SUPPORTING INFORMATION

SUB-MICRON CU/SSZ-13: SYNTHESIS AND APPLICATION AS SELECTIVE

CATALYTIC REDUCTION (SCR) CATALYSTS

Sebastian Prodinger,a Miroslaw A. Derewinski,a,* Yilin Wang,a Nancy M. Washton,b János Szanyi,a
Eric. D. Walter,b Feng Gao,a,* Yong Wang,a,c and Charles H. F. Pedena

a)
Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352, United States
b)
Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA
99352, United States
c)
School of Chemical and Biological Engineering, Washington State University, Pullman, WA 99364 (USA)

KEYWORDS. selective catalytic reduction, Cu/SSZ-13, zeolite synthesis, particle size, hydrothermal aging.

Table of Content

X-ray diffraction

N2-physisorption

Particle size analysis

Thermogravimetric Analysis
27
Al MAS NMR Spectroscopy

Electron Paramagnetic Resonance (EPR) Data analysis

NH3-TPD Results

S1
X-ray diffraction

Figure S1. X-ray diffractograms of as-made and calcined Na/SSZ-13 synthesized under varying condi-
tions. Color-coding is reported in the legend.

Figure S2. X-ray diffractograms showing the effects of hydrothermal aging and copper ion-exchange on
the synthesized materials. Color-coding is reported in the legend.

S2
X-ray crystallite analysis

Table S1. Crystallite size analysis results of the X-ray diffractograms shown in Figures S1 and S2.

Crystallite size
Sample ID GOF Rexp Rp wRp
(nm)
Na/SSZ-13 A 44.8 (3) 1.99 7.12 9.2 14.19
Na/SSZ-13HTA* A 41.3 (3) 2.03 6.83 9.13 13.88
Cu/SSZ-13 A 41.1 (3) 1.82 6.46 7.94 11.79
Cu/SSZ-13HTA A 36.5 (2) 1.79 6.38 7.82 11.48

Na/SSZ-13 B 35.6 (3) 1.68 7.08 8.64 11.96

Na/SSZ-13HTA* B 36.5 (2) 1.81 6.84 8.92 12.41
Cu/SSZ-13 B 34.1 (3) 1.64 6.4 7.63 10.54
Cu/SSZ-13HTA B 31.4 (1) 1.56 6.29 7.03 9.83

Na/SSZ-13 C 29.3 (2) 2 7.17 9.44 14.4

Na/SSZ-13HTA* C 29.8 (1) 1.84 6.92 8.56 12.8
Cu/SSZ-13 C 26.9 (2) 1.7 655 7.8 11.16
Cu/SSZ-13HTA C 26.3 (2) 1.74 6.37 7.84 11.1

The X’pert Highscore Plus software was used for detailed crystalline size analysis. The sample displace-
ment was set at 0.1mm and the zero shift at 0.00025. These parameters were kept constant for each fit.
In order to obtain the crystallite size, each diffractogram was first fitted using a Voigt function. The
FWMH values of the respective peaks thus obtained were then used to calculate the crystallite size using
the Scherrer equation. A shape factor of 0.9 was used. The crystallite sizes reported here are an average
for the whole diffractograms.
The agreement indices (GOF – goodness of fit; Rexp – R expected; Rp – Rpattern; wRp – weighted Rpattern) re-
ported in Table S1 indicate a good refinement of the data, as the GOF values are well below 4. The wRp
values are close to twice of the R (Rexp) values for all refinements, again demonstrating good fittings.
It should be noted that R-values lower than these reported here could only be obtained with the use of
high-quality synchrotron data. However, the benchtop diffractometer used in this study still produces
data satisfactory to extract information on the crystallite sizes.

S3
N2-physisorption

Figure S3. N2 sorption isotherms for Na and Cu/SSZ-13. Agglomeration can be deduced by the large
hysteresis at p/p0 >0.7. Color-coding is reported in the legend.

Figure S4. N2 sorption isotherms for fresh and hydrothermally aged Na and Cu/SSZ-13 samples ob-
tained by methods A and B. Color-coding is reported in the legend.

S4
Table S2. Pore volumes determined with NL-DFT methods and single point adsorption close to p/p 0=
0.99.

Micropore volume Mesopore volume Total pore volume

Method A
[cm3/g] [cm3/g] [cm3/g]
Na/SSZ-13 0.29 0.02 0.34
Cu/SSZ-13 0.28 0.05 0.32
Na/SSZ-13HTA* 0.27 0.02 0.29
Cu/SSZ-13HTA 0.25 0.05 0.30

Method B
Na/SSZ-13 0.29 0.06 0.35
Cu/SSZ-13 0.25 0.07 0.32
Na/SSZ-13HTA* 0.27 0.06 0.33
Cu/SSZ-13HTA 0.26 0.09 0.35

Method C
Na/SSZ-13 0.27 0.22 0.49
Cu/SSZ-13 0.26 0.22 0.48
Na/SSZ-13HTA* 0.22 0.26 0.48
Cu/SSZ-13HTA 0.24 0.24 0.48

S5
Particle size analysis

Figure S5. Particle size analysis determined by visually analyzing 100 particles seen in helium ion mi-
crographs and measuring their diameter.

S6
Thermogravimetric Analysis

Figure S6. Thermogravimetric and calorimetric curves illustrating the template removal process.
By measuring the mass loss (20 wt% associated with template in all samples, corresponding to a
SDA/Al of 0.55), as well as the released heat associated with the removal of organic templating
agent, a differential heat curve can be plotted. The position of the maximum indicates the ease of
template removal, with a maximum at lower temperature being the result of template that is more
readily removed. Such a result is observed for the small particles obtained with procedure C, show -
ing a 10 degree difference compared to procedure A. The diffusion path lengths for the released heat
are shorter as opposed to the large crystals. It should be noted, that other factors can also play a role
in the position of the maximum. For example, method B results in a slightly higher peak maximum,
which we attribute to the difference in morphology, not just particle size. The intergrowth of the cu-
bic particles leads to an increase in the diffusion path lengths, making template removal more diffi -
cult.

S7
27
Al MAS NMR

Figure S7. 27Al MAS NMR spectra for the series of samples obtained by methods A and B. The initial
Na/SSZ-13 and Cu/SSZ-13 forms as well as their respective hydrothermally aged (HTA) forms are pre-
sented. Color-coding is reported in the legend.

Figure S8. Measured 27Al MAS NMR spectra for Cu/SSZ-13HTA A is shown along with the respective
line fitting used to determine the contribution of various Al species presented in Figures 7 and 8.

S8
Table S3. Relative contribution of tetrahedral framework as well as penta- and octahedral extra-frame-
work Al species. Simple line fitting shown in Figure S7 was used to determine these contributions.
Method Form Tetra- Penta- Octa- Total Al wt% Loss

Na/SSZ-13 92% 0% 8% 4.55 -

Cu/SSZ-13 95% 0% 5% 3.94 13%

A
Na/SSZ-13HTA* 65% 2% 32% 3.80 16%

Cu/SSZ-13HTA 48% 39% 13% 2.66 41%

Na/SSZ-13 88% 0% 12% 4.50 -

Cu/SSZ-13 98% 0% 2% 3.50 22%

B
Na/SSZ-13HTA* 58% 11% 31% 3.47 23%

Cu/SSZ-13HTA 56% 28% 16% 2.68 40%

Na/SSZ-13 82% 0% 18% 4.72 -

Cu/SSZ-13 94% 0% 6% 3.71 21%

C
Na/SSZ-13HTA* 49% 14% 37% 4.07 14%

Cu/SSZ-13HTA 67% 19% 14% 2.98 37%

Table S4. Estimation on the amount of invisible Al in Cu/SSZ-13 due to the presence of paramagnetic
Cu2+ and highly distorted extra-framework Al species via comparisons between elemental analysis
(AAS) and 27Al MAS NMR.
‘Invisible’
Method Form Total Al wt% AAS Loss % Al wt% NMR Loss %
Al [%]
Na/SSZ-13 4.5 - 4.72* - -

Cu/SSZ-13 4.11 9% 3.71 21% 10%

C
Na/SSZ-13HTA* 4.13 9% 4.07 14% 2%

Cu/SSZ-13HTA 4.20 7% 2.98 37% 29%

* Al wt% determined by referencing to an external Na/SSZ-13 standard of comparable composition (see main text). Similar -
ity between AAS and NMR quantifications indicates that there is no invisible Al in fresh Na/SSZ-13.

S9
EPR Spectroscopy

Table S5. Quantification of EPR active Cu2+ and the respective Al wt% corrected for invisible Al yield-
ing isolated Cu/Al ratios for fresh and hydrothermally aged Cu/SSZ-13.
Al wt% Al wt%
Cu wt% EPR CuEPR/Alcorrected
Method Sample NMR corrected
(±10%) (± 20%)
(±10%) (±10%)

Cu/SSZ-13 3.94 4.39% 1.57% 0.15

A
Cu/SSZ-13HTA 2.66 3.75% 0.73% 0.08

Cu/SSZ-13 3.50 3.88% 1.58% 0.17

B
Cu/SSZ-13HTA 2.68 3.77% 0.69% 0.08

Cu/SSZ-13 3.71 4.11% 1.35% 0.14

C
Cu/SSZ-13HTA 2.98 4.20% 0.99% 0.10

S10
NH3-TPD

350 Cu/SSZ-13 A Experimental

350 Cu/SSZ-13 C
NH3 Desorption Signal (ppm)

Fit Peak 1 Experimental

NH3 Desorption Signal (ppm)

300 Fit Peak 2 Fit Peak 1
300 Fit Peak 2
Cumulative Fit Peak
250 Cumulative Fit Peak
250

200 200

150 150

100 100

50 50

0 0

200 300 400 500 600 700 800 900

200 300 400 500 600 700 800 900
Temperature (C) Temperature (C)

200
NH3 Desorption Signal (ppm)

Cu/SSZ-13HTA A
150
Cu/SSZ-13HTA C

100

50

0
200 300 400 500 600 700 800 900
Temperature (C)

Figure S9: NH3-TPD on fresh Cu/SSZ-13 A (upper, left) and C (upper, right), and on Cu/SSZ-13HTA A and C
samples (bottom).

Samples (0.10g) were treated in flowing 20% O2/N2 at 550 C for 30 min, cooled to 160 C in the same atmos-
phere, and saturated with 1% NH3/He at the same temperature. Following a purging with 300 sccm N2 at 160 C
for 3 h to remove weakly adsorbed species, samples were ramped at a heating rate of 10 C/min until total NH3
desorption monitored with a FTIR gas analyzer (MKS 2030). For the two fresh samples, two NH 3 desorption
states are found. The state centered at ~300 C can be assigned to NH3 desorption from Cu-ions, and the state
centered at ~450 C to NH3 desorption from residual Brønsted acid sites. A simple peak fitting allows one to con-
clude that fresh sample Cu/SSZ-13 C contains ~8% more residual Brønsted acid sites, consistent with somewhat
lower isolated Cu-ion loading for this sample. For the two HTA samples, Cu/SSZ-13HTA C displays ~15% higher
NH3 storage capacity and somewhat stronger bindings with NH3. This is consistent with the higher remaining
tetrahedral Al in this sample.

It is important to note, however, that NH3 yields from the two fresh samples are similar; NH3-TPD results alone
cannot be used to gain a better understanding of the SCR reaction resutls shown in Fig. 2. A simialr situation is
found for the HTA samples.

S11