Straightforward synthesis of MTW-type magnesium silicalite for CO2 fixation with epoxides under mild conditions

Article abstract of DOI:10.1039/c9cy01329f

Aluminum-free magnesium silicalite with MTW topology (Mg-Si-ZSM-12) was fabricated via a straightforward hydrothermal synthesis route involving an initial acid co-hydrolysis step. Mg incorporation endowed superior basic properties to the MTW framework, as illustrated by CO₂ sorption and temperature programmed desorption plus the activity in a typical basic reaction, Knoevenagel condensation. Mg-Si-ZSM-12 catalyzed the coupling of atmospheric CO₂ with epoxides and led to the efficient production of cyclic carbonates with high yield and selectivity at relatively low temperature (down to 60 °C). The present strategy afforded a zeolitic solid base with regular 12-membered ring microporous channels that has potential application in CO₂ fixation.

Full text of DOI:10.1039/c9cy01329f

View Article Online
View Journal
Catalysis
Science &
Technology
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: H. Wen, J. Xie, Y.
Zhou, Y. Zhou and J. Wang, Catal. Sci. Technol., 2019, DOI: 10.1039/C9CY01329F.
Volume
Number
21 January 2017
Pages 313-534
7
2
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Catalysis
Science &
Technology
rsc.li/catalysis
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 2044-4761
PAPER
Chaoqiu Chen, Yong Qin et al.
Highly dispersed Pt nanoparticles supported on carbon
nanotubes produced by atomic layer deposition for hydrogen
generation from hydrolysis of ammonia borane
rsc.li/catalysis

Please do not adjust margins
Catalysis Science & Technology
Page 1 of 11
View Article Online
DOI: 10.1039/C9CY01329F
ARTICLE
Straightforward synthesis of MTW-type magnesium silicalite for
CO2 fixation with epoxides under mild conditions†
Haimeng Wen, a Jingyan Xie, a,b Yang Zhou,a Yu Zhou*a and Jun Wang *a
Received 00th January 20xx,
Accepted 00th January 20xx
Aluminum-free magnesium silicalite with MTW topology (Mg-Si-ZSM-12) was fabricated in a straightforward hydrothermal
synthesis route involving an initial acid co-hydrolysis step. Mg incorporation endowed superior basic properties in the MTW
framework, as illustrated by CO2 sorption and temperature programmed desorption plus the activity in a typical basic
reaction, Knoevenagel condensation. Mg-Si-ZSM-12 catalyzed coupling of atmospheric CO2 with epoxides led the efficient
production of cyclic carbonates with high yield and selectivity at relatively low temperature (down to 60 °C). The present
strategy afforded a kind of zeolitic solid base with regular 12-membered ring microporous channels that possesses potential
application in CO2 fixation.
DOI: 10.1039/x0xx00000x
conditions (high temperature and pressure).22-24 For example, KX and
Cs-loaded KX zeolites exhibited low yields in the conversion of high-
pressure CO2 (3.8 MPa) and epoxides at high temperature of 150 °C.
Introduction
Carbon dioxide (CO2) conversion into value-added chemicals have
attracted significant growing academic and industrial attentions.1-3
The importance of this issue is not only because CO2 is one of the
main contributors to the greenhouse effect for climate change, but
also CO2 is widely regarded as a naturally abundant, inexpensive,
eco-friendly and renewable C1 resource.4-6 So far, various chemicals
have been produced through CO2 transformation,7-10 and
cycloaddition of CO2 with epoxides is a promising methodology to
produce cyclic carbonates that have found wide applications in the
pharmaceutical and fine chemical industries.11-13 Great efforts have
been denoted to design efficient catalysts such as metal complexes,
organic molecules, metal organic frameworks (MOFs), covalent
organic frameworks (COFs) and porous organic polymers (POPs).14-18
Despite these progresses, it is exceedingly desirable but still one
challenge to develop easily available heterogeneous catalysts to
catalyze the CO2 fixation under mild conditions.
Porous materials are preferred in a heterogeneous catalysis due to
the abundant porosity that can improve the dispersion and
accessibility of active sites. Zeolites, crystalline aluminosilicates, are
among the most important porous materials and have been
extensively applied as adsorbents and catalysts in industry,
attributable to their large surface areas, regular microporous
channels, high thermal/hydrothermal stability, adjustable chemical
composition, topology and morphology.19-21 Up to now, only several
zeolites and their analogues have been tried in the CO2 cycloaddition
with epoxides and the reaction was normally carried out under harsh
The activity was related to the basicity of these zeolites and the one
having occluded alkali metal oxides was more active.22 An organic-
inorganic hybrid zeolite with organic structure-directing agents in the
MFI-type lamellar structure was active in the coupling of CO2 (2 MPa)
with a variety of epoxides at 140 °C.23 The zeolite analogues,
lanthanide zeolite assembled by [Ln60] nanocages with strong
basicity, effectively catalyzed the coupling of CO2 with multiple
epoxides in the presence of tetrabutylammonium bromide (TBAB).24
Therefore, efficient zeolites for the CO2 conversion via cycloaddition
reaction are still to be explored.
Ring-opening via nucleophilic attack, CO2 insertion, and ring-
closure with the leaving of nucleophile are the three primary steps in
the CO2 cycloaddition with high energy three-membered
heterocyclic compounds such as epoxides.10-15 Because CO2
molecules are naturally acidic and inert, strengthening the basicity of
a heterogeneous catalyst benefits to promote the CO2 activation for
improving the activity. Such phenomenon was also found in the
above-mentioned zeolites catalyzed CO2 cycloaddition reaction.22
However, zeolites usually have weak basicity that is disadvantageous
for the CO2 activation in the cycloadditions. The reason is attributable
to that the classic zeolites are crystalline aluminosilicates composed
-
of SiO4 and AlO4 units, and conventional modifications usually
generate acid or acid-base sites due to the intrinsic acidity provided
by the aluminum (Al) species.25-28 Several approaches have been
proposed to prepare Al-free zeolites to construct basic zeolites and
exclude the potential Al species derived shielding on basic sites.29-31
Compared with post-modifications, straightforward synthesis
simplifies the procedure and preserves the zeolitic crystalline
microporous channels to a great extent,32-34 but fabrication of Al-free
basic zeolites was extremely scarce in the hydrothermal synthesis.
Incorporation of metal ions with low electronegativity can improve
the basicity of zeolites.35-38 Mg-containing Silicalite-1 with MFI
topology (MgS-1) was synthesized as efficient zeolitic solid base,39
a. State Key Laboratory of Materials-Oriented Chemical Engineering, College of
Chemical Engineering, Nanjing Tech University, Nanjing 210009, Jiangsu, P. R.
China. E-mails: njutzhouyu@njtech.edu.cn (Y. Zhou), junwang@njtech.edu.cn (J.
Wang)
b. Maoming Branch R&D Institute, SINOPEC, Maoming 525011, P. R. China.
† These two authors contributed equally: Haimeng Wen and Jingyan Xie.
Electronic Supplementary Information (ESI) available: [Figure S1-S9]. See
DOI: 10.1039/x0xx00000x
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 2 of 11
ARTICLE
Journal Name
but such methodology has not been expanded to other topological comparison, Mg2+-incorporated silicate-1 sample (MgS-1) was
View Article Online
zeolites, due to the synthetic difficulty in the synthesis of metal synthesized according to the literature.39
DOI: 10.1039/C9CY01329F
containing and Al-free zeolites.
Characterization
In this work, we report the direct synthesis of Al-free MTW-type
The crystalline structure was characterized by X-ray diffraction
magnesium silicalite (Mg-Si-ZSM-12) that affords a new kind of
analysis (XRD) with a SmartLab diffractmeter from Rigaku equipped
zeolitic solid base with large 12-membered ring (12-MR)
with a 9 kW rotating anode Cu source at 45 kV and 100 mA, from 5°
microporous channels. The synthesis was achieved in a hydrothermal
to 50° with a scan rate of 0.2° s-1. Field-emission scanning electron
route with an initial acid co-hydrolysis stage that facilitates a fine
microscope (SEM) instrument (HITACHI S-4800) was used to reveal
control of co-hydrolysis and condensation of metal and silica
the morphology information. Nitrogen sorption experiment for the
precursors to enable the incorporation of Mg species in the zeolitic
measurement of surface area and pore volume was carried out at 77
skeleton.40-42 Multiple synthetic parameters were investigated to
K on a BELSORP-MAX analyzer. The samples were pre-degassed at
provide high crystalline zeolite structure. The basicity of Mg-Si-ZSM-
300 °C for 3 h. Fourier Transform infrared spectroscopy (FT-IR)
12 was illustrated by CO2 sorption and temperature programmed
spectra were recorded on an Agilent Cary 660 FT-IR instrument in the
desorption (CO2-TPD) plus the efficiency in a typical basic reaction,
region 4000-400 cm-1. In situ FT-IR spectra were recorded on the
Knoevenagel condensation. The topology of zeolites is intrinsically
Agilent Cary 660 spectrometer equipped with a mercury cadmium
essential for their applications, and herein, we demonstrated that
telluride (MCT) detector and a Harrick Scientific DRIFTS cell at a
the large 12-MR of Mg-Si-ZSM-12 apparently accelerated the
resolution of 4 cm-1. The samples were pretreated at 473 K for 5 h
reaction rate and gave high yields in the condensation between
under N2 atmosphere. Spectra were collected at 0, 1, 5, 15 and 30
various aromatic aldehydes and ethyl cyanoacetate or malononitrile.
min after adsorption of dynamic CO2 or epoxypropane stream.
Owing to the superior basicity, Mg-Si-ZSM-12 was active in the
Epoxypropane was introduced through bubbling by carrier gas (N2).
cycloaddition of CO2 with epoxides under mild conditions. A series of
Solid UV-vis spectra were measured on a SHIMADZU UV-2600
epoxides including the long alkyl chain terminal ones were effectively
spectrometer and barium sulfate (BaSO4) was used as an internal
converted into the corresponding cyclic carbonates by coupling with
standard. Chemical compositions were analyzed by using Jarrell-Ash
atmospheric CO2. After reaction, the catalyst was facilely recovered
1100 inductively coupling plasma (ICP) spectrometer. Temperature
and reused. The activity of Mg-Si-ZSM-12 was also compared with
programmed desorption of carbon dioxide (CO2-TPD) was performed
previous Mg-containing silicalite MgS-1 and commercial solid base
on an instrument of Catalyst Analyzer BELCAT-B. Samples were
MgO.
pretreated at 550 °C for 2 h, and then cooled to 50 °C under helium
(He) gas. Adsorption of CO2 was carried out at 50 °C for 30 min under
the flow rate of 30 mL min-1. After the samples were purged under
Experimental
Synthesis
He gas for 30 min, the temperature was heated to 700 °C (8 °C min-
1). The desorbed gas was determined by a Gow-Mac thermal
MTW-type magnesium silicalite (Mg-Si-ZSM-12), was hydrothermally
synthesized in an acidic co-hydrolysis route. Typically, concentrated
aqueous hydrochloric acid (HCl, 36.5 wt.%) was slowly dropped into
a mixed aqueous solution of TEOS (28.4 wt. % SiO2, Shanghai Chem.
Reagent Co., AR) and Mg(NO3)2•6H2O (99 wt.%, Sinopharm Chem.
Reagent Co., AR) to reach pH=0.8 and then the mixture was stirred
at 90 °C for 4 h. The H2O/SiO2 molar ratio was adjusted by
evaporation at 100 °C. A slight lower temperature of 90 oC than the
conductivity detector (TCD). Basic sites are determined by using
ChemMaster software. 29Si magic angle spinning nuclear magnetic
resonance (MAS NMR) spectrum was obtained on a Bruker Avance III
spectrometer at an external magnetic field of 9.4 T with a 7 mm
double-tuned MAS probe at a spinning rate of 6 kHz. CO2 sorption
isotherms at 273 and 298 K up to 1.0 bar were recorded on BELSORP-
MAX analyser. Isosteric heat of CO2 adsorption (Qst) was calculated
according to Clausius-Clapeyron equation by fitting CO2 isotherms
with Virial equation.44
o
boiling point of water (100 C) was adopted in the initial acid co-
hydrolysis step to enable sufficient hydrolysis and condensation of
silica precursor tetraethyl orthosilicate (TEOS) and avoid the rapid
evaporation of water in the initial stage. After that, the temperature
of 100 oC was used to reach more sufficient hydrolysis and
Catalysis test
Knoevenagel condensation of aromatic aldehyde with malononitrile
or ethyl cyanoacetate was carried out in a round bottom flask. In a
typical run, aromatic aldehyde (8 mmol) and malononitrile or ethyl
cyanoacetate (8 mmol) was dissolved in ethanol, followed by
addition of catalyst (0.1 g). The reaction mixture was stirred at 70 oC
for 4 h. After reaction, the mixture solution was cooled down to room
temperature and diluted by ethanol. N-dodecane (0.5 g) as internal
standard was added and the reaction mixture was centrifuged to
remove the solid catalyst. The products were analyzed by gas
chromatograph (GC, Agilent 7890B) equipped with an FID detector
and a capillary column (HP-5, 30 m×0.25 mm×0.25 mm).
condensation
of
silica
precursor.40,43
Subsequently,
tetraethylammonium hydroxide (TEAOH, 25 wt. %, Jintan Huadong
Chem. Res. Institute, AR) was dropwise added into the gel, followed
by a further aging at room temperature for 24 h. The molar
composition of the resulting gel mixture was 40 SiO2: 8 TEAOH: 0.8
MgO: 320 H2O. The pH value of the gel was then adjusted to be 12.3
by adding alkali source such as sodium hydroxide (NaOH) or
potassium hydroxide (KOH). After that, the gel was transferred to a
Teflon-lined stainless-steel autoclave and statically crystallized at
140 °C for 14 d. The solid was isolated by centrifugation, washed with
water and dried at 100 °C. The obtained as-synthesized sample was
calcined at 550 °C for 5 h in air to give the as-calcined product. For
The synthesis of cyclic carbonates through the cycloaddition of
CO2 with epoxides was performed under atmospheric condition. In a
typical procedure, epichlorohydrin (5 mmol), catalyst (0.12 g) and
tetrabutylammonium bromide (TBAB, 0.048 g, 3 mol% with respect
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 11
Catalysis Science & Technology
Please do not adjust margins
Journal Name
ARTICLE
phenomenon suggests that the presence of Mg2+ is important for the
View Article Online
DOI: 10.1039/C9CY01329F
formation of MTW structure.
Various parameters including the alkali source, gel composition
and crystallization condition were investigated to gain insight into
the synthesis. Alkali metal ions were vital for the synthesis of zeolites
by influencing the crystallization rate, crystal size and
morphology.25,26 Herein, the influence of Na+ and K+ cations on the
synthesis process was studied by varying the alkali source. In the case
of NaOH, Mg-Si-ZSM-12 was synthesized with the crystallization pH
value from 11.7 to 12.5, reaching the highest crystallinity at pH=12.3
(Fig. S2A†). By contrast, Mg-Si-ZSM-12 was obtained only with the
crystallization at pH=12.5 by using KOH (Fig. S2B†). Further, the
Scheme 1 Schematic illustration of the synthesis procedure and synthesis of Mg-Si-ZSM-12 was tried in the co-existence of NaOH and
structural skeleton of Mg-Si-ZSM-12.
KOH. The suitable pH value during the crystallization was 11.5-11.9
by using equal weight amount NaOH and KOH (Fig. S2C†). These
to the substrate) were placed in a 25 mL Schlenk flask with a CO2 results indicate that both NaOH and KOH are effective in the
balloon (1.0 bar). The reaction proceeded at the specified synthesis, with broader synthesizable scope by using NaOH.
temperature for preset time. After reaction, the reaction mixture
Notably, the water content in the gel is a critical factor. Fig. S2D†
was diluted with ethyl acetate, followed with the addition of the shows the XRD patterns of Mg-Si-ZSM-12 samples synthesized with
internal standard n-dodecane (0.5 g). The solid catalyst was removed different molar ratios of water to silica in the gel (H2O/SiO2 ratio).
by centrifugation, and the filtrate was analyzed by GC and GC-MS Amorphous structure was formed with low H2O/SiO2 ratio (<7), which
(Bruker Scion 436 GCMS). Reusability was investigated in a five-run is assigned to the failure of the dissolution of the raw materials under
recycling test. After reaction, the recovered catalyst was washed such conditions. By increasing H2O/SiO2 ratio to 7, only certain feeble
with ethanol and charged into next run.
characteristic peaks assignable to MTW topology appeared, implying
Adsorption of bulky epoxide
The adsorption of 1,2-epoxytetradecane was measured in a glass
tube. Typically, catalyst (50 mg), 1,2-epoxytetradecane (5 mg) and
ethyl acetate (1 mL) were stirred at room temperature for a
quarantine period. After that, the solid was removed by filtration and
the filtrate was analyzed by GC. The adsorption amounts were
determined from the variation in adsorbate concentration.
Results and discussion
Formation of magnesium silicalite
Scheme 1 shows the synthetic procedure of MTW-type magnesium
silicalite (Mg-Si-ZSM-12) involving an acid co-hydrolysis step. Three
typical Mg-Si-ZSM-12 samples were synthesized with the initial gel
composition of 40 SiO2: 8 TEAOH: 0.4 (0.8 and 1.6) MgO: 320 H2O.
They are termed Mg-Si-ZSM-12(n), in which n (n=100, 50 and 25)
denotes the Si/Mg molar ratio in the gel. XRD patterns of them
showed typical diffraction peaks at 2θ values of 7.4°, 8.8°, 20.8° and
23.1° for MTW zeolites (Fig. 1A).45 No impurity for other phase was
observable, revealing the well crystalline structure. The Mg content
in the gel affects the synthesis as well as the crystallinity of the
product and the highest crystallinity was obtained at n=50. Excessive
Mg salt in the gel (e.g. n=20) caused amorphous structure (Fig. S1†).
Because of longer bond length of Mg-O (0.185 nm) in comparison
with Si-O (0.161 nm) and Al-O (0.175 nm), incorporation of Mg will
distort the tetrahedron inevitably and become a disadvantage for the
crystallization.39,46 Meanwhile, not all of the Mg ions added in the
initial stage were incorporated into zeolites, and the dissociative or
extra-framework metal ions affect the crystallization.47,48 The
preparation of pure silica ZSM-12 failed in this system, resulting
either amorphous structure or no solid after crystallization. This
Figure 1 (A) XRD patterns, (B) FT-IR spectra, (C) UV-vis spectra, (D) N2
sorption isotherms and (E) TG curves of Mg-Si-ZSM-12(n) series; (F)
29Si MAS NMR spectrum of Mg-Si-ZSM-12(50).
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 4 of 11
ARTICLE
Journal Name
Table 1 Textural properties.
View Article Online
Unit cell parDaOmIe: 1t0e.r1s0b39/C9CY01329F
Surface
area
(m2 g-1)
Pore
volume
(cm3 g-1)
Basic
sites
(mmol g-1)
Mg/Sia
Sample
a
b
(nm)
c
V
(nm3)
(mol/mol)
(nm)
(nm)
Mg-Si-ZSM-12(100)
Mg-Si-ZSM-12(50)
Mg-Si-ZSM-12(25)
0.0079
0.0091
0.0083
244
312
256
0.32
0.41
0.35
0.914
1.451
0.892
24.84
24.93
24.90
5.03
5.05
5.04
12.17
12.21
12.19
1462.30
1498.47
1479.24
aMg/Si molar ratios in the final solid products. Unit cell parameters determined by using MDI Jade software (Jade 7 XRD Pattern
b
processing Software).
characteristic of stretching vibrations of the double five-membered
rings of the MTW structure.51 Fig. 1C shows the UV-vis spectra. No
absorption in the 220-800 nm range is observed over the Mg-free
sample,52 while all the Mg-Si-ZSM-12(n) samples exhibited a distinct
absorption band at 260 nm, same as the Mg2+-incorporated silicalite-
1.39 Such a signal can be assigned to theexcitation of O atoms around
the framework Mg species, which is highly distorted or possesses
vacancies compared to the regular MgO topology.53
The porosity was quantitatively measured by N2 sorption
experiment. The corresponding N2 sorption isotherms are presented
in Fig. 1D and the related textural properties are shown in Table 1.
All the samples have the isotherms of mixed type I and IV, according
to the IUPAC classification. A H3 type hysteresis loop is observed at
region of P/P0>0.4 due to capillary condensation, implying the
formation of mesopores derived from the aggregation of small
particles. These features demonstrate the co-existence of
micropores and mesopores.54 The presence of abundant mesopores
Figure 2 (A, B) SEM images (the inset images are the corresponding was further reflected by the relative narrow pore size distribution
energy-dispersive X-ray spectrometry elemental mapping analysis) with the most probable pore size located at 3.7 nm (Fig. S4†). All the
and (C, D) TEM images of Mg-Si-ZSM-12(50).
samples possess high surface area and large pore volume, similar to
previously reported ZSM-12.55 The concrete values depend on the
Mg content. Mg-Si-ZSM-12(50) has the highest surface area of 312
the low crystallinity. Well-defined crystal structure emerged as
H2O/SiO2 ratio increased to 8. Further increased H2O/SiO2 ratio
caused amorphous structure. The crystallization time and template
content in the gel were also investigated, giving the highest
crystallinity with TEAOH/SiO2 molar ratio of 0.2 (Fig. S3A†) and the
crystallization time of 14 d (Fig. S3B†).
Further structural characterization
Systematical structure characterizations were performed on Mg-Si-
ZSM-12(n) (n=100, 50 and 25) zeolites. Their chemical composition
was analysed by ICP and the results in Table 1 indicate the
incorporation of Mg ions. The molar ratio of Mg to Si (nMg/nSi) was
0.0079 for n=100. This value varies to 0.0091 and 0.0083 for n=50
and 25. Lower nMg/nSi values were in the final products than those in
the gel, due to that part Mg species stay in the solution after
crystallization. Mg-Si-ZSM-12(25) has lower Mg content than Mg-Si-
ZSM-12(50), attributable to the salt effect that is frequently observed
in the synthesis of zeolite, especially for heteroatomic zeolite.40,49,50
The crystallization would be disturbed when higher condensation of
metal salt existed in the synthetic system, and thus cause declined
content of heteroatom in the solid. The unit cell parameters are
calculated from XRD patterns and summarized in Table 1. The unit
cell of Mg-Si-ZSM-12(n) expands with Mg loadings and achieves the
maximum at n=50 (Table 1), suggesting the Mg incorporation.
In the FT-IR spectra (Fig. 1B), the band near 580 cm-1 is
Figure 3 (A) CO2-TPD profiles; CO2 sorption isotherms at (B) 273 K and
(C) 298 K; (D) Isosteric heats (Qst) of CO2 adsorption.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 11
Catalysis Science & Technology
Please do not adjust margins
Journal Name
ARTICLE
Table 2 Knoevenagel condensation catalyzed by Mg-Si-ZSM-12(50)a
View Article Online
DOI: 10.1039/C9CY01329F
Molecule size
(Å)
Methylene
compounds
Entry
1
Aromatic aldehyde
Product
Conv. (%)b
100/37d
Blank (%)c
O
CN
H
6.64×4.64
7.25×4.64
6.65×5.41
6.64×4.64
7.25×4.64
27
CN
CN
CN
NC
NC
NC
NC
O
CN
H
2
3
4
5
100
100
100
100
25
20
20
27
NC
Cl
Cl
OH
O
OH
CN
H
NC
O
CN
O
O
H
CN
CN
O
O
O
O
O
CN
H
Cl
O
O
Cl
OH
OH
O
O
O
CN
H
6
7
6.65×5.41
7.60×6.43
91
60
23
20
CN
CN
O
O
O
O
O
H3CO
CN
H3CO
HO
H
HO
O
O
aReaction condition: aromatic aldehydes (8 mmol), ethyl cyanoacetate or malononitrile (8 mmol), catalyst (0.1 g), ethanol (5 mL), 70 °C, 4 h.
bGC conversion with the selectivity of target product above >99%. cConversion in the absence of catalyst. dKnoevenagel condensation
between benzaldehyde (5 mmol) and diethyl malonate (5 mmol).
m2 g-1 and largest pore volume of 0.41 cm3 g-1.
images in Fig. 2A, 2B and S5†. All of them are the crystallites with
Fig. 1E displays the TG curves of as-synthesized Mg-Si-ZSM-12(n) well-defined rice-like shape and the size of ca. 1 μm. Amplified SEM
o
samples. The slow weight loss before 150 C comes from the water image indicated that these particles were aggregations of sheet-like
desorption. Drastic weight loss occurs in the temperature range from primary particles and closely connected with each other. As the Mg
150 to 550 oC, attributable to the decomposition of organic template. content increases, these particles became flatter and longer,
Only feeble weight loss happened at high temperature above 600 oC, accompanying with increase of their average size. The inset images
reflecting the well thermal structural stability. Fig. 1F shows the 29Si of Fig. 2B are the corresponding EDX elemental mapping images,
MAS NMR spectrum of Mg-Si-ZSM-12(50). Relatively sharp peaks depicting a highly dispersive of Mg species. The rice-like morphology
appearing in the range of -105 to -120 ppm are attributable to Q4 was further revealed by TEM image (Fig. 2C). Well-ordered lattice
[(Si(OSi)4] sites, reflecting the well crystalline structure .56
The morphologies of Mg-Si-ZSM-12(n) series are reflected by SEM image (Fig. 2D), visualizing the crystalline structure.
fringe over a large area was observed in the high-resolution TEM
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 6 of 11
ARTICLE
Journal Name
Table 3 Cycloaddition of CO2 with epoxides catalyzed by Mg-Si-ZSM-12(50)a
View Article Online
DOI: 10.1039/C9CY01329F
Entry
1
Epoxide
Molecule size (Å)
Product
T [°C]
Time [h]
10/3b
Conv. [%]
Sel. [%]
O
O
4.13×3.38
O
60/150b
96/87b
>99/>99 b
O
Cl
Cl
O
O
O
96c
95c
O
O
2
3
7.21×2.34
7.41×4.66
90
90
9
9
96
96
C4H9
C4H9
O
O
O
O
O
O
O
O
O
O
O
4
5
8.56×4.67
8.62×3.41
90
90
9
9
95
99
>99
O
O
O
95c
O
O
O
O
O
O
O
6
7
8
10.12×3.25
12.26×3.32
14.31×3.28
100
100
100
9
9
9
98
98
95c
96c
C8H17
C10H21
C12H25
C8H17
O
O
O
O
C10H21
96/28d
96c/99d
O
O
C12H25
aReaction condition: epoxide (5 mmol), catalyst (0.12 g), CO2 (1.0 bar), TBAB (3 mol%). bActivity of Mg-Si-ZSM-12(50) in the absence of TBAB
with epichlorohydrin (15 mmol) and CO2 (3 MPa). cMain by-product is 1,2-diol. dActivity of TBAB alone (3 mol%).
Basicity
position and area. As shown in Fig. 3A, only one desorption peak
ranging 50-250 °C appeared in the CO2-TPD curves, reflecting that
these samples have weak and moderate basicity. The number of
basic sites calculated from the desorption peak area is 0.914, 1.451
Incorporation of Mg species into zeolitic skeleton can produce basic
sites.46,57 CO2-TPD analysis was utilized to investigate the relative
basic strength and total amount of basic sites, according to the peak
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 11
Catalysis Science & Technology
Please do not adjust margins
Journal Name
ARTICLE
and 0.892 mmol g-1 respectively for Mg-Si-ZSM-12(100), Mg-Si-ZSM- by using small substrates of benzaldehyde (6.64×4.64 Å) and p-
View Article Online
DOI: 10.1039/C9CY01329F
12(50) and Mg-Si-ZSM-12(25). Moreover, the desorption peak in the chlorobenzaldehyde (7.25×4.64 Å). The larger salicylaldehyde
TPD curve of Mg-Si-ZSM-12(50) shifted to higher temperature, (6.65×5.41 Å) gave a slightly decreased conversion of 91 %. The bulky
reflecting that this sample has superior basicity to the other two.
vanillic aldehyde (7.60×6.43 Å) only afforded the conversion of 60%,
The static single component CO2 sorption isotherms of Mg-Si-ZSM- attributable to the enhanced steric hindrance in the confined space.
12(n) were collected up to 1.0 bar at 273 K and 298 K (Fig. 3B and 3C). The diffusion of molecules in the zeolites’ microchannels locates in
At each temperature, the highest CO2 uptakes of 1.35 mmol g-1 (273 the range of structure-activity diffusion when the size of molecules is
K, 1 bar) and 0.78 mmol g-1 (298 K, 1 bar) were achieved on Mg-Si- close to the pore diameter of zeolites’ channels. In such case, the
ZSM-12(50) with the highest Mg content, in line with its superior diffusion rate is sensitive to the molecular size. Slightly increasing the
basicity. The isosteric heat of CO2 adsorption (Qst) for Mg-Si-ZSM- molecule size would dramatically enhance the mass transfer
12(50), calculated by Virial equation (Fig. S6-S8†), gave high value of resistance. Small size reactant can easily enter the pore channel and
54 kJ mol-1 at zero coverage and decreases slightly along with access to the active species, facilitating the conversion. The size of
increasing CO2 loading (Fig. 3D). The large CO2 adsorption uptakes bulky vanillic aldehyde (7.60×6.43 Å) is close to that (5.6×7.7 Å) of 12-
and high Qst of Mg-Si-ZSM-12(50) indicate that this zeolite possesses membered ring of Al-free ZSM-12, and thus its diffusion in the
considerable CO2 affinity, attributable to the enhanced basicity microchannels is limited, demonstrating the low activity. In the
derived from Mg-incorporation.
Knoevenagel condensation, the size of carbonyl compounds is larger
than ethyl cyanoacetate or malononitrile, therefore the conversion
depends on the molecular size of the carbonyl compounds.
Compared with previous heteroatom zeolites and zeolitic-like
materials in this reaction,47,65, 66 Mg-Si-ZSM-12(50) exhibits superior
activity in converting a broad spectrum of substrates.
Knoevenagel condensation
Knoevenagel condensation between an active methylene compound
and a carbonyl group (C=O) is a classical base-catalyzed reaction for
C-C bond coupling to prepare many important chemicals.58-60 This
reaction was preliminarily used to evaluate the base properties of
Mg-Si-ZSM-12(50) with the highest Mg content and surface area.
Cycloaddition of CO2 with epoxides
Initially, the kinetic curve in the Knoevenagel condensation of Given the superior basic properties, Mg-Si-ZSM-12(50) was further
benzaldehyde and ethyl cyanoacetate catalyzed by Mg-Si-ZSM-12(50) used as a heterogeneous catalyst in the solvent-free cycloaddition of
was compared with that by MgS-1, previous Mg containing zeolite CO2 with epoxides to produce cyclic carbonates (Table 3). Mg-Si-
with MFI topology.39 As shown in Fig. S9†, the conversion over Mg- ZSM-12(50) exhibited high activity and selectivity towards a variety
Si-ZSM-12(50) increased with reaction time and reached 100% at 4 of terminal epoxides under mild conditions of atmospheric CO2
h. By contrast, the conversion of blank control was merely 20% in the pressure and relatively low temperature (≤100 °C) in the presence of
absence of catalyst (entry 4, Table 2) and 92% by using MgS-1. a conventional additive of tetrabutylammonium bromide (TBAB).
Besides, the conversion over Mg-Si-ZSM-12(50) was always higher The pore size of the orifice (5.6×7.7 Å) is larger than the epoxides in
than that over MgS-1 throughout the whole kinetic curves, reflecting Table 3, and thus these substrates can enter the microchannels of
the faster reaction rate over Mg-Si-ZSM-12(50). The reason can be Mg-Si-ZSM-12 and then converted into corresponding cyclic
assigned to the larger pore of MTW topologic zeolite with the size of carbonates. In addition, the adsorption kinetic curve of 1,2-
(5.6×7.7 Å) than that of MFI type zeolite (5.1×5.5 Å, 5.3×5.6 Å).61 epoxytetradecane (the most bulky epoxide in this work) on Mg-Si-
These results indicate that Mg incorporation into MTW zeolites ZSM-12(50) was collected and compared with that on Mg-Si-ZSM-
fabricates active base sites and its 12-membered ring can improve 12(50)-as (the as-synthesized Mg-Si-ZSM-12(50) without the removal
the mass transfer in a heterogeneous catalysis.
of template, a nonporous counterpart of Mg-Si-ZSM-12(50)). As
The scope of Mg-Si-ZSM-12(50) was investigated in the displayed in Fig. S10†, continuous adsorption of 1,2-
Knoevenagel condensation of different aromatic aldehydes and ethyl epoxytetradecane on Mg-Si-ZSM-12(50) was observable, whereas
cyanoacetate or malononitrile. Initially, Knoevenagel condensation rare adsorption occurred on Mg-Si-ZSM-12(50)-as due to the
between benzaldehyde and diethyl malonate was tried, but Mg-Si- blockage of pore by the organic template. This phenomenon
ZSM-12(50) exhibited low activity (conversion: 37%, entry 1, Table 2), validates the entrance of the bulky epoxide into the internal
attributable to the inertness of diethyl malonate.62 Therefore, micropores of Mg-Si-ZSM-12(50). This is in line with previous
Knoevenagel condensation of benzaldehyde and ethyl cyanoacetate catalytic behavior of zeolites and related microporous materials in
or malononitrile were employed to evaluate the activity of Mg-Si- isomerization of long-chain n-alkanes (>C10),67,68 and the results of
ZSM-12(50). In general, the aromatic aldehydes with electron- cycloaddition of CO2 with bulky epoxides catalyzed by Metal-Organic
donating or electron-withdrawing groups would affect the activity Frameworks (MOFs) with micropores.69,70 Terminal epoxide with
and the later usually affords better performance.63 Besides, the electron-withdrawing group (epichlorohydrin) was transformed
aromatic aldehydes with different substituted groups significantly completely (conversion: 96%, selectivity: >99%) at a low temperature
influences the mass transfer in the heterogeneous catalysis.64 Table of 60 °C (entry 1). Mg-Si-ZSM-12(50) catalyzed cycloaddition of CO2
2 demonstrates the catalytic results and corresponding molecular with epichlorohydrin was carried out at different temperatures and
sizes of reactants. Nearly complete conversion was observed in the the kinetic curves at 60 and 80 oC were collected (Fig. S11†). With the
malononitrile related reactions due to the high activity of this elevated temperature, the conversion increased from 70% (40 oC) to
substrate. In the Knoevenagel condensation of different aromatic 99% (70 and 80 oC) (Fig. S11A†). In addition, rapider conversion rate
aldehydes and ethyl cyanoacetate, the conversion depends on the was observed at 80 oC than that at 60oC (Fig. S11B†). Slightly
molecular size of carbonyl compounds. The conversions were 100% increasing the temperature to be 90 °C enabled the high activity in
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 8 of 11
ARTICLE
Journal Name
that the activity of TBAB alone varied with the reaction conditions. In
View Article Online
order to unravel the catalytic behavior ofDTOBIA: 1B0,.1T0B39A/BC9cCaYt0a1ly3z2e9dF
conversion of 1,2-epoxytetradecane via cycloaddition with CO2 was
carried under the chosen reaction condition (entry 8, Table 3). The
conversion was 28% by using TBAB alone, whereas increased to be
96% when the reaction was catalyzed by Mg-Si-ZSM-12(50) and TBAB
(entry 8, Table 3). This result further reveals the synergistic catalysis
of Mg-Si-ZSM-12(50) and TBAB.
In situ FT-IR spectra of adsorbed CO2 and epoxide (epoxypropane)
on Mg-Si-ZSM-12(50) were collected respectively to gain insight into
Mg-Si-ZSM-12(50) catalyzed CO2 cycloaddition with epoxide. Fig.
Figure 4 (A) Cycloaddition of CO2 with 1,2-epoxyhexane. Reaction S13A† shows the IR spectra of adsorbed CO2 on Mg-Si-ZSM-12(50)
condition: 1,2-epoxyhexane (5 mmol), catalyst (0.12 g), CO2 (1.0 bar), under dynamic CO2 atmosphere. The peaks around 1680 and 1600
TBAB (3 mol%, 0.048 g), 90 °C, 9 h; (B) Reusability of Mg-Si-ZSM- cm-1 are attributable to the asymmetric and symmetric stretching
12(50) in the cycloaddition of CO2 with styrene oxide. Reaction vibrations of carbonyl group and these characteristic peaks of C=O
condition: styrene oxide (5 mmol), catalyst (0.12 g), CO2 (1.0 bar), increased with the adsorption duration, suggesting the formation of
TBAB (3 mol%, 0.048 g), 90 °C, 9 h.
carbonate.78,79 The IR spectra of epoxypropane adsorbed on Mg-Si-
ZSM-12(50) were shown in Fig. S13B†. The peaks around 2996 cm-1
the coupling of CO2 with terminal epoxides containing either short- are assignable to the stretching vibration of C-H bound; further peaks
chain branch or benzene ring (entry 2-5). Even the inert long carbon- at 1470 and 1400 cm-1 are attributed to the C-H bending vibration of
chain alkyl epoxides were effectively coupled with atmospheric CO2 three-membered epoxy ring and CH3 connected to the epoxy ring,
into the corresponding cyclic carbonates with high conversions and
respectively. The epoxide ring breathing and stretching vibration of
selectivities at 100 °C (entry 6-8). Herein, to the best of our C-O were reflected by the peaks of 1265 and 1120 cm-1. The
knowledge, it is the first time to reach the efficient conversion of a emerging of these peaks with certain shifts from those observed in
broad spectrum of epoxides into cyclic carbonates over zeolite liquid epoxypropane,80,81 suggests the chemisorption of epoxide on
catalysts. The activity of Mg-Si-ZSM-12(50) outperforms previous Mg-Si-ZSM-12(50). This is further reflected by the observation of the
zeolites that usually catalyzed the cycloaddition of CO2 with epoxides negative peak at 3700 cm-1, which is attributable to the interaction
under high pressure and temperature.22,23 Mg-Si-ZSM-12(50) also of surface hydroxyl groups and epoxypropane. Generally, three
exhibited superior or at least comparable yield to previous zeolite primary steps of ring-opening via nucleophilic attack, CO2 insertion,
analogues such as multifunctional lanthanide-zeolites in the and ring-closure with the leaving of nucleophile are involved in the
conversion of epichlorohydrin, styrene oxide and so on.24 More CO2 cycloaddition with epoxides. The ring opening step can be
importantly, it was found that Mg-Si-ZSM-12(50) effectively facilitated by the activation of epoxides by a H-bonding donor or
transformed various inert long alkyl chain epoxides in the presence Lewis acid compound and then attached by nucleophiles such as
of atmospheric CO2, which was normally catalyzed by those most halide ions.82,83 Based on these studies and the in situ FT-IR result,
efficient ionic liquids derived materials.71-73 All of these reveal the the probable reaction routes in the absence and presence of TBAB
high efficiency of constructed Mg-containing MTW zeolite in this CO2 are proposed in Scheme S1†(ESI). Epoxide is adsorbed and activated
fixation under mild conditions.
on the Mg sites through the static electron interaction between the
For comparison, the activity of Mg-Si-ZSM-12(50) was compared O atom of epoxide and Mg cations. Besides, the surface hydroxyl
with MgS-1 and commercial solid base MgO in the CO2 cycloaddition groups also served as hydrogen bond donors to activate
with 1,2-epoxyhexane (Fig. 4A). The conversion was only 70% by epoxides.84,85 CO2 was adsorbed on the surface to form carbonate
using MgS-1 and even lower than that (75%) in the MgO catalyzed species via interacting with the basic sites (e.g., the oxygen linked
reaction. By contrast, Mg-Si-ZSM-12(50) demonstrated a greatly with Mg (O-Mg)). In the absence of TBAB, these carbonates served
enhanced yield of 96% under the identical reaction condition. The as the nucleophile to attack the less steric hindered carbon atom of
higher activity of Mg-Si-ZSM-12(50) relative to those of MgO and the epoxide to generate the intermediate by inserting CO2 into the
MgS-1 highlights the significance of generating superior basic sites in covalent bond of C−O (Scheme S1A†).15,22,86 Therefore, Mg-Si-ZSM-
the zeolites’ skeleton. On the contrary, the conversion was 49 % 12(50) alone also can catalyze the CO2 cycloaddition with epoxide
when the reaction was catalyzed by 3 mol% of TBAB alone, and under high temperature and pressure. For instance, Mg-Si-ZSM-
increased to be 60%, 71% and 83% by using 6 mol%, 9 mol%, and 12 12(50) itself gave a conversion of 87% (selectivity: >99%) in catalyzing
mol% of TBAB (Fig. S12†). TBAB was widely used as the efficient co- the CO2 cycloaddition with epichlorohydrin (entry 1, Table 3). In the
catalyst in the CO2 cycloaddition with epoxides.74-77 For example, FJI- presence of TBAB, the more nucleophilic reagent, Br- from TBAB can
H14 catalyzed cycloaddition of CO2 with styrene oxide resulted in a accelerate the ring-opening to yield Br-substituted intermediate,
yield of 86% in the presence of TBAB, while TBAB (2.5 mol%) alone which further interact with the adsorbed CO2 to cause the CO2
gave a yield of 52% under the identical conditions.74 The yield was 99% insertion (Scheme S1B†). The final product cyclic carbonate is
when CO2 cycloaddition with epichlorohydrin catalyzed by Cu/POP- obtained with the ring closure of the intermediates above. The
Bpy and TBAB, while changed to be 60.2% by using TBAB (7 mol%).75 potential bi-product 1,2-diol formed via the ring-opening of epoxide
Besides, slightly lower yields were observable in many other by trace water (Scheme S1C†).87,88 The high performance comes from
cycloadditions catalyzed by TBAB.76,77 These phenomena suggest a synergistic effect of Mg-Si-ZSM-12(50) and TBAB. Especially, the
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 9 of 11
Catalysis Science & Technology
Please do not adjust margins
Journal Name
ARTICLE
4
5
6
L. Zhang, Z. J. Zhao and J. L. Gong, Angew. Chem.VInietw. AErdtic.,le2O0n1lin7e,
superior basicity of Mg-Si-ZSM-12(50) is beneficial for CO2 activation.
Though the epoxide activation is crucial as the first step is normally
the rate-determining step, CO2 activation also significantly
contributes the catalytic performance. The combination of CO2-TPD
analysis, static CO2 adsorption and activity evaluation Knoevenagel
condensation, indicated that Mg-Si-ZSM-12(50) has superior basicity.
In addition, Mg-Si-ZSM-12(50) exhibited higher conversion over Mg-
Si-ZSM-12(50) than MgO and MgS-1 in the CO2 cycloaddition with
epoxide. These phenomena suggest that the superior basicity of Mg-
Si-ZSM-12(50) is important for the CO2 activation and corresponding
to its higher activity in the CO2 cycloaddition with epoxide. The
potential advantage of Mg-Si-ZSM-12(50) also include abundant
micropores and mesopores that promote the dispersion and
accessibility of the basic sites. Compared with previous MgS-1 with
relatively small 10-membered ring, Mg-Si-ZSM-12(50) possessing
larger 12-membered ring channels provides improved mass transfer
and thus promotes the activity, in line with the results found in the
Knoevenagel condensation. To evaluate the catalyst’s reusability, a
five-run recycling test was carried out in the coupling of atmospheric
CO2 with styrene oxide. As shown in Fig. 4B, the conversion and
selectivity of the product obtained from the second to fifth runs were
similar to that of the fresh catalyst, reflecting the favorable recycling
performance.
56, 11326.
DOI: 10.1039/C9CY01329F
F. J. Quan, G. M. Zhan, C. L. Mao, Z. H. Ai, F. L. Jia, L. Z. Zhang,
H. G. Gu and S. Y. Liu, Catal. Sci. Technol., 2018, 8, 6503.
M. W. Jia, C. Choi, T. S. Wu, C. Ma, P. Kang, H. C. Tao, Q. Fan,
S. Hong, S. Z. Liu, Y. Soo, Y. Jung, J. S. Qiu and Z. Y. Sun, Chem.
Sci., 2018, 9, 8775.
A. Bansode and A. Urakawa, ACS Catal., 2014, 4, 3877.
H. Zhong, G. D. Yao, X. Cui, P. Yan, X. G. Wang and F. M. Jin,
Chem. Eng. J., 2019, 357, 421.
7
8
9
W. F. Xiong, C. R. Qi, H. T. He, L. Ouyang, M. Zhang and H. F.
Jiang, Angew. Chem. Int. Ed., 2015, 54, 3084.
10 Q. W. Song, Z. H. Zhou and L. N. He, Green Chem., 2017, 19,
3707.
11 C. Maeda, S. Sasaki and T. Ema, ChemCatChem, 2017, 9, 946.
12 J. Liang, R. P. Chen, X. Y. Wang, T. T. Liu, X. S. Wang, Y. B. Huang
and R. Cao, Chem. Sci., 2017, 8, 1570.
13 J. F. Kurisingal, R. Babu, S. H. Kim, Y. X. Li, J. S. Chang, S. J. Cho
and D. W. Park, Catal. Sci. Technol., 2018, 8, 591.
14 K. Yamaguchi, K. Ebitani, T. Yoshida, H. Yoshida and K. Kaneda,
J. Am. Chem. Soc., 1999, 121, 4526.
15 Z. J. Guo, X. C. Cai, J. Y. Xie, X. C. Wang, Y. Zhou and J. Wang,
ACS Appl. Mater. Interfaces, 2016, 8, 12812.
16 P. Z. Li, X. J. Wang, J. Liu, J. S. Lim, R. Zou and Y. Zhao, J. Am.
Chem. Soc., 2016, 138, 2142.
17 B. Dong, L. Y. Wang, S. Zhao, R. Ge, X. D. Song, Y. Wang and Y.
N. Gao, Chem. Commun., 2016, 52, 7082.
18 W. L. Wang, C. Y. Li, L. Yan, Y. Q. Wang, M. Jiang and Y. J. Ding,
ACS Catal., 2016, 6, 6091.
19 J. Zhang, L. Wang, Y. Shao, Y. Q. Wang, B. C. Gates and F. S.
Xiao, Angew. Chem. Int. Ed., 2017, 56, 9747.
20 G. Q. Zhang, P. Feng, W. P. Zhang, H. liu, C. X. Wang, H. J. Ma,
D. D. E. Wang and Z. J. Tian, Microporous Mesoporous Mater.,
2017, 247, 158.
21 V. J. Margarit, M. E. Martnez-Armero, M. T. Navarro, C.
Martnez and A. Corma, Angew. Chem. Int. Ed., 2015, 54,
13724.
22 M. Tu and R. J. Davi, J. Catal., 2001,199, 85.
23 C. G. Li, L. Xu, P. Wu, H. H. Wu and M. Y. He, Chem. Commun.,
2014, 50, 15764.
Conclusions
In summary, a family of zeolitic solid base with well-defined 12-
MR channels (Mg-Si-ZSM-12) was fabricated by incorporating
Mg species into MTW type zeolite. The synthesis was achieved
in an acid co-hydrolysis route. The obtained zeolite exhibited
improved basic properties, and hence served as efficient solid
base in traditional base reaction (Knoevenagel condensation)
and cycloaddition of CO2 with epoxides under relative mild
conditions. This work highlights the potential of basic zeolites in
the CO2 fixation.
24 J. Dong, P. Cui, P. F. Shi, P. Cheng and B. Zhao, J. Am. Chem.
Soc., 2015, 137, 15988.
25 H. Li, Z. Fang, J. Luo and S. Yang, Appl. Catal. B: Environ., 2017,
200, 182.
26 R. Locus, D. Verboekend, R. Zhong, K. Houthoofd, T. Jaumann,
S. Oswald, L. Giebeler, G. Baron and B. F. Sels, Chem. Mater.,
2016, 28, 7731.
Conflicts of interest
There are no conflicts to declare.
27 L. Zhang, T. N. Pham, J. Faria, D. Santhanaraj, T. Sooknoi, Q. H.
Tan, Z. Zhao and D. E. Resasco, ChemSusChem, 2016, 7, 736.
28 S. C. Chen, Z. Shao, Z. X. Fang, Q. Chen, T. Tang, W. Q. Fu, L.
Zhang and T. D. Tang, J. Catal., 2016, 338, 38.
29 M. Miyamoto, T. Nakatani, Y. Fujioka and K. Yogo,
Microporous Mesoporous Mater., 2015, 206, 67.
30 A. Corma, F. Rey, J. Rius, M. J. Sabater and S. Valencia, Nature,
2004, 431, 287.
Acknowledgements
The authors thank the National Natural Science Foundation of
China (No. U1662107, 21476109, 21136005 and 21303084)
and the Project of Priority Academic Program Development of
Jiangsu Higher Education Institutions (PAPD).
31 B. W. Boal, J. E. Schmidt, M. A. Deimund, M. W. Deem, L. M.
Henling, S. K. Brand, S. I. Zones and M. E. Davis, Chem. Mater.,
2015, 27, 7774.
32 C. W. Lopes, L. G. Hortigüela, A. Rojas and S. B. C. Pergher,
Microporous Mesoporous Mater., 2017, 252, 29.
33 Y. X. Li, D. Bernin, F. F. Gao and N. Hedin, Microporous
Mesoporous Mater., 2017, 237, 222.
34 H. M. Wen, Y. Zhou, J. Y. Xie, Z. Y. Long, W. Zhang and J. Wang,
RSC Adv., 2014, 4, 49647.
35 S. Song, G. J. Wu, W. L. Dai, N. J. Guan and L. D. Li, Catal. Sci.
Technol., 2016, 6, 8325.
36 H. Xu, X. D. Wang, P. Ji, H. H. Wu, Y. J. Guan and P. Wu, Inorg.
Chem. Front., 2018, 5, 2763.
Notes and references
1
2
3
A. Banerjee, G. R. Dick, T. Yoshino and M. W. Kanan, Nature,
2016, 531, 215.
J. Klankermayer, S. Wesselbaum, K. Beydoun and W. Leitner,
Angew. Chem. Int. Ed., 2016, 55, 7296.
M. Alves, B. Grignard, R. Mereau, C. Jerome, T. Tassaing and
C. Detrembleur, Catal. Sci. Technol., 2017, 7, 2651.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
Please do not adjust margins

Please do not adjust margins
Catalysis Science & Technology
Page 10 of 11
ARTICLE
Journal Name
37 Z. Sun, T. Li, G. Li, Y. H. Zhang and Y. Tang, RSC Adv., 2017, 7, 69 W. Jiang, J. Yang, Y. Y. Liu, S. Y. Song and J. F. MVaie,wCAhreticmle.OEnulinre.
35252.
J., 2016, 22, 16991.
38 A Thangaraj, M. J. Eapen, S. Sivasanker and P. Ratnasamy, 70 J. Liang, R. P. Chen, X. Y. Wang, T. T. Liu,DXO. SI:.1W0.1a0n3g9,/YC.9BC.YH01u3a2n9gF
Zeolites, 1992, 12, 943.
and R. Cao, Chem. Sci., 2017, 8, 1570.
39 Y. Zhou, Y. H. Jin, M. Wang, W. Zhang, J. Y. Xie, J. Gu, H. M. 71 S. Ghazali-Esfahani, H. B. Song, E. Päunescu, F. D. Bobbink, H.
Wen, J. Wang and L. M. Peng, Chem. Eur. J., 2015, 21, 15412.
40 Y. J. Wu, J. Wang, P. Liu, W. Zhang, J. Gu and X. J. Wang, J. Am.
Chem. Soc., 2010, 132, 17989.
41 W. Zhang, W. Hou, T. S. Meng, W. X. Zhuang, J. Y. Xie, Y. Zhou
and J. Wang, Catal. Sci. Technol., 2017, 7, 6050.
42 J. Gu, Y. H. Jin, Y. Zhou, M. J. Zhang, Y. J. Wu and J. Wang, J.
Mater. Chem. A, 2013, 1, 2453.
43 J. Y. Xie, W. X. Zhuang, N. Yan, Y. H. Du, S. B. Xi, W. Zhang, J. J.
Tang, Y. Zhou and J. Wang, Chem. Eng. J., 2017, 328, 1031.
Z. Liu, Z. F. Fei, G. Laurenczy, M. Bagherzadeh, N. Yan and P.
J. Dyson, Green Chem., 2013, 15, 1584.
72 W. Zhang, T. Y. Liu, H. H. Wu, P. Wu and M. Y. He, Chem.
Commun., 2015, 51, 682.
73 R. R. Shaikh, S. Pornpraprom and V. D’Elia, ACS Catal., 2018, 8,
419.
74 L. F. Liang, C. P. Liu, F. L. Jiang, Q. H. Chen, L. J. Zhang, H. Xue,
H. L. Jiang, J. J. Qian, D. Q. Yuan and M. C. Hong, Nat. Commun.,
2017, 8, 1233.
44 Q. G. Zhai, X. H. Bu, C. Y. Mao, X. Zhao and P. Y. Feng, J. Am. 75 Z. F. Dai, Q. Sun, X. L. Liu, L. P. Guo, J. X. Li, S. X. Pan, C. Q. Bian,
Chem. Soc., 2016, 138, 2524.
45 D. F. Shantz, H. Koller and R. F. Lobo, J. Am. Chem. Soc., 2000,
122, 6659.
L. Wang, X. Hu, X. J. Meng, L. H. Zhao, F. Deng and F. S. Xiao,
ChemSusChem, 2017, 10, 1186.
76 Z. F. Dai, Q. Sun, X. L. Liu, C. Q. Bian, Q. M. Wu, S. X. Pan, L.
Wang, X. J. Meng, F. Deng and F. S. Xiao, J. Catal., 2016, 338,
202.
46 J. Y. Xie, W. X. Zhuang, W. Zhang, Y. Zhou and J. Wang,
ChemCatChem, 2017, 9, 1076.
47 G. D. Feng, P. Cheng, W. F. Yan, M. Boronat, X. Li, J. H. Su, J. Y. 77 Y. Xie, T. T. Wang, X. H. Liu, K. Zou and W. Q. Deng, Nat.
Wang, Y. Li, A. Corma, R. R. Xu and J. H. Yu, Science, 2016, 351,
1188.
48 Y. X. Tan, F. Wang and J. Zhang, Chem. Soc. Rev., 2018, 47,
2130.
Commun., 2013, 4, 1960.
78 C. Knöfel, C. Martin, V. Hornebecq and P. L. Liewellyn, J. Phys,
Chem. C, 2009, 113, 21726.
79 Y. Zhou, W. L. Zhang, L. Ma, Y. Zhou and J. Wang, ACS
Sustainable Chem. Eng., 2019, 7, 9387.
80 G. Mul, A. Zwijnenburg, B. V. D. Linden, M. Makkee and J. A.
Moulijn, J. Catal., 2001, 201, 128.
49 W. Zhang, J. Y. Xie, W. Hou, Y. Q. Liu, Y. Zhou and J. Wang, ACS
Appl. Mater. Interfaces, 2016, 8, 23122.
50 Y. Li, Z. C. Feng, Y. X. Lian, K. Q. Sun, L. Zhang, G. Q. Jia, Q. H.
Yang and C. Li, Microporous Mesoporous Mater., 2005, 84, 41. 81 W. Zhang, H. Wang, Q. Li, Q. Dong, N. Zhao, W. Wei, Y Sun,
51 C. Paris, N. Martin, J. Martinez-Triguero, M. Moliner and A.
Appl. Catal. A: Gen. 2005, 294, 188.
82 F. D. Bobbink and P. J. Dyson, J. Catal., 2016, 343, 52.
Corma, New J. Chem., 2016, 40, 4140.
52 J. Y. Xie, H. M. Wen, W. Zhang, Y. Zhou and J. Wang, 83 F. D. Bobbink D. Vasilyev, M. Hulla, S. Chamam, F. Menoud, G.
CrystEngComm, 2016, 18, 1164.
53 M. M. Forde, R. D. Armstrong, C. J. Kiely and G. J. Hutchings, J.
Am. Chem. Soc., 2013, 135, 11087.
Laurenczy, S. Katsyuba and P. J. Dyson, ACS Catal., 2018, 8,
2589.
84 C. L. Thomas, Ind. Eng. Chem., 1949, 41, 2564.
54 K. S. W. Sing, D. H. Everett, R. A. W. Haul, L. Moscou, R. A. 85 L. Sandoval-Díaz, J. González-Amaya and C. Trujillo,
Pierott, J. Rouquerol and T. Siemieniewska, Pure Appl. Chem.,
1985, 57, 603.
Microporous Mesoporous Mater., 2015, 215, 229.
86 T. Ema, K. Fukuhara, T. Sakai, M. Ohbo, F. Q. Bai and J. Y.
Hasegawa, Catal. Sci. Technol., 2015, 5, 2314.
55 Y. Kamimura, K. Iyoki, S. P. Elangovan, K. Itabashi, A.
Shimojima and T. Okubo, Microporous Mesoporous Mater., 87 Y. Morimoto, E. Takeuchi, H. Kambara, T. Kodama, Y. Tachi
2012, 163, 282.
and K. Nishikawa, Org. Lett., 2013, 15, 2966.
56 K. Arishtirova, P. Kovacheva and N. Davidova, Appl. Catal. A- 88 J. Liang, L. N. Soucie, D. R. Blechschmidt, A. Yoder, A.
Gen., 1998, 167, 271.
Gustafson and Y. Liu, Org. Lett., 2019, 21, 513.
57 F. Frusteri, M. Cordaro, C. Cannilla and G. Bonura, Appl. Catal.
B: Environ., 2015, 162, 57.
58 L. Zhu, X. Q. Liu, H. L. Jiang and L. B. Sun, Chem. Rev., 2017,
117, 8129.
59 Y. Zhang, Y. X. Wang, L. Liu, N. Wei, M. L. Gao, D. Zhao and Z.
B. Han, Inorg. Chem., 2018, 57, 2193.
60 H. F. Wang, C. Y. Wang, Y. F. Yang, M. Zhao and Y. J. Wang,
Catal. Sci. Technol., 2017, 7, 405.
61 C. A. Fyfe, H. Gies, G. T. Kokotailo, B. Marler and D. E. Cox, J.
Phys. Chem., 1990, 94, 3718.
62 K. Sugahara, T. Kimura, K. Kamata, K. Yamaguchi and N.
Mizuno, Chem. Commun., 2012, 48, 8422.
63 Y. Ogiwara, K. Takahashi, T. Kitazawa and N. Sakai, J. Org.
Chem., 2015, 80, 3101.
64 H. Zhu, L. F. Xiong, M. H. Zhou and K. Huang, Polym. Chem.,
2016, 7, 4975.
65 H. K. Min, S. H. Cha and S. B. Hong, Chem. Commun., 2013, 49,
1115.
66 V. N. Panchenko, M. M. Matrosova, J. Jeon and S. H. Jhung, J.
Catal., 2014, 316, 251.
67 C. Zschiesche, D. Himsl, R. Rakoczy, A. Reitzmann, J. Freiding,
N. Wilde and R. Gläser, Chem. Eng. Technol., 2018, 41, 199.
68 M. Zhang, Y. J. Chen, L. Wang, Q. M. Zhang, C. Tsang and C. H.
Liang, Ind. Eng. Chem. Res., 2016, 55, 6069.
10 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 11 of 11
Catalysis Science & Technology
View Article Online
DOI: 10.1039/C9CY01329F
Straightforward synthesis of MTW-type magnesium silicalite for
CO2 fixation with epoxides under mild conditions†
Haimeng Wen,a Jingyan Xie,a,b Yang Zhou,a Yu Zhou*a and Jun Wang*a
aState Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical
Engineering, Nanjing Tech University, Nanjing 210009, Jiangsu, P. R. China.
bMaoming Branch R&D Institute, SINOPEC, Maoming 525011, P. R. China.
† These two authors contributed equally: Haimeng Wen and Jingyan Xie.
* Corresponding authors
E-mails: njutzhouyu@njtech.edu.cn (Y. Zhou), junwang@njtech.edu.cn (J. Wang)
Mg-Si-ZSM-12 was hydrothermally synthesized and effective for CO2 fixation under mild
conditions.