Controlling the Isolation and Pairing of Aluminum in Chabazite Zeolites Using Mixtures of Organic and Inorganic Structure-Directing Agents

Transcription

1 Controlling the Isolation and Pairing of Aluminum in Chabazite Zeolites Using Mixtures of Organic and Inorganic Structure-Directing Agents John R. Di Iorio, Rajamani Gounder * SUPPORTING INFORMATION Section S.1. Synthesis of SSZ-13(5) Zeolites The synthesis recipe for SSZ-13(5) was adapted from the procedure described by Fickel et al. 1, which is a modified version of the original synthesis reported by Zones 2. A synthesis molar ratio of 1 SiO2/ Al2O3/ TMAdaOH/ Na2O/ 12.1 H2O was used. A typical synthesis involved adding 3.14 g of a 1M NaOH solution (3.3 wt% NaOH, Alfa Aesar) to 4.82 g of deionized water (18.2 MΩ) in a PFA jar and stirring the solution for 15 minutes at ambient conditions g of sodium silicate (10.6 wt % Na2O, 25.6 wt% SiO2; Sigma Aldrich) was added and homogenized for 15 minutes under ambient conditions g of NH4-Y zeolite (Zeolyst CBV300, Si/Al = 2.6) were added and the mixture was homogenized for 30 minutes under ambient conditions g of a 1M TMAdaOH solution (25 wt% Sachem) was then added to the mixture and stirred for 30 minutes under ambient conditions. All synthesis reagents were used without further purification. The synthesis solution was then transferred to a 45 ml Teflon-lined stainless steel autoclave (Parr Instruments) and placed in a forced convection oven (Yamato DKN-402C) at 413 K and rotated at 60 RPM for 6 days.

2 Section S.2. Synthesis of SSZ-13(15, 1) and SSZ-13(25, 1) Zeolites The synthesis recipe for SSZ-13(15, 1) and SSZ(25, 1) zeolites was adapted from the procedure described by Deka et al. 3, which is a modified version of the original synthesis reported by Zones 4. A synthesis molar ratio of 1 SiO2/ X Al2O3/ 0.25 TMAdaOH/ 0.25 Na2O/ 44 H2O was used, where X = or for Si/Al = 15 and 25, respectively. A typical synthesis involved adding g of a 1M aqueous TMAdaOH solution (25 wt%, Sachem) to g of deionized H2O (18.2 MΩ) to a perfluoroalkoxy alkane (PFA) jar and stirring the solution under ambient conditions for 15 minutes. Next, or g (for Si/Al = 15 or 25) of Al(OH)3 (98 wt%, SPI Pharma) and g of a 5M sodium hydroxide solution (NaOH: 16.7 wt% NaOH in deionized water; NaOH pellets 98 wt%, Alfa Aesar) was added to the aqueous TMAdaOH solution and the mixture was stirred under ambient conditions for 15 minutes to homogenize the contents. Finally, g of colloidal silica (Ludox HS40, 40 wt%, Sigma Aldrich) was added to the mixture and stirred for 2 h under ambient conditions. All synthesis reagents were used without further purification. The synthesis solution was then transferred to a 45 ml Teflon-lined stainless steel autoclave (Parr Instruments) and placed in a forced convection oven (Yamato DKN-402C) at 433 K and rotated at 40 RPM for 6 days.

3 Section S.3. Synthesis of Pure-silica Chabazite (Si-CHA). Pure SiO2 chabazite was synthesized following the procedure reported by Díaz-Cabañas et al. 5 using a synthesis solution molar ratio of 1 SiO2/ 0.5 TMAdaOH/ 0.5 HF/ 3 H2O. In a typical synthesis 13 g of tetraethylorthosilicate (TEOS; 98 wt%, Sigma Aldrich) were added to a PFA jar containing g of a 1M TMAdaOH solution (25 wt%, Sachem) and stirred under ambient conditions. Ethanol, formed from the hydrolysis of TEOS, and excess water were then evaporated to reach the target molar ratios by placing the TEOS and TMAdaOH solution under flowing air while stirring at ambient conditions. During the evaporation process, once the solution mass came within 5 g of the desired final mass, an additional 10 g of water were added to ensure complete hydrolysis of TEOS and to allow additional time to completely evaporate the ethanol. This rehydration process was performed twice during the evaporation step. As the synthesis solution neared the desired H2O/SiO2 ratio of 3, the solution began to solidify and had to be stirred by hand for three additional hours in order to complete the water evaporation process. Once the synthesis solution had reached the desired H2O/SiO2 ratio, g of concentrated hydrofluoric acid (HF; 48 wt%, Sigma Aldrich) was added dropwise to the synthesis and homogenized for 15 minutes. Caution: when working with hydrofluoric acid use appropriate personal protective equipment, ventilation, and other safety measures. Upon addition of HF to the solidified synthesis solution, the solution immediately became a thick paste that became more solution-like under stirring. The solution was then left to sit uncovered under ambient conditions for 30 minutes to allow for any residual HF to evaporate before transferring the solution to a 45 ml Teflon-lined stainless steel autoclave (Parr Instruments) and heated in a forced convection oven (Yamato DKN-402C) at 423 K under rotation at 40 RPM for 40 h. All synthesis reagents were used without further purification.

4 Section S.4. Synthesis and Characterization of SSZ-13 Zeolites without Na + For the synthesis of Na + -free SSZ-13 zeolites in hydroxide media, a molar ratio of 1 SiO2/ X Al2O3/ 0.5 TMAdaOH/ 44 H2O was used, where X = 0.20, 0.133, 0.10, 0.08, 0.067, or for Si/Al = 10, 15, 20, 25, 30 and 60, respectively. In a typical synthesis g of a 1M TMAdaOH solution (25 wt% Sachem) were added to g of deionized water (18.2 MΩ) in a PFA jar and stirred for 15 minutes under ambient conditions. Next 0.260, 0.173, 0.130, 0.104, 0.087, or g (Si/Al = 10, 15, 20, 25, 30, and 60, respectively) of Al(OH)3 (98 wt%, SPI Pharma) were added to the TMAda + solution and the mixture was homogenized for 15 minutes under ambient conditions. Then 5 g of colloidal silica (Ludox HS40, 40 wt%, Sigma Aldrich) were added to the mixture and the contents were stirred for 2 h at ambient conditions until a homogeneous solution was obtained. All synthesis reagents were used without further purification. The synthesis solution was then transferred to a 45 ml Teflon-lined stainless steel autoclave (Parr Instruments) and heated in a forced convection oven (Yamato DKN-402C) at 433 K and rotated at 40 RPM for 6 days.

5 Section S.5. Synthesis of SSZ-13 Zeolites at Constant Na + /TMAda + and Varied Si/Al Ratio SSZ-13 zeolites were synthesized at a constant Na + /TMAda + ratio of 2/3 and with gel Si/Al ratios ranging from in hydroxide media. A synthesis gel molar ratio of 1 SiO2/ X Al2O3/ 0.3 TMAdaOH/ 0.2 NaOH/ 44 H2O was used, where X = 0.40, 0.20, 0.13, 0.08, 0.04, 0.02, and 0.01, for Si/Al ratios of 5, 10, 15, 25, 50, 100, and 200, respectively. In a typical synthesis g of a 1M TMAdaOH solution (25 wt% Sachem) were added to g of deionized water (18.2 MΩ) in a PFA jar and stirred for 15 minutes under ambient conditions. Next 0.519, 0.260, 0.173, 0.104, 0.052, 0.026, or g (Si/Al = 5, 10, 15, 25, 50, 100, and 200, respectively) of Al(OH)3 (98 wt%, SPI Pharma) were added to the TMAda + solution and the mixture was homogenized for 15 minutes under ambient conditions. Then 5 g of colloidal silica (Ludox HS40, 40 wt%, Sigma Aldrich) were added to the mixture and the contents were stirred for 2 h at ambient conditions. All synthesis reagents were used without further purification. The synthesis gel was then transferred to a 45 ml Teflon-lined stainless steel autoclave (Parr Instruments) and heated in a forced convection oven (Yamato DKN-402C) at 433 K and rotated at 40 RPM for 6 days.

6 Section S.6. Synthesis of SSZ-13 Zeolites at Si/Al = 15 and 25 at Constant (Na + +TMAda + )/Al with Varying Na + /TMAda + Ratio The synthesis of SSZ-13 zeolites in synthesis solutions with varying charge density, but with constant total charge, was performed at a Si/Al = 15 and 25 at a constant ratio of (Na + +TMAda + )/Al = 7.5 while letting the Na + /TMAda + ratio vary from 0 to 3. A synthesis solution molar ratio of 1 SiO2/ Y Al2O3/ X TMAdaOH/ (0.5 X) NaOH/ 44 H2O was used, where X = 0.50, 0.40, 0.33, 0.30, 0.25, 0.20, 0.17, 0.14, and 0.125, for Na + /TMAda + ratios of 0, 1/4, 1/2, 2/3, 1, 3/2, 2, 2.5, and 3, respectively, and Y = and 0.08 for Si/Al = 15 and 25, respectively. In a typical synthesis , , 9.381, 8.443, 7.036, 5.628, 4.690, 4.020, or g (Na + /TMAda + = 0, 1/4, 1/2, 2/3, 1, 3/2, 2, 2.5, and 3, respectively) of a 1M TMAdaOH solution (25 wt% Sachem) were added to , , , , , , , , or g (Na + /TMAda + = 0, 1/4, 1/2, 2/3, 1, 3/2, 2, 2.5, and 3, respectively) of deionized water (18.2 MΩ) in a PFA jar and stirred for 15 minutes under ambient conditions. Next or g (Si/Al = 15 or 25, respectively) of Al(OH)3 (98 wt%, SPI Pharma) were added to the TMAda solution and then 0, 0.815, 1.359, 1.630, 2.038, 2.446, 2.717, 2.911, or g (Na + /TMAda + = 0, 1/4, 1/2, 2/3, 1, 3/2, 2, 2.5, and 3, respectively) of a 5M sodium hydroxide solution (NaOH: 16.7 wt% NaOH in deionized water; NaOH 98 wt% Alfa Aesar) were added and the mixture was homogenized for 15 minutes under ambient conditions. Then 5 g of colloidal silica (Ludox HS40, 40 wt%, Sigma Aldrich) were added to the mixture and the contents were stirred for 2 h at ambient conditions. All synthesis reagents were used without further purification. The synthesis solution was then transferred to a 45 ml Teflon-lined stainless steel autoclave (Parr Instruments) and heated in a forced convection oven (Yamato DKN-402C) at 433 K and rotated at 40 RPM for 6 days.

7 Section S.7. Synthesis of SSZ-13 Zeolites at Si/Al = 15 with Varying (Na + +TMAda + )/Al and Varying Na + /TMAda + Synthesis of SSZ-13 zeolites with varying total charge and charge density were performed at a solution Si/Al ratio of 15 while varying the Na + /TMAda + (charge density) from 0 to 5.6 and (Na + +TMAda + )/Al (total charge) from 5.4 to 7.1. A synthesis solution molar ratio of 1 SiO2/ Al2O3/ X TMAdaOH/ (0.5 X) NaOH/ 44 H2O was used, where X = 0.50, 0.37, 0.29, 0.26, 0.21, 0.16, 0.11, 0.097, and 0.076, for Na + /TMAda + ratios of 0, 0.35, 0.70, 0.93, 1.38, 2.09, 3.45, 4.16, and 5.55, respectively. In a typical synthesis 8.443, 6.254, 4.966, 4.374, 3.547, 2.732, 1.897, 1.636, or g (Na + /TMAda + = 0, 0.35, 0.70, 0.93, 1.38, 2.09, 3.45, 4.16, and 5.55, respectively) of a 1M TMAdaOH solution (25 wt% Sachem) were added to 7.704, 8.816, 9.469, 9.770, , , , , or g (Na + /TMAda + = 0, 0.35, 0.70, 0.93, 1.38, 2.09, 3.45, 4.16, and 5.55, respectively) of deionized water (18.2 MΩ) in a PFA jar and stirred for 15 minutes under ambient conditions. Next g of Al(OH)3 (98 wt%, SPI Pharma) were added to the TMAda solution and then 0, 0.634, 1.007, 1.178, 1.418, 1.654, 1.896, 1.972, or g (Na + /TMAda + = 0, 0.35, 0.70, 0.93, 1.38, 2.09, 3.45, 4.16, and 5.55, respectively) of a 5M sodium hydroxide solution (NaOH: 16.7 wt% NaOH in deionized water; NaOH 98 wt% Alfa Aesar) were added and the mixture was homogenized for 15 minutes under ambient conditions. Then 3 g of colloidal silica (Ludox HS40, 40 wt%, Sigma Aldrich) were added to the mixture and the contents were stirred for 2 h at ambient conditions. All synthesis reagents were used without further purification. The synthesis solution was then transferred to a 23 ml Teflon-lined stainless steel autoclave (Parr Instruments) and heated in a forced convection oven (Yamato DKN-402C) at 433 K and rotated at 40 RPM for 6 days.

8 Normlized Intensity Section S.8. Powder X-Ray Diffraction Patterns of SSZ-13 Zeolites. Figure S.1. Powder X-ray diffraction patterns for a) SSZ-13(5), b) SSZ-13(15, 1) and, c) SSZ- 13(25, 1). 3 c) 2 b) 1 a) θ

9 Normalized Intensity Figure S.2. Powder X-ray diffraction patterns for a) SSZ-13(10, 0), b) SSZ-13(15, 0), c) SSZ- 13(20, 0), d) SSZ-13(25, 0), e) SSZ-13(30, 0), f) SSZ-13(60, 0), and g) Si-CHA samples synthesized in the absence of Na + at varying Si/Al ratios 7 g) 6 f) 5 e) 4 d) 3 c) 2 b) 1 a) θ

10 Normalized Intensity Figure S.3. Powder X-ray diffraction patterns for six independent syntheses of SSZ-13(15, 0) θ

11 Normalized Intensity Figure S.4. Powder X-ray diffraction patterns for a) SSZ-13(5, 0.67), b) SSZ-13(10, 0.67), c) SSZ-13(15, 0.67), d) SSZ-13(25, 0.67), e) SSZ-13(50, 0.67), f) SSZ-13(100, 0.67), and g) SSZ-13(200, 0.67) samples synthesized with constant Na + /TMAda + = 0.67 and varying Si/Al ratios 7 g) 6 f) 5 e) 4 d) 3 c) 2 b) 1 a) θ

12 Normalized Intensity Figure S.5. Powder X-ray diffraction patterns for a) SSZ-13(15, 0), b) SSZ-13(15, 0.25), c) SSZ- 13(15, 0.50), d) SSZ-13(15, 0.67), e) SSZ-13(15, 1.00), f) SSZ-13(15, 1.50), g) SSZ-13(15, 2.00), h) MOR(15, 2.50), and i) MOR(15, 3.00) samples synthesized with constant solution Si/Al = 15, (Na + +TMAda + )/Al (total charge), and varying Na + /TMAda + ratios (charge density) 9 i) 8 h) 7 g) 6 f) 5 e) 4 d) 3 c) 2 b) 1 a) θ

13 Normalized Intensity Figure S.6. Powder X-ray diffraction patterns for a) SSZ-13(25, 0), b) SSZ-13(25, 0.50), c) SSZ- 13(25, 0.67), d) SSZ-13(25, 1.00), and e) SSZ-13(25, 2.00) samples synthesized with constant solution Si/Al = 25 and (Na + +TMAda + )/Al (total charge), and varying Na + /TMAda + ratios (charge density). 5 e) 4 d) 3 c) 2 b) 1 a) θ

14 Normalized Intensity Figure S.7. Powder X-ray diffraction patterns for a) SSZ-13(15, 0), b) SSZ-13(15, 0.35), c) SSZ- 13(15, 0.70), d) SSZ-13(15, 0.93), e) SSZ-13(15, 1.38), f) SSZ-13(15, 2.09), g) MOR(15, 3.45), h) MOR(15, 4.16, and i) MOR(15, 5.55) samples synthesized with constant solution Si/Al = 15 and varying (Na + +TMAda + )/Al (total charge) and Na + /TMAda + ratios (charge density). 9 i) 8 h) 7 g) 6 f) 5 e) 4 d) 3 c) 2 b) 1 a) θ

15 Quantity Adsorbed (cm³/g STP) Section S.9. Ar Adsorption Isotherms of Catalyst Samples Figure S.8. Ar adsorption isotherms at measured at 87 K on a) SSZ-13(5), b) SSZ-13(15, 1), and c) SSZ-13(25, 1). 600 c) b) a) Relative Pressure (P/Po)

16 Quantity Adsorbed (cm³/g STP) Figure S.9. Ar adsorption isotherms at measured at 87 K on a) SSZ-13(15, 0), b) SSZ-13(20, 0), c) SSZ-13(25, 0), d) SSZ-13(30, 0), and e) Si-CHA. 900 e) d) c) 400 b) a) Relative Pressure (P/Po)

17 Quantity Adsorbed (cm³/g STP) Figure S.10. Ar adsorption isotherms at measured at 87 K on a) H-SSZ-13(15, 0), b) H-SSZ- 13(15, 0.25), c) H-SSZ-13(15, 0.50), d) H-SSZ-13(15, 0.67), e) H-SSZ-13(15, 1.00), f) H-SSZ- 13(15, 1.50), and g) H-SSZ-13(15, 2.00) g) 1100 f) e) d) c) b) a) Relative Pressure (P/Po)

18 Quantity Adsorbed (cm³/g STP) Figure S.11. Ar adsorption isotherms at measured at 87 K on a) H-SSZ-13(25, 0), b) H-SSZ- 13(25, 0.25), c) H-SSZ-13(25, 0.50), d) H-SSZ-13(25, 1.00), and e) H-SSZ-13(25, 2.00). 900 e) d) c) 400 b) a) Relative Pressure (P/Po)

19 Section S.10. Thermogravimetric Analysis (TGA) to Measure the Organic Content of As- Synthesized Zeolites Table S.1. Calculation of the number of TMAda + per cage for SSZ-13(X,0) and SSZ-13(15,X) with maintaining a constant (Na + +TMAda + )/Al ratio. Sample ID Si/Al TMAda + /Al TMAda + /Cage SSZ-13(15, 0) SSZ-13(20, 0) SSZ-13(25, 0) SSZ-13(30, 0) SSZ-13(15, 0.25) SSZ-13(15, 0.50) SSZ-13(15, 0.67) SSZ-13(15, 1.00) SSZ-13(15, 1.50) SSZ-13(15, 2.00)

20 Section S Al Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) The 27 Al MAS NMR spectra for SSZ-13 samples synthesized without Na + are shown in Figure S.12 and those synthesized at constant Si/Al = 15, (Na + +TMAda + )/Al, and varying Na + /TMAda + are shown in Figure S.13. Tetrahedrally-coordinated Al atoms were characterized by a resonance centered around 60 ppm. There was no shoulder present at about 48 ppm, representative of pentacoordinated Al, and a minimal (0-5%) amount of octahedral Al present at about 0 ppm 6-8. Spectra were recorded with different sample masses so a quantitative comparison of the line intensities between different samples is not possible because the intensity is a function of the total Al content in the rotor, therefore the intensity of each H-SSZ-13 spectra was normalized by the maximum intensity in each spectrum to allow for qualitative comparison of the different H- SSZ-13 samples.

21 Intensity / a.u. Figure S Al MAS NMR spectra for a) H-SSZ-13(15, 0), b) H-SSZ-13(20, 0), c) H-SSZ- 13(25, 0), and d) H-SSZ-13(30, 0) d) c) b) a) Chemical Shift / ppm

22 Figure S Al MAS NMR spectra for a) H-SSZ-13(15, 0), b) H-SSZ-13(15, 0.25), c) H-SSZ- 13(15, 0.50), d) H-SSZ-13(15, 0.67), e) H-SSZ-13(15, 1.00), f) H-SSZ-13(15, 1.50), and g) H- SSZ-13(15, 2.00) g) f) e) Intensity / a.u. d) c) b) a) Chemical Shift / ppm

23 Section S.12. Copper Cation Speciation in SSZ-13 Zeolites. Table S.2. Cu/Al, saturation Co/Al, predicted M 2+ /Al, and residual H + /Al on H-SSZ-13(5), H- SSZ-13(15, 1), and H-SSZ-13(25, 1). Sample Si/Al Micropore Volume (cm 3 g cat -1 ) H + /Al a Co/Al H + /Al b Predicted M 2+ /Al SSZ-13(5) SSZ-13(15, 1) SSZ-13(25, 1) a H + /Al measured on the parent H-SSZ-13 sample b H + /Al measured after saturation with Co 2+ c H + /Al measured after ion-exchange with Cu 2+ Cu/Al H + /Al c

24 Figure S.14. Number of residual H + sites, normalized to the parent H + /Al for each sample, after Cu 2+ exchange (circles) as a function of the Cu/Al ratio, after Co 2+ saturation (squares) on H-SSZ- 13(5) (black), H-SSZ-13(15, 1) (dark grey), and H-SSZ-13(25, 1) (grey). Dashed lines indicate predictions from statistical calculations of random Al distributions and the sequential exchange of Cu 2+ at ed Al sites (2 Al in 6-MR) followed by exchange of [CuOH] + at isolated Al sites H + /H + parent M 2+ /H + parent

25 Maximum M 2+ /Al f in d6r Section S.13. Statistical Estimates of Paired Aluminum in CHA Zeolites. Figure S.15: Statistical calculations for the random distribution of Al in CHA at varying Si/Al ratios, obeying Lowenstein s Rule 9. The circles denote SSZ-13 materials synthesized at Si/Al = 5, 15, and 25 and correspond to theoretical M 2+ /Al = 0.22, 0.09, and 0.05, respectively Si/Al f

26 Section S.14. Derivation of Cobalt Ion-Exchange Isotherm In order to demonstrate complete saturation of H-SSZ-13 samples with Co 2+, an ionexchange isotherm was measured on both H-SSZ-13(15, 0) and H-SSZ-13(15, 1) using Co(NO3)2 molarities ranging from M-0.5 M and the procedure described previously in the main text. The Langmuirian ion-exchange isotherm was derived by first assuming that the total Al atoms on a given sample (Altot) are equal to the number of Al atoms that cannot exchange a cation (Alnon,exch) and the number of Al atoms that can be ion-exchanged (Alexch): = Al non,exch + Al exch (S.1) The number of Alexch atoms is equal to the sum of the number of isolated Al sites, which can exchange a monovalent cation ( iso ), and twice the number of ed Al sites, which can exchange a divalent cation ( ): Al exch = tot iso + 2Al (S.2) A mole balance on each of the tot iso and Al exchange: terms describes the types of cations they can H iso = Al + iso (S.3) tot Al H = Al +,H + Co + Al 2+ (S.4) H where Al + iso are isolated Al sites charge-balanced by a single H + H, Al +,H + are ed Al sites chargebalanced by two H + Co sites, and Al 2+ are ed Al sites charge-balanced by a Co 2+ ion. In this derivation, isolated Co 2+ cations are assumed to be the only Co species present and can only exchanged at a ed Al site, while H + are the only monovalent cations present and can exchange at both isolated and ed Al sites. Substituting Eq. (S.2)-(S.4) into Eq. (S.1) results in a site balance equation relating Altot to the number of Al sites occupied by different cations:

27 H = Al non,exch + Al + H iso + 2 (Al +,H + Co + Al 2+ ) (S.5) The exchange of aqueous Co 2+ ions (Co 2+ (aq) ) onto ed Al sites occupied by two protons H (Al +,H + ) to form aqueous H + (H + (aq) ) and ed Al sites occupied by Co 2+ Co (Al 2+ ) is given by the following equilibrium reaction: Co 2+ H (aq) + Al +,H + K + 2H (aq) Co + Al 2+ (S.6) where K is the equilibrium constant and is defined in terms of the following concentrations as: K = [H (aq) + ] 2 Co [Al 2+ ] H +,H + ] ( 1 C 0) [Co 2+ (aq) ][Al (S.7) where C 0 is the standard state reference concentration of 1 M. Dividing Eq. (S.5) by Altot yields a site balance equation expressed in terms of the fractional coverages (θ) for each species: 1 = Al non,exch H + θ + H iso + 2 (θ +,H + Co + θ 2+ ) (S.8) H where θ + H iso is the coverage of Al + H iso species, θ +,H + H is the coverage of Al +,H + Co species, and θ 2+ Co is the coverage of Al 2+ and each coverage term is defined as follows: H θ + iso = Al H + iso H θ +,H + = Al H +,H + θ Co 2+ = Al Co 2+ (S.9) (S.10) (S.11)

28 Dividing Eq. (S.1) by Altot also results in an expression for the fraction of Alexch ( Al exch ) in terms of the fraction of Alnon.exch ( Al non,exch ): 1 - Al non,exch = Al exch (S.12) Substituting Eq. (S.12) into Eq. (S.8) results in the following equation that describes the Al exch in terms of the fractional coverages of each species: Al exch H = θ + H iso + 2 (θ +,H + Co + θ 2+ ) (S.13) H where 2 (θ +,H + Co + θ 2+ ) is equal to the fraction of Al present ( Al ) The equilibrium constant, K (Eq. (S.7)), can be rewritten in terms of coverages to derive H an expression for θ +,H + : H θ +,H + = [H (aq) + ] 2 Co θ 2+ K[Co 2+ (aq) ] (S.14) Eq. (S.14) can then be substituted into Eq. (S.13) to obtain an expression in terms of quantities that can be measured experimentally: Al exch = θ iso H ( [H 2 + (aq) ] Co 2+ θ K[Co 2+ (aq) ] Co + θ 2+ ) (S.15) Co Eq. (S.15) can be rearranged to solve for θ 2+, which is a mathematical representation of the Co 2+ exchange isotherm: Co θ 2+ = ( 1 2 ) (Al exch H θ + Al iso ) ( K [Co (aq) 2+ ] [H (aq) tot 1 + K [Co 2+ ] [H (aq) (aq) + ] 2 + ] 2 ) (S.16)

29 where the term [Co 2+ (aq) ] [H (aq) represents the ratio of Co 2+ + (aq) and H (aq) in the exchange solution + ] 2 at equilibrium, and where the term ( 1 2 ) (Al exch represents the saturation limit of the Co 2+ exchange isotherm. H θ + iso ) is equal to Al from Eq. (S.13) and Co θ 2+ = Al ( K [Co (aq) 2+ ] [H (aq) 1 + K [Co 2+ ] [H (aq) (aq) + ] 2 + ] 2 ) (S.17) Eq. (S.17) can be regressed to the experimental data to estimate K and Al. The isotherms fit to the experimental data on both H-SSZ-13(15, 1) and H-SSZ-13(15, 0) are shown in Figure 1a of the main text. For H-SSZ-13(15, 1) the value of the equilibrium constant, K, was and the value of Al was 0.087, which is the predicted maximum number of sites capable of exchanging a divalent cation (e.g., Co 2+ ). For H-SSZ-13(15, 0), K was and Al was

30 Section S.15. UV-Vis Spectroscopy of Co-SSZ-13(15, 1) Figure S.16. Ambient UV-Vis spectra of Co-SSZ-13(15, 1) with Co/Al values of (faint grey trace), (light grey trace), (grey trace), 0.08 (dark grey trace), and (black trace) F(%R) / Kubelka-Munk Units (a.u.) Wavenumbers / cm -1

31 Section S.16. Sodium Cation Exchange Procedure and Derivation of Ion-Exchange Isotherm A Langmuirian isotherm model for Na + exchange was derived starting from Eq. (S.1), but using only a single adsorption site to describe the Al exch since a monovalent cation cannot distinguish between isolated and ed Al sites. Therefore, Al exch can be described by the sum of the total number of Al exchange sites with a H + and with a Na + present: Al exch = Al H+ + Al Na+ (S.18) The equilibrium reaction of aqueous Na + ions (Na + (aq) ) with proton-occupied Al exchange sites (Al H+ ) to form aqueous H + (H + (aq) ) and sodium-occupied Al sites (Al Na+ ) is given by: + Na (aq) + Al H+ K + H(aq) + Al Na+ (S.19) where K is the equilibrium constant defined in terms of concentrations as: K = [H (aq) + ][Al Na+ ] [Na + (aq) ][Al H+ ] (S.20) Substituting Eq. (S.18) into Eq. (S.1) and dividing by Altot provides an expression in terms of the fractional coverages (θ) of each species: 1 = Al non,exch + θ H+ + θ Na+ (S.21) where θ H+ is the coverage of Al H+ and θ Na+ is the coverage of Al Na+ defined as follows: θ H+ = AlH+ (S.22) θ Na+ = AlNa+ (S.23) Substituting Eq. (S.12) into Eq. (S.21) results in an equation that describes Al exch in terms of the fractional coverage of H + and Na + :

32 Al exch = θ H+ + θ Na+ (S.24) The equilibrium constant, K (Eq. (S.20)), can be rewritten in terms of coverages to obtain an explicit expression for θ H+ : θ H+ = [H (aq) + ]θ Na+ K[Na + (aq) ] (S.25) Eq. (S.25) can be substituted into Eq. (S.24) to obtain an expression in terms of quantities that can be measured experimentally: Al exch + ] ) K[Na + (aq) ] = θ Na+ (1 + [H (aq) (S.26) Eq. (S.26) can be rearranged to obtain an expression for θ Na+, which is the Na + exchange isotherm: θ Na+ = ( Al exch ) ( K [Na (aq) + ] [H + ] (aq) 1 + K [Na + ] [H + ) (aq) ] (aq) (S.27) The term [Na + (aq) ] [H + + (aq) ] represents the ratio of Na (aq) + and H (aq) ions in the exchange solution at equilibrium. Eq. (S.27) can be regressed to the experimental data to estimate K and Al exch. The isotherm fit to the experimental data is shown in Figure 1b of the main text. For H-SSZ-13(15, 0) the value of the equilibrium constant, K, was and the value of Al exch 13(15, 1), K was 0.14 and the value of Al exch was For H-SSZ- was 0.91, which is in agreement with the experimental results for the H + /Al determined from NH3 TPD (Table 2 in main text).

33 Section S.17. Characterization Data for SSZ-13(15) with Varying (Na + +TMAda + )/Al (Total Charge) and Varying Na + /TMAda + Ratios (Charge Density) Table S.3. Characterization for SSZ-13 samples synthesized at a constant Na + /TMAda + = 0.67 and varying Si/Al. Sample Si/Al Micropore Volume (cm 3 g -1 ) H + /Al Na + /Al TMAda + /Al (Na + +TMAda + )/Al Co/Al SSZ-13(10, 0.67) SSZ-13(15, 0.67) SSZ-13(25, 0.67) SSZ-13(50, 0.67) SSZ-13(100, 0.67)

34 Si/Al ratio of Solid Product Section S.18. Characterization Data for SSZ-13(15) with Varying (Na + +TMAda + )/Al (Total Charge) and Varying Na + /TMAda + Ratios (Charge Density) Table S.4. Characterization data for SSZ-13(15) and MOR samples synthesized with constant synthesis solution Si/Al and varying total solution charge and Na + /TMAda +. Sample Si/Al Micropore Volume (cm 3 g -1 ) H + /Al Na + /Al TMAda + /Al (Na + +TMAda + )/Al Co/Al SSZ-13(15, 0) SSZ-13(15, 0.35) SSZ-13(15, 0.70) SSZ-13(15, 0.93) SSZ-13(15, 1.38) SSZ-13(15, 2.09) MOR(15, 3.45) MOR(15, 4.16) MOR(15, 5.55) Figure S.17. Si/Al ratio as a function of Na + /TMAda + ratio for SSZ-13(15) samples synthesized with (squares) and without (circles) a constant (Na + +TMAda + )/Al ratio. The dashed line is a linear fit to the samples synthesized without constant (Na + +TMAda + )/Al (circles) Na + /TMAda + in Synthesis Solution

35 Co 2+ /Al Section S.19. Characterization Data for SSZ-13(25) with Constant (Na + +TMAda + )/Al (Total Charge) and Varying Na + /TMAda + Ratios (Charge Density) Table S.5. Characterization data for SSZ-13(25) samples synthesized with constant synthesis solution Si/Al and total solution charge and varying Na + /TMAda +. Sample Si/Al Micropore Volume (cm 3 g -1 ) H + /Al Na + /Al TMAda + /Al (Na + +TMAda + )/Al Co/Al SSZ-13(25, 0.25) SSZ-13(25, 0.50) SSZ-13(25, 1.00) SSZ-13(25, 2.00) Figure S.18. Fraction of ed Al atoms measured by titration with Co 2+ as a function of the synthesis solution charge density on SSZ-13(25) synthesized with constant total solution charge Na+/TMAda+ in Synthesis Solution

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