DOI: 10.1002/cctc.
201500771 Full Papers
Template Design and Economical Strategy for the
Synthesis of SSZ-13 (CHA-Type) Zeolite as an Excellent
Catalyst for the Selective Catalytic Reduction of NOx by
Ammonia
Ruinian Xu,[a] Runduo Zhang,*[a] Ning Liu,[a] Biaohua Chen,[a] and Shi Zhang Qiao*[b]
SSZ-13 zeolite, a CHA-type aluminosilicate, has attracted wide
attention recently because of its extraordinary physiochemical
properties and excellent potential for applications in catalysis.
In this work, SSZ-13 zeolite was synthesized using choline chlo-
ride as a CHA-topology construction template. This new tem-
plate has a low cost and is environmentally friendly. Specifically
it has the appropriate geometry and functional groups for easy
self-assembly as dual molecules to form the CHA topology,
Introduction
Zeolites, especially aluminosilicates, are industrially important
microporous materials because of their numerous excellent
properties such as ion-exchange capacity, shape selectivity,
well-defined pore structure, remarkable surface area, and
strong adsorption ability. Zeolites are used widely in the petro-
chemical industry, oil refinery, and fine chemical production.[1–3]
In addition, zeolites are also applied in the control of harmful
exhaust gases (such as NOx) that come from automobile en-
gines and power plants, which can cause serious environmen-
tal issues, such as acid rain, the greenhouse effect, and photo-
chemical smog.[4, 5] Previously, we presented a catalyst combi-
nation of MnCeTi and VWTi active materials that had a wide
de-NOx temperature window (150–400 8C, > 85 %).[6] However,
as a result of the presence of poisonous V2O5 and secondary
pollution by V2O5 sublimation and fall off, the USA and Japan
have already forbidden the use of V-containing catalysts in
diesel-engine exhausts. In this study we present a zeolite-
based catalyst that has a wider de-NOx temperature window
and better NOx conversion than MnCeTi/VWTi. Importantly, en-
vironmentally friendly zeolite-based catalysts have a high po-
tential to be utilized in diesel-engine exhaust control.[7–10] The
[a] Dr. R. Xu, Prof. Dr. R. Zhang, Dr. N. Liu, Dr. B. Chen
State Key Laboratory of Chemical Resource Engineering
Beijing University of Chemical Technology
Beijing, 100029 (P.R. China)
E-mail: zhangrd@mail.buct.edu.cn
[b] Prof. Dr. S. Zhang Qiao
School of Chemical Engineering
The University of Adelaide
Adelaide, SA 5005 (Australia)
E-mail: s.qiao@adelaide.edu.au
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/cctc.201500771.
ChemCatChem 2015, 7, 3842 – 3847
which was verified by self-prepared organic templates with
similar structure and functional groups as well as IR spectros-
copy and DFT and potential energy distribution calculations.
After ion exchange by Cu cations, the as-synthesized SSZ-13
exhibited an outstanding performance for the selective catalyt-
ic reduction of NO and showed 100 % NO conversions across
a wide temperature window of 150–450 8C.
typical method of zeolite synthesis is the use of a structure-di-
recting agent (SDA) as a template, which consist mainly of or-
ganic amines or quaternary ammonium groups, to direct the
self-assembly pathway and ultimately to create the pore
space.[11–18]
SSZ-13 zeolite is a kind of aluminosilicate with CHA cages
connected by an eight-membered-ring (8-MR) pore system,
and it was reported recently that Cu-SSZ-13 has a superior ac-
tivity for selective catalytic reduction (SCR) of NOx with
NH3.[18–22] Nevertheless, SSZ-13 zeolite cannot be synthesized
easily because of the use of the extremely expensive and toxic
template N,N,N-trimethyl-1-1-adamantammonium hydroxide
(TMAdaOH), which limits its wide application. It is thus highly
desirable to synthesize this CHA-type zeolite by using a low-
cost template. From this background, a Cu amine complex,
copper tetraethylenepentamine (Cu-TEPA), was used as an effi-
cient template because of its appropriate geometric size to
prepare Cu-SSZ-13 zeolite.[23] However, a large amount of ionic
Cu contained in this template could not be removed entirely
even after the ion exchange of the as-prepared Cu-SSZ-13 with
1 m ammonium nitrate solution. As a result, this method hardly
provides a pure SSZ-13 zeolite, which limits its further modifi-
cation and practical application.
In 2011, Sano et al. reported the inspiring synthesis of a LEV-
type zeolite through interzeolite conversion from a FAU-type
zeolite using choline hydroxide as a SDA.[24, 25] We considered
the similarity between the LEV and CHA topologies as well as
the major role played by choline cations on the construction
of the zeolite crystalline structure and we synthesized CHA-
type SSZ-13 zeolite using choline chloride (CC) as the SDA in
this work. As a result of the low cost and nontoxic nature of
CC, this new synthesis strategy is economical and environmen-
3842 Ó 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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tally friendly. Furthermore, DFT and potential energy distribu-
tion (PED) calculations and IR spectroscopy reveal the design
rule for templates for the preparation of CHA-type SSZ-13 zeo-
lite. The activity of ion-exchanged Cu-SSZ-13 for NH3-SCR is
also compared with other synthesis protocols. The Cu-SSZ-13
by prepared from CC has an exceptional performance. Addi-
tionally, detailed characterization (X-ray fluorescence (XRF), X-
ray photoelectron spectroscopy (XPS), H2 temperature-pro-
grammed reduction (TPR), and NH3 temperature-programmed
desorption (TPD)) and SO2 resistance measurements of Cu-SSZ-
13 were performed, and Cu-SSZ-13 was compared with com-
mercial ZSM-5 to study the structure–function relationship of
Cu-SSZ-13 for an excellent SCR performance.

Results and Discussion

The synthesis conditions and physiochemical properties of four
SSZ-13 samples are presented in Table 1. SEM and high-resolu-
tion transmission electron microscopy (HRTEM) images show
that the product (Sample 4 as an example) is well crystallized
(Figure 1 a and b). In particular, the HRTEM image exhibits the
crystal-structured channels. XRD patterns of all four samples
exhibit the typical peaks associated with the CHA-type zeolite Figure 1. a) SEM and b) HRTEM images of SSZ-13 zeolites (Sample 4), c) XRD
(Figure 1 c).[26] XPS shows that the Si atoms of all samples are patterns, d) Si 2p XPS, e) Al 2p XPS, and f) 29Si NMR spectra of Samples 1, 2, 3,
coordinated at the same valence (+ +4) and that the Al atoms and 4 (see details in Table 1).
are also four-coordinate (Figure 1 d and e). The Al 2p binding

Thermogravimetry with differ-

Table 1. Hydrothermal synthesis conditions for SSZ-13 zeolites and their physiochemical properties.
ential scanning calorimetry (TG-
Sample Synthesis conditions[a] Products (calcined) DSC) curves of the uncalcined
Starting SiO2/Al2O3 ratio CC/Al2O3 ratio T [8C] t [days] SiO2/Al2O3 ratio SBET [m2 g¢1] hybrid sample (Sample 4) show
XRF[b] 29
Si NMR[c]
a 12.5 % weight loss before
1 22 3.5 140 5 6.47 6.64 584 300 8C, which is related to the
2 28 3.5 140 5 8.05 7.92 589
evaporation of adsorbed water
3 34 4 140 5 12.56 11.25 603
4 40 4.7 140 5 16.25 17.29 626 (Figure 2 a). Thereafter, a sharp
exothermic peak accompanied
[a] H2O/SiO2 = 7 and Na2O/SiO2 = 0.4, [b] SiO2/Al2O3 ratios obtained by XRF, [c] SiO2/Al2O3 ratios obtained from
29
Si NMR spectroscopy.
by a weight loss of 9.64 %
emerged at 385 8C, which
is attributed to the decomposi-
energy (BE) does not shift to the hexacoordinate state (BE = tion of CC. N2 sorption analysis of the uncalcined and calcined
75.5 eV) with an increasing amount of Al, which indicates that (at 550 8C for 8 h) SSZ-13 samples (Figure 2 b) show typical
there is little nonframework alumina in the samples. Typical Langmuir isotherms for both samples, and the calcined
29
Si NMR spectra of SSZ-13 (Figure 1 f) show that the molar sample displays a higher surface area and a larger pore
ratios of SiO2/Al2O3 in framework are from 6.64 to 17.29. volume after organic the CC template is removed. FTIR spec-
The SiO2/Al2O3 ratios were also determined by XRF (Table 1). troscopy shows that the uncalcined sample exhibits some no-
The two values for SiO2/Al2O3 (determined by 29Si NMR spec- ticeable peaks at ñ = 1380–1480 and 2850–3000 cm¢1 (Fig-
troscopy and XRF) are close to each other, which confirms that ure 2 c), which are attributed to stretching and bending C¢H
there is little nonframework alumina in the products. All of vibrations of the methyl group, respectively. These results sug-
these results suggest that well-crystallized SSZ-13 zeolites with gest that choline cations are incorporated inside the pores and
SiO2/Al2O3 ratios of 6–17 can be prepared by using CC as channels of the hybrid products and can be eliminated by cal-
a SDA. In contrast, the CHA topology was not formed in the cination.
absence of CC (Table S1). The optimal crystallization time and IR spectroscopy can also be used to characterize the frame-
temperature were also investigated (Tables S2 and S3). An work topology of zeolites. Accordingly, the bands at ñ = 400–
amorphous phase was produced at T < 100 8C, and a FAU 1250 cm¢1 were analyzed by a documentary Flanigan–Khata-
phase appeared at T > 180 8C (Table S2). A time of 5 days is mi–Szymanski (FKS) method (Figure 2 c, inset),[27] and these IR
necessary to ensure CHA-type structural crystallization spectra show the typical vibration frequencies of CHA topolo-
(Table S3). gy.[28] Similarly, the fact that calcination scarcely changed the

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Figure 3. Comparison between the theoretical and experimental FTIR spec-

tra: a) calculated IR spectra of single-CC and CC dimer (dual-CC) models and
b) experimental spectrum.

a poor match with the calculated spectrum in accordance with

some previous reports.[31, 32]
As a result of the complicated vibrational coupling of the di-
verse functional groups at ñ = 800–1500 cm¢1, it is difficult to
Figure 2. a) TG-DSC curves of the uncalcined hybrid SSZ-13, b) N2 sorption
isotherms, and c) IR spectra of the uncalcined and calcined SSZ-13 samples. assign these complex IR bands. Fortunately, the results of the
PED calculations obtained from a normal model analysis (by
using the GAR2PED program; see details in the Supporting In-
essential crystal structure of SSZ-13 zeolite is also evidenced formation) allowed us to identify these vibrations. A compari-
by the XRD patterns (Figure S1). son of the single-CC and CC dimer models (Tables S4 and S5),
As mentioned above, the template molecule is able to especially in the ñ = 500–1500 cm¢1 region, verifies the exis-
induce a self-assembly between the initial precursor and the tence of an interaction between two template molecules in
SDA to form the cavities and/or channels of the zeolite during the CC dimer model. The PED analysis also showed that the CC
the synthesis process. Accordingly, the spatial dimensions of dimer model displays C¢OH bending vibrations at ñ = 1098
a template should match the pore structure of the target zeo- and 1126 cm¢1 (these two peaks are absent in the single-CC
lite. For the CHA-type zeolite in this study, the CHA cage is its model but appear in the experimental spectrum). C¢OH is
basic and crucial unit and has a geometric size of 7.3 Õ generally regarded as an important functional group in the
12.0 æ.[26, 29, 30] A stable molecular model of CC was calculated SDA. Moreover, the theoretical calculation also gives the geo-
by DFT (Figure S2). Surprisingly, the optimized single CC mole- metric dimension of the dual-CC model as 7.21 Õ 10.72 æ (Fig-
cule shows a much smaller geometric size (4.23 Õ 7.24 æ) than ure S3), which fits well with the volume of the CHA cage
the CHA cage. This unexpected result implies that a single CC (Scheme 1). Furthermore, this calculation result is in accord-
is not suitable to construct the CHA-type structure. However, ance with the size of the Cu-TEPA template (7.28 Õ 9.22 æ)
the SSZ-13 zeolite was synthesized by using CC as a SDA in reported previously.[23]
the present work. Based on above results and the spatial di-
mension of the CHA cage, it is speculated that a CC dimer is
confined in the CHA cage as template.
To verify our hypothesis, the CC template was characterized
by FTIR spectroscopy. Correspondingly, the vibration frequen-
cies of the CC dimer model were also calculated by DFT (see
Supporting Information). A comparison of the theoretical and
experimental IR spectra is shown in Figure 3. The experimental
IR spectrum of CC, in which the wavenumbers vary from ñ =
800 to 1500 cm¢1, is in good agreement with the theoretical
spectrum of the CC dimer model rather than that of the
single-CC model. Notably, the vibrational calculation essentially
matches the observed IR spectrum in the low-wavenumber
range (below ñ = 2000 cm¢1). However, the IR bands in the
high-wavenumber region at ñ = 2850–2960 cm¢1 assigned to
the stretching vibrations of C¢H (alkyl group) and those at ñ =
3300–3645 cm¢1 related to the O¢H stretching vibrations show Scheme 1. Match of the optimized CC dimer model within the CHA cage.

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The CC dimer model for the synthesis of SSZ-13 confirms
the importance of the steric dimensions of the template. Si-
multaneously, in this study attention was also paid to the role
of the functional groups of the template on the structure of
the SSZ-13 zeolite. To clarify the principle for template design
for SSZ-13, series of new templates NT-X (X = 1, 2, 3; see
Table S6 for NT-X preparation) with diverse functional groups
(Scheme 2) was proposed for the possible synthesis of SSZ-13
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tally nontoxic, used widely in agriculture as a growth promoter,
and can even be used as a medicine for liver diseases. Further-
more, it is much cheaper than the traditional SSZ-13 template
(TMAdaOH). These advantages mean that it has a great poten-
tial in the industrialization and commercialization of SSZ-13.
The SSZ-13 zeolite can be modified with Cu ions to test its
SCR activity in effective NOx elimination. Cu-SSZ-13 prepared
traditionally with TMAdaOH,[18] one-pot-synthesized Cu-SSZ-
13,[23] and commercial Cu-ZSM-5 were tested as a comparison.
The physiochemical properties of these Cu-zeolites are listed in
Table 2, and the SCR performance of each sample is shown in
Figure 4. Clearly, the Cu-SSZ-13 samples exhibit a much higher
activity than Cu-ZSM-5 at both low and high temperatures.
Furthermore, the Cu-SSZ-13 (CC) sample shows the best per-
formance of the three Cu-SSZ-13 samples. The Cu-SSZ-13 (CC)
sample can rapidly achieve the complete conversion of NO
and exhibits a superior activity even at low temperatures
(< 140 8C). In addition, Cu-SSZ-13 (CC) displays an extremely
wide temperature window (150–450 8C) for high NO conver-
sion (almost 100 %), which may be because of its well-crystal-
lized CHA topology.
Further studies focused on the comparison of Cu-SSZ-13
(CC) and commercial Cu-ZSM-5 to reveal the reason behind

Table 2. Basic physiochemical properties of Cu-zeolites for NH3-SCR tests.

Sample SiO2/Al2O3 SBET Micropore volume Cu loading

ratio[a] [m2 g¢1] [cm3 g¢1] [wt %]
Scheme 2. Optimized structures of NT-X (X = 1, 2, 3) templates within the
CHA cage calculated by DFT. Cu-SSZ-13 8.05 546 0.27 4.93
(CC)
Cu-SSZ-13 7.36 528 0.26 4.96
(TMAdaOH)
based on the structure optimization of molecules within the Cu-SSZ-13 6.48 520 0.25 8.66
(Cu-TEPA)
CHA cage of SSZ-13 by DFT calculations. Template NT-2, which Cu-ZSM-5 26.8 286 0.18 5.04
has a spatial size (7.28 Õ 10.88 æ) similar to that of Cu-TEPA
[a] SiO2/Al2O3 ratios obtained by XRF.
(7.28 Õ 9.22 æ) and the CC dimer (7.21 Õ 10.72 æ) and has
(CHx)4N+ and C¢OH functional groups, can be used successfully
in the synthesis of SSZ-13. Conversely, NT-1, which contains
both (CHx)4N+ and C¢OH groups but has a slightly smaller size
(7.06 Õ 8.24 æ) than NT-2, did not induced the desired CHA
structure. A frustrating preparation of SSZ-13 also occurred
with the use of NT-3 (which has no C¢OH groups), although its
geometry is suitable (7.14 Õ 10.65 æ). These results demonstrate
that a template with an appropriate geometric size (which
matches that of the CHA cage) and both (CHx)4N+ and C¢OH
functional groups is vital for the framework construction of the
CHA topology. The optimized structures of NT-X (X = 1, 2, 3)
within a CHA cage (Scheme 2) indicate that NT-1 and NT-3 do
not match the SSZ-13 structure and only NT-2 has a suitable
association with the CHA cage, which is consistent with the ex-
perimental results.
Although NT-2 is available to prepare SSZ-13, its preparation
is complicated and involves hazardous raw materials. The de-
sired template should be safe, economical, and obtained easily.
Figure 4. NO conversion on the Cu-SSZ-13 (CC) sample compared with that
CC is herein deemed as an ideal template because it has an
on Cu-SSZ-13 prepared by TMAdaOH, one-pot-synthesized Cu-SSZ-13 (Cu-
appropriate geometric size and contains both (CHx)4N+ and C¢ TEPA), and commercial Cu-ZSM-5 for NH3-SCR. Conditions: 1000 ppm NH3,
OH functional groups. Moreover, CC is a type of vitamin B, to- 1000 ppm NO, 10 vol % O2 balanced by He, GHSV = 30 000 h¢1.

ChemCatChem 2015, 7, 3842 – 3847 www.chemcatchem.org 3845 Ó 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

the excellent SCR performance. The characterization, which in-
cluded XPS and H2-TPR, indicated that Cu-SSZ-13 (CC) has a sig-
nificantly higher Cu+/Cu2++ ion ratio than Cu-ZSM-5 (Sec-
tion S2.5). The chemisorption and activation of NH3 on the sur-
face acid sites of the catalysts are generally viewed as the pri-
mary process in the NH3-SCR of NO. Thus, NH3-TPD was per-
formed (Figure S7), which showed that Cu-SSZ-13 (CC) has
a higher amount of acidic sites and a stronger acidity than Cu-
ZSM-5. The strongly acidic sites could provide adsorbed active
NH3 even at high temperatures, which can reduce NO. It is ac-
cepted that during the NH3-SCR process over metal-exchanged
zeolites, the catalyst plays two roles: the transition-metal spe-
cies take responsibility for the oxidation of NO and subsequent
formation of surface-adsorbed NOx complexes; and the zeolite
support provides Brønsted acid sites to activate NH3 to form
NH4+ ions that react with NO2 to form (NH4)xNO2 (x = 1, 2), then
NH4NO2 decomposes quickly at a low temperature to yield N2
and H2O. Apparently, Cu-SSZ-13 has an abundance of Cu+ ions,
which may be why Cu-SSZ-13 exhibited a better de-NOx per-
formance at low temperatures. To verify the function of Cu+,
Cu(l)-ZSM-5 was prepared (with the same Cu content as Cu-
ZSM-5) by a solid-state ion-exchange method to maintain the
high amount of Cu+ ions (Section S2.8). The SCR test shows
that the quantity of Cu+ ions is essentially responsible for the
low-temperature activity. Possible locations of the Cu ions in
the zeolite frameworks are discussed in Section S2.6. The resist-
ance of H2O and SO2 was also investigated (Section S2.9). The
small pores (3.8 æ) of SSZ-13 can efficiently prevent the cover-
age of the inner active sites by sulfurous compounds.
Conclusions
Cheap and nontoxic choline chloride (CC) is used successfully
as an effective structure-directing agent in the synthesis of
SSZ-13. It is verified that a dimer of CC has spatial dimensions
that match that of the CHA cage. Experimental and theoretical
calculation results indicate that the appropriate geometry and
suitable functional groups, which include (CHx)4N+ and C¢OH,
of the CC dimer are responsible for the construction of the
CHA structure. After ion exchange by Cu ions, the SSZ-13 zeo-
lite performs with an extremely high activity for the NH3 selec-
tive catalytic reduction of NOx because of its well-crystallized
structure and special topology. The CHA topology tends to
form highly active Cu+ ions and Cu2++ ions instead of CuO spe-
cies, and the stable Cu+ ions are responsible for the superior
low-temperature de-NOx activity. Moreover, Cu-SSZ-13 has
a good resistance to SO2 poisoning because of its super-small
pore size.
Experimental Section
Materials preparation
Na-SSZ-13 zeolite: SSZ-13 zeolite was synthesized by a hydrother-
mal method with the low-cost template CC as the SDA. Details of
the synthesis conditions, chemical composition of starting gels,
and corresponding products are given in Table 1. The chemicals
are obtained from the commercial suppliers as follows: sodium
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meta-aluminate (> 98 %, Aldrich), sodium hydroxide (> 99 %,
Sigma), choline chloride (> 99 %, Aldrich), and colloidal silica
(LUDOX-AS-40, 40 wt %, Aldrich). Typically: sodium meta-aluminate
(0.492 g) and NaOH (3.6 g) were dissolved in deionized water
(15.8 g). CC (2.3 g) was added under stirring over 15 min, and
LUDOX-AS-40 colloidal silica (18 g) was added dropwise under vio-
lent stirring for 2 h. In some cases, SSZ-13 seeds were introduced.
The final gel was transferred into a Teflon-lined stainless-steel auto-
clave and heated at 140 8C for 5 days. After the crystallization, the
products were washed with deionized water and collected by fil-
tration. SSZ-13 was prepared traditionally with TMAdaOH as de-
scribed previously.[18] The products were dried in a vacuum oven at
100 8C for 12–24 h and calcined at 550 8C for 8 h to eliminate the
organic template.
H-SSZ-13 and Cu-zeolites: The as-prepared SSZ-13 zeolite existed
initially as Na-SSZ-13, which was transformed to H-SSZ-13 by ion
exchange with 0.5 m NH4NO3 (> 98 %, Sigma) solution for 12 h at
80 8C and subsequent calcination at 550 8C for 4 h. H-ZSM-5 (SiO2/
Al2O3 = 26) was a commercial zeolite (The Novel Zeolites Co.).
Subsequently, Cu-zeolites (Cu-SSZ-13, Cu-ZSM-5) with 5 wt %
metal loading were prepared by an ordinary ion-exchange proce-
dure. The parent zeolites were immersed in a solution that con-
tained the desired amount of copper nitrate under stirring at 80 8C
for 24 h. The slurry was transferred into a vacuum evaporator to
eliminate the solvent. The residue was dried at 100 8C for 12 h and
further calcined at 550 8C for 6 h. The one-pot-synthesized Cu-SSZ-
13 was prepared as described previously.[23] Before the activity
tests, the catalysts were sieved into 40–60 meshes.
Physicochemical characterization
Zeolite crystallization was confirmed by XRD by using a D5005 dif-
fractometer from Bruker equipped with CuKa radiation (k =
1.5406 æ). The XRD patterns were recorded in the 2 q range of 5–
458 for the wide-angle profiles. The crystal phases were confirmed
according to the International Zeolite Association (IZA). XPS was
performed by using a Thermofisher ESCALAB 250 system and AlKa
radiation under ultrahigh vacuum (UHV). The binding energies
were calibrated with respect to the C 1s energy of incidental graph-
itic carbon at BE = 285.0 eV. The SiO2/Al2O3 ratios of the products
were measured by XRF by using a Rigaku Industrial Corporation
3271E spectrometer. FTIR spectra were recorded by using a Bruker
Model D8FOCUS. 29Si magic-angle spinning (MAS) NMR spectra
were collected by using a Bruker Model AV300 with TMS as a refer-
ence. The Si/Al ratios were determined by Equation (1):
Si=Al ¼ Sn In =ðI4 þ0:75 I3 þ0:5 I2 þ0:25 I1 Þ ð1Þ
in which In is the intensity of Q4(nAl) signals in the 29
Si MAS NMR
spectra and n = 0–4.
TG-DSC was performed by using a SETARAM SetsysEV24. H2-TPR
was performed by using an AUTOCHEM instrument from Micro-
meritics. Approximately 0.2 g of sample was introduced into a mi-
croreactor. The material was initially activated under simulated air
(total flow rate = 30 mL min¢1) at the calcination temperature for
1 h. After cooling to RT, a reducing flow (5 vol % of H2 in Ar) was
stabilized at a flow rate of 30 mL min¢1, and then the temperature
of the reactor was increased from 100 to 900 8C with a ramp of
5 8C min¢1. The evolution of H2 consumption with temperature was
recorded by using an online thermal conductivity detector (TCD).
The gas responses obtained by TCD were calibrated using the cor-
responding standard gases that contained known components and
Ó 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

concentrations. NH3-TPD was performed by using a Micromeritics
AutoChem II 2920 instrument (Micromeritics Instrument Corpora-
tion) also equipped with a TCD. First, approximately 0.100 g of the [4]
[5]
sample was pretreated at 550 8C in a 5 vol % O2/He stream
(20 mL min¢1) for 30 min, then cooled to 100 8C, and further satu-
[6]
rated with NH3 (4 vol % in He, 20 mL min¢1) for 1 h. Thereafter, the
loosely bonded ammonia was removed by purging with [7]
20 mL min¢1 of He for 1 h. Finally, the desorption was performed
from 100–550 8C at a heating rate of 10 8C min¢1 in a He stream [8]
(20 mL min¢1).
[9]
A Sorptomatic 1990 instrument (Thermo Electron) was used to
measure N2 sorption isotherms. The specific surface area and mi- [10]
cropore volume of the samples were calculated according to the
adsorption/desorption isotherms, and the surface area was deter- [11]
mined by the BET method. TEM was performed by using a JEOL- [12]
2100 instrument (operated at 200 kV with a LaB6 source and
equipped with a Gatan UltraScan camera). A Supra 55 (Carl Zeiss)
[13]
scanning electron microscope was used to characterize the surface
[14]
morphology of SSZ-13 zeolite (accelerating voltage applied at
20 kV). [15]
[16]
Catalytic activity test
[17]
NH3-SCR activity measurement was performed by using a quartz
fixed-bed reactor (0.6 cm i.d.) loaded with 0.25 g catalyst under [18]
a typical reaction atmosphere of 1000 ppm NO, 1000 ppm NH3, 10 [19]
vol % O2, and balanced by He with a total flow rate of
100 mL min¢1 (which corresponds to a gas hourly space velocity
(GHSV) of 30 000 h¢1). The reactor was regulated continuously by [20]
using a temperature controller with a thermocouple inserted into
[21]
the catalyst bed. The effluent gases (NH3, N2O, NO, and NO2) were
monitored by using an IR gas analyzer (Nicolet Nexus 670)
[22]
equipped with a 2.4 m gas cell and TQ analysis software. The N2
concentration was determined by GC (HP5890) equipped with [23]
a TCD for quantification analysis and combined columns of 5 æ
and TDX-01 for separation. [24]
[25]
Acknowledgements
[26]
The authors thank the National Natural Science Foundation of [27]
China (Grant Nos. 21177008 and 21477007), the Fundamental
Research Funds for the Central Universities (YS1401), and the Na- [28]
tional 863 Program (2013AA065900) for financial support.
[29]
Keywords: copper · ion exchange · template synthesis ·
[30]
reduction · zeolites
[31]
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