ChemCatChem - 2015 - Xu - Template Design and Economical Strategy For The Synthesis of SSZ 13 CHA Type Zeolite As An

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 which was verified by self-prepared organic templates with
attention recently because of its extraordinary physiochemical similar structure and functional groups as well as IR spectros-
properties and excellent potential for applications in catalysis. copy and DFT and potential energy distribution calculations.
In this work, SSZ-13 zeolite was synthesized using choline chlo- After ion exchange by Cu cations, the as-synthesized SSZ-13
ride as a CHA-topology construction template. This new tem- exhibited an outstanding performance for the selective catalyt-
plate has a low cost and is environmentally friendly. Specifically ic reduction of NO and showed 100 % NO conversions across
it has the appropriate geometry and functional groups for easy a wide temperature window of 150–450 8C.
self-assembly as dual molecules to form the CHA topology,
Introduction
Zeolites, especially aluminosilicates, are industrially important typical method of zeolite synthesis is the use of a structure-di-
microporous materials because of their numerous excellent recting agent (SDA) as a template, which consist mainly of or-
properties such as ion-exchange capacity, shape selectivity, ganic amines or quaternary ammonium groups, to direct the
well-defined pore structure, remarkable surface area, and self-assembly pathway and ultimately to create the pore
strong adsorption ability. Zeolites are used widely in the petro- space.[11–18]
chemical industry, oil refinery, and fine chemical production.[1–3] SSZ-13 zeolite is a kind of aluminosilicate with CHA cages
In addition, zeolites are also applied in the control of harmful connected by an eight-membered-ring (8-MR) pore system,
exhaust gases (such as NOx) that come from automobile en- and it was reported recently that Cu-SSZ-13 has a superior ac-
gines and power plants, which can cause serious environmen- tivity for selective catalytic reduction (SCR) of NOx with
tal issues, such as acid rain, the greenhouse effect, and photo- NH3.[18–22] Nevertheless, SSZ-13 zeolite cannot be synthesized
chemical smog.[4, 5] Previously, we presented a catalyst combi- easily because of the use of the extremely expensive and toxic
nation of MnCeTi and VWTi active materials that had a wide template N,N,N-trimethyl-1-1-adamantammonium hydroxide
de-NOx temperature window (150–400 8C, > 85 %).[6] However, (TMAdaOH), which limits its wide application. It is thus highly
as a result of the presence of poisonous V2O5 and secondary desirable to synthesize this CHA-type zeolite by using a low-
pollution by V2O5 sublimation and fall off, the USA and Japan cost template. From this background, a Cu amine complex,
have already forbidden the use of V-containing catalysts in copper tetraethylenepentamine (Cu-TEPA), was used as an effi-
diesel-engine exhausts. In this study we present a zeolite- cient template because of its appropriate geometric size to
based catalyst that has a wider de-NOx temperature window prepare Cu-SSZ-13 zeolite.[23] However, a large amount of ionic
and better NOx conversion than MnCeTi/VWTi. Importantly, en- Cu contained in this template could not be removed entirely
vironmentally friendly zeolite-based catalysts have a high po- even after the ion exchange of the as-prepared Cu-SSZ-13 with
tential to be utilized in diesel-engine exhaust control.[7–10] The 1 m ammonium nitrate solution. As a result, this method hardly
provides a pure SSZ-13 zeolite, which limits its further modifi-
[a] Dr. R. Xu, Prof. Dr. R. Zhang, Dr. N. Liu, Dr. B. Chen cation and practical application.
State Key Laboratory of Chemical Resource Engineering
In 2011, Sano et al. reported the inspiring synthesis of a LEV-
Beijing University of Chemical Technology
Beijing, 100029 (P.R. China) type zeolite through interzeolite conversion from a FAU-type
E-mail: [email protected] zeolite using choline hydroxide as a SDA.[24, 25] We considered
[b] Prof. Dr. S. Zhang Qiao the similarity between the LEV and CHA topologies as well as
School of Chemical Engineering the major role played by choline cations on the construction
The University of Adelaide
of the zeolite crystalline structure and we synthesized CHA-
Adelaide, SA 5005 (Australia)
E-mail: [email protected] type SSZ-13 zeolite using choline chloride (CC) as the SDA in
Supporting information for this article is available on the WWW under this work. As a result of the low cost and nontoxic nature of
http://dx.doi.org/10.1002/cctc.201500771. CC, this new synthesis strategy is economical and environmen-
ChemCatChem 2015, 7, 3842 – 3847 3842 Ó 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
18673899, 2015, 23, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.201500771 by UFAL - Universidade Federal de Alagoas, Wiley Online Library on [20/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Full Papers
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
ChemCatChem 2015, 7, 3842 – 3847 www.chemcatchem.org 3843 Ó 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Full Papers
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.
Full Papers
The CC dimer model for the synthesis of SSZ-13 confirms tally nontoxic, used widely in agriculture as a growth promoter,
the importance of the steric dimensions of the template. Si- and can even be used as a medicine for liver diseases. Further-
multaneously, in this study attention was also paid to the role more, it is much cheaper than the traditional SSZ-13 template
of the functional groups of the template on the structure of (TMAdaOH). These advantages mean that it has a great poten-
the SSZ-13 zeolite. To clarify the principle for template design tial in the industrialization and commercialization of SSZ-13.
for SSZ-13, series of new templates NT-X (X = 1, 2, 3; see The SSZ-13 zeolite can be modified with Cu ions to test its
Table S6 for NT-X preparation) with diverse functional groups SCR activity in effective NOx elimination. Cu-SSZ-13 prepared
(Scheme 2) was proposed for the possible synthesis of SSZ-13 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.
Full Papers
the excellent SCR performance. The characterization, which in- meta-aluminate (> 98 %, Aldrich), sodium hydroxide (> 99 %,
cluded XPS and H2-TPR, indicated that Cu-SSZ-13 (CC) has a sig- Sigma), choline chloride (> 99 %, Aldrich), and colloidal silica
nificantly higher Cu+/Cu2++ ion ratio than Cu-ZSM-5 (Sec- (LUDOX-AS-40, 40 wt %, Aldrich). Typically: sodium meta-aluminate
(0.492 g) and NaOH (3.6 g) were dissolved in deionized water
tion S2.5). The chemisorption and activation of NH3 on the sur-
(15.8 g). CC (2.3 g) was added under stirring over 15 min, and
face acid sites of the catalysts are generally viewed as the pri-
LUDOX-AS-40 colloidal silica (18 g) was added dropwise under vio-
mary process in the NH3-SCR of NO. Thus, NH3-TPD was per- lent stirring for 2 h. In some cases, SSZ-13 seeds were introduced.
formed (Figure S7), which showed that Cu-SSZ-13 (CC) has The final gel was transferred into a Teflon-lined stainless-steel auto-
a higher amount of acidic sites and a stronger acidity than Cu- clave and heated at 140 8C for 5 days. After the crystallization, the
ZSM-5. The strongly acidic sites could provide adsorbed active products were washed with deionized water and collected by fil-
NH3 even at high temperatures, which can reduce NO. It is ac- tration. SSZ-13 was prepared traditionally with TMAdaOH as de-
cepted that during the NH3-SCR process over metal-exchanged 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
zeolites, the catalyst plays two roles: the transition-metal spe-
organic template.
cies take responsibility for the oxidation of NO and subsequent
formation of surface-adsorbed NOx complexes; and the zeolite H-SSZ-13 and Cu-zeolites: The as-prepared SSZ-13 zeolite existed
support provides Brønsted acid sites to activate NH3 to form initially as Na-SSZ-13, which was transformed to H-SSZ-13 by ion
NH4+ ions that react with NO2 to form (NH4)xNO2 (x = 1, 2), then exchange with 0.5 m NH4NO3 (> 98 %, Sigma) solution for 12 h at
NH4NO2 decomposes quickly at a low temperature to yield N2 80 8C and subsequent calcination at 550 8C for 4 h. H-ZSM-5 (SiO2/
and H2O. Apparently, Cu-SSZ-13 has an abundance of Cu+ ions, Al2O3 = 26) was a commercial zeolite (The Novel Zeolites Co.).
which may be why Cu-SSZ-13 exhibited a better de-NOx per- Subsequently, Cu-zeolites (Cu-SSZ-13, Cu-ZSM-5) with 5 wt %
metal loading were prepared by an ordinary ion-exchange proce-
formance at low temperatures. To verify the function of Cu+,
dure. The parent zeolites were immersed in a solution that con-
Cu(l)-ZSM-5 was prepared (with the same Cu content as Cu-
tained the desired amount of copper nitrate under stirring at 80 8C
ZSM-5) by a solid-state ion-exchange method to maintain the for 24 h. The slurry was transferred into a vacuum evaporator to
high amount of Cu+ ions (Section S2.8). The SCR test shows eliminate the solvent. The residue was dried at 100 8C for 12 h and
that the quantity of Cu+ ions is essentially responsible for the further calcined at 550 8C for 6 h. The one-pot-synthesized Cu-SSZ-
low-temperature activity. Possible locations of the Cu ions in 13 was prepared as described previously.[23] Before the activity
the zeolite frameworks are discussed in Section S2.6. The resist- tests, the catalysts were sieved into 40–60 meshes.
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. Physicochemical characterization
Zeolite crystallization was confirmed by XRD by using a D5005 dif-
fractometer from Bruker equipped with CuKa radiation (k =
Conclusions 1.5406 æ). The XRD patterns were recorded in the 2 q range of 5–
Cheap and nontoxic choline chloride (CC) is used successfully 458 for the wide-angle profiles. The crystal phases were confirmed
according to the International Zeolite Association (IZA). XPS was
as an effective structure-directing agent in the synthesis of
performed by using a Thermofisher ESCALAB 250 system and AlKa
SSZ-13. It is verified that a dimer of CC has spatial dimensions radiation under ultrahigh vacuum (UHV). The binding energies
that match that of the CHA cage. Experimental and theoretical were calibrated with respect to the C 1s energy of incidental graph-
calculation results indicate that the appropriate geometry and itic carbon at BE = 285.0 eV. The SiO2/Al2O3 ratios of the products
suitable functional groups, which include (CHx)4N+ and C¢OH, were measured by XRF by using a Rigaku Industrial Corporation
of the CC dimer are responsible for the construction of the 3271E spectrometer. FTIR spectra were recorded by using a Bruker
CHA structure. After ion exchange by Cu ions, the SSZ-13 zeo- Model D8FOCUS. 29Si magic-angle spinning (MAS) NMR spectra
lite performs with an extremely high activity for the NH3 selec- were collected by using a Bruker Model AV300 with TMS as a refer-
ence. The Si/Al ratios were determined by Equation (1):
tive catalytic reduction of NOx because of its well-crystallized
structure and special topology. The CHA topology tends to Si=Al ¼ Sn In =ðI4 þ0:75 I3 þ0:5 I2 þ0:25 I1 Þ ð1Þ
form highly active Cu+ ions and Cu2++ ions instead of CuO spe-
cies, and the stable Cu+ ions are responsible for the superior in which In is the intensity of Q4(nAl) signals in the 29
Si MAS NMR
low-temperature de-NOx activity. Moreover, Cu-SSZ-13 has spectra and n = 0–4.
a good resistance to SO2 poisoning because of its super-small TG-DSC was performed by using a SETARAM SetsysEV24. H2-TPR
pore size. 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
Experimental Section (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
Materials preparation
stabilized at a flow rate of 30 mL min¢1, and then the temperature
Na-SSZ-13 zeolite: SSZ-13 zeolite was synthesized by a hydrother- of the reactor was increased from 100 to 900 8C with a ramp of
mal method with the low-cost template CC as the SDA. Details of 5 8C min¢1. The evolution of H2 consumption with temperature was
the synthesis conditions, chemical composition of starting gels, recorded by using an online thermal conductivity detector (TCD).
and corresponding products are given in Table 1. The chemicals The gas responses obtained by TCD were calibrated using the cor-
are obtained from the commercial suppliers as follows: sodium responding standard gases that contained known components and
Full Papers
concentrations. NH3-TPD was performed by using a Micromeritics Blanc, D. J. Adams, S. G. Kazarian, C. E. Snape, T. C. Drage, A. I. Cooper, J.
AutoChem II 2920 instrument (Micromeritics Instrument Corpora- Am. Chem. Soc. 2014, 136, 9028 – 9035.
tion) also equipped with a TCD. First, approximately 0.100 g of the [4] Z. Liu, J. Li, S. I. Woo, Energy Environ. Sci. 2012, 5, 8799 – 8814.
[5] S. Heylen, S. Smeekens, C. Kirschhock, T. Parac-Vogt, J. A. Martens,
sample was pretreated at 550 8C in a 5 vol % O2/He stream
Energy Environ. Sci. 2010, 3, 910 – 916.
(20 mL min¢1) for 30 min, then cooled to 100 8C, and further satu-
[6] R. Zhang, N. Liu, Z. Luo, W. Yang, X. Liang, R. Xu, B. Chen, D. Duprez, S.
rated with NH3 (4 vol % in He, 20 mL min¢1) for 1 h. Thereafter, the Royer, ChemCatChem 2014, 6, 2143 – 2143.
loosely bonded ammonia was removed by purging with [7] D. Xie, L. B. McCusker, C. Baerlocher, S. I. Zones, W. Wan, X. Zou, J. Am.
20 mL min¢1 of He for 1 h. Finally, the desorption was performed Chem. Soc. 2013, 135, 10519 – 10524.
from 100–550 8C at a heating rate of 10 8C min¢1 in a He stream [8] L. Zhang, D. Zhang, J. Zhang, S. Cai, C. Fang, L. Huang, H. Li, R. Gao, L.
(20 mL min¢1). Shi, Nanoscale 2013, 5, 9821 – 9829.
[9] L. Zhang, L. Shi, L. Huang, J. Zhang, R. Gao, D. Zhang, ACS Catal. 2014,
A Sorptomatic 1990 instrument (Thermo Electron) was used to 4, 1753 – 1763.
measure N2 sorption isotherms. The specific surface area and mi- [10] Y. Liu, J. Xu, H. Li, S. Cai, H. Hu, C. Fang, L. Shi, D. Zhang, J. Mater. Chem.
cropore volume of the samples were calculated according to the A 2015, 3, 11543 – 11553.
adsorption/desorption isotherms, and the surface area was deter- [11] X. Meng, F.-S. Xiao, Chem. Rev. 2014, 114, 1521 – 1543.
mined by the BET method. TEM was performed by using a JEOL- [12] Q. Wu, X. Wang, G. Qi, Q. Guo, S. Pan, X. Meng, J. Xu, F. Deng, F. Fan, Z.
2100 instrument (operated at 200 kV with a LaB6 source and Feng, C. Li, S. Maurer, U. Mìller, F.-S. Xiao, J. Am. Chem. Soc. 2014, 136,
4019 – 4025.
equipped with a Gatan UltraScan camera). A Supra 55 (Carl Zeiss)
[13] A. Corma, F. Rey, S. Valencia, Nature 2004, 431, 287 – 290.
scanning electron microscope was used to characterize the surface
[14] J. H. Lee, M. B. Park, J. K. Lee, H.-K. Min, M. K. Song, S. B. Hong, J. Am.
morphology of SSZ-13 zeolite (accelerating voltage applied at Chem. Soc. 2010, 132, 12971 – 12982.
20 kV). [15] R. J. White, A. Fischer, C. Goebel, A. Thomas, J. Am. Chem. Soc. 2014,
136, 2715 – 2718.
[16] A. Jackowski, S. I. Zones, S.-J. Hwang, A. W. Burton, J. Am. Chem. Soc.
Catalytic activity test 2009, 131, 1092 – 1100.
[17] Y. Li, J. Yu, R. Xu, Angew. Chem. Int. Ed. 2013, 52, 1673 – 1677; Angew.
NH3-SCR activity measurement was performed by using a quartz Chem. 2013, 125, 1717 – 1721.
fixed-bed reactor (0.6 cm i.d.) loaded with 0.25 g catalyst under [18] S. I. Zones, US Patent, 4544538, 1985.
a typical reaction atmosphere of 1000 ppm NO, 1000 ppm NH3, 10 [19] C. Paolucci, A. A. Verma, S. A. Bates, V. F. Kispersky, J. T. Miller, R. Goun-
vol % O2, and balanced by He with a total flow rate of der, W. N. Delgass, F. H. Ribeiro, W. F. Schneider, Angew. Chem. Int. Ed.
100 mL min¢1 (which corresponds to a gas hourly space velocity 2014, 53, 11828 – 11833; Angew. Chem. 2014, 126, 12022 – 12027.
(GHSV) of 30 000 h¢1). The reactor was regulated continuously by [20] S. T. Korhonen, D. W. Fickel, R. F. Lobo, B. M. Weckhuysen, A. M. Beale,
using a temperature controller with a thermocouple inserted into Chem. Commun. 2011, 47, 800 – 802.
[21] D. W. Fickel, E. D’Addio, J. A. Lauterbach, R. F. Lobo, Appl. Catal. B 2011,
the catalyst bed. The effluent gases (NH3, N2O, NO, and NO2) were
102, 441 – 448.
monitored by using an IR gas analyzer (Nicolet Nexus 670)
[22] J. H. Kwak, R. G. Tonkyn, D. H. Kim, J. Szanyi, C. H. Peden, J. Catal. 2010,
equipped with a 2.4 m gas cell and TQ analysis software. The N2 275, 187 – 190.
concentration was determined by GC (HP5890) equipped with [23] L. Ren, L. Zhu, C. Yang, Y. Chen, Q. Sun, H. Zhang, C. Li, F. Nawaz, X.
a TCD for quantification analysis and combined columns of 5 æ Meng, F.-S. Xiao, Chem. Commun. 2011, 47, 9789 – 9791.
and TDX-01 for separation. [24] M. Itakura, I. Goto, A. Takahashi, T. Fujitani, Y. Ide, M. Sadakane, T. Sano,
Microporous Mesoporous Mater. 2011, 144, 91 – 96.
[25] T. Inoue, M. Itakura, H. Jon, Y. Oumi, A. Takahashi, T. Fujitani, T. Sano, Mi-
Acknowledgements croporous Mesoporous Mater. 2009, 122, 149 – 154.
[26] C. Baerlocher, L. B. McCusker, D. H. Olson, Atlas of Zeolite Framework
Types, Elsevier, Amsterdam, 2007.
The authors thank the National Natural Science Foundation of [27] H. G. Karge, E. Geidel in Characterization I, Springer, Berlin, 2004, pp. 1 –
China (Grant Nos. 21177008 and 21477007), the Fundamental 200.
Research Funds for the Central Universities (YS1401), and the Na- [28] R. Xu, W. Pang, J. Yu, Q. Huo, J. Chen, Chemistry of Zeolites and Related
tional 863 Program (2013AA065900) for financial support. Porous Materials: Synthesis and Structure, Wiley-VCH, Weinheim, 2009,
pp. 189 – 209.
[29] B. P. Hereijgers, F. Bleken, M. H. Nilsen, S. Svelle, K.-P. Lillerud, M. Bjør-
Keywords: copper · ion exchange · template synthesis · gen, B. M. Weckhuysen, U. Olsbye, J. Catal. 2009, 264, 77 – 87.
[30] M. M. Treacy, J. B. Higgins, Collection of Simulated XRD Powder Patterns
reduction · zeolites
for Zeolites, Elsevier, Amsterdam, 2001.
[31] S. Ramalingam, S. Periandy, B. Narayanan, S. Mohan, Spectrochim. Acta
[1] C. Minkowski, R. Pansu, M. Takano, G. Calzaferri, Adv. Funct. Mater. 2006, Part A 2010, 76, 84 – 92.
16, 273 – 285. [32] V. Krishnakumar, N. Surumbarkuzhali, S. Muthunatesan, Spectrochim.
[2] A. Boubnov, H. W. P. Carvalho, D. E. Doronkin, T. Gìnter, E. Gallo, A. J. Acta Part A 2009, 71, 1810 – 1813.
Atkins, C. R. Jacob, J.-D. Grunwaldt, J. Am. Chem. Soc. 2014, 136, 13006 –
13015.
[3] R. T. Woodward, L. A. Stevens, R. Dawson, M. Vijayaraghavan, T. Hasell, Received: July 10, 2015
I. P. Silverwood, A. V. Ewing, T. Ratvijitvech, J. D. Exley, S. Y. Chong, F. Published online on September 28, 2015

ChemCatChem - 2015 - Xu - Template Design and Economical Strategy For The Synthesis of SSZ 13 CHA Type Zeolite As An

Uploaded by

Copyright:

Available Formats

ChemCatChem - 2015 - Xu - Template Design and Economical Strategy For The Synthesis of SSZ 13 CHA Type Zeolite As An

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

ChemCatChem - 2015 - Xu - Template Design and Economical Strategy For The Synthesis of SSZ 13 CHA Type Zeolite As An

Uploaded by

Copyright:

Available Formats

DOI: 10.1002/cctc.

201500771 Full Papers

Template Design and Economical Strategy for the

Results and Discussion

Thermogravimetry with differ-

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

a poor match with the calculated spectrum in accordance with

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

Sample SiO2/Al2O3 SBET Micropore volume Cu loading

You might also like