Separation and Purification Technology 331 (2024) 125638

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Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

Improving catalytic performance of Cu-SSZ-13 for NOx abatement via

in-situ introduction of La and Ce from spent catalyst
Xueqin Wang a, Tiesen Li a, b, Chan Wang a, b, *, Qingyan Cui a, b, Tinghai Wang a, b, Xiaojun Bao a, b,
Yuanyuan Yue a, b, *
a
National Engineering Research Center of Chemical Fertilizer Catalyst, College of Chemical Engineering, Fuzhou University, Fuzhou 350002, PR China
b
Qingyuan Innovation Laboratory, Quanzhou 362801, Fujian Province, PR China

A R T I C L E I N F O A B S T R A C T

Edited by: Z Bao Designing a cost-effective and fast fabrication Cu-SSZ-13 with improved selective catalytic reduction of NO by
ammonia (NH3-SCR) performance remains an open question. Here we report that LaCe-SSZ-13 zeolites were
Keywords: synthesized from spent fluid catalytic cracking catalyst within 12 h. After ion-exchanging with CuSO4 solution,
Cu-SSZ-13 the obtained LaCeCu-SSZ-13 catalysts exhibit significantly higher catalytic activity and hydrothermal stability
NH3-SCR
than conventional Cu-SSZ-13. Various characterizations reveal that La and Ce modification not only facilitates
Hydrothermal stability
the disperse of isolated Cu2+ species, but also effectively mitigates dealumination and inhibits copper species
LaCe-modification
Spent catalyst aggregation after hydrothermal aging. In-situ diffuse reflection infrared Fourier transform spectrum analyses
demonstrate that La and Ce modification can accelerate the adsorption capacity for NH3 and NOx and promote
the decomposition of NH4NO3 intermediate species on the catalyst, benefiting the improvement of low-
temperature activity. The combination of experiments and theoretical calculations further demonstrate that
the most stable positions of La and Ce are on different eight-membered rings in SSZ-13, and then Cu2+ ions tend
to enter eight-membered rings to enhance the NH3 adsorption capacity and decrease the H2O adsorption ca­
pacity, which results in higher low-temperature activity and hydrothermal stability than Cu-SSZ-13. Our work
provides a feasible strategy for preparing the efficient rare-earth-modified Cu-zeolite based NH3-SCR catalyst for
nitrogen oxide abatement.

1. Introduction temperature during the engine starting. Moreover, the hydrothermal

Controlling nitrogen oxide (NOx) emissions from diesel vehicle
exhaust is the primary goal and important task to prevent air pollution
from becoming an increasingly serious problem [1,2]. Selective catalytic
reduction of NO by ammonia (NH3-SCR) has been extensively utilized
for reducing NOx emissions by virtue of its high efficiency [3–6]. Cu-SSZ-
13 has been marketed for eliminating NOx by NH3-SCR relying on its
exceptional catalytic activity, high N2 selectivity and relatively good
hydrothermal stability comparing to the traditional three-way V2O5-
WO3/TiO2 and other zeolites catalysts (e.g., Cu-ZSM-5, Cu-Beta and Fe-
SSZ-13) [4,7,8]. However, some challenges arise from the highly
changeable working conditions of diesel engine in practical applications
and the increasingly stringent requirements for limiting emissions. For
example, the catalytic activity of Cu-SSZ-13 at low temperature (below
200 ◦ C) cannot meet the current requirement due to its lower ignition
stability is unsatisfactory when the diesel particulate filter is regener­
ated, especially at high temperatures above 800 ◦ C.
Introducing extra metal cations to modify Cu-SSZ-13 is an efficient
approach to upgrade its NH3-SCR capability. A variety of metal cations
including alkali metal (such as Li, Na and K) [9–11], transition metal
(such as Fe, Zn and Co) [12–14] and rare-earth (RE) metal (such as Ce,
La, Y and Sm) [15–22] ions have been effectively doped into Cu-SSZ-13
to improve its catalytic activity and hydrothermal stability. In partic­
ular, RE-modification has been shown to provide definite improvement
in NOx removal efficiency and hydrothermal stability of Cu-SSZ-13
catalysts, which has attracted extensive attention. Reviewing some
previous studies, the introduction of RE metal may precede or follow the
introduction of copper ions, in which the introduced RE metal ions in
Cu-SSZ-13 were thought to occupy the ion exchange sites of the CHA
cage, causing Cu2+ ions to preferentially occupy the comparatively

* Corresponding authors at: National Engineering Research Center of Chemical Fertilizer Catalyst, College of Chemical Engineering, Fuzhou University, Fuzhou
350002, PR China.
E-mail addresses: chan.wang@fzu.edu.cn (C. Wang), yueyy@fzu.edu.cn (Y. Yue).

https://doi.org/10.1016/j.seppur.2023.125638
Received 30 August 2023; Received in revised form 27 October 2023; Accepted 5 November 2023
Available online 7 November 2023
1383-5866/© 2023 Elsevier B.V. All rights reserved.
X. Wang et al.
stable 6-membered rings (6MRs), thus improved hydrothermal stability
is obtained [17–20]. Moreover, by combining experiments and theo­
retical calculations, Chen et al. [21] found that the introduction of Sm3+
could generate more active [ZCu2+(OH)]+ species locating at eight-
membered rings (8MRs) and thus improving the low-temperature ac­
tivity and stability of Cu-SSZ-13.
The traditional post-synthetic preparation methods (e.g., ion-
exchange and wet impregnation) have been widely used for intro­
ducing RE metal ions into the zeolite support. However, it is difficult for
RE metal ions with large ionic radius to enter small pore zeolites due to
the intense steric hindrance. Therefore, an in-situ synthesis strategy for
metal introduction has been proposed, in which metal precursors are
added into the zeolite synthesis gel. Chen et al. [15] successfully syn­
thesized multi-metal Cu-Ce-La-SSZ-13 via a one-step method using Cu-
Ce-La-tetraethylenepentamine as template, the synergistic effect be­
tween various active species conferred good low-temperature activity to
the catalyst. Unfortunately, the SCR activity of catalysts decreased
greatly after HTA at 750 ◦ C for 12 h, and no study was conducted on the
reaction mechanism after Ce and La modification. Moreover, the syn­
thesis of the catalyst takes a long time (96 h). To date, the development
of a convenient and affordable method for fast in-situ production of RE-
modified Cu-SSZ-13 catalysts with outstanding catalytic capability in
NH3-SCR reaction remains a challenge.
Our interest to synthesize RE-modified Cu-SSZ-13 catalysts is
inspired by our previous successful construction of SSZ-13 via inter­
zeolite conversion of FAU-type zeolite based on “common composite
structure unit (CBU) hypothesis”, which dramatically reduces and even
avoids the need for organic structure-directing agents [23,24]. However,
the expensive zeolite Y raises the synthesis cost of SSZ-13 which ulti­
mately reduces the profitability of the synthesis strategy. As we all
know, RE (La and Ce)-exchanged Y zeolites are major constituents of the
cutting-edge fluid catalytic cracking (FCC) catalyst, but the spent FCC
catalyst is simply landfilled as hazardous waste. In view of the remained
crystalline framework of zeolite Y despite deactivation, the spent FCC
catalyst could probably be used as a raw material for high value-added
zeolite synthesis via interzeolite conversion. Besides silicon and
aluminum sources, the RE component in the deactivated FCC catalyst
could be simultaneously utilized as RE precursors for the in-situ intro­
duction of them into the obtained zeolite. Therefore, the synthesis of
SSZ-13 zeolite from spent FCC catalyst would be really favorable for in-
situ introducing Ce and La into SSZ-13, lowering the synthesis cost of
SSZ-13 zeolite, as well as reducing environmental pollution by spent
FCC catalyst.
In this work, La and Ce ions were in-situ introduced into SSZ-13 from
spent FCC catalyst via one-step synthesis. The effects of La and Ce on the
obtained LaCeCu-SSZ-13 catalysts in terms of the physicochemical fea­
tures, along with the catalytic activity and hydrothermal stability in
NH3-SCR reaction were revealed by the combined use of the diversified
ex-situ and in-situ characterization methods. The density functional
theory (DFT) calculations further demonstrate the positions of La and Ce
in LaCeCu-SSZ-13, and their influence on the regulation of Cu sites.
2. Experimental
2.1. Materials
The raw spent FCC catalyst (denoted as SFC) was kindly provided by
Sinochem Quanzhou Petrochemical Co., Ltd. (P. R. China). Hydrochloric
acid (HCl, 36 ~ 38 wt%) and sodium hydroxide (NaOH, 96 wt%) were
bought from Sinopharm Chemical Reagents Co., Ltd. (P. R. China).
Colloidal silica (LUDOX HS-40, 40 wt%) was acquired by Sigma-Aldrich
(USA). Aluminum sulfate octadecahydrate (Al2(SO4)3⋅18H2O, 99 wt%)
was obtained from Beijing Yili Fine Chemicals Co., Ltd. (P. R. China). N,
N, N-trimethyl-1–1-adamant-ammonium hydroxide (TMAdaOH, 25 wt
%) and ammonium sulfate ((NH4)2SO4, 99 wt%) were supplied from
Macklin Reagent Co., Ltd. (P. R. China). Copper sulfate (CuSO4, 99 wt
2
Separation and Purification Technology 331 (2024) 125638
%), Lanthanum nitrate hexahydrate (La(NO3)3⋅6H2O, AR) and Cerium
nitrate hexahydrate (Ce(NO3)3⋅6H2O, AR) was purchased from Shanghai
Aladdin Biochemical Technology Co., Ltd. (P. R. China).
2.2. Preparation of LaCeCu-SSZ-13 catalysts
Preparation of SFCx with different La and Ce contents. The raw
SFC was leached with HCl at 80 ◦ C for 1 h to dissolve La and Ce after
washing thoroughly with deionized water and drying at 120 ◦ C over­
night. A series of SFCx (x = 0, 0.5, 1.0, 1.5 and 2.0, where × denotes the
molar concentrations of HCl used) with different La and Ce contents
were obtained by adjusting the molar concentration of HCl to dissolve
different La and Ce contents.
Preparation of LaCe-SSZ-13 zeolites. Various LaCe-SSZ-13 zeolites
with different La and Ce contents were synthesized using the above
obtained SFCx as the main Si and Al sources as well as the sole La and Ce
sources via a typical steam-assisted dry gel conversion (DGC) strategy
[25]. Firstly, SFCx, TMAdaOH, colloidal silica and Al2(SO4)3⋅18H2O
were added sequentially into a NaOH solution under vigorous stirring at
40 ◦ C to obtain a mixture with the molar ratio of 1 SiO2: 0.196 Al2O3:
0.18 TMAdaOH: 0.18 NaOH: 29 H2O. Following continuous stirring at
80 ◦ C to dry the mixture, the formed dry lumps were crushed into
powder. Afterwards, the powder was moved to a specially designed open
Teflon vial, which was positioned into an autoclave containing a certain
amount of water (the mass ratio of water to powder was 5/2) in another
open Teflon vial. In the autoclave, the powder was unable to directly
touch with the liquid water. After heating the autoclave at 180 ◦ C for 12
h, the resultant substance was extracted by filtration, washing to
neutrality, drying at 100 ◦ C overnight and calcining within the muffle
oven at 580 ◦ C for 8 h. The zeolites synthesized from SFCx are designated
as LaCe-SSZ-13-x (x = 0, 0.5, 1.0, 1.5 and 2.0).
Preparation of LaCeCu-SSZ-13 catalysts. The as-synthesized Na-
form LaCe-SSZ-13 zeolites were changed into H-form ones via repeat­
edly ion-exchange in a 1.0 M (NH4)2SO4 liquor and calcination at 550 ◦ C
for 5 h. Subsequently, copper ions (~2.2 wt%) were added via the ion-
exchange of H-form LaCe-SSZ-13 zeolite in a 0.1 M CuSO4 liquor at 80 ◦ C
for 4 h, after filtering, washing to neutrality and drying at 100 ◦ C
overnight. The catalysts obtained from LaCe-SSZ-13-x are denoted as
LayCezCu-SSZ-13, where y and z denote the contents of La and Ce
measured by inductively coupled plasma optical emission spectrometer
(ICP-OES), respectively.
For comparison, La0.28Ce0.21Cu-SSZ-13-C was prepared by loading
CuSO4, La(NO3)3⋅6H2O and Ce(NO3)3⋅6H2O onto commercial SSZ-13
(Si/Al = 7.5) via wet impregnation. Subsequently, the obtained mate­
rials dried at 100 ◦ C for 12 h and then calcined at 520 ◦ C for 4 h. The
hydrothermal aged catalyst was denoted as La0.28Ce0.21Cu-SSZ-13-C-A.
2.3. Characterizations
The powder X-ray diffraction (XRD) diffractometer (Rigaku D/max
Ultima IV, Japan) was utilized to investigate the crystal structure and
relative crystallinity of the catalysts with Cu Kα radiation. The relative
crystallinity was calculated by comparing the integrated area of the
peaks at 2θ = 9.6◦ , 13.0◦ , 16.3◦ , 20.8◦ , 31.0◦ and 31.5◦ of the synthe­
sized samples to that of the selected standard sample. ICP-OES (Thermo
ICAP PRO, USA) was employed to analyze the contents of Si, Al, La, Ce,
and Cu in the samples. The shape and crystal size of the samples were
examined via scanning electron microscopy (SEM) taken on a Hitachi S-
4700 instrument (Japan). Solid-state 27Al and 29Si magic angle spinning
nuclear magnetic resonance (MAS NMR) spectra were performed using
Bruker Advance III 600 and 500 MHz equipment (Germany), respec­
tively. Ultraviolet–visible diffuse reflection spectra (UV–vis DRS) were
generated over a Lambda 950 spectrometer (PerkinElmer, Massachu­
setts, USA) in a wavelength range of 200–800 nm. The temperature-
programmed desorption of NH3 (NH3-TPD) was performed via a He
flow utilizing AutoChem II 2920 TPD instrument (USA) equipped with a
X. Wang et al.
thermal conductivity detector (TCD). In detail, 100 mg of catalyst
sample (20–40 mesh) was heated at 350 ◦ C under a He flow for 30 min,
and then cooled to 50 ◦ C, changed gas flow to 10% NH3/He and hold 30
min, then it was purged with pure He for 60 min to remove the physi­
cally adsorbed NH3. Afterwards, the temperature was ramped from
100 ◦ C to 700 ◦ C at a flow rate of 15 ◦ C/min− 1. The temperature-
programmed reduction of hydrogen (H2-TPR) was carried out upon
the Quanta chrome Chem BET Pulsar TPR instrument (USA). Typically,
40 mg of catalyst sample (20–40 mesh) was pretreated under pure argon
(Ar) at 300 ◦ C for 1 h and then cooled down to 50 ◦ C. Finally, the catalyst
was heated to 600 ◦ C at 15 ◦ C/min− 1 in a 10% H2/Ar. Electron para­
magnetic resonance (EPR) experiments were conducted via a Bruker
EMX plus instrument (USA) at − 150 ◦ C. X-ray photoelectron spectros­
copy (XPS) characterization was carried out with a K-Alpha spectrom­
eter (Thermo Fisher, USA). As an internal reference, the C1s peak of the
contaminant carbon (284.8 eV) was utilized for calibrating the binding
energy. The in-situ diffuse reflection infrared Fourier transform (DRIFT)
spectrum was collected in a wavelength range of 1400–4000 cm− 1
implemented via a Bruker VERTEX 70 FTIR spectrometer equipped with
a mercury cadmium telluride (MCT) sensor.
2.4. Catalytic test
The NH3-SCR activity assessment experiments of the catalysts were
carried out in an established quartz microreactor with a diameter of 7
mm. To obtain the appropriate particles of 20–40 mesh, the LaCeCu-SSZ-
13 catalyst was tableted, crushed and sieved. The reactant gas mixture
included N2 as the balancing gas along with 500 ppm NO, 500 ppm NH3,
5 v% O2, and 5 v% H2O. The gaseous hourly space velocity (GHSV) was
120,000 h− 1. Testo340 flue gas analyzer (Germany) was utilized to
analyze the amount of NO and NO2 in the outlet gas mixture. The con­
centration of N2O in the outlet gas mixture was analyzed by a Nicolet
iS50 Fourier-transform infrared (FT-IR) spectrometer (Thermo Fisher,
USA). The following are the calculations for NO conversion and N2
selectivity:
NO conversion (%) =
NO(inlet) − NOx (outlet)
× 100% (1)
NO(inlet)
[ ]
N2 selectivity = 1 −
N2 O (outlet)
× 100% (2)
NO (inlet) − NOx (outlet)
where NO(inlet) represents the amount of NO at the inlet of reactor, and
NOx(outlet) is the concentration of NO and NO2 at the outlet of reactor,
and N2O(outlet) is the concentration of N2O at the outlet of reactor.
All of the fresh catalysts were hydrothermally aged at 800 ◦ C with 10
v% H2O/air for 12 h, to analyze the hydrothermal stability of the cat­
alysts. These aged catalysts were denoted as LayCezCu-SSZ-13-A.
2.5. DFT calculations
The Vienna Ab initio Simulation Package (VASP) [26,27] was used
for all calculations. The core-valence electron interaction was described
using the projector-augmented wave (PAW) method [28,29], and the
exchange correlation between electrons was handled using the Perdew-
Burke-Ernzerhof (PBE) generalized gradient approximation [30]. There
was no restriction on spin polarization, and the plane-wave cutoff en­
ergy was set at 450 eV. The Kohn-Sham equation was iteratively solved
with the energy criterion set to 10–5 eV. The DFT-D3 technique was used
to model the long-range van der Waals interaction [31]. A k-point grid
with a 3 × 3 × 3 Gamma-center was used to sample the Brillouin zone.
As soon as the remaining stresses on the atoms decreased to less than
0.02 eV/Å, all the structures were loosened.
Using a hexagonal unit cell with the size parameters of 13.6750 ×
13.6750 × 14.7670 Å3, the periodic SSZ-13 zeolite model was created.
In order to create an approximate Si/Al ratio of 3, 9Si atoms in the SSZ-
3
Separation and Purification Technology 331 (2024) 125638
13 were swapped out for 9 Al atoms, mimicking the experimental Si/Al
ratio of 3.3 in SSZ-13 zeolites. As in earlier research [21], the model SSZ-
13 zeolite of H9Al9Si27O72 was created by adding the same amount of H
atoms to the O atoms as the dopant Al atoms to balance the charges.
3. Results and discussion
3.1. Fast and economic preparation of LaCe-SSZ-13-x from SFCs
LaCe-SSZ-13-x with various La and Ce contents were synthesized by
utilizing SFCs as the main Si and Al sources as well as the sole La and Ce
sources via the stream-assisted DGC method. The chemical compositions
(Table S1) and XRD patterns (Fig. S1) of the SFCs show that a series of
SFCs with different La and Ce contents have been prepared, while the
crystallized Y structure in SFCs is still preserved. To analyze the struc­
tural changes during crystallization, XRD patterns of the solid products
prepared from raw SFC0 at various crystallization times were collected.
As we can see from Fig. 1, the characteristic peaks assigned to the FAU
topology structure can be observed in the initial dry gel (0 h), and then
fade away with prolonging of the crystallization time, indicating that the
zeolite Y in SFC0 is gradually dissolved in the alkaline media. After
crystallization for 4 h, the crystallized Y structure still remains while the
typical peaks of CHA topology structure appear, which suggests that
SSZ-13 zeolite has already been formed before Y zeolite is completely
consumed. Subsequently, the intensity of the typical peaks attributed to
SSZ-13 zeolite increases, meanwhile, the characteristic peaks of FAU
topology structure totally disappear (6–14 h in Fig. 1a). Finally, the well-
crystallized SSZ-13 zeolite is quickly produced in 12 h. When the crys­
tallization time is prolonged to 48 h, the diffraction peak intensity of the
obtained product has no obvious change, indicating that the crystalli­
zation can be completed within 12 h. Although the spent MFI zeolite can
be converted into CHA zeolite through the DGC strategy, it still takes 48
h to achieve complete crystallization [32]. To reveal the effect of crys­
tallized Y structure during crystallization, SFC0 was pretreated with
aqueous alkali to destroy the crystallized Y structure, and then was
employed as a raw material for preparing SSZ-13 zeolite. XRD patterns
of the solid products prepared from alkali-treated SFC0 at various crys­
tallization times were collected (Fig. S2). In the XRD pattern of the initial
dry gel, the characteristic peaks assigned to the FAU topology structure
cannot be detected, indicating that the crystallized Y structure has
collapsed during the alkali treatment. After crystallization for 6 h, no
crystalline phase is observed, and then weak CHA characteristic peaks
emerge at the crystallization time of 14 h. At last, it takes as long as 22 h
for well-crystallized SSZ-13 zeolite to complete the crystallization pro­
cess. Therefore, it can be assumed that, similarly to the interzeolite
transformation from FAU type zeolite into SSZ-13, the crystallized Y
structure in SFC0 plays a critical role in accelerating the construction of
SSZ-13 framework [23]. Moreover, it is notable that the TMAdaOH/SiO2
molar ratio (0.18) used for synthesizing SSZ-13 zeolite in this work is
much smaller than that (0.35) reported in the literature [33], suggesting
that only a small amount of template is needed by using our proposed
strategy. Therefore, it is a rapid and economic strategy for preparing
SSZ-13 from spent FCC catalyst via the DGC method. Various pure-phase
SSZ-13 zeolites can also be obtained from a series of SFCs with different
La and Ce contents, as demonstrated by the XRD patterns (Fig. S3) and
SEM images (Fig. S4).
3.2. NH3-SCR performance
The ICP-OES analysis shows that 0–0.7 wt% La and 0–0.5 wt% Ce
have been introduced into Cu-SSZ-13 containing ~ 2.2 wt% Cu
(Table S2). The performance of the catalysts loaded with different
amounts of La and Ce was evaluated to reveal the impacts of La and Ce
on NH3-SCR reaction (Fig. 2). All the fresh catalysts give a high catalytic
activity (NO conversion above 90%) at reaction temperatures ranging
from approximately 200 to 450 ◦ C as shown in Fig. 2a. Surprisingly, at
X. Wang et al. Separation and Purification Technology 331 (2024) 125638

Fig. 1. (a) Original and (b) magnified XRD patterns of the solid products synthesized from raw SFC0 at various crystallization times.

Fig. 2. NO conversion and N2 selectivity in NH3-SCR reaction over (a and c) fresh and (b and d) hydrothermally aged catalysts.

4
X. Wang et al.
both low (150–200 ◦ C) and high (450–550 ◦ C) temperatures, LaCe-
modified catalysts exhibit greater NO conversion than LaCe-free cata­
lyst (Cu-SSZ-13). The activity of LayCezCu-SSZ-13 catalysts increases
with La and Ce contents up to 0.28 wt% and 0.21 wt%, respectively, and
then it decreases for the catalysts with higher La and Ce contents
(La0.48Ce0.31Cu-SSZ-13 and La0.62Ce0.43Cu-SSZ-13), which follows the
order of La0.28Ce0.21Cu-SSZ-13 > La0.48Ce0.31Cu-SSZ-13 >
La0.17Ce0.13Cu-SSZ-13 > La0.62Ce0.43Cu-SSZ-13. The NO conversion can
reach so high up to ca. 80% at 150 ◦ C, and maintain above 90% at
temperatures of 175–550 ◦ C over La0.28Ce0.21Cu-SSZ-13. The NO con­
version over the hydrothermally aged samples is presented in Fig. 2b.
After HTA, the NH3-SCR activity over LaCe-free catalyst (Cu-SSZ-13-A)
decreases dramatically, and the NO conversions are quite low both at
low and high temperatures (56.2% at 200 ◦ C and 84.2% at 450 ◦ C). In
contrast, the hydrothermal aged LaCe-modified catalysts maintain high
catalytic activity over wide temperature ranges. Compared with the
fresh counterparts, LayCezCu-SSZ-13-A catalysts exhibit nearly identical
catalytic activity (NO conversion over 90%) at moderate temperatures
from 250 to 450 ◦ C, and slightly lower activity for low/high tempera­
tures. The activity over the hydrothermal aged samples decreased in the
same order with that of the fresh ones: La0.28Ce0.21Cu-SSZ-13-A >
La0.48Ce0.31Cu-SSZ-13-A > La0.17Ce0.13Cu-SSZ-13-A > La0.62Ce0.43Cu-
SSZ-13-A > Cu-SSZ-13-A. Despite being subjected to harsh HTA,
outstanding activity (NO conversion over 90% at 200–500 ◦ C) is ob­
tained over La0.28Ce0.21Cu-SSZ-13-A. On the other hand, the LaCe-SSZ-
13–1.0 zeolite exhibits negligible SCR activity, and the maximum NO
conversion is only 26% at 500 ◦ C. It can be concluded that the NH3-SCR
capacity of Cu-SSZ-13 catalyst, especially for low-temperature activity
and hydrothermal stability, enables significantly enhanced by in-situ
addition of La and Ce from spent FCC catalyst into Cu-SSZ-13,
although the amount of La and Ce should be regulated to get the best
NH3-SCR performance. High N2 selectivity (＞99%) is obtained over all
fresh catalysts in the whole temperature window (Fig. 2c and 2d). After
HTA, the N2 selectivity of all catalysts decline slightly, and Cu-SSZ-13-A
shows the lowest selectivity, but it is still higher than 96%.
When compared with the reference sample prepared by wet
impregnation (La0.28Ce0.21Cu-SSZ-13-C in Fig. S5), La0.28Ce0.21Cu-SSZ-
13 prepared in this study showed higher catalytic activity at low tem­
peratures (below 200 ℃) than the commercial Cu-SSZ-13 modified with
the same La and Ce contents. After HTA, La0.28Ce0.21Cu-SSZ-13-A
exhibited better catalytic activity than La0.28Ce0.21Cu-SSZ-13-C-A at
both low temperature (below 225℃) and high temperature (above 400
℃). The results showed that the traditional post-treatment method had
less significant effect on catalytic activity and hydrothermal stability
improvement.
Fig. 3. XRD patterns of the (a) fresh and (b) hydrothermally aged catalysts.
5
Separation and Purification Technology 331 (2024) 125638
3.3. Characterizations of fresh and aged catalysts
Fig. 3 displays the XRD patterns of the fresh and hydrothermal aged
samples. Besides of the characteristic peaks in connection with CHA
topology structure, no diffraction peak belonged to metal oxides (e.g.,
CuO, CeO2 and La2O3) in the XRD patterns is detected both over the
fresh and hydrothermal aged samples. It suggests that Cu, La and Ce are
highly dispersed in all of the SSZ-13 zeolites even when the sum of La
and Ce content in La0.62Ce0.43Cu-SSZ-13 is over 1.0 wt%. The relative
crystallinity of the catalysts calculated by reference to Cu-SSZ-13 is
displayed above each pattern. It appears that the addition of La and Ce
cannot influence the crystallization of SSZ-13 zeolite, as the fresh LaCe-
free and LaCe-modified catalysts show a close relative crystallinity
(100%-104%, Fig. 3a). After HTA, the relative crystallinity of LaCe-free
Cu-SSZ-13-A declines greatly to 49.2%, while those of La0.28Ce0.21Cu-
SSZ-13-A and La0.48Ce0.31Cu-SSZ-13-A are almost preserved (Fig. 3b).
Small degradation is observed for the crystallinity of La0.17Ce0.13Cu-SSZ-
13-A and La0.62Ce0.43Cu-SSZ-13-A, but still retains at 84.9% and 77.7%,
respectively (Fig. 3b). These results indicate that the introduction of La
and Ce does greatly enhance the hydrothermal stability of Cu-SSZ-13.
The coordination environments of the aluminum and silicon species
in the various catalysts were investigated by using 27Al and 29Si MAS
NMR spectroscopy techniques, respectively. According to Fig. 4a, all the
fresh and hydrothermal aged samples exhibit one strong peak at 61 ppm
associated with tetrahedral Al species in the zeolite framework [34], and
one broad peak at about 10 ppm caused by the octahedral extra-
framework Al species [35]. The peak area of the extra-framework Al
species in every catalyst is normalized and displayed above each spec­
trum. All of the fresh catalysts contain similar content (~4%) of extra-
framework Al species, suggesting that the coordination of Al atoms is
not significantly changed by the addition of La or Ce. After enduring
severe HTA, the content of extra-framework Al species considerably
rises to 61.7% over Cu-SSZ-13-A, indicating that the substantial frame­
work degradation has occurred. The content of extra-framework Al
species in La0.28Ce0.21Cu-SSZ-A and La0.48Ce0.31Cu-SSZ-13-A, in
contrast, almost remains constant, implying the excellent effect of La
and Ce on stabilizing the structure of catalysts under severe HTA. Fig. S6
shows the 29Si MAS NMR spectra of all samples. Compared with the
fresh catalyst, the ratio of Si(1Al) over Cu-SSZ-13-A reduces evidently
due to dealuminization during HTA. However, inconspicuous reduction
is observed in the spectra of LaCe-modified catalysts, which corresponds
to the 27Al MAS NMR result. It can be concluded through 27Al and 29Si
MAS NMR that the presence of La and Ce can prevent dealuminization of
Cu-SSZ-13 after HTA, improving its hydrothermal stability. This result
corresponds with the higher relative crystallinity of the hydrothermally
aged LaCe-modified catalysts confirmed by XRD analysis.
UV–Vis DRS of all catalysts were performed to study the coordination
for La, Ce and Cu species [36,37], and the corresponding spectra are
X. Wang et al.
27
Fig. 4. Al MAS NMR spectra of the (a) fresh and (b) hydrothermally aged catalysts.
presented in Fig. 5. A distinct band at around 211 nm and a broad band
within 600–800 nm are noticed in the spectra of all the catalysts
(Fig. 5a), which represent the charge transferring by framework oxygen
to isolated Cu2+ ions and the d-d transition of the Cu2+ ions in scattered
CuOx, respectively [36–40]. For LaCe-modified catalysts, a shoulder
band at about 268 nm associated with the charge transferring from
framework oxygen to La3+ and Ce3+ cations [15,16,41–43] is detected,
indicating that La3+ and Ce3+ are effectively added to the cation ex­
change sites on the catalyst. Simultaneously, the peaks at 211 nm related
to isolated Cu2+ become stronger in the spectra of La0.17Ce0.13Cu-SSZ-
13, La0.28Ce0.21Cu-SSZ and La0.48Ce0.31Cu-SSZ-13 when compared with
that over Cu-SSZ-13, indicating that the addition of La3+ and Ce3+ can
effectively promote Cu2+ to occupy the cation exchange sites in SSZ-13
zeolite. After HTA, according to Fig. 5b, an additional peak associated
with CuOx at 255 nm [44] is found over Cu-SSZ-13-A, while it is almost
invisible in the spectra of hydrothermally aged LaCe-modified catalysts,
which implies that the La3+ and Ce3+ for SSZ-13 are able to suppress the
generation of CuOx during HTA. Moreover, the band corresponding to
O2– to La3+ and Ce3+ ions shifted a little compared with their fresh
counterparts, which should be due to the partial collapse of zeolite
framework causing the recombination between the metal ions and SSZ-
13 [45]. The dispersion of elements in La0.28Ce0.21Cu-SSZ-13 before and
after HTA was also investigated by elemental mapping characterization
(Fig. S7), showing that each element in La0.28Ce0.21Cu-SSZ-13 and
Fig. 5. UV–vis DRS spectra of the (a) fresh and (b) hydrothermally aged catalysts: (i) Cu-SSZ-13 and Cu-SSZ-13-A, (ii) La0.17Ce0.13Cu-SSZ-13 and La0.17Ce0.13Cu-SSZ-
13-A, (iii) La0.28Ce0.21Cu-SSZ-13 and La0.28Ce0.21Cu-SSZ-13-A, (iv) La0.48Ce0.31Cu-SSZ-13 and La0.48Ce0.31Cu-SSZ-13-A, and (v) La0.62Ce0.43Cu-SSZ-13 and
La0.62Ce0.43Cu-SSZ-13-A, respectively.
6
Separation and Purification Technology 331 (2024) 125638
La0.28Ce0.21Cu-SSZ-13-A is well-dispersed.
XPS was used to investigate the chemical situation about Cu species
on catalysts’ surfaces, and the related Cu 2p3/2 spectra can be found in
Fig. S8. The bands can be deconvoluted into two peaks that are attrib­
uted to isolated Cu2+ coordinated by surface oxygen atoms (934.3 ~
935.4 eV) and CuO (933.4 eV), respectively [13,46]. When compared to
Cu-SSZ-13, the band linked to isolated Cu2+ over LaCe-modified cata­
lysts shows a shift toward lower binding energy, illustrating the
enhanced electronegativity of Cu2+ over LaCe-Cu-SSZ-13, which is
probably because of an association involving La3+/Ce3+ and Cu2+.
Table S3 contains the computed ratio of Cu2+/(Cu2++CuO) determined
by the peak area. It shows that the ratios (20.79%-27.02%) of Cu2+/
(Cu2++CuO) in LaCe-modified catalysts are greater than that (17.14%)
over Cu-SSZ-13 (Table S3), demonstrating that the modification of La
and Ce promotes the dispersion of Cu2+. After HTA, the ratio of Cu2+/
(Cu2++CuO) over Cu-SSZ-13-A drops obviously to 11.27%, but the ratio
remains almost unchanged over LaCe-modified catalysts (Fig. S7 and
Table S3), showing that the existence of La and Ce restrains the aggre­
gation of Cu2+ after HTA. The Ce 3d XPS spectra in Fig. S9 show that Ce
ions are mainly present as Ce3+ with small amount of Ce4+. Based on the
previous research [47], the redox couple of Ce3+ and Ce4+ could
improve the redox behavior in SCR.
EPR was utilized to determine the coordination environment of
isolated Cu2+ ions in all catalysts [48,49]. Fig. 6 displays the EPR
X. Wang et al. Separation and Purification Technology 331 (2024) 125638

Fig. 6. EPR spectra of hydrated (a, c) fresh and (b, d) hydrothermally aged catalysts.

spectrum and the magnified low-field hyperfine information. All cata­
lysts present the identical features with g‖ = 2.36, A‖ = 151 G and
g⊥=2.05 ascribed to the five-coordinate Cu2+ species in 6MRs [15,50].
As a result of the HTA process, a certain amount of Cu2+ ions are con­
verted to EPR-silent Cu species (CuOx), as evidenced by the significantly
weaker signal intensity of the hydrothermally aged catalysts than that of
their fresh counterparts. The quantity of Cu2+ in the catalysts was
determined by area normalization and reference to the peak area of Cu-
SSZ-13 (Fig. S10). For fresh catalysts, the amount of Cu2+ increases to a
peak value and then decreases with the growing content of La and Ce,
and the amount of Cu2+ in La0.28Ce0.21Cu-SSZ-13 is 1.45 times of that in
Cu-SSZ-13. After HTA, the quantity of Cu2+ decreases sharply over Cu-
SSZ-13-A with only 7% retaining, whereas more isolated Cu2+ ions are
preserved for LaCe-modified catalysts (69.6% for La0.28Ce0.21Cu-SSZ-13
and 49.6% for La0.48Ce0.31Cu-SSZ-13).
H2-TPR studies were implemented to investigate the Cu species over

Fig. 7. H2-TPR profiles of (a) fresh and (b) hydrothermally aged catalysts: (i) Cu-SSZ-13 and Cu-SSZ-13-A, (ii) La0.17Ce0.13Cu-SSZ-13 and La0.17Ce0.13Cu-SSZ-13-A,
(iii) La0.28Ce0.21Cu-SSZ-13 and La0.28Ce0.21Cu-SSZ-13-A, (iv) La0.48Ce0.31Cu-SSZ-13 and La0.48Ce0.31Cu-SSZ-13-A, and (v) La0.62Ce0.43Cu-SSZ-13 and La0.62Ce0.43Cu-
SSZ-13-A, respectively.

7
X. Wang et al. Separation and Purification Technology 331 (2024) 125638

all catalysts. According to Fig. 7a, two strong peaks centered at 190 and Table 2
459–488 ◦ C are found from the curves over all fresh catalysts, which are NH3 desorption amounts for the fresh and hydrothermally aged catalysts.
connected with the reduction of [ZCu2+(OH)]+ locating at 8MRs and Catalyst Weak acid Moderate Strong acid Total acid
Z2Cu2+ locating at 6MRs, respectively [12,16,20,51,52]. Another faint sites acid sites sites sites
peak at 330 ◦ C linked to the reduction of CuO is also detected on Cu-SSZ- (μmol⋅g− 1) (μmol⋅g− 1) (μmol⋅g− 1) (μmol⋅g− 1)
13, whereas it is almost invisible in the profiles of LaCe-modified cata­ La0.62Ce0.43Cu- 506 330 447 1283
lysts, revealing that the modification of La and Ce can limit the gener­ SSZ-13
ation of CuO, consistent with the above results. Comparing with Cu-SSZ- La0.48Ce0.31Cu- 544 372 438 1355
SSZ-13
13, the high-temperature reduction peaks related to Z2Cu2+ over LaCe- La0.28Ce0.21Cu- 585 402 429 1416
modified catalysts shift from 459 ◦ C to 485 ◦ C, suggesting that the SSZ-13
addition of La and Ce changes the chemical environment of Cu2+ ions. La0.17Ce0.13Cu- 525 352 442 1319
The quantity of the isolated Cu2+ was calculated from the H2 con­ SSZ-13
Cu-SSZ-13 502 293 460 1255
sumption and summarized in Table 1. As is found that the number of
La0.62Ce0.43Cu- 491 295 280 1066
[ZCu2+(OH)]+ and Z2Cu2+ in the catalysts increases following the order SSZ-13-A
of Cu-SSZ-13 < La0.62Ce0.43Cu-SSZ-13 < La0.17Ce0.13Cu-SSZ-13 < La0.48Ce0.31Cu- 511 337 338 1186
La0.48Ce0.31Cu-SSZ-13 < La0.28Ce0.21Cu-SSZ, which is closely related to SSZ-13-A
the NH3-SCR activity. Notably, the number of [ZCu2+(OH)]+ presented La0.28Ce0.21Cu- 564 380 341 1285
SSZ-13-A
in LaCe-modified catalysts increases significantly and reaches to 15.77 La0.17Ce0.13Cu- 497 318 316 1131
μmol⋅g− 1 for La0.28Ce0.21Cu-SSZ-13, which is much higher than that SSZ-13-A
(10.18 μmol⋅g− 1) of Cu-SSZ-13 by 1.5 times. The result implies that the Cu-SSZ-13-A 417 219 248 894
introduction of La3+ and Ce3+ promotes more Cu2+ to occupy the cation
exchange sites, especially the sites near 8MR, which has a favorable
(Fig. 8). There are three peaks in the profiles of the fresh catalysts: peak I
connection to the SCR activity. After HTA, the H2 reduction peak
at 142–151 ◦ C is connected with the physical adsorption NH3 and NH3
changes significantly, as shown in Fig. 7b. The reduction peaks related to
adsorbed on weak Lewis acid sites produced by extra-framework Al
[ZCu2+(OH)]+ and Z2Cu2+ shift to lower temperatures, which is most
species [39,53]; peak II at 300–307 ◦ C is attributed to the NH3 adsorbed
likely a consequence of a weaker interaction between the Cu2+ species
on the moderate Lewis acid sites, which are mainly associated with the
and SSZ-13 caused by the partial collapse of zeolite framework. For
Cu2+ ions in the cation exchange sites of SSZ-13; peak III at 479–495 ◦ C
hydrothermally aged LaCe-modified catalysts, the peaks below 200 ◦ C
is associated with the NH3 adsorbed on the strong Brønsted acid sites
become much flatter, and simultaneously the signals assigned to Cu+
[19,54,55]. The NH3 desorption quantities calculated via curve-fitting
reduction (above 500 ◦ C) appear, revealing that the Cu(OH)+-Z species
the NH3-TPD curves are presented in Table 2. It can be seen that the
are partially reduced into Cu+. However, the peak assigned to CuO
amounts (330–402 μmol⋅g− 1) of NH3 desorbed from the moderate Lewis
reduction is dominant for Cu-SSZ-13-A, and the reduction peak about
acid sites in LaCe-modified catalysts are higher than that (293 μmol⋅g− 1)
[ZCu2+(OH)]+ and Z2Cu2+ virtually vanishes, implying the severe ag­
in Cu-SSZ-13, which indicates that more Cu2+ ions are accessible for the
gregation of Cu2+ species during HTA. The isolated Cu2+ species in these
NH3 adsorption in LaCe-modified catalysts than in Cu-SSZ-13. After
catalysts were analyzed quantitatively and the results are listed in
HTA, regarding to all aged catalysts, the intensity of these three peaks,
Table 2. With regard to Cu-SSZ-13-A, it shows that the amount about
peak III in particular, decreases obviously (Fig. 7b). As shown in Table 2,
[ZCu2+(OH)]+ and Z2Cu2+ decreases dramatically from 10.18 μmol⋅g− 1
the quantities of NH3 desorbed from the moderate Lewis and strong
and 11.53 μmol⋅g− 1 to 3.23 μmol⋅g− 1 and 6.87 μmol⋅g− 1 with low
Brønsted acid sites decline significantly, which is probably caused by
retention rates of 31.7% and 59.6%, respectively. By contrast, the
Cu2+ accumulation and the collapse of the SSZ-13 framework. The most
retention rates of [ZCu2+(OH)]+ and Z2Cu2+ reach to 50–68% and
conspicuous decrease occurs over Cu-SSZ-13-A, but the hydrothermally
77–96%, respectively, for the hydrothermally aged LaCe-modified cat­
aged LaCe-modified catalysts still preserve more acid sites than Cu-SSZ-
alysts, revealing that much more isolated Cu2+ species are retained. It
13-A. The amounts of the moderate Lewis and strong Brønsted acid sites
suggests that the addition of La and Ce improves the stability of
decrease in the order of Cu-SSZ-13-A < La0.62Ce0.43Cu-SSZ-13-A <
[ZCu2+(OH)]+ and Z2Cu2+, and inhibits their transformation into
La0.17Ce0.13Cu-SSZ-13-A < La0.48Ce0.31Cu-SSZ-13-A < La0.28Ce0.21Cu-
inactive CuOx under hydrothermal conditions. Combining the XPS and
SSZ-A, which corresponds well with the number of isolated Cu2+ and
EPR results described above, it can be concluded that the introduction of
dealuminization confirmed by H2-TPR and 27Al MAS NMR, respectively.
La and Ce into Cu-SSZ-13 catalyst not only facilitates the dispersion of
It can be concluded from the above discussion, compared to the
Cu2+, but also restrains Cu2+ aggregation after HTA, leading to the
LaCe-free catalyst (Cu-SSZ-13), the introduction of La and Ce in Cu-SSZ-
improved SCR activity and hydrothermal stability.
13 can inhibit the dealumination and copper accumulation as well as
NH3-TPD was employed to evaluate the acidity of all catalysts
retain more acid sites, thus boosting the hydrothermal stability of the
LaCe-modified catalysts. Among the various LaxCeyCu-SSZ-13 catalysts,
Table 1 La0.28Ce0.21Cu-SSZ-13 shows the best crystallinity and the most AlIV
Quantification of isolated Cu2+ species in fresh and hydrothermally aged species, isolated Cu2+, moderate Lewis and strong Brønsted acid sites
catalysts. after hydrothermal stability, and thereby providing the best hydro­
Sample Isolated Cu2+ (μmol⋅g− 1) Total Cu2+ thermal stability.
2+ 2+ (μmol⋅g− 1)
[ZCu (OH)] +
Z2Cu

La0.62Ce0.43Cu-SSZ-13 12.79 11.57 24.36 3.4. In-situ DRIFT study

La0.48Ce0.31Cu-SSZ-13 15.13 12.26 27.39
La0.28Ce0.21Cu-SSZ-13 15.77 12.46 28.23 3.4.1. NH3 adsorption
La0.17Ce0.13Cu-SSZ-13 14.06 11.62 25.59
To analyze the adsorption of NH3 on the surface of Cu-SSZ-13 and
Cu-SSZ-13 10.18 11.53 21.28
La0.62Ce0.43Cu-SSZ-13-A 6.38 8.91 15.29 La0.28Ce0.21Cu-SSZ-13, in-situ DRIFT spectra of NH3 adsorption were
La0.48Ce0.31Cu-SSZ-13-A 10.11 11.02 21.13 measured at 100 ◦ C for a varying time. As illustrated in Fig. 9, the band
La0.28Ce0.21Cu-SSZ-13-A 10.62 11.87 22.49 located at 1626 cm− 1 is concerned with the asymmetric coordinated
La0.17Ce0.13Cu-SSZ-13-A 7.12 10.35 17.47 N–H bending vibrations of NH3 bounded to Lewis acid sites [56]; the
Cu-SSZ-13-A 3.23 6.87 10.10
bands at around 1438 and 3272 cm− 1 are ascribed to the NH+ 4 ions

8
X. Wang et al. Separation and Purification Technology 331 (2024) 125638

Fig. 8. NH3-TPD curves of (a) fresh and (b) hydrothermally aged catalysts.

Fig. 9. In-situ DRIFTS spectra of NH3 adsorption over (a) CuSSZ-13 and (b) La0.28Ce0.21Cu-SSZ-13 at 100 ◦ C for a varying time.

linked to the Brønsted acid sites [57–59]; the bands at 3333 and 3734 band intensity of the different NH3 adsorbed species steadily rises with
cm− 1 are related to the NH+ 4 and NH3 adsorbed on the Si-OH sites, prolonging the adsorption time, reaches its maximum in 15 min, and
respectively [60]; and the band at 3660 cm− 1 is associated with the NH+
4 then keeps unchanged. Cu-SSZ-13 and La0.28Ce0.21Cu-SSZ-13 show
adsorbed on the structural hydroxyl of the catalyst surface [57]. The identical NH3 adsorbed species, whereas the band intensity of

Fig. 10. In-situ DRIFTS spectra of the adsorption of 500 ppm NO + 5 v% O2 over (a) Cu-SSZ-13 and (b) La0.28Ce0.21Cu-SSZ-13 at 100 ◦ C for a varying time.

9
X. Wang et al.
La0.28Ce0.21Cu-SSZ-13 is significantly stronger than that of Cu-SSZ-13,
which suggests that the addition of La and Ce promotes the NH3
adsorption capacity, corresponding with the findings of NH3-TPD. It is
widely recognized that the NO conversion is highly linked to the NH3
adsorption capacity on the catalysts, especially at low temperature, and
thus La0.28Ce0.21Cu-SSZ-13 shows excellent low-temperature activity.
3.4.2. NO + O2 co-adsorption
Fig. 10 displays the in-situ DRIFT spectra of 500 ppm NO + 5 v% O2
co-adsorption for CuSSZ-13 and La0.28Ce0.21Cu-SSZ-13 at 100 ◦ C for a
varying time. There are three common kinds of NOx adsorbed sites found
on these two catalysts at the spectral range of 1400 ~ 1700 cm− 1. They
are ascribed to the bidentate nitrates (1573, 1597 and 1608 cm− 1),
bridged nitrates (1626 cm− 1) and nitrites formed by adsorbed NO2
(1454 and 1679 cm− 1), respectively [61–64]. With prolonging the
adsorption time, the band intensities of bidentate and bridged nitrates
over the two catalysts increase gradually, and a distinctive band
assigned to monodentate nitrates (1507 cm− 1) emerges in
La0.28Ce0.21Cu-SSZ-13 (Fig. S11). Compared with Cu-SSZ-13, the band
intensities of bidentate and bridged nitrates over La0.28Ce0.21Cu-SSZ-13
are significantly stronger, suggesting that the La and Ce play a key role
for the oxidation by NO to various NOx and improve the adsorption
capacity of NOx because of their good oxygen storage capacity. It is
known that bidentate and bridged nitrates tend to translate into mon­
odentate nitrates in SCR reaction, which has been identified as the key
intermediates for low-temperature NH3-SCR [65], and thus more mon­
odentate nitrates are formed over La0.28Ce0.21Cu-SSZ-13 promoting the
low-temperature activity.
Fig. 11. In-situ DRIFTS spectra of the surface adsorbed species arising from reaction of 500 ppm NO + 5 v% O2 with pre-adsorbed NH3 over (a) Cu-SSZ-13 and (b)
La0.28Ce0.21Cu-SSZ-13, and reaction of 500 ppm NH3 with pre-adsorbed NO + O2 over (c) Cu-SSZ-13 and (d) La0.28Ce0.21Cu-SSZ-13 for a varying time at 150 ◦ C.
10
Separation and Purification Technology 331 (2024) 125638
3.4.3. Reactions between NH3 and NO + O2 co-adsorption
Fig. 11 depicts the DRIFT spectra about the reaction of feeding NO +
O2/NH3 with the pre-adsorbed species changing with reaction time to
investigate the behavior of the pre-adsorbed NH3 (NOx) species on the
catalysts’ surface. As presented in Fig. 11a and 11b, the features of NH3
species adsorbed on the Lewis acid sites (1298 and 1624 cm− 1) and
Brønsted acid sites (1432 cm− 1) as well as N–H stretching vibration
(3182, 3272 and 3336 cm− 1) are detected prior to the addition of NO +
O2. Upon introducing NO + O2 to the pre-adsorbed NH3 on Cu-SSZ-13
− 1
(Fig. 11a), the NH+ 4 ions bounded to the Brønsted acid (1432 cm )
are gradually consumed and vanish in 10 min, while no significant
decrease in the NH3 linked to Lewis acid sites (1626 cm− 1), indicating
that NH+ 4 ions adsorbed on the Brønsted acid sites as a main part of the
reaction with NOx. Unlike Cu-SSZ-13, both of the NH+ 4 ions bounded to
the Brønsted acid sites (1432 cm− 1) and the NH3 linked to Lewis acid
sites (1626 cm− 1) over La0.28Ce0.21Cu-SSZ-13 decrease dramatically
with prolonging the reaction time (Fig. 11b). The adsorbed NH3 species
can be gradually consumed in the reaction with gaseous NO + O2,
suggesting that the SCR reaction on Cu-SSZ-13 and LaCeCu-SSZ-13 oc­
curs “Eley-Rideal (E-R)” mechanism [41]. When NH3 is fed with the pre-
adsorbed NO + O2, the bands assigned to bidentate nitrates (1573
cm− 1), bridged nitrates (1608 and 1626 cm− 1) and monodentate nitrates
(1507 cm− 1) decrease quickly and disappear in 2 min, and the bands of
different adsorbed NH3 species arise subsequently (Fig. 11c and 11d),
suggesting that the adsorbed nitrate species are highly reactive with NH3
species. It demonstrates that the NH3-SCR reaction on both the catalysts
also follows the “Langmuir-Hinshelwood (L-H)” mechanism [61,66].
Over Cu-SSZ-13, given the low adsorption capacity of NOx, but the rapid
consumption of the NH+ 4 ions bounded to Brønsted acid sites during the
reaction of the pre-adsorbed NH3 species with gaseous NO + O2, it is
X. Wang et al.
reasonable to speculate that gaseous NO preferentially participates in
the NH3-SCR reaction on Cu-SSZ-13. This speculation will be supported
by the NO + O2 + NH3 co-adsorption experiment presented by Fig. 12.
3.4.4. Co-adsorption of NH3 + NO + O2
The active intermediates on the surface of the two catalysts during
the real NH3-SCR reaction were studied via the experiments of co-
adsorption of NH3 + NO + O2, and Fig. 12 illustrates the interrelated
DRIFT spectra varying with reaction time. The features of NH3 species
adsorbed on the Brønsted acid sites (1458/1399 cm− 1), N–H stretching
vibration (3180/3184 and 3335 cm− 1), and indecomposable NH4NO3
(3276 cm− 1) formed during the reaction are detected over both cata­
lysts. The overlapped signals at 1626 cm− 1 associated with the NH3
species adsorbed on Lewis acid sites as well as the adsorbed bridged
nitrates are invisible over Cu-SSZ-13, while it appears in the spectra of
La0.28Ce0.21Cu-SSZ-13. These findings imply that the NH3 species
adsorbed on Brønsted acid sites are the primary active intermediates,
and NO participates in the reaction in gaseous state over Cu-SSZ-13.
However, over La0.28Ce0.21Cu-SSZ-13, both NH3 species adsorbed on
Brønsted and Lewis acid sites play crucial roles during the reaction, and
the adsorbed nitrate species are inclined to participate in the reaction. It
demonstrates that NH3-SCR reaction over Cu-SSZ-13 and La0.28Ce0.21Cu-
SSZ-13 primarily follows the E-R and L-H route, respectively, which may
originate from the distinctive adsorption capacities for NH3 and NOx
reactants on the two catalysts. Comparing the spectra at the varied
times, it is found that no intermediate is detected before 4 min over Cu-
SSZ-13, whereas various intermediates appear at 1 min over
La0.28Ce0.21Cu-SSZ-13, suggesting the much higher reactivity of re­
actants over La0.28Ce0.21Cu-SSZ-13 than over Cu-SSZ-13. Besides, the
feature at 3276 cm− 1 associated with NH4NO3 formed by adsorbed NO2
on Cu-SSZ-13 is noticeably higher than that on La0.28Ce0.21Cu-SSZ-13,
indicating that much more NH4NO3 species are generated on the surface
over Cu-SSZ-13 than over La0.28Ce0.21Cu-SSZ-13. It is difficult for
NH4NO3 to decompose at low temperature, and thus it brings about pore
blockage and active sites coverage on Cu-SSZ-13, reducing the NH3-SCR
activity. It demonstrates that the accumulation of NH4NO3 intermediate
species over the catalyst is suppressed by La and Ce introduction, hence
the low-temperature activity on La0.28Ce0.21Cu-SSZ-13 is promoted.
The above in-situ DRIFT results demonstrate that La and Ce modi­
fications can improve the adsorption capacity for NH3 and NOx species,
and promote the decomposition of NH4NO3 intermediate species formed
on the catalyst, benefiting the improvement of low-temperature activity.
The NH3-SCR reaction of Cu-SSZ-13 catalyst primarily follows the E-R
route, while over La0.28Ce0.21Cu-SSZ-13 dominantly conforms to the L-H
route.
Fig. 12. In-situ DRIFTS spectra of the surface adsorbed species arising from reaction of 500 ppm NH3 + 500 ppm NO + 5 v% O2 over (a) Cu-SSZ-13 and (b)
La0.28Ce0.21Cu-SSZ-13 at 150 ◦ C for a varying time.
11
Separation and Purification Technology 331 (2024) 125638
3.5. DFT calculations
In order to determine the position of La and Ce ions in H-SSZ-13, six
possible structural models of LaCe-SSZ-13 were formulated (Fig. 13, e.g.,
LaCe6MR-SSZ-13 indicates that Ce and La are located on the same 6MR,
while La6MR-Ce8MR-SSZ-13 indicates that La is located on the 6MR and
Ce on the 8MR, etc.). The energies of the different structures were
calculated and shown in Table 3. The model with the lowest energy (the
model with the strongest stability of the structure) was selected as the
reference zero point, and the relative energies (△E) of the other
structures were determined. The results show that the La8MR-Ce8MR-
SSZ-13 structure has the lowest energy, i.e., La and Ce located at two
different 8MRs is the most stable structure.
Based on the stable structure of La8MR-Ce8MR-SSZ-13, Cu ions were
introduced into 6MR and 8MR, respectively (Fig. 14, La8MR-Ce8MR-
Cu6MR-SSZ-13 and La8MR-Ce8MR-Cu8MR-SSZ-13). Comparing the
relative energies of the two structures (Table 4), it is found that the
introduced Cu ions prefer to enter into the 8MR (lower energy for the
La8MR-Ce8MR-Cu8MR-SSZ-13 structure). This result associations with
the H2-TPR analysis, i.e., the LaCe modification drives a significant in­
crease [ZCu2+(OH)]+ in the 8MR while the Z2Cu2+ in the 6MR does not
change significantly. It should be noted that this result is different from
previous Ce/La modification studies in which Cu ions in Cu-SSZ-13
tended to occupy the 6MR [17,19,20]. Such difference is probably
caused by different catalyst synthesis methods.
To further verify the effect of La and Ce modification on the NH3
adsorption capacity of the catalyst, NH3 molecule was introduced into
the above optimized La8MR-Ce8MR-Cu8MR-SSZ-13 to calculate the
adsorption energies at each site (La, Ce and Cu). For comparative
analysis, a Cu6MR-Cu8MR-SSZ-13 model was constructed. The adsorp­
tion energy Ead was calculated according to the following equation Ead
= E(model with NH3 molecule) - E(model without NH3 molecule) - E
(NH3 molecule), and the results are summarized in Table 5. In contrast
to the La8MR and Ce8MR sites in La8MR-Ce8MR-Cu8MR-SSZ-13, the
adsorption energy of NH3 on Cu8MR is the lowest (-2.465 ＜ − 1.562 ＜
− 1.446), indicating that Cu ions are still the dominant NH3 adsorption
sites in the rare earth-modified Cu-SSZ-13. By contrast, the NH3
adsorption capacity of Cu8MR in the catalyst without La and Ce
(Cu6MR-Cu8MR-SSZ-13) is weaker than that of Cu8MR in La8MR-
Ce8MR-Cu8MR-SSZ-13 (-2.465 < -2.300), suggesting that the intro­
duction of La and Ce enhances the NH3 adsorption capacity of the
catalyst, which corresponds to the NH3 adsorption of in-situ FTIR and
NH3-TPD results.
The adsorption capacity of the catalyst active sites for H2O de­
termines its potential to be attacked by H2O during the hydrothermal
ageing process. Similar to the introduction of NH3 molecule, the
adsorption energy of each site (La, Ce and Cu) was calculated by
X. Wang et al. Separation and Purification Technology 331 (2024) 125638

Fig. 13. Different models of LaCe-SSZ-13.

Table 3 Table 5
The △E of different LaCe-SSZ-13 models. The Adsorption energy (Ead) of NH3 and H2O on La8MR-Ce8MR-Cu8MR-SSZ-13
Model name △E/eV
and Cu6MR-Cu8MR-SSZ-13.
Model name Conditions E/eV Ead/eV
LaCe6MR-SSZ-13 5.037
LaCe8MR-SSZ-13 4.464 NH3 / − 19.538
La8MR-Ce6MR-SSZ-13 3.492 H2O / − 14.220
La6MR-Ce8MR-SSZ-13 3.256 La8MR-Ce8MR-Cu8MR-SSZ-13 La8MR without NH3 − 893.304
La6MR-Ce6MR-SSZ-13 5.745 NH3 on La8MR − 914.288 − 1.446
La8MR-Ce8MR-SSZ-13 0.000 Ce8MR without NH3 − 893.357
NH3 on Ce8MR − 914.457 − 1.562
Cu8MR without NH3 − 893.235
NH3 on Cu8MR − 915.238 − 2.465
Cu6MR-Cu8MR-SSZ-13 Cu6MR without NH3 − 877.008
NH3 on Cu6MR − 898.099 − 1.553
Cu8MR without NH3 − 878.502
NH3 on Cu8MR − 900.340 − 2.300
La8MR-Ce8MR-Cu8MR-SSZ-13 La8MR without H2O − 893.238
H2O on La8MR − 908.920 − 1.462
Ce8MR without H2O − 893.310
H2O on Ce8MR − 909.071 − 1.541
Cu8MR without H2O − 893.247
H2O on Cu8MR − 909.290 − 1.823
Cu6MR-Cu8MR-SSZ-13 Cu6MR without H2O − 876.358
H2O on Cu6MR − 892.435 − 1.857
Cu8MR without H2O − 877.078
H2O on Cu8MR − 893.391 − 2.093

introducing H2O molecule into La8MR-Ce8MR-Cu8MR-SSZ-13 and

compared with Cu6MR-Cu8MR-SSZ-13. As shown in Table 5, the
Fig. 14. The models of La8MR-Ce8MR-Cu6MR-SSZ-13 and La8MR-Ce8MR- Cu8MR in Cu6MR-Cu8MR-SSZ-13 is more susceptible to water attack
Cu8MR-SSZ-13. (-2.093 < -1.857), which is in agreement with previous studies that Cu
ions in 8MR are more susceptible to aggregation by hydrothermal aging
[21]. While in La8MR-Ce8MR-Cu8MR-SSZ-13, the adsorption capacity
Table 4
of Cu8MR sites for H2O becomes weaker (-1.823 > -2.093), suggesting
The △E of La8MR-Ce8MR-Cu6MR-SSZ-13 and La8MR- Ce8MR-
that the introduction of La and Ce strengthen the water resistance
Cu8MR-SSZ-13.
capability of the catalyst.
Model name △E/eV

La8MR-Ce8MR-Cu6MR-SSZ-13 1.589 4. Conclusions

La8MR-Ce8MR-Cu8MR-SSZ-13 0

In summary, La and Ce-modified SSZ-13 zeolites have been rapidly

prepared via a one-step method from spent FCC catalyst. The resulting

12
X. Wang et al.
LaCeCu-SSZ-13 catalysts outperform Cu-SSZ-13 in terms of hydrother­
mal stability and low-temperature NH3-SCR activity. The DFT calcula­
tions confirm that La and Ce located on different 8MRs (La8MR-Ce8MR-
SSZ-13) in SSZ-13 can not only promote the formation of active
[ZCuOH]+ on the 8MRs, but also improve the NH3 adsorption capacity
and reduce the adsorption capacity of the active site for H2O, which are
the main driving forces for an increase in NH3-SCR activity. In partic­
ular, over La0.28Ce0.21Cu-SSZ-13, the NO conversion can reach 80% at
150 ◦ C and maintain above 90% at temperatures of 175–550 ◦ C, and the
catalytic activity hardly decreases at temperatures from 250 to 450 ◦ C
after HTA at 800 ◦ C for 12 h. Additionally, the La and Ce modification
promotes the decomposition of NH4NO3 intermediate species on the
catalyst, and thus the low-temperature NH3-SCR activity on LaCeCu-
SSZ-13 is improved via L-H mechanism. This work may offer a cost-
efficient method for fast synthesis of LaCe-modified zeolite catalysts
for NH3-SCR reaction as well as some insights into the roles of La and Ce
species in the LaCeCu-SSZ-13 catalyst.
CRediT authorship contribution statement
Xueqin Wang: Conceptualization, Methodology, Writing – original
draft, Data curation. Tiesen Li: Formal analysis, Methodology. Chan
Wang: Methodology, Supervision, Funding acquisition, Data curation,
Writing – review & editing. Qingyan Cui: Formal analysis. Tinghai
Wang: Formal analysis. Xiaojun Bao: Funding acquisition, Project
administration, Resources. Yuanyuan Yue: Methodology, Funding
acquisition, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
The funding from the National Natural Science Foundation of China
(grants 22322803, 22178059, 22208054, 22221005 and 22072019),
Natural Science Foundation of Fujian Province, China (grant 2022
J01572), Key Technologies Innovation and Industrialization Projects of
Fujian Province, China (grant 2022G031), and Qingyuan Innovation
Laboratory (grant 00121002) are gratefully acknowledged.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.seppur.2023.125638.
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