Supporting Information

Interface engineering of bifunctional Cu-SSZ-13@CZO core-shell

catalyst for boosting the potassium ion and SO2 tolerance

Lingfeng Jia,[a] Jixing Liu,*[b,c] Deqi Huang,[d] Jingchen Zhao,[a] Jianning Zhang,[a] Kaixiang Li,[c]

Zhenguo Li,*[c] Wenshuai Zhu,[a,b] Zhen Zhao,[a] and Jian Liu*[a]

[a] State Key Laboratory of Heavy Oil Processing, China University of Petroleum (Beijing), Beijing

102249, P. R. China;
[b] School of Chemistry and Chemical Engineering, Institution for Energy Research, Jiangsu University,

Zhenjiang 212013, P. R. China;

[c] National Engineering Laboratory for Mobile Source Emission Control Technology, China

Automotive Technology & Research Center Co., Ltd., Tianjin 300300, China;
[d] College of Chemical Engineering, Yangzhou Polytechnic Institute, Yangzhou, 225127, P. R.

China

*Corresponding author. Email: liujian@cup.edu.cn; jxliu0804@ujs.edu.cn; lizhenguo@catarc.ac.cn

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1. Experimental Details
1.1 Chemicals

H-SSZ-13 zeolite was purchased from Shanghai Gechi Chemical Co., Ltd. Cerium (III) nitrate

hexahydrate, zirconium (IV) nitrate pentahydrate, oxalic acid and polyethylene glycol average Mn

~4000 (PEG4000) were purchased from Macklin Technology Co., Ltd. Copper (II) nitrate trihydrate

and potassium nitrate were purchased from Aladdin Technology Co., Ltd. Ethanol and ammonium

metavanadate were purchased from Tianjin Kemiou Chemical Reagent Co., Ltd. PEG-PPG-PEG

average Mn ~4000 (P123) was purchased from Sigma Aldrich. Titanium tungsten powder was

purchased from National Engineering Laboratory for Mobile Source Emission Control Technology.

All reagents and solvents were of analytical grade and used without additional purification.

1.2 Catalysis preparation

The preparation process of Cu-SSZ-13@CZO core-shell-structured catalyst is illustrated in

Scheme 1. At first, the fresh H-SSZ-13 sample (Si/Al = 6) was ion-exchanged with a Cu(NO3)2·3H2O

solution (0.001 mol‧L−1) at room temperature for 4h, followed by drying at 110°C for 12 h and

calcining at 550°C for 4 h. The Cu-SSZ-13 sample contained 0.54 wt.% Cu as determined by XRF.

Then, 5.0 g of P123 was added to a 100 mL mixed solution of water/ethanol (v/v = 1) and stirred until

completely dissolved. 5.0 g of Cu-SSZ-13 was added to the above mixture and stirred to obtain mixture

A. Next, 3.1 g of Ce(NO3)3‧6H2O, 1.04 g of Zr(NO3)4‧5H2O, and 1.0 g of polyethylene glycol

(PEG4000) were dissolved in 25 ml of deionized water to obtain a solution B. The solution B was

introduced dropwise into mixture A and stirred for 12 h at 35°C. Subsequently, the temperature was

increased to 75°C and continued to stir for another 24 h. Finally, the product was obtained after stirring

until the water evaporates then drying at 110°C, calcining at 550°C for 4 h and denoted as Cu-SSZ-

13@CZO.

The SO2 and K+ poisoned samples were prepared by being treated in the flow of 200 ppm SO2

and 10 % H2O balanced with N2 in a tube furnace with a gas hourly space velocity (GHSV) of 60000

h−1 at 280°C for 12 h followed by depositing 1.0 wt.% K+ with KNO3 to the above samples and named

as Cu-SSZ-13-S-K and Cu-SSZ-13@CZO-S-K, respectively.

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 For comparison, CeZrCu-SSZ-13 with the same Ce, Zr and Cu content as Cu-SSZ-13@CZO

core-shell catalyst was prepared by a conventional incipient-wetness impregnation method. In brief,

1.92 g of Ce(NO3)3‧6H2O, 0.85 g of Zr(NO3)4‧5H2O, and 0.081 g of Cu(NO3)2·3H2O were dissolved

in 30 ml of deionized water. Then, 5 g of H-SSZ-13 was added to the solution and mixed thoroughly.

The catalysts were dried at 110°C for 12 h, calcined at 500°C for 5 h and denoted as CeZrCu-SSZ-13.

The synthesis method of V2O5-WO3/TiO2 catalysts is as follows. First, 1.05 g of oxalic acid was

dissolved in 27.6 g of deionized water, and 1.16 g of ammonium metavanadate was added to the above

solution after heating to 80°C and stirred until the precipitation disappeared. Then, 10 g of titanium

tungsten powder was added to the above solution and stirred for 3 h. Finally, The sample was dried at

90°C for 12 h and subsequently calcined at 550°C for 3 h to obtain the V2O5-WO3/TiO2.

1.2 Activity Test

The activity tests were carried out in a fixed-bed quartz flow reactor with 0.5 mL of catalyst

(40~60 mesh). The reaction gas consisted of 500 ppm of NO, 500 ppm of NH3, and 5% O2 balanced

with N2. The total flow rate was 500 mL‧min–1, with a gas hourly space velocity (GHSV) of 60000

h−1. The concentrations of NO, NO2, N2O, and NH3 were continuously analyzed by a Fourier transform

infrared gas analyzer (Thermo Fisher IGS). The NOx conversion, NH3 conversion, and N2 selectivity

were calculated using the following equations:

[NOx]inlet - [NOx]outlet
NOx conversion = [NOx]inlet × 100% (1)
[NH3]inlet ― [NH3]outlet
NH3 conversion = [NH3]inlet × 100% (2)
2[N2O]outlet
( )
N2 selectivity = 1 - [NOx]inlet + [NH3]inlet - [NOx]outlet - [NH3]outlet × 100% (3)

1.3 Catalyst Characterization

Powder X-ray diffraction (XRD) measurements of the samples were conducted at 40 mA and 40

kV using Cu Kα radiation by a Rigaku Smart lab-SE XRD diffractometer. The 2θ data from 5° to 80°

were recorded with a step size of 0.05° at 2°·min–1.

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 27Al MAS NMR was carried out on a Bruker AVANCE III 600 spectrometer at a resonance

frequency of 156.4 MHz using a 4 mm HX double-resonance MAS probe at a sample spinning rate of

14 kHz. 27Al MAS NMR spectra were recorded by small-flip angle technique with a pulse length of

0.68 μs (<π/12) and a 1s recycle delay. The chemical shift of 27Al was referenced to 1 M aqueous

Al(NO3)3.

High-resolution transmission electron microscopy (HR-TEM) micrographs were conducted on a

JEOL JEM-F200 electron microscope equipped with a field emission source operating at 200 kV. The

elemental local, mapping and line-scanning analyses were collected by energy dispersive spectroscopy

(EDS) using a JED-2300T electron microscope.

The XRF experiments were performed using Thermo Scientific ARL PERFORM'X 4200W.

A Micromeritics ASAP 2460 automatic adsorption instrument was used to measure the Brunauer–

Emmett-Teller (BET) surface area at 77 K. Before N2 physisorption, the samples were outgassed for

4 h at 210°C. The specific surface area was calculated using the Brunauer-Emmett-Teller (BET)

method. The micropore volume was calculated using the t-plot method and the corresponding pore

size distribution was calculated using Horvath + Saito Foley method. Both the mesopore volume and

corresponding pore size distribution were calculated using the Barrett-Joyner-Halenda (BJH) method.

A Micromeritics AutoChem 2920 instrument was applied to perform temperature-programmed

reduction with NH3 (NH3-TPD) experiments. Before each test, 100 mg of the catalyst was purged by

a flowing N2 (50 mL·min−1) at 500°C for 30 min, and then the sample was cooled down to 100°C.

Subsequently, ammonia was adsorbed at this temperature for 30 min to ensure the sufficient adsorption

of NH3. Before desorption, the sample was purged by a flowing He stream at 100°C for 1 h to remove

excessive and physically adsorbed NH3. Finally, the sample was heated from 100 to 700°C at a rate of

15 °C·min−1 in a pure N2 (50 mL·min−1) flow and the desorption pattern was recorded.

Temperature programmed reduction of H2 (H2-TPR) experiment was conducted on a

Micromeritics AutoChem 2920 chemisorption analyzer. Before reduction, 100 mg of the catalyst was

purged by a flowing N2 (50 mL·min−1) at 500°C for 1 h, and then the sample was cooled down to 80°C

in an N2 flow. The temperature-programmed reduction process was performed in flow of 10% H2/N2

(50 mL·min−1) up to 1100°C at a rate of 15 °C·min−1.

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 Electron paramagnetic resonance (EPR) spectra were collected on a Bruker EMX PLUS

spectrometer. Powder samples (~20 mg) were contained in 4 mm OD quartz tubes. The measurement

conditions were the following: modulation frequency was 100 kHz; power was 6.325 mW; the center

field was 3510.0 G; sweep width was 100.0 G; microwave frequency was 9.291 GHz and sweep time

was 30 s. Before the EPR test, all the catalysts were calcined at 550°C for 3 h in air and all spectra of

catalysts were obtained at 125 K By fitting the spectrum, the spin quantum numbers were calculated.

The electron orbital arrangement of Cu2+ is [Ar] 3d9, containing an unpaired electron, and the ratio of

Cu2+ contents to unpaired number is 1:1. Therefore, the quantum spins number detected by EPR is

equal to the number of Cu2+. The g factor was calculated by the equation:
v( MHz )
g  0.71447736 (4)
B0 (Gauss )

Where v is the actual test frequency of each spectrum, B0 is the magnetic field strength.

X-ray photoelectron spectroscopy (XPS) was carried out on a Thermo Scientific K-Alpha using

a monochromatic Al Kα source (1486.6 eV). High-resolution O 1s, C 1s, Cu 2p, and Ce 3d core-level

spectra were systematically recorded with an analyzer pass energy of 50 eV resulting in 0.1 eV energy

resolution.

The Raman spectra were measured on a Thermo Fisher DXR Raman microscope. The 532 nm

line was used as the excitation source.

In-situ diffuse reflectance infrared Fourier transform spectroscopy (in-situ DRIFTS) experiments

were carried out on a FTIR spectrometer (Nicolet iS50) equipped with a MCT detector and KBr

window. It was worth noting that before the gas was switched, two spectra were collected in the N2

atmosphere. All characterizations are dehydrated catalysts in this work, and the dehydration conditions

were calcined at 550°C for 3 h in a muffle furnace. All DRIFTS spectra were recorded by accumulating

64 scans with a resolution of 4 cm−1.

1.4 Kinetics Measurements

The SCR kinetics tests over the catalysts were performed in the same fixed-bed reactor. To

eliminate the effects of internal and external diffusion, the GHSV was increased to 1200000 h–1. The

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kinetics data were recorded from 250 to 400°C with the NOx conversion less than 20%. The NH3-SCR

reaction rates and turnover frequency (TOF) were calculated based on the following equations:
FNO[L(NOx)·min ―1] ∗ ln (1 ― XNOx[%])
Rate [mol NOx·gcatal·s ―1] = - mcatal[g] ∗ 60[s·min ―1] ∗ 22.4[L·mol ―1] (5)
FNO[L(NOx)·min ―1] ∗ ln (1 ― XNOx[%]) ∗ 63.5[g·mol ―1]
TOF [s ―1] = - mcatal[g] ∗ MCu2 + [%] ∗ 60[s·min ―1] ∗ 22.4[L·mol ―1]
(6)

where XNOx represents the NOx conversion at different temperatures, FNO is the volumetric flow

rate of NO during testing, and metal is the mass of the powder catalyst.

Turnover frequency (TOF) was defined as the moles of NOx molecules converted per second on

the moles of Cu2+ ions in the fresh and poisoned catalysts. Furthermore, based on electron

paramagnetic resonance (EPR) analyses of the content of Cu2+ ions, the moles of Cu2+ ions were

calculated.

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 Table S1. The elemental contents of Cu-SSZ-13 based catalysts determined by XRF.

Sample Si/Al K (wt.%) Ce (wt.%) Zr (wt.%) Cu (wt.%)

Cu-SSZ-13 6.14 − − − 0.52
Cu-SSZ-13@CZO 6.07 − 12.39 3.62 0.43
Cu-SSZ-13-S-K 6.12 1.09 − − 0.52
Cu-SSZ-13@CZO-S-K 6.06 1.06 12.36 3.61 0.43

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 Table S2. Textural properties of Cu-SSZ-13 based catalysts.

Sample SBET (m2‧g−1) c SExt (m2‧g−1) b VMic (cm3‧g−1) b VMes (cm3‧g−1)a

Cu-SSZ-13 601.3 19.4 0.30 0.34

Cu-SSZ-13@CZO 488.8 74.6 0.22 0.28
Cu-SSZ-13-S-K 562.1 27.5 0.28 0.38
Cu-SSZ-13@CZO-S-K 484.6 75.3 0.21 0.29
CZO 92.6 89.5 <0.01 0.14
a Derived by the BJH method;

b Derived by the t-plot method;

c Derived by the BET method.

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Table S3. Atomic distributions of fresh and poisoning CZO, Cu-SSZ-13, and Cu-SSZ-13@CZO.
Sample Cu (wt.%) a Cu2+ (wt.%) b Ce3+/(Ce3++Ce4+) (wt.%)c
Cu-SSZ-13 0.52 0.42 −
Cu-SSZ-13-S-K 0.52 0.31 −
CeZrCu-SSZ-13 0.42 − 23.5
CeZrCu-SSZ-13-S-K 0.43 − 18.6
Cu-SSZ-13@CZO 0.43 0.35 18.4
Cu-SSZ-13@CZO-S-K 0.43 0.36 21.8
CZO − − 10.1
CZO-S-K − − 10.3
a The total Cu content determined by XRF method;

b The isolated Cu content determined by EPR method from dehydrated samples;

c Determined by XPS method;

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Figure S1. TEM images of Cu-SSZ-13@CZO-S-K.

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Figure S2. Relative amounts of different Cu species (I) ZCuII(OH), (Ⅱ) CuO, (Ⅲ) Z2CuII in a) Cu-
SSZ-13, b) Cu-SSZ-13@CZO, c) Cu-SSZ-13-S-K, d) Cu-SSZ-13@CZO-S-K based on H2-TPR.

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Figure S3. NOx conversion of V2O5-WO3/TiO2 and V2O5-WO3/TiO2-S-K catalysts.

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 100
A 100 B
NOx Conversion (%)

N2 Selectivity (%)
80
80

60
60

CeZrCu-SSZ-13
40
40 CeZrCu-SSZ-13 CeZrCu-SSZ-13-S-K
CeZrCu-SSZ-13-S-K
20
20

0
150 200 250 300 350 400 450 500 150 200 250 300 350 400 450
Temperature (℃ ) Temperature (℃ )
Figure S4. (A) NOx conversion and (B) N2 selectivity of CeZrCu-SSZ-13 and CeZrCu-SSZ-13-S-K
catalysts.

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 30 5 30 0.6
a1 a2 b1 1450
b2
Kubelka-Munk F(R)

Kubelka-Munk F(R)
1625 1256
25 bidentate 25
1624
1170 nitrate B-NH3 bidentate

Time (min)

Time (min)
1598 0 min 20 bridge 1575 20

Intensity (a.u.)

Intensity (a.u.)
1523 0 min nitrate B-NH3
1578 nitrate L-NH3 1256
1578
15 L-NH3 1170 15 L-NH3

10 10 L-NH3

5 5
30 min 30 min
0 0 0 0
1700 1600 1500 1400 1300 1200 1100 1700 1600 1500 1400 1300 1200 1100 1700 1600 1500 1400 1300 1200 1100 1700 1600 1500 1400 1300 1200 1100
-1 -1 -1 -1
Wavenumber (cm ) Wavenumber (cm ) Wavenumber (cm ) Wavenumber (cm )
30 1.5 30 0.5
c1 c2 d1 1450
d2
Kubelka-Munk F(R)

Kubelka-Munk F(R)
1625 25 25
bidentate bridge
1624 1256 bridge nitrate B-NH3 nitrate
Time (min)

Time (min)
1598 0 min 1170 1624
20 nitrate 0 min 20 B-NH3

Intensity (a.u.)

Intensity (a.u.)
1578 1625 1256
L-NH3 L-NH3
15 L-NH3 1170 15
L-NH3
10 10

5 5
30 min 30 min
0 0 0 0
1700 1600 1500 1400 1300 1200 1100 1700 1600 1500 1400 1300 1200 1100 1700 1600 1500 1400 1300 1200 1100 1700 1600 1500 1400 1300 1200 1100
-1 -1 -1 -1
Wavenumber (cm ) Wavenumber (cm ) Wavenumber (cm ) Wavenumber (cm )

Figure S5. In-situ DRIFTS of NO+O2 co-adsorption with the preabsorbed NH3 and corresponding
color mapping spectra of the catalysts at 225°C: (a1, a2) Cu-SSZ-13, (b1, b2) Cu-SSZ-13@CZO, (c1,
c2) Cu-SSZ-13-S-K, (d1, d2) Cu-SSZ-13@CZO-S-K.

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 30 30
a1 a2
5
b1 1450
b2
0.8
Kubelka-Munk F(R)

Kubelka-Munk F(R)
1256 25 1256 25
1470
1598 30 min

Time (min)

Time (min)
1598 1170
1170 20 1575 20

Intensity (a.u.)

Intensity (a.u.)
1625 1575 1625
30 min
15 15

bridge B-NH3
10 10 bridge L-NH3
nitrate bidentate L-NH3 B-NH3
nitrate
5 nitrate 5 bidentate
nitrate
0 min 0 min
0 0 0 0
1700 1600 1500 1400 1300 1200 1100 1700 1600 1500 1400 1300 1200 1100 1700 1600 1500 1400 1300 1200 1100 1700 1600 1500 1400 1300 1200 1100
-1 -1 -1 -1
Wavenumber (cm ) Wavenumber (cm ) Wavenumber (cm ) Wavenumber (cm )
30 3.6 30 0.4
c1 c2 d1 d2
Kubelka-Munk F(R)

Kubelka-Munk F(R)
25 1450 25
1256
bidentate
1470 30 min 1256
Time (min)

Time (min)
1598 1598 nitrate
1170 20 20

Intensity (a.u.)

Intensity (a.u.)
30 min 1625 1575 1170
1625 1575

15 15
L-NH3 L-NH3
10 bridge B-NH3 10 B-NH3
bridge
nitrate bidentate nitrate
5 nitrate 5

0 min 0 min
0 0 0 0
1700 1600 1500 1400 1300 1200 1100 1700 1600 1500 1400 1300 1200 1100 1700 1600 1500 1400 1300 1200 1100 1700 1600 1500 1400 1300 1200 1100
-1 -1 -1 -1
Wavenumber (cm ) Wavenumber (cm ) Wavenumber (cm ) Wavenumber (cm )

Figure S6. In-situ DRIFTS of NH3 adsorption with the preabsorbed NO + O2 and corresponding color
mapping spectra of the catalysts at 225°C: (a1, a2) Cu-SSZ-13, (b1, b2) Cu-SSZ-13@CZO, (c1, c2) Cu-
SSZ-13-S-K and (d1, d2) Cu-SSZ-13@CZO-S-K.

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