to the alumina solution and stirred for 1 h at room temperature. Then 0.64 g of Ludox AS-40 was added and stirred until homogeneous. Then 3.26 g of TEAOH (Alfa Aesar, 35 wt %) was added, followed by 1.15 g of dipropylamine (Aldrich) and the mixture was stirred for 2 h. The solution was then charged in a Teflon lined Parr reactor and placed in an oven at 200 °C and allowed to react for 24 h. SAPO-34 (TEAOH only, sample 15) SAPO-34 was synthesized by mixing 1.00 g of finely ground aluminum isopropoxide (Aldrich) with 3.33 g of water and 4.12 g of TEAOH (Alfa Aesar, 35 wt %) and stirring for 1 h. Then 0.31 g of tetraethylorthosilicate (Aldrich) was added with stirring. Finally 1.13 g of phosphoric acid (Aldrich, 85 wt %) was added with stirring. Once a homogeneous gel was obtained the solution was charged in a Teflon lined Parr reactor and placed in an oven at 200 °C and allowed to react for 40 h. ZnAPO-34 (sample 16) ZnAPO-34 was prepared according to the method described in reference [6]. First, 2.18 g of phosphoric acid (Aldrich, 85 wt %) was combined with 2.82 g of distilled water. Then 0.83 g of zinc acetate dihydrate (Aldrich) was added and stirred until dissolved. Next, 1.00 g of aluminum hydroxide hydrate (Aldrich) was added with stirring, and stirred for 10 min at room temperature. Finally, 4.25 g of TEAOH (Alfa Aesar, 35

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wt %) was added and stirred by hand until a homogeneous gel was obtained. Final molar ratios were: 0.7Al(OH)3:0.3Zn:1.5H3PO4:0.8TEAOH:26H2O. The mixture was sealed inside an acid digestion Savillex jar and allowed to react at 77 °C for 3 h. LTA (Na-UZM-9, sample 17) Aluminosilicate LTA (UZM-9) was synthesized following the method of reference [7]. In a typical synthesis, 0.74 g of finely powdered aluminum isopropoxide (Aldrich) was mixed with 12.12 g of 35 wt % TEAOH (Alfa Aesar) and stirred for 2 h. Then 6.00 g of tetraethylorthosilicate (Aldrich) was added and the mixture was stirred covered overnight. The mixture was uncovered, and ethanol was allowed to evaporate along with some water. Finally, a solution of 0.20 g of TMACl and 0.11 g of NaCl in water was added to the mixture to achieve a final mass of 21.93 g, which was stirred until a homogeneous solution was obtained. The solution was charged in a Teflon lined Parr reactor and placed in a static oven at 95 °C and allowed to react for 9 days. Aluminosilicate MFI (sample 18) Aluminosilicate MFI was prepared by combining 1.42 g of TEAOH (Alfa Aesar, 35 wt %) with 0.27 g of NaOH and 3.44 g of water. Next 0.032 of alumina (Condea Plural SB) was added and stirred for 1 h. Finally, 1.00 g of Cabosil M-5 was added and stirred by hand until a homogeneous gel was obtained. Final molar ratios were: 1SiO2:0.014Al2O3:0.2TEAOH:0.2NaOH:15H2O. The solution was charged in a Teflon lined Parr reactor and placed in an oven at 140 °C time, with time intervals shown in Figures 1 and S3. Mordenite (sample 19) Mordenite (MOR) was synthesized by combining 2.14 g of TEAOH (Alfa Aesar, 35 wt %) with 0.15 g of NaOH and stirred until the NaOH dissolved. Then 1.00 g of CBV-720 zeolite Y (Zeolyst, lot #72000N00989t) was added and stirred until a thick paste was added. The solution was charged in a Teflon lined Parr reactor and placed in an oven at 160 °C and allowed to react for 4 days. UFI (UZM-5, sample 20) Aluminosilicate UFI (UZM-5) was synthesized in the same manner as LTA (UZM-9) except that the solution was charged in a Teflon lined Parr reactor and placed in a rotating oven at 150 °C and allowed to react for 6 days.

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S2. Powder X-ray diffraction patterns Powder X-ray diffraction (PXRD) was used to confirm phase purity of all as-made samples. Diffraction patterns were collected using a Bruker D2 Phaser (2nd Gen) using a cobalt radiation source, Co kα = 1.789 Å. Powdered samples were rotated at 15 revolutions/min. All diffraction patterns were normalized to the highest peak.

20 19 18 17

Normalized intensity

16 15 14 13 12

11 3 2 1 5

10

15

20

25

30

35

40

Degrees 2Theta Figure S1. PXRD patterns of samples 1-3, 11-20 for the as-made materials. All diffraction patterns have been normalized relative to the most intense peak. Only as-made materials were considered in this study, and it is well known that relative peak intensities may differ significantly from calcined materials. Note that the samples were measured using a cobalt radiation source, Co kα = 1.789 Å.

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10

9

Normalized intensity

8

7

6

5

4 5

10

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25

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35

40

Degrees 2Theta Figure S2. PXRD patterns of BEA, samples 4-10, for the as-made materials. All diffraction patterns have been normalized relative to the most intense peak. Only as-made materials were considered in this study, and it is well known that relative peak intensities may differ significantly from calcined materials. Note that the samples were measured using a cobalt radiation source, Co kα = 1.789 Å.

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Normalized intensity

96 h

72 h

48 h

24 h

5

10

15

20

25

30

35

40

Degrees 2Theta Figure S3. PXRD patterns of MFI as a function of synthesis time of the recovered, solid product, with the measured conformer distributions given in Figure 1d. Note that the samples were measured using a cobalt radiation source, Co kα = 1.789 Å, and diffraction patterns are normalized to the most intense peak.

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S3. Raman data collection and analysis The Raman spectra of TEAOH (35 wt %, Alfa Aesar) at both room temperature and elevated temperatures were measured using a 532 nm laser with a RamanRxn1 Analyzer (Kaiser Optical Systems, Inc., model RXN1-532). To prevent any change in the TEAOH concentration due to evaporation, the liquid was contained in an Ace pressure tube, which was heated in an aluminum block. At each measurement temperature, the exposure time was 30 s and was averaged over 5 accumulations. The Raman spectra of all solid samples were acquired using a Leica DMLP Raman microscope using a RamanRxn1 Analyzer (Kaiser Optical Systems, Inc., model RXN1-785) with a 785 nm laser. For each sample, the exposure time was 30 s and was averaged over at least 5 accumulations. The data were recorded using the HoloGRAM software (version 4.0, Kaiser Optical Systems, Inc.) and analysis of the Raman spectra was conducted using the GRAMS/AI Spectroscopy Software (version 7.0). The Raman spectra of TEA+ as solid salts, as a solution and occluded in various MMs has been well established in a number of previous reports.[6,8,9] Based on the precedent established in these works, the integrated intensities of the bands at ~662 cm-1 and ~672 cm-1 give a quantitative evaluation of the amount of TEA+ present in the tg.tg or tt.tt conformer, respectively (small changes in the shifts are reported depending on the local environment of TEA+). The GRAMS/AI software was used to perform a multi-point baseline correction, and then the peaks were deconvoluted using the built-in Gaussian fitting routine in order to find the integrated peak intensities as well as goodness of fit (R2 values) for the deconvolutions. Representative Raman spectra for each framework are given in Figure 1a and complete results are in Figure S4. An example of data fitting is shown in Figure 1b, and examples of Gaussian fits for TEAOH, BEA, MFI and CHA (SAPO-34) are in Figure S5. In this work, the distributions of all conformers are given as percent tg.tg, as the use of conformer ratios becomes problematic with systems that contain only a single conformer.

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tg.tg

tg.tg

tt.tt

tt.tt 9

20

8

19

7 18 6 17

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Raman intensity (a.u.)

Raman intensity (a.u.)

5

4

3

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1

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600

650

700

Raman shift (cm‐1)

TEAF

11

TEAOH

10

TEABr 750

600

650

700

750

Raman shift (cm‐1)

Figure S4. Raman spectra of TEA+ salts and samples 1-20 after performing a multipoint baseline correction. Spectra were collected using a 532 nm laser and a RamanRxn1 Analyzer (Kaiser Optical Systems, Inc., model RXN1-532) for TEAOH and a Leica DMLP Raman microscope using a RamanRxn1 Analyzer (Kaiser Optical Systems, Inc., model RXN1-785) with a 785 nm laser for TEABr, TEAF and samples 1-20. The positions of the peaks corresponding to the tt.tt and tg.tg conformers of TEA+ are indicated.

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Raman intensity (a.u.)

CHA (SAPO‐34)

MFI

BEA

TEAOH 600

650 700 Raman shift (cm‐1)

750

Figure S5. Examples of Gaussian curve fitting for Raman spectra of TEAOH (35% in water at room temperature), BEA (sample 6), MFI (sample 18) and SAPO-34 (sample 14). In each spectra the collected data is shown in black after a multipoint baseline correction was performed, and the Guassian fit is in gray. All spectra have been normalized to the highest peak . The TEAOH spectrum was collected using a 532 nm laser and a RamanRxn1 Analyzer (Kaiser Optical Systems, Inc., model RXN1-532), the spectra for the other samples was collected using a Leica DMLP Raman microscope using a RamanRxn1 Analyzer (Kaiser Optical Systems, Inc., model RXN1-785) with a 785 nm laser.

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S4. Occupancy determination The organic content of MMs was determined using thermogravimetric analysis (TGA) and considering all mass loss over 250 °C as organic. TGA analysis was conducted using a PerkinElmer Pyris 1 instrument with a ramp rate of 10°C/min from room temperature to 800°C in an air atmosphere. The OSDA content (weight percent) of the analyzed materials and calculated occupancies can be found in Table S1 and the weight loss versus temperature traces are shown in Figure S8. In both LTA and UFI, the TGA analysis was not considered as the presence of a second OSDA complicates the analysis, so literature reports were used instead.[10]

Table S2. Organic content of selected materials determined using TGA analysis. Ramp rate of 10 C/min, from room temperature to 800 C in an air atmosphere. Organic weight loss was calculated considering all mass loss above 250 °C. Number of TEA+ per unit cell was calculated using the unit cell from the IZA website and accounting for the composition of the synthesized material. Framework AFI AEI BEA CHA LTA MFI MOR UFI

Sample 1 2 4 7 11 13 17 18 19 20

Organic weight loss (%) 11 10 17 18 13 14 -10 12 --

+

TEA /u. c. (cal.) 1.2 2.2 6.1 6.3 2.7 3.1 [10] 2 [11] 4.9 (Ideally 4) 3.0 [10] 4

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S5. Molecular modelling results One of us has recently described a method to computationally predict OSDAs likely to lead to the synthesis of targeted MM frameworks.[12,13] This approach enabled the prediction and evaluation of several new OSDAs for novel MM synthesis procedures.[14–18] Here, we use this method to calculate the stabilization energy between TEA+ in the tt.tt or tg.tg conformer and the target framework. The stabilization energy is defined as the difference in energy between n of these OSDAs occluded per unit cell of the framework and the energy of n isolated OSDAs and the empty framework. The DREIDING interatomic potential was used in the molecular dynamics program GULP to calculate these energies.[19–23] The framework properties were taken from the IZA website and all frameworks were treated as neutral puresilica frameworks, thus electrostatic interactions are not included in the model. OSDAs were fixed in their specified conformations and allowed to settle to their most energetically favorable position. The reported energy values are taken as the average energy calculated from the last 5 ps of a 30 ps molecular dynamics calculation at 343 K. It was found that during the 30 ps of simulation at 343 K, the tt.tt and tg.tg conformers did not interconvert. A more negative energy means that the structure is more stabilized by the OSDA. Complete results are given in Table S3. One of the key parameters of the model is the occupancy of the frameworks. This was experimentally examined using thermogravimetric analysis (TGA), as well as from previous literature reports,[10,11] and the results can be found in Table S2. In some cases, the occupancy is simple to consider, such as AEI or CHA, where there should be one TEA+ molecule per large cage. However, in other materials this determination is not as straightforward, as it is possible that not all the frameworks are optimally filled with TEA+. We have attempted to use the occupancy most in line with literature, TGA analysis and stabilization energy in terms of the framework (kJ/mol Si). The stabilization energy values are reported in Table S3, and the stabilization energies calculated for all occupancies considered can be found in the Supporting Information, Table S2. All graphics of the frameworks and occluded molecules were created sing Avogadro: an open-source molecular builder and visualization tool. Version 1.2.0, .[24]

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Table S3. Stabilization energy results from molecular modelling based on the ideal unit cell from the IZA website.[1] Stabilization energies are calculated based on the energy difference between the empty unit cell and isolated OSDA, and the unit cell with the OSDA loaded inside. OSDAs were fixed in their specified conformations and allowed to settle to their most energetically favorable position. It was found that during the 30 ps of simulation at 343 K, the tt.tt and tg.tg conformers did not interconvert. A more negative energy means that the structure is more stabilized by the OSDA. Stabilization energies are presented in terms of the framework (kJ/mol Si) as well as the TEA+ (kJ/mol TEA+). tg.tg conformer stabilization tt.tt conformer stabilization ∆Etg.tg-tt.tt Simulation occupancy + + energy (kJ/mol Si) energy (kJ/mol Si) (kJ/mol TEA ) (TEA /unit cell) 4 -12.78 -13.05 3.2 AEI 8 NF NF NF AFI 1 -5.37 -5.37 0.0 4 -7.87 -7.98 1.8 6 -8.91 -9.73 8.7 BEA 8 -9.40 -10.03 5.1 10 NF NF NF 3 -12.7 -12.98 3.4 CHA 6 NF NF NF 2 -6.81 -8.25 17.3 LTA 4 NF NF NF 3 -5.01 -4.48 -17.0 4 -6.76 -6.35 -9.8 MFI 5 -5.09 -5.13 0.8 6 -2.22 -3.22 16.0 2 -5.41 -5.50 2.1 3 NF NF NF MOR 4 NF NF NF 2 -3.4 -3.64 7.7 3 -5.01 -5.03 0.4 4 -1.24 -1.36 1.9 UFI 6 NF NF NF NF=no fit, in this case the number of specified molecules did not fit inside the unit cell so no stabilization energy was reported from the simulation. Framework

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S6. Supporting information references [1]

C. Baerlocher, L. B. McCusker, “Database structure.org/databases/>. Accessed July 6, 2016.

of

Zeolite

Structures,