Microporous and Mesoporous Materials 303 (2020) 110277

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Microporous and Mesoporous Materials

journal homepage: http://www.elsevier.com/locate/micromeso

Hydrothermal synthesis of tungsten-tin bimetallic MFI type zeolites and

their catalytic properties for cyclohexene epoxidation
Haoyang Zhang , Xiaotong Yang , Xiaojing Song , Xinyu Chang , Mingjun Jia *
Key Laboratory of Surface and Interface Chemistry of Jilin Province, College of Chemistry, Jilin University, Changchun, 130012, PR China

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

Keywords: A series of tungsten-tin bimetallic MFI type zeolites (WSn-MFI) with different Sn and W contents were hydro­
Tungsten thermally synthesized using tetrapropyl ammonium hydroxide (TPAOH) as a template and polypyrrolidone as a
Tin co-surfactant. Tetraethylorthosilicate (TEOS), ammonium tungstate hydrate and tin (IV) chloride pentahydrate
Bimetallic MFI zeolites
were used as the Si, W and Sn sources, respectively. The resultant samples were characterized by various
One-pot synthesis
Cyclohexene epoxidation
techniques, and were evaluated as catalysts for the epoxidation of cyclohexene with hydrogen peroxide. The
results reveal that all the W–Sn bimetallic zeolites have the typical MFI structure, and their relative crystallinities
and morphologies change somewhat with the variety of W and Sn contents. Both the isolated framework SnO4
species and the extra-framework SnO2 species could be detected in all WSn-MFI samples, while only trace
amount of extra-framework W species are present inside the channels/cages of the bimetallic zeolites. Compared
with the monometallic zeolites of W-MFI and Sn-MFI, the bimetallic WSn-MFI zeolites exhibit much higher
catalytic activity for the epoxidation of cyclohexene. Of these, the sample named WSn-MFI-a could efficiently
convert cyclohexene to the corresponding epoxide with a high yield of 79% under an optimized reaction con­
dition. A synergistic effect between the W and Sn species should play critical role in improving the catalytic
activity and the epoxide selectivity of the bimetallic zeolite catalysts.

1. Introduction Moreover, it was reported that incorporation of a small amount of

Various metals incorporated porous materials have received
considerable attention due to their wide application as efficient het­
erogeneous catalysts in many industrially important processes [1–5]. It
is well known that incorporation of metal species in porous materials
like mesoporous molecular sieves, metal organic framework (MOF) and
zeolites can regulate the chemical composition, surface property and the
nature of active sites, which may bring significant promotion in their
catalytic performances. Of these, the zeolites with MFI structure have
shown versatility towards isomorphous substitution of framework Si
atoms by metal ions such as B3þ, Ga3þ, Sn4þ or Ti4þ [6–8]. For example,
Ti-incorporated MFI zeolites (TS-1) exhibited high catalytic activity and
stability for a variety of H2O2-based catalytic oxidation processes, such
as phenol hydroxylation, cyclohexanone ammoximation, oxidative
desulfurization, and propylene epoxidation [9–12]. Another interesting
example is Sn-MFI zeolite, which has shown high efficiency for hy­
droxylation of phenol [13], isomerization of sugar [14,15], methylation
of aniline [16], Baeyer-Villiger oxidation of cyclic ketones [17].
tungsten species into MFI type zeolites could bring distinctive hydro­
phobicity and Lewis acidity, which may have great potential for the
application in catalysis, adsorption/separation, selective exhaust gas
detection, and so on [18–20].
For further improving the catalytic performance of the metal-
incorporated MFI zeolites, the addition of the second metallic compo­
nent has been achieved, which may generate more efficient bimetallic
MFI-type zeolite catalysts [21–26]. For instance, Guo and coauthors
reported that bimetallic FeCu supported mesoporous ZSM-5 zeolites,
prepared by post-impregnation method, display very high catalytic ac­
tivity for phenol oxidation due mainly to the existence of strong bime­
tallic interaction [27]. Arca and coworkers found that zinc salts
pretreated TS-1 zeolites exhibit enhanced epoxide selectivity for pro­
pylene epoxidation as direct consequence of coordination of zinc to
Ti-sites [22]. Zou et al. reported that Mn modified TS-1 zeolites, ob­
tained via recrystallization of TS-1 in presence of TPAOH and manga­
nese acetylacetonate, show higher catalytic activity than conventional
TS-1 for selective oxidation of cyclohexene. For this industrially

* Corresponding author.
E-mail address: jiamj@jlu.edu.cn (M. Jia).

https://doi.org/10.1016/j.micromeso.2020.110277
Received 23 December 2019; Received in revised form 16 April 2020; Accepted 20 April 2020
Available online 6 May 2020
1387-1811/© 2020 Elsevier Inc. All rights reserved.
H. Zhang et al. Microporous and Mesoporous Materials 303 (2020) 110277

important reaction, the selectivity control is always a persisting and and placed in an oven at 453 K for 48 h under static condition. The
challenging issue due mainly to the high reactivity of the C– – C double composite obtained after crystallization was filtrated and washed with
bonds and the allylic hydrogen atoms in cyclohexene, which may result ethanol and water. The solid was dried overnight at 110 � C and calcined
in different products of cyclohexene epoxide, 2-cyclohexene-1-ol and in O2 at 550 � C for 5 h at a heating rate of 2 � C/min to remove the
2-cyclohexene-1-one. template. Notations for the synthesized samples were Sn-MFI-I,
In general, the metallic components especially the second metallic Sn-MFI-II, respectively, where I, II represents the SnO2 contents (in the
component could be introduced into the MFI-type zeolites via a simple initial sol) of 0.0062 and 0.0124, respectively. The Sn contents in the
post-impregnation method [28–32]. However, the bimetallic zeolite final zeolites sample were determined by ICP-AES analysis as shown in
catalysts prepared by this way usually suffer from non-uniform distri­ Table 1.
bution of the active metal components on zeolite supports. Besides, The W-MFI zeolites were synthesized by the similar method, just
leaching of surface dispersed metallic species from the parent zeolites using 3(NH4)2O–7WO3–6H2O to replace SnCl4⋅5H2O. The correspond­
may easily occur during the catalytic reaction course, especially for the ing samples are designated as W-MFI-I, W-MFI-II, respectively, where I,
H2O2-based liquid-phase catalytic oxidation processes. Compared with II represents the contents of W measured from ICP-AES measurements as
the post-impregnation method, direct hydrothermal method would be a shown in Table 1.
more idea way to incorporate uniform distributed and structure stable Tungsten-tin bimetallic MFI type zeolites with different molar ratios
bimetallic species into zeolites [32–35]. However, the examples of direct of Si/Sn/W were hydrothermally synthesized as follows. Typically, 18
hydrothermal synthesis of bimetallic MFI zeolites are quite rare, possibly mL of TEOS were added in 21 mL of TPAOH solution. After stirring at
due mainly to the difficulty in matching the hydrolysis and condensation room temperature for 1.5 h, required amount of SnCl4⋅5H2O in 20 mL
rates of the two different metallic species during the sol-gel process and water was dropwise added under vigorous stirring. After 2 h, required
the hydrothermal crystallization process. So far, only a few bimetallic amount of 3(NH4)2O–7WO3–6H2O in 20 mL water was dropwise added
MFI-type zeolites were obtained by direct hydrothermal method, and the generated sol was stirred for 2 h. Then, the pH value of the sol
including Pd-M(OH)2 (M ¼ Ni, Co) clusters confined in silicalite-1 zeo­ was adjusted to 12 with sodium hydroxide solution. 4.0 g of PVP was
lites, Sn–Al-containing MFI zeolites and Ce–Ni incorporated MFI zeolites added to the synthesis mixture, and the stirring was continued for 4 h.
[33–35]. In these cases, the distribution state of the bimetal species The molar composition of the final sol was 1.0SiO2: xSnO2: yWO3:
varied with the change of the types of the elements and the synthesis 0.32TPAOH: 27.5H2O (x ¼ 0.0062 or 0.0124, y ¼ 0.0062 or 0.0124).
parameters. More significantly, all the condition-optimized bimetallic Subsequently, crystallization and post-treatment were carried out
MFI-based zeolite catalysts showed enhanced catalytic activity and following the procedure for synthesizing Sn-MFI. Notations for the
stability compared with the corresponded single metallic catalysts. synthesized samples were WSn-MFI-a, WSn-MFI-b, WSn-MFI-c, WSn-
In this work, we reported the direct hydrothermal synthesis of a se­ MFI-d, respectively, where a, b, c, d represent the samples with different
ries of tungsten-tin bimetallic MFI type zeolites (WSn-MFI) through contents of W and Sn measured from ICP-AES measurements as shown in
introducing a certain amount of co-surfactant of polypyrrolidone. The Table 1. Moreover, a reference sample of purely siliceous silicalite-1 was
resultant bimetallic zeolites were characterized in detail by a variety of also synthesized by using the similar procedure just without addition of
means, and their catalytic properties were investigated for the liquid W and Sn sources.
phase epoxidation of cyclohexene with H2O2. The composition-
optimized catalyst, named WSn-MFI-a, exhibited very high catalytic
activity and excellent epoxide selectivity under a mild reaction condi­ 2.3. Characterization of synthesis samples
tion. Besides, this bimetallic WSn-MFI zeolite catalyst could be easily
recycled after simple filtration and washing, and showed excellent sta­ The XRD patterns were obtained on an ARL/X’TRA X-ray diffrac­
bility for the H2O2-mediated catalytic epoxidation reaction. tometer (ARL, Switzerland) using CuKα radiation (λ ¼ 0.154 nm) in the
2θ range of 5� –40� . The morphology of the zeolites was examined by a
2. Experimental section scanning electron microscope (FESEM, QUANT FEG450, FEI). Prior to
the SEM measurement, the samples were coated with platinum. The
2.1. Chemicals and materials specific surface area and pore volume of the WSn-MFI samples were
measured by nitrogen adsorption at 77 K using the conventional
Tetraethyl orthosilicate (TEOS, AR) and tetrapropyl ammonium
hydroxide (TPAOH, 25% aqueous solution) were purchased from Table 1
Aladdin Reagent (Shanghai) Co., Ltd. 3(NH4)2O–7WO3–6H2O (AR) and The chemical compositions, relative crystallinity, specific surface areas and pore
SnCl4⋅5H2O (AR) were obtained from Guangdong Wengjiang Chemical volumes of all samples.
Reagent Co., Ltd. Acetonitrile (AR), methanol (AR), ethanol (AR), N,N- Samples W contenta Sn contenta Surf. areab Vporec RCd
dimethylformamide (DMF, AR), 1,4-dioxane and 30 wt% hydrogen (wt%) (wt%) (m2g 1) (m3g 1) (%)
peroxide were purchased from Sinopharm Chemical Reagent (Shanghai) WSn- 0.058 3.65 405 0.2364 90
Co., Ltd. Cyclohexene (AR), polypyrrolidone (PVP, AR, M ¼ 350,000) MFI-a
were ordered from Sigma-Aldrich. All the chemicals were used as WSn- 0.056 3.57 372 0.2051 68
MFI-b
received without further purification or modifications.
WSn- 0.066 3.68 374 0.2068 74
MFI-c
2.2. Synthesis of Sn-MFI, W-MFI and WSn-MFI zeolites WSn- 0.051 4.90 375 0.1988 56
MFI-d
Sn-MFI zeolites with different molar ratios of Si/Sn were synthesized W-MFI-I 0.036 / 387 0.2025 68
W-MFI-II 0.062 / 400 0.2342 47
according to a procedure reported in literature [36]. In brief, 18 mL of Sn-MFI-I / 2.97 376 0.2027 99
TEOS were added in 21 mL of TPAOH aqueous solution. After stirring at Sn-MFI-II / 6.58 376 0.1845 100
room temperature for 2 h, required amounts of SnCl4⋅5H2O in 20 mL Silicate-1 / / 391 0.2028 71
water were dropwise added under vigorous stirring and the generated a
Determined by ICP-OES.
sol was stirred for 2 h. Then, 20 mL water and 4.0 g of PVP were added to b
Calculated using BET equation.
the synthesis mixture, and stirred right along for 4 h. The final sol with c
Calculated by the BJH method.
the molar composition of 1.0SiO2: 0.0062 (or 0.0124) SnO2: d
The relative crystallinities (RCs) of the zeolites are calculated by comparing
0.32TPAOH: 27.5H2O, was charged into a Teflon-lined autoclave, sealed the total intensity of the five characteristic peaks of the samples.

2
H. Zhang et al.
technique on a 3Flex (Micromeritics, America). DRUV-vis spectra were
registered on UV–visible spectrophotometer (UV-3600, Shimadzu) using
BaSO4 as a reference. X-ray Photoelectron spectra (XPS) were collected
by an AXISUltraDLD Scientific Instrument spectrometer (Shimadzu),
equipped with a standard AlKα excitation source. The binding energy
(BE) scale was calibrated by measuring C 1s peak (BE ¼ 285.1eV). FT-IR
analysis was conducted using a Thermo Scientific NicoletiS50 F T-IR
spectrometer. An average of 16 scans was accumulated for every sample.
Elemental analysis (W, Sn, Si) were conducted by the ICP-OES method
with an Optima 2000DV (PerkinElmer) spectrometer after solubilisation
of the samples in HCl: HNO3: HF solutions. Raman spectra of the samples
were obtained on a Renishaw in Via Raman Micro-scope system with a
514.5 nm laser as the excitation source.
2.4. Catalytic epoxidation of cyclohexene
All the synthesized zeolites were used as catalysts for the epoxidation
of cyclohexene with hydrogen peroxide as oxidant. The catalytic reac­
tion was performed at 338 K in liquid-phase using acetonitrile as a
solvent. In a typical run, acetonitrile (5 mL), hydrogen peroxide (H2O2,
30 wt%, 40 mmol) were taken in a round-bottomed glass flask (25 mL)
immersed in an oil bath and connected to a water cooled reflux
condenser. 0.3 g of a calcined zeolites catalyst was placed into the flask
and the resulting suspension was stirred and refluxed for 15 min at static
temperature of 338 K. Then, cyclohexene (20 mmol) was added to start
the reaction. The reaction temperature is maintained at 338 K. The
resulted mixture was collected at intervals of an hour from the beginning
of the reaction and confirmed by GC-MS on an Agilent 7890 gas chro­
matography coupled to an Agilent 5975 mass spectrometer. After the
compositions have been confirmed, the products were analyzed with a
GC-2014C equipped (Shimadzu) with an FID detector and a capillary
column HP-5.
3. Results and discussion
3.1. Catalyst characterization
The XRD patterns of the calcined WSn-MFI, W-MFI, Sn-MFI and
silicalite-1 zeolites are displayed in Fig. 1. All the metallic zeolites show
Fig. 1. XRD patterns of WSn-MFI (A), and intensity contrast patterns of W-MFI, Sn-MFI with Sillicate-1 (B) samples.
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Microporous and Mesoporous Materials 303 (2020) 110277
the typical diffraction lines of MFI-type structure, which are quite
consistent with the pure siliceous silicalite-1 (JCPDS 44–0696) [29,37,
38]. The five diffraction peaks of W-MFI, Sn-MFI and WSn-MFI zeolites
appeared at around 8.2� , 9.0� , 23.3� , 24.1� , 24.6� , are slightly different
from the characteristic peaks of silicate-1 located at 8.0� , 8.9� , 23.2� ,
24.0� , 24.5� . The subtle changes in the 2θ values should be mainly
related to the incorporation of small amount of metallic species into the
zeolites. The detailed analysis of the XRD patterns for WSn-MFI shows
two weak signals at 2θ ¼ 26.76� and 34.98� , indicating the presence of
trace amount of SnO2 crystallites (JCPDS 41–1445) [39]. The absence of
diffraction peaks at 2θ ¼ 13.9� , 28.1� , 33.4� , 34.2� (JCPDS 43–1035)
suggests that no obvious segregated crystalline WO3 phase exists on the
samples of WSn-MFI zeolites [40].
The relative crystallinities (RCs) of the various zeolites, which are
calculated by comparing the total intensity of the five characteristic
peaks of the samples, are quite different (Table 1). The RC of Sn-MFI-II is
considered as 100% since it is the highest one among the investigated
zeolites, even much higher than the purely siliceous silicalite-1 zeolites
(71% RC) synthesized under the similar conditions. For the four WSn-
MFI samples, RCs decrease with the increase of the tungsten contents
in synthesis sol system when the amount of SnCl4⋅H2O is fixed. However,
the RCs have a little relation to the amount of SnCl4⋅H2O in the sol when
the W content is fixed in the initial synthesis sol. This might be due to the
fact that Sn species was incompletely incorporated into the framework
of WSn-MFI, which led to the existence of different amount of SnO2
clusters in the zeolite samples. As shown in Fig. 1B (inset), splitting of
the 2θ peaks at ~24.6� and ~29.6� in the XRD patterns of W-MFI occurs,
suggesting that the crystal structure of this zeolites has a monoclinic
symmetry, and implying that tungsten species may be not incorporated
into the silicon framework [38,41]. For W-MFI and WSn-MFI zeolites,
the intensity of the main diffraction peaks at around 8� and 9� turns to
lower compared with that of Sn-MFI, suggesting that the addition of W
source in the sol-gel system could decrease the RCs of the zeolites to a
certain extent. From Table 1, it is also found that only trace W species are
present in the as-synthesized W-containing zeolites. This phenomenon
suggests that most of the W species, which were added in the synthesis
sol, could not be introduced into the final metallic MFI zeolites. Besides,
the lack of splitting of the 2θ peaks at 24.7� and 29.6� in XRD patterns of
WSn-MFI (see insert in Fig. 1A) could be attributed to a change of
H. Zhang et al.
symmetry from monoclinic to orthorhombic caused by the incorporation
of tin into the framework of the zeolites.
Fig. 2 displays the SEM images of various WSn-MFI samples. WSn-
MFI-d shows well-shaped single particle with ellipsoid morphology.
The other three WSn-MFI samples exhibit a coffin-like morphology, and
the primary particles have a close packing arrangement. The particle
sizes of the four WSn-MFI samples change somewhat with the change of
addition contents of W and Sn in the initial synthesis sol. The particle
sizes of WSn-MFI-a, WSn-MFI-b are around 1 μm, which are larger than
that of WSn-MFI-c and WSn-MFI-d (ca. 0.6 μm and 0.3 μm, respectively).
The difference in morphology and particle size of the four WSn-MFI
zeolites suggests that changing the concentrations of the tungsten and
tin species in the synthesis sol system could affect the crystallization of
the zeolites to a certain extent.
The N2 adsorption-desorption isotherms of various WSn-MFI samples
are shown in Fig. 3. All samples exhibit type I isotherms, demonstrating
the micropore characteristic of these zeolites. From Table 1, it can be
seen that all of the WSn-MFI zeolites have relatively high surface area
(>370 m2/g) and large pore volume (~0.2 cm3/g), which are quite near
from the silicalite-1 as well as the single metallic W- or Sn-MFI zeolites,
indicating the high quality of these bimetallic zeolites [26].
FT-IR spectra of the four WSn-MFI samples are shown in Fig. 4A. All
samples possess obvious absorption peaks at 451, 555, 803, 1104 and
1232 cm 1, these are in good agreement with the typical FT-IR spectra of
MFI zeolites reported in the literatures [39,40]. Notably, the band at
~960 cm 1, which is commonly regarded as an indicator of Sn incor­
poration in the zeolite framework [42], could not be detected in the
present study. Similar result was also reported by Yuan et al., and they
suggested that the lack of the band at 960 cm 1 should be due mainly to
the low concentration of Si–OH defects and/or framework Sn species
[26]. Moreover, the absorption peak at 625 cm 1 can be assigned to
Sn–O stretching vibration in SnO2 [43]. No obvious signal related to W
species could be observed in the FT-IR spectra of the WSn-MFI samples,
which should be an indication of the very low concentration of the W
species.
DRUV-vis measurements were carried out to investigate the local
environment of the Sn and W coordination states in the WSn-MFI zeo­
lites. As shown in Fig. 4B, all of the samples show two major peaks at
227 nm and 317 nm. Concerning the fact that W contents in the bime­
tallic MFI-zeolites are quite low (as shown in Table 1), the peaks of 227
nm and 317 nm should be mainly related to tetrahedrally coordinated
tin in the zeolite framework (SnA) and octahedrally coordinated tin on
extra-framework (SnB), respectively [44]. Compared with that of
Fig. 2. SEM images of various WSn-MFI samples. A: WSn-MFI-a, B: WSn-MFI-b,
C: WSn-MFI-c, D: WSn-MFI-d.
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Microporous and Mesoporous Materials 303 (2020) 110277
Fig. 3. N2 adsorption–desorption isotherms of various WSn-MFI samples.
WSn-MFI-a and WSn-MFI-b, the intensity of 317 nm bands in the spectra
of WSn-MFI-c and WSn-MFI-d turns to higher, inferring the presence of
more SnO2 clusters or nanosized crystallites in these two bimetallic
zeolites.
Raman measurements were carried out for getting more subtle in­
formation of the bimetallic zeolites (Fig. 4C). The absorption bands
appeared at around 290 cm 1, 380 cm 1, and 795–830 cm 1 are the
characteristic absorption of the MFI topology. The difference in band
intensities is an indication that the relative crystallinities of the bime­
tallic zeolites are different, which agrees with the above XRD results.
The absorption bands sited at 443 cm 1 and 978 cm 1 could be assigned
to the symmetric stretching and bending vibrations of the Sn–O–Si
species [45], which provides another proof of the existence of frame­
work tin species (SnO4). The absorption bands sited at ca. 473 cm 1 is
assigned to the stretching vibrations of the Sn–O species of SnO2 [46].
The vibration intensity of this band increases with the increase of tin
content in the WSn-MFI samples. All of the Raman spectra of the
WSn-MFI zeolites do not exhibit sensitive bands related to the W species.
These are in accordance with the results of FT-IR and XRD
characterization.
The chemical states of Sn and W species in the bimetallic MFI zeolites
were characterized by XPS measurements (Fig. 5). Two binding energy
(BE) values of 487.3 and 495.7 eV could be assigned to Sn 3d5/2 and 3d3/
B
2 of SnO2 (Sn ) species in the bimetallic WSn-MFI zeolites. According to
the related literature [26], it was known that the BE values of bulk SnO2
appear at 486.6 and 495.0 eV. The increase of BE values may be caused
by the weak interaction between the SnO2 and zeolitic framework. Two
other BE values appeared at 487.6 and 496.0 eV should be attributed to
Sn 3d5/2 and 3d3/2 of framework SnO4 (SnA) species, which can be
detected for all the WSn-MFI samples. The fact no any XPS signals
related to W species implies that the trace amount of W species should be
mainly distributed inside the channel/cage of WSn-MFI zeolites rather
than on the external surface of the zeolites.
3.2. Catalytic performance for epoxidation of cyclohexene
The catalytic properties of the WSn-MFI zeolites were investigated
for the epoxidation of cyclohexene with hydrogen peroxide (H2O2). By
the analysis with gas chromatography-mass spectrometry, it was found
that the main product is epoxycyclohexane (epoxide), while the side
products include 2-cyclohexen-1-ol (CyH-ol), 2-cyclohexen-1-one (CyH-
one) and 1, 2-cyclohexanediol (diol), as illustrated below:
H. Zhang et al. Microporous and Mesoporous Materials 303 (2020) 110277

Fig. 4. FT-IR spectra (A), DRUV-vis spectroscopy (B) and Raman spectra (C) of the WSn-MFI samples.

cyclohexene after 9 h reaction, respectively, which are lower than that of

W-MFI-I (69.2%) and W-MFI-II (68.4%). All the single metallic zeolites
exhibit relatively high selectivity to epoxide (>84%). Under the iden­
tification conditions, the bimetallic WSn-MFI zeolites exhibit much
higher catalytic activity and similar epoxide selectivity. Among them,
WSn-MFI-a affords the highest catalytic activities, a 92.3% cyclohexene
conversion and 85.6% epoxide selectivity could be obtained after 9 h.
The catalytic performance of this bimetallic zeolites catalyst is compa­
rable with the relatively active and selective epoxidation catalysts re­
ported in literatures, and better than most of the investigated catalysts
(see Table S1, ESI).

Table 2
Catalytic performance of the different catalysts for epoxidation of cyclohexene.a
Catalyst Conv.b Sel./% mol
/% mol
epoxide CyH-ol CyH-one diol
Fig. 5. Sn 3d XPS spectra of various WSn-MFI samples.
WSn-MFI-a 92.3 85.6 4.6 3.5 6.3
WSn-MFI-b 89.1 86.1 3.1 3.3 7.5
WSn-MFI-c 90.1 87.6 3.8 3.6 5.0
WSn-MFI-d 91.7 76.6 5.9 8.3 9.2
W-MFI-I 69.2 88.7 2.6 3.1 4.3
W-MFI-II 68.4 88.1 2.5 4.8 4.6
Sn-MFI-I 33.3 89.7 3.3 3.0 4.0
Sn-MFI-II 47.7 84.6 3.6 3,8 8.0
a
Reaction conditions: cyclohexene (20 mmol), catalyst (0.300 g), H2O2 (30 wt
The catalytic results of the four bimetallic WSn-MFI samples and the
%, 40 mmol), 5 mL of acetonitrile, 338 K. The data came from the 9th hour
single metallic W-MFI and Sn-MFI samples are given in Table 2. It can be
measurement.
seen that Sn-MFI-I and Sn-MFI-II show 33.3% and 47.7% conversion of b
Cyclohexene conversion based on cyclohexenone consumed.

5
H. Zhang et al.
Concerning the fact that all the bimetallic WSn-MFI zeolites exhibit
much higher catalytic activity than that of the single metallic W-MFI or
Sn-MFI zeolites, we may proposed that a synergistic effect between Sn
and W species should exist on the bimetallic WSn-MFI catalysts, which
can cooperatively achieve the H2O2-mediated olefin epoxidation pro­
cess. The fact that there is no significant difference in the contents of tin
and tungsten among the three catalysts of WSn-MFI-a, WSn-MFI-b and
WSn-MFI-c, implies that the slightly higher activity of WSn-MFI-a might
be mainly originated from the relatively high the specific surface area of
this sample as given in Table 1. As for WSn-MFI-d, obvious decrease in
epoxide selectivity could be observed, which seems related to the rela­
tively high tin content (4.9 wt %) in this catalyst. As revealed by DRUV-
Vis spectra, more extra-framework tin species (SnO2) are present in the
catalyst of WSn-MFI-d, which could act as Lewis acid centers for the
formation of the side products of CyH-ol, CyH-one and diol.
Fig. 6 shows the time-dependence profiles of the catalytic properties
over WSn-MFI-a and WSn-MFI-d. It can be seen that the conversion of
cyclohexene increases gradually with increasing time, while the selec­
tivity of epoxide increases firstly and then decreases somewhat with
further extending reaction time. These results suggest that the formed
epoxide can be further converted to other side products with time. In
particularly, the catalyst of WSn-MFI-d, which contains more Sn species,
has stronger ability to induce the hydrolysis of epoxide to generate diol.
Similar situation has already been reported in previous literature on
studying the olefin epoxidation over supported metal (group IV) oxides
catalysts [47].
Fig. 6. Catalytic epoxidation of cyclohexene over WSn-MFI-a (A) and WSn-
MFI-d (B). Reaction conditions: 20 mmol of cyclohexene, 0.300 g of catalyst,
5 mL of acetonitrile, reaction temperature 338 K.
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Microporous and Mesoporous Materials 303 (2020) 110277
The effect of the amount of hydrogen peroxide on the catalytic per­
formance of WSn-MFI-a and WSn-MFI-d was also investigated (Fig. S1,
ESI). For WSn-MFI-a, the conversion of cyclohexene increases with the
usage amount of H2O2. The selectivity of epoxide increases rapidly when
the molar ratio of H2O2: cyclohexene increases from 1.0 to 2.0, then
decrease somewhat with further increasing the amount of H2O2. This
result is consistent with the literature data on the study of cyclohexene
oxidation over V-containing MIL-47 catalyst [48]. As for WSn-MFI-d,
similar trend in selectivity could also be observed. Notably, the con­
version of cyclohexene could reach about 94% in the case of H2O2:
cyclohexene ¼ 1.0, implying the utilization efficiency of H2O2 is quite
high for this WSn bimetallic zeolite catalyst.
The effect of solvents on the catalytic properties of WSn-MFI cata­
lysts was also investigated. Besides acetonitrile, other solvents including
DMF, methanol, ethanol and 1, 4-dioxane were also used. As shown in
Fig. 7, acetonitrile is a more suitable solvent for obtaining epoxide
product in comparison with other solvents. Using 1, 4-dioxane as sol­
vent, the cyclohexene conversion is the lowest. As for DMF, the cyclo­
hexene conversion is quite high, near from the solvent of acetonitrile.
However, the main product turns to diol upon using other solvents.
Previously, it has been proposed that the types of solvents might play
profound influence on the catalytic activity and selectivity of the cata­
lysts of metallosilicates, since the nature of solvents can significantly
change the local environment of the active cation sites in the
H2O2–mediated system [49–51]. In the present case, acetonitrile, an
aprotic solvent with higher dipole moment (3.92 D), is more in favor of
the formation of epoxide compared with other solvents.
The Reusability of WSn-MFI-a and WSn-MFI-d catalysts is shown in
Fig. 8. As expected, the activity of the used catalysts keeps well after 7
runs, indicating the excellent recyclability and stability. For WSn-MFI-d,
slight decrease in epoxide selectivity could be observed, might be an
indication that the reagents including the products may change a little
bit of the surface property and/or the local environment of the active
center of the bimetallic zeolites during the reaction course.
Some additional characterization measurements on the used cata­
lysts (after running 7 times), such as SEM, FT-IR, XRD and N2-adsorp­
tion/desorption profiles, were also carried out to study the structure
stability of the WSn-MFI-a and WSn-MFI-d catalysts. As shown in Fig­
s. S2–S4 (ESI), the characteristic IR bands and XRD peaks of the used
WSn-MFI catalysts remain well in comparison with the fresh catalysts.
ICP results showed that the W contents keep well in the used WSn-MFI-a
and WSn-MFI-d catalysts (Table S2, ESI). These results confirm further
that the introduced trace amount of W species should be mainly
distributed inside the channels/cages of the MFI-type zeolites, other­
wise, they may easily leach into the H2O2-mediated solution. Mean­
while, the Sn contents in the used WSn-MFI-a and WSn-MFI-d catalysts
decrease a little bit, possibly due to the loss of a small potion of SnO2
species, which are distributed on the external surface of the zeolite
catalysts. Concerning the fact that the catalytic activities of these used
catalysts keep well after several consecutive recycled tests, we may
conclude that the external SnO2 species should be not the main active
sites for the reaction. The SEM images show that the particle
morphology of the used WSn-MFI zeolites turn to irregular and smaller
compared to the fresh catalysts. This might be caused by the force of
friction during the long-time stirring. Moreover, the N2-adsorption/
desorption characterization results revealed that the textural parameters
of the used catalysts keep well compared with the fresh one. For
instance, the specific surface area of the used WSn-MFI-a zeolites is 377
m2/g, just reduced by about 6% after running 7 times reaction (Table S2,
ESI). The slightly decrease in the surface area might be mainly caused by
the adsorption of a small amount of reagents on the bimetallic zeolites.
All the above results demonstrate clearly the excellent structure stability
of the WSn-MFI catalysts.
H. Zhang et al. Microporous and Mesoporous Materials 303 (2020) 110277

Fig. 7. Effects of the solvents on the catalytic performance of WSn-MFI-a (A) and WSn-MFI-d (B). Reaction conditions: 20 mmol of cyclohexene, 0.300 g of catalyst, 5
mL of acetonitrile, reaction temperature 338 K, reaction time 9 h.

Fig. 8. Recycling experiments over WSn-MFI-a (A) and WSn-MFI-d (B). Reaction conditions: 20 mmol of cyclohexene, 0.300 g of catalyst, 5 mL of acetonitrile,
reaction temperature 338 K, reaction time 9 h.

4. Conclusions Declaration of competing interest

Bimetallic tungsten-tin MFI type zeolites were successfully synthe­
sized by direct hydrothermal method. The addition amount of W and Sn
ions in the initial sol-gel synthesis system could considerably influence
the chemical state of active metal species, the morphology, the particle
size and the crystallinity of the WSn-MFI zeolites. The introduced trace
amount of W species are mainly distributed inside the channels/cages of
the bimetallic WSn-MFI zeolites, while both the isolated framework
SnO4 species and the extra-framework SnO2 species are present in the
zeolites. The resultant WSn-MFI zeolites show enhanced catalytic ac­
tivity compared with the monometallic W-MFI and Sn-MFI zeolites for
the epoxidation of cyclohexene with H2O2 as the oxidant, implying the
existence of a synergistic effect between the incorporated Sn species and
W species. The presence of relatively more extra-framework SnO2 spe­
cies may result in the generation of more side products, thus leading to
the decrease of epoxide selectivity. Moreover, the resultant bimetallic
WSn-MFI zeolite catalysts have excellent recyclability and structure
stability, and can be easily recycled for many times by simple filtration
without need of calcination. Further work is still required in order to get
deep understanding on the nature of active sites and the concrete syn­
ergistic effect mechanism of the bimetallic species, which are very sig­
nificant for designing and developing more efficient olefin epoxidation
catalysts for practical application.
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.
CRediT authorship contribution statement
Haoyang Zhang: Investigation, Formal analysis, Writing - original
draft. Xiaotong Yang: Formal analysis. Xiaojing Song: Methodology.
Xinyu Chang: Methodology. Mingjun Jia: Writing - review & editing,
Supervision.
Acknowledgment
Financial support from the National Natural Science Foundation of
China (No. 21173100) is gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.micromeso.2020.110277.

7
H. Zhang et al. Microporous and Mesoporous Materials 303 (2020) 110277

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