Ordered mesoporous SBA-15 functionalized with yttrium(III) and cerium(III) complexes: Towards active heterogeneous catalysts for oxidation of sulfides and preparation of 5-substituted 1H-tetrazoles

Article abstract of DOI:10.1002/aoc.4649

Mesoporous SBA-15 was synthesized and modified with 3-chloropropyltrimethoxysilane and then used in immobilization of creatinine groups, which were employed to introduce Y³⁺ and Ce³⁺ to give rise to two novel yttrium and cerium catalysts: SBA-15@Creatinine@M (M?=?Y and Ce). The structures of the SBA-15@Creatinine@M catalysts were determined using various techniques. These catalysts offered outstanding catalytic performances in the oxidation of sulfides to sulfoxides and in the preparation of 5-substituted 1H-tetrazoles. An important characteristic of the SBA-15@Creatinine@M catalysts is that they are very stable without a considerable decrease in their catalytic performance lasting seven cycles.

Full text of DOI:10.1002/aoc.4649

Received: 30 July 2018
DOI: 10.1002/aoc.4649
Revised: 12 September 2018
Accepted: 23 September 2018
F U L L P A P E R
Ordered mesoporous SBA‐15 functionalized with
yttrium(III) and cerium(III) complexes: Towards active
heterogeneous catalysts for oxidation of sulfides and
preparation of 5‐substituted 1H‐tetrazoles
1
1
1
Somayeh Molaei | Taiebeh Tamoradi
| Mohammad Ghadermazi
|
2
Arash Ghorbani‐Choghamarani
1
Department of Chemistry, Faculty of
Mesoporous
SBA‐15 was
synthesized
and
modified
with
3‐
Science, University of Kurdistan,
Sanandaj, Iran
chloropropyltrimethoxysilane and then used in immobilization of creatinine
2
Department of Chemistry, Faculty of
3+
3+
groups, which were employed to introduce Y and Ce to give rise to two
novel yttrium and cerium catalysts: SBA‐15@Creatinine@M (M = Y and Ce).
The structures of the SBA‐15@Creatinine@M catalysts were determined using
various techniques. These catalysts offered outstanding catalytic performances
in the oxidation of sulfides to sulfoxides and in the preparation of 5‐substituted
1H‐tetrazoles. An important characteristic of the SBA‐15@Creatinine@M cata-
lysts is that they are very stable without a considerable decrease in their cata-
lytic performance lasting seven cycles.
Science, Ilam University, PO Box,
69315516 Ilam, Iran
Correspondence
Mohammad Ghadermazi, University of
Kurdistan, Department of Chemistry,
Faculty of Science, Sanandaj, Iran.
Email: mghadermazi@yahoo.com
KEYWORDS
heterogeneous catalyst, SBA‐15, sulfoxides, tetrazoles, yttrium and cerium
1
| INTRODUCTION
mesostructured catalysts, ordered mesoporous SBA‐15
with a regular two‐dimensional hexagonal array of pores
Recently, recoverable and reusable catalysts have
attracted much attention because of their industrial pro-
cesses and environmental impacts. However, the use of
homogeneous catalysts in organic reactions can be chal-
lenging due to their complicated recovery process from
reaction mixtures. In general, the synthesis of heteroge-
neous catalysts via surface grafting of homogeneous cata-
lysts to heterogeneous supports such as SBA‐15, MCM‐41,
MCM‐48, carbon nanotubes, metal oxides, clays, ionic
liquids and polymers is a primary solution in catalysis
and long one‐dimensional channels has already garnered
increasing regard due to its ease of preparation, large
internal surface area, excellent thermal and chemical
stability, thick silica walls (2–6 nm), low cost and great
[
9–13]
density of surface Si─ OH groups.
Functionalization
of SBA‐15 can be performed by the incorporation of vari-
ous groups. In particular, organically modified SBA‐15
silica has attracted significant interest in the past few
decades and it can be regarded as effective in the develop-
ment of inorganic–organic hybrid solid‐based catalysts.
Recent studies have reported the grafting of organic
groups on the silica surface for efficient catalysts. Exam-
ples include: biguanide‐functionalized mesoporous SBA‐
15 silica as an efficient solid catalyst for interesterification
[1–5]
processes.
Among the supports mentioned above,
mesostructured catalysts, due to their extremely high sur-
face area and extreme efficiency, have attracted attention
over homogeneous catalysts, and they have applications
in various fields such as gas storage, catalysis, adsorption,
[
14]
of vegetable oils,
propylsulfonic‐ and arenesulfonic‐
[6–8]
sensing, light harvesting and so on.
Among various
functionalized SBA‐15 silica as an efficient and reusable
Appl Organometal Chem. 2018;e4649.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
1 of 14
https://doi.org/10.1002/aoc.4649

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MOLAEI ET AL.
catalyst for the acidolysis of soybean oil with medium‐chain
[15]
fatty acids,
SBA‐15‐pr‐NR OH as an efficient heteroge-
3
neous catalyst for the interesterification of soybean oil
[16]
and lard blends
and 1,3‐dicyclohexyl‐2‐octylguanidine
anchored onto the surface of mesoporous SBA‐15 for
soybean oil transesterification with methanol.
[17]
SCHEME 2 Oxidation of sulfides
SCHEME 1 (a) Preparation of SBA‐
5@Creatinine@M (M = Y and Ce). (b)
Mechanism for preparation of SBA‐
5@Creatinine@M (M = Y and Ce)
1
1

MOLAEI ET AL.
3 of 14
The incorporation of metal catalysts onto supports has
received significant attention due to the sustainable green
1H‐tetrazoles and oxidation reactions for the first time.
Yttrium is reactive, inexpensive, readily available and with
[18]
[19–21]
chemistry uses it presents.
In this regard, we anchored
a variety of industrial applications.
Also, cerium has
cerium and yttrium complexes onto the surface of silica
SBA‐15 as efficient and recyclable solid catalysts for the
synthesis of 5‐substituted 1H‐tetrazoles and oxidation reac-
tions. The novelty of this study is the use of these metals as
the active sites of catalysts in the synthesis of 5‐substituted
attracted significant research interest due to its low toxic-
[
22,23]
ity.
Interestingly, a number of transition metal
(Zn, Cu, Pd, Co, Mn, Ni, La, Pr, Fe, Hg, Cd, etc.) complexes
which are employed for catalytic applications can be intro-
[
24–28]
duced onto silica materials.
A diversity of procedures
have been utilized in the grafting of transition metals
for heterogeneous catalysts usually involving the
functionalization of the transition metals either without
any connector or with a connector to the surfaces of the
supports. In one method, metals are bound to the substrate
without any connector. Although this strategy is simple and
inexpensive, and hence is very popular, the metals are eas-
ily washed out from the surface due to the weak bonding
between them. In other methods, an organic ligand is used
as a connector and fixative agent to anchor the metal onto
the surface. In these methods, because of the fixative
ligands, catalytic species have higher activity and are more
stable. Most of the catalysts designed in this category are
highly efficient in reactions and they have good
FIGURE 2 TGA curves of SBA‐15, SBA‐15@Creatinine@Y and
SBA‐15@Creatinine@Ce
FIGURE 1 FT‐IR spectra of (a) SBA‐15, (b) SBA‐15‐ Cl, (c) SBA‐
1
1
5@Creatinine, (d) SBA‐15@Creatinine@Y and (e) SBA‐
5@Creatinine@Ce
FIGURE 3 Nitrogen adsorption–desorption isotherms of SBA‐15,
SBA‐15@Creatinine@Y and SBA‐15@Creatinine@Ce

4
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MOLAEI ET AL.
recyclability. For instance, the direct synthesis of Fe‐
incorporated SBA‐15 was reported for dehydrogenation
chemistry, catalysis technology and organic chemistry,
and in medicinal chemistry because of their antiprolifera-
tive, antiviral, analgesic and anti‐inflammatory proper-
[28]
of isobutene.
Also, there is a report of the grafting of
[
30–33]
a Cu(II) complex onto the surface of MCM‐41 for the
ties.
Furthermore, interest in the synthesis of
synthesis of heterocyclic compounds and for oxidation
sulfoxides has increased because of their applications in
the laboratory, industry, agrochemicals and pharmaceuti-
cals such as omeprazole and fipronil.
[29]
reactions.
However, to date, there are few reports of
[
34–37]
the grafting of cerium and yttrium complexes onto the
surface of functionalized mesoporous materials.
In the work reported in the present paper, in order to
develop green and novel procedures for the preparation
of efficient and novel heterogeneous catalysts, we
employed two transition metals (Y and Ce) supported on
pure silica SBA‐15. It should be noted that there are few
reports of the grafting of these transition metals on SBA‐
15 as a catalyst. Also, the structures of the final catalysts
were investigated using scanning electron microscopy
Cerium and yttrium complexes can be used as versa-
tile and green reagents for organic synthesis, such as
for the synthesis of 5‐substituted 1H‐tetrazoles and for
oxidation reactions. Over the past few decades, tetrazole
derivatives have attained considerable popularity because
of their usage in pharmaceuticals, coordination
TABLE 1 Textural parameters obtained from nitrogen adsorption
analysis
(
SEM), Fourier transform infrared (FT‐IR) spectroscopy,
thermogravimetric analysis (TGA), X‐ray diffraction
XRD), inductively coupled plasma (ICP) analysis,
(
Pore diameter Pore
S
BET
2
by BJH
volume
energy‐dispersive X‐ray (EDX) analysis and Brunauer–
Emmett–Teller (BET) measurements. Their catalytic
applications were investigated for the preparation of
sulfoxide and tetrazole derivatives. The smooth progress,
utilization of green transition metals for the synthesis of
catalysts, easy separation of catalysts from reaction
mixtures by simple filtration, short reaction time, high
yield and inexpensive and non‐toxic catalysts are attractive
and important features of this reported procedure.
−1
3
−1
Sample
(m g ) method (nm) (cm g
)
SBA‐15
555.2
2.4
1.6
1.6
0.553
0.224
0.261
SBA‐15@Creatinine@Y 232.7
SBA‐15@Creatinine@Ce 304.2
2
| EXPERIMENTAL
.1 | Characterization
2
Small‐angle XRD measurements were achieved using an
X’pert MPD diffractometer with Cu Kα radiation. FT‐IR
spectra were obtained with a VERTEX70 (Bruker). The
TGA data were obtained with a Shimadzu DTG‐60
analyser. The metal content in the catalysts was
FIGURE 4 XRD patterns of SBA‐15, SBA‐15@Creatinine@Y and
SBA‐15@Creatinine@Ce
FIGURE 5 EDX patterns of SBA‐15@Creatinine@Y (left) and SBA‐15@Creatinine@Ce (right)

MOLAEI ET AL.
5 of 14
determined using ICP analysis (730‐ES, Varian). To col-
lect SEM images, an FESEM‐TESCAN MIRA3 was used.
2.2 | SBA‐15 preparation
Mesoporous SBA‐15 was obtained using a reported proce-
[38]
dure.
First, 4.0 g of Pluronic P123 was added to a solu-
tion (90 ml of HCl (2 M) and 30 ml of water) and stirred
for 5 h at 30°C. Then, 9.04 ml of tetraethylorthosilicate
was introduced gradually and stirred for 20 h. The
resulting product was isolated then washed and dried.
Afterwards, the sample was calcined at 823 K (5 h).
2
.3 | Functionalization of mesoporous
SBA‐15 with
‐chloropropyltrimethoxysilane (CPTMS)
3
Typically, 1.0 g of SBA‐15 was dispersed in toluene
40 ml), and CPTMS (3 ml) was introduced followed by
(
refluxing (24 h). The resulting product (SBA‐15‐Cl) was
isolated then washed with n‐hexane and dried at 80°C.
2.4 | Immobilization of creatinine onto
SBA‐15‐Cl
SBA‐15‐Cl (1.0 g) was dispersed in toluene (40 ml), and
creatinine (2 mmol) and triethylamine (3 ml) were intro-
duced followed by refluxing (48 h). The resulting product
(SBA‐15@Creatinine) was isolated, washed repeatedly
with water and finally dried at 80°C.
2
.5 | Introduction of yttrium(III) onto
SBA‐15@Creatinine (SBA‐
5@Creatinine@Y)
1
SBA‐15@Creatinine (1 g) was dispersed into ethanol
40 ml), Y(NO ) ⋅6H O (0.687 g) was introduced and then
(
3
3
2
refluxed for about 16 h. The product was separated and
dried after washing with ethanol.
2
.6 | Introduction of cerium(III) onto
SBA‐15@Creatinine (SBA‐
5@Creatinine@Ce)
1
SBA‐15@Creatinine (1 g) was dispersed into ethanol
40 ml), Ce(NO ) ⋅6H O (1.09 g) was introduced and then
(
3
3
2
FIGURE
6
SEM images of (a) SBA‐15, (b) SBA‐
refluxed for about 16 h. The product was separated and
washed repeatedly. Finally, it was dried at 80°C.
15@Creatinine@Y and (c) SBA‐15@Creatinine@Ce (scale bar:
2 μm)

6
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MOLAEI ET AL.
2
.7 | Typical approach for synthesis of
the organic product was extracted with ethyl acetate
and dried after washing.
sulfoxides
2
.8 | Typical approach for synthesis of
Typically, SBA‐15@Creatinine@M (5 mg) was dispersed
tetrazoles
in H O (0.5 ml) and sulfide (1 mmol) with stirring at
2
2
room temperature. (The progression of the reaction was
monitored using TLC.) When the reaction was finished,
Typically, SBA‐15@Creatinine@M (30 mg) was spread in
water (3 ml) and nitrile (1 mmol), then NaN (1.2 mmol)
3
FIGURE 7 TEM images of (a) SBA‐15@Creatinine@Y and (b) SBA‐15@Creatinine@Ce
2 2
TABLE 2 Optimization of parameters for synthesis of methylphenyl sulfoxide catalysed by SBA‐15@Creatinine@Y using H O
a
Entry
Solvent
Catalyst (mg)
H
2
O
2
(ml)
Time (min)
Yield (%)
1
2
3
4
5
6
7
EtOH
3
5
7
5
5
5
5
0.5
0.5
0.5
0.4
0.5
0.5
0.5
90
80
96
97
90
76
82
78
EtOH
60
EtOH
60
EtOH
120
110
150
160
Solvent free
Ethyl acetate
Acetonitrile
a
Isolated yield.

MOLAEI ET AL.
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TABLE 3 Oxidation of sulfides catalysed by SBA‐15@Creatinine@M (M = Y and Ce)
Time (min)
Y; Ce
Yield (%)
Y; Ce
Entry
Substrate
Product
1
60; 60
96; 98
2
3
5; 3
1; 1
94; 96
97; 98
4
30; 20
94; 96
5
6
4; 4
2; 2
90; 92
93; 93
7
8
4; 4
91; 94
92; 94
10; 5
9
5; 4
94; 95
90; 93
1
0
70; 60
was introduced with stirring at 100°C. (The progression
of the reaction was monitored using TLC.) When the
reaction was completed, the organic product was isolated
with ethyl acetate and dried after washing.
2.9.2 | 2,2′‐Sulfinyldiacetic acid (Table 3,
entry 2)
1
H NMR (400 MHz, DMSO, δ, ppm): 4.364–4.386 (m, 4H),
6.382 (br. s, 2H, 2 COOH).
2
2
.9 | Selected spectral data
.9.1 | Methylphenyl sulfoxide (Table 3,
2.9.3 | 5‐(3‐Nitrophenyl)‐1H‐tetrazole
(Table 5, entry 3)
entry 1)
1
1
H NMR (400 MHz, CDCl , δ, ppm): 2.98 (s, 3H), 7.46–
H NMR (400 MHz, DMSO, δ, ppm): 8.86 (s, 1H), 8.51–
3
7
.50 (m, 2H), 7.55–7.57 (m, 1H), 7.85–7.87 (m, 2H).
8.44 (m, 2H), 7.95–7.91 (m, 1H).

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MOLAEI ET AL.
2
.9.4 | 5‐(3‐Chlorophenyl)‐1H‐tetrazole)
3 | RESULTS AND DISCUSSION
(Table 5, entry 10)
In this study, we employed two transition metals (Y and
Ce) supported on pure SBA‐15 silica for the first time
and their catalytic application was studied for the synthe-
sis of 5‐substituted 1H‐tetrazoles and sulfoxides. In
Scheme 1, the preparation of SBA‐15@Creatinine@M
1
H NMR (400 MHz, DMSO, δ, ppm): 8.10–8.02 (m, 1H),
.05–8.02 (m, 1H), 7.70–7.64 (m, 2H).
8
(
M = Y and Ce) and the mechanism for the preparation
of SBA‐15@Creatinine@M are shown.
3.1 | Catalyst characterization
The FT‐IR spectrum for pure SBA‐15 (Figure 1a) exhibits
−
1
bands at 1081, 805 and 462 cm which are assigned to
Si─O asymmetric and symmetric stretching and Si─O─Si
[
39]
bending, respectively.
The FT‐IR spectrum for SBA‐
1
2
5@Cl (Figure 1b) demonstrated bands at 2923 and
854 cm , which are assigned to the stretching vibra-
−
1
SCHEME 3 Proposed mechanism for oxidation of sulfides into
sulfoxides in presence of SBA‐15@Creatinine@M (M = Y and Ce)
as catalysts
tions of C─H bonds of CPTMS. The FT‐IR spectrum for
SBA‐15@Creatinine (Figure 1c) showed new bands at
−
1
1680 and 1498 cm which were owing to the vibration
[40]
of the C═O and C═N bonds of creatinine, respectively.
The FT‐IR spectrum confirmed that grafting of creatinine
to SBA‐15@Cl had been done successfully. As shown in
the spectra of SBA‐15@Creatinine@M (Figure 1d,e), the
−
1
presence of bands at around 1081, 805 and 462 cm con-
firm that, with immobilization of SBA‐15, the phase has
not been changed.
SCHEME 4 Preparation of 5‐substituted 1H‐tetrazoles
TABLE 4 Optimization of parameters for preparation of 5‐(3‐nitrophenyl)‐1H‐tetrazole catalysed by SBA‐15@Creatinine@Y using NaN
3
a
Entry
Solvent
Catalyst (mg)
Temperature (°C)
Time (min)
220
Yield (%)
1
2
3
4
5
6
7
8
9
H
H
H
H
H
2
2
2
2
2
O
O
O
O
O
30
50
70
50
50
50
50
50
50
100
100
100
80
88
97
98
95
92
85
75
71
70
195
195
210
60
240
PEG
120
120
120
80
250
DMSO
DMF
EtOH
210
220
240
a
Isolated yield.

MOLAEI ET AL.
9 of 14
TABLE 5 Preparation of 5‐substituted 1H‐tetrazoles catalysed by SBA‐15@Creatinine@M (M = Y and Ce)
Time (min)
Yield (%)
Y; Ce
Entry
Substrate
Product
Y; Ce
1
7; 4
97; 98
2
3
50; 40
98; 99
195; 180
95; 97
4
5
6
20; 25
92; 93
94; 97
94; 96
500; 485
15; 10
7
8
7; 5
3; 3
97; 98
93; 93
9
5; 5
5; 5
95; 97
96; 96
1
1
0
1
193; 184
96; 98

10 of 14
MOLAEI ET AL.
The amount of Y and Ce creatinine complexes loaded
into the mesoporous SBA‐15 was determined using TGA
Figure 2). In all samples, desorption of the solvents
occurs below 200°C. Combustion of the organic groups
appeared at 200–550°C. From the TGA curves, the load-
ing amounts of organic materials bound to the SBA‐15
surface in the SBA‐15@Creatinine@Y and SBA‐15-
structure. The textural data derived from nitrogen
adsorption–desorption measurements are presented in
Table 1. With functionalization of SBA‐15 with
Creatinine@M, the resulting SBA‐15@Creatinine@Y
and SBA‐15@Creatinine@Ce exhibit a lower BET surface
area, pore size and total pore volume, which might corre-
spond to the occupation of the pore channels by
(
[
42]
@Creatinine@Ce substrates were found to be 10 and
Creatinine@Y and Creatinine@Ce.
2
0%, respectively. The results confirmed that creatinine
The small‐angle XRD pattern of mesoporous SBA‐15
(Figure 4) displays one strong peak indexed as (100) plane
and two weak peaks corresponding to (110) and (200)
planes of the two‐dimensional hexagonal mesoporous
was anchored into the silicate frameworks.
Nitrogen adsorption–desorption (Figure 3) of SBA‐15,
SBA‐15@Creatinine@Y and SBA‐15@Creatinine@Ce
displays a type IV isotherm, which indicates that these
[
43]
structure.
After the functionalization with metal
[41]
samples have an ordered mesoporous structure.
With
complex,
SBA‐15@Creatinine@Y and SBA‐15-
functionalization of SBA‐15, the adsorbed volume
decreased, which was indicative of a less ordered pore
@Creatinine@Ce also showed one peak corresponding
to the (100) diffraction, which indicated that the
[
44]
mesostructure had been retained.
of (100) diffraction was decreased. Also, the (110) and
200) diffractions were absent in the patterns of these
The peak intensity
(
samples, indicating that the degree of ordering of meso-
porous SBA‐15 was decreased with the introduction of
[
42]
the metal complex.
The EDX analyses for SBA‐15@Creatinine@Y and
SBA‐15@Creatinine@Ce are shown in Figure 5. Peaks
related to Si, C, O, N, Y and Ce were observed. Using ICP
analysis, the amount of Y and Ce anchored into the pores
of SBA‐15 was found to be 2.2 and 5.1%, respectively.
From the SEM images of SBA‐15, SBA‐15-
@
Creatinine@Y and SBA‐15@Creatinine@Ce (Figure 6),
it can be observed that they possess rod‐like shape with-
out significant changes in the morphology upon the
functionalization process.
The transmission electron microscopy (TEM) images
of SBA‐15@Creatinine@Y and SBA‐15@Creatinine@Ce
(
Figure 7) displayed the existence of ordered
mesostructures in these samples.
3.2 | Catalytic studies
SCHEME
substituted 1H‐tetrazoles in presence of SBA‐15@Creatinine@M
M = Y and Ce) as catalysts
5
Proposed mechanism for preparation of 5‐
We first investigated the catalytic activities of SBA‐15-
@Creatinine@Y and SBA‐15@Creatinine@Ce for the
(
FIGURE 8 Reusability of SBA‐15@Creatinine@M (a, M = Ce; b, M = Y) catalysts for synthesis of methylphenyl sulfoxide (left) and
synthesis of 5‐phenyl‐1H‐tetrazole (right)

MOLAEI ET AL.
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TABLE 6 Textural parameters obtained from nitrogen adsorption
analysis
Pore diameter Pore
S
BET
2
by BJH
volume
−1
3
−1
Sample
(m g ) method (nm) (cm g )
Reused SBA‐
223.1
296.3
1.6
0.218
0.255
15@Creatinine@Y
Reused SBA‐
1.6
15@Creatinine@Ce
The catalytic activity of SBA‐15@Creatinine@M was
studied in the preparation of 5‐substituted 1H‐tetrazoles
FIGURE 9 XRD patterns of recovered SBA‐15@Creatinine@Y
and SBA‐15@Creatinine@Ce
oxidation of sulfides) Scheme (2. Initially, methylphenyl
sulfide was oxidized as an example using various
amounts of H O and each catalyst with a variety of sol-
2
2
vents (Table 2). First, various concentrations of SBA‐15-
Creatinine@Y at room temperature were studied. From
@
Table 1, the best concentration of SBA‐15@Creatinine@Y
was 5 mg. With an increase in the catalyst dosage, no sub-
stantial change in the product yield was obtained. Then,
the effect of the amount of H O on the catalyst activity
2
2
was studied. Subsequently, oxidation of methylphenyl
sulfide was performed in a variety of solvents including
ethyl acetate, acetonitrile and ethanol, and under
solvent‐free conditions. Results suggest that ethanol
showed a good effect for the oxidation reaction.
Finally, to show the high activity of SBA‐15-
@
Creatinine@M as heterogeneous catalysts, other sub-
strates with diverse functional groups were employed
Table 3). As evident from Table 3, these catalysts show
(
excellent activity in the oxidation of sulfides. As shown
in Scheme 3, a reaction mechanism for the oxidation of
[13]
sulfides is proposed.
FIGURE 10 Nitrogen adsorption–desorption isotherms of
recovered SBA‐15@Creatinine@Y and SBA‐15@Creatinine@Ce
FIGURE 11 SEM images
15@Creatinine@Y and (b) SBA‐15@Creatinine@Ce
of
(a)
recovered
SBA‐

12 of 14
MOLAEI ET AL.
FIGURE 12 EDX patterns of recovered SBA‐15@Creatinine@Y (left) and SBA‐15@Creatinine@Ce (right)
(Scheme 4). To examine the optimal reaction conditions,
15@Creatinine@Y in water with 1.2 mmol of NaN at
3
the influences of a variety of factors, e.g. solvent, reaction
temperature and quantity of catalyst, were investigated
for the preparation of 5‐(3‐nitrophenyl)‐1H‐tetrazole. With
100°C are determined to be the optimal reaction conditions
for the preparation of 5‐substituted 1H‐tetrazoles.
The catalytic activity of SBA‐15@Creatinine@M was
further examined for other substrates with diverse func-
tional groups. The results are summarized in Table 5.
As shown in Scheme 5, a reaction mechanism for the
preparation of the 5‐substituted 1H‐tetrazoles is
1
5 mg of SBA‐15@Creatinine@Y to catalyse the reaction,
the product was observed in 88% yield. With an increase
in the quantity of catalyst from 30 to 50 mg, an increase
in the yield from 88 to 97% was obtained. Whereas, on
further increasing the catalyst dosage (from 50 to 70 mg),
no change in reaction results was obtained. Among
the various solvents examined, e.g. dimethylsulfoxide
[
45]
suggested.
(DMSO), poly(ethylene glycol) (PEG), water, ethanol and
3.3 | Reusability and leaching study of
dimethylformamide (DMF), water provided excellent
yield. Then, the influence of temperature was studied.
The highest conversions were obtained at 100°C (97%;
Table 4, entry 2). Therefore, 50 mg of SBA‐
catalysts
A recycling study was conducted using the synthesis of
methylphenyl sulfoxide and the preparation of 5‐phenyl‐
TABLE 7 Comparison of SBA‐15@Creatinine@M (M = Y and Ce) catalysts for preparation of dibenzyl sulfoxide and 5‐(4‐chlorophenyl)‐
1H‐tetrazole with previously reported catalysts
Temp. (°
C)
Time
(min)
Entry
Product
Catalyst: amount
Fe @S‐ABENZ@VO: 5 mg
Solvent
Yield (%)
a
[46]
1
2
3
4
5
6
7
8
9
Dibenzyl sulfoxide
3
O
4
Solvent‐free
Ethanol
Ethanol
Solvent‐free
Ethanol
Ethanol
Ethanol
PEG
r.t.
140
30
94
[
[
[
[
47]
48]
49]
50]
Dibenzyl sulfoxide
Zr (IV)/isatin‐MCM‐48: 10 mg
r.t.
35
99
95
99
96
Dibenzyl sulfoxide
Cu‐ Schiff base@MCM‐41: 40 mg
70
Dibenzyl sulfoxide
Fe
3
O
4
‐Schiff base‐Cu (II): 20 mg
40
180
137
4
Dibenzyl sulfoxide
Cd‐salen‐MCM‐41: 20 mg
r.t.
r.t.
r.t.
120
120
Dibenzyl sulfoxide
SBA‐15@Creatinine@Y: 5 mg
SBA‐15@Creatinine@Ce: 5 mg
90; this work
92; this work
Dibenzyl sulfoxide
4
[
33]
5‐(4‐Chlorophenyl)‐1H‐tetrazole
5‐(4‐Chlorophenyl)‐1H‐tetrazole
Fe
Copper (II) immobilized on
Fe @SiO2@L‐histidine: 50 mg
3
O
4
‐Adenine‐Zn: 50 mg
80
96
95
[51]
PEG
240
3 4
O
[
[
[
52]
53]
54]
10
11
12
13
14
5‐(4‐Chlorophenyl)‐1H‐tetrazole
5‐(4‐Chlorophenyl)‐1H‐tetrazole
5‐(4‐Chlorophenyl)‐1H‐tetrazole
5‐(4‐Chlorophenyl)‐1H‐tetrazole
5‐(4‐Chlorophenyl)‐1H‐tetrazole
Pd‐SBT@MCM‐41: 30 mg
Pd‐isatin‐boehmite: 30 mg
PEG
PEG
PEG
120
120
120
100
100
480
450
600
5
91
88
91
3 4
Fe O @SBTU@Ni(II): 40 mg
SBA‐15@Creatinine@Y: 50 mg
SBA‐15@Creatinine@Ce: 50 mg
H
2
2
O
O
95; this work
97; this work
H
5
a
Room temperature.

MOLAEI ET AL.
13 of 14
1H‐tetrazole as examples. After finishing the reaction, the
Mohammad Ghadermazi
http://orcid.org/0000-0001-
SBA‐15@Creatinine@M catalysts were recovered by
effortless filtration, washed, dried at 60°C and finally
recycled for a subsequent reaction run. As shown in
Figure 8, the catalyst activity decreased smoothly during
seven runs. Also, using ICP analysis, the yttrium(III)
and cerium(III) contents of recovered SBA‐15-
8631-6361
REFERENCES
[1] M. A. Zolfigol, M. Navazeni, M. Yarie, R. Ayazi‐Nasrabadi, Res.
Chem. Intermed. 2018, 44, 191.
[2] T. Tamoradi, A. Ghorbani‐Choghamarani, M. Ghadermazi,
Appl. Organometal. Chem. 2018, 32, 3974.
@Creatinine@Y and SBA‐15@Creatinine@Ce were
determined, which were found to be 2.0 and 5.0% (w/
w), respectively.
[3] M. Nikoorazm, A. Ghorbani‐Choghamarani, N. Noori, B.
Tahmasbi, Appl. Organometal. Chem. 2016, 30, 843.
The XRD patterns of the recovered catalysts after
recycling (seventh reuse) are shown in Figure 9. It can
be seen that the mesostructure was retained in the recov-
[4] D. Saberi, M. Sheykhan, K. Niknam, A. Heydari, Catal. Sci.
Technol. 2013, 3, 2025.
ered
SBA‐15@Creatinine@Y
and
SBA‐15-
adsorption–
[5] M. B. Gawande, P. S. Branco, R. S. Varma, Chem. Soc. Rev.
2013, 42, 3371.
@Creatinine@Ce
samples. Nitrogen
desorption (Figure 10) of the spent SBA‐15-
Creatinine@Y and SBA‐15@Creatinine@Ce samples
[6] P. Bhanja, R. Gomes, L. Satyanarayana, A. Bhaumik, J. Mol.
Catal. Chem. 2016, 415, 104.
@
shows a type IV isotherm, which indicates that in these
samples, the ordered mesoporous structure was retained.
Also, the textural data derived from nitrogen adsorption–
desorption measurements are presented in Table 6.
Figure 11 shows SEM images of the reused catalysts.
They do not show any changes in the morphology of
the catalysts. From EDX analysis (Figure 12), it can be
seen that Y and Ce species exist on the surface of the
spent catalysts.
[
7] T. Tamoradi, M. Ghadermazi, A. Ghorbani‐Choghamarani,
J. Porous Mater. 2018. https://doi.org/10.1007/s10934-018-
0623-2
[8] N. A. Brunelli, K. Venkatasubbaiah, C. W. Jones, Chem. Mater.
2012, 24, 2433.
[9] T. Tamoradi, M. Ghadermazi, A. Ghorbani‐Choghamarani, S.
Molaei, Res. Chem. Intermed. 2018, 44, 4259.
[
10] R. Barranco‐García, J. M. López‐Majada, J. C. Martínez, J. M.
Gómez‐Elvira, E. Pérez, M. L. Cerrada, Micropor. Mesopor.
Mater. 2018, 272, 209.
[
11] K. S. Lakhi, G. Singh, S. Kim, A. V. Baskar, S. Joseph, J.‐H.
Yang, H. Ilbeygi, S. J. M. Ruban, V. T. H. Vu, A. Vinu,
Micropor. Mesopor. Mater. 2018, 267, 134.
3.4 | Comparison of catalysts
To assess the performance of the catalysts under investi-
gation with that of previously reported catalysts, results
for the synthesis of dibenzyl sulfoxide and 5‐(4‐
chlorophenyl)‐1H‐tetrazole, as model examples, are pre-
sented in Table 7. The SBA‐15@Creatinine@M catalysts
are more effective than other reported catalysts.
[
12] Y.‐Y. Meng, Q.‐D. An, Z.‐Y. Xiao, S.‐R. Zhai, Z. Shi, Micropor.
Mesopor. Mater. 2018, 266, 64.
[
13] T. Tamoradi, A. Ghorbani‐Choghamarani, M. Ghadermazi,
Appl. Organometal. Chem. 2018, 32, e4340.
[
[
[
[
[
14] W. Xie, L. Hu, Food Chem. 2016, 197, 92.
15] W. Xie, C. Zhang, Food Chem. 2016, 211, 74.
16] W. Xie, C. Qi, J. Agric, Food Chem. 2013, 61, 3373.
17] W. Xie, X. Yang, M. Fan, Renewable Energy 2015, 80, 230.
18] E. Tyrrell, L. Whiteman, N. Williams, J. Organometal. Chem.
4
| CONCLUSIONS
In
summary,
two
novels
catalysts
(SBA‐
2011, 696, 3465.
1
5@Creatinine@Y and SBA‐15@Creatinine@Ce) were
[19] A. G. B. Getsoian, B. Hu, J. T. Miller, A. S. Hock, Organometal-
successfully synthesized. The structures of the catalysts
were studied using SEM, FT‐IR spectroscopy, TGA,
XRD, ICP analysis, EDX analysis and BET measure-
ments. The catalytic activities of SBA‐15@Creatinine@Y
and SBA‐15@Creatinine@Ce were investigated in the
oxidation of sulfides and the preparation of 5‐substituted
lics 2017, 36, 3677.
[20] P. E. Sues, A. J. Lough, R. H. Morris, Inorg. Chem. 2012, 51,
322.
9
[21] X. Wang, J. L. Brosmer, A. Thevenon, P. L. Diaconescu, Organ-
ometallics 2015, 34, 4700.
1
H‐tetrazoles. The catalysts could be reused a number of
[22] N. Ahmed, Z. N. Siddiqui, ACS Sustain. Chem. Eng. 2015, 3,
times with a slight decrease in their activity.
1701.
[23] F. R. Cassee, E. C. van Balen, C. Singh, D. Green, H. Muijser, J.
Weinstein, K. Dreher, Crit. Rev. Toxicol. 2011, 41, 213.
ORCID
[
24] T. Tamoradi, M. Ghadermazi, A. Ghorbani‐Choghamarani,
New J. Chem. 2018, 42, 5479.
Taiebeh Tamoradi http://orcid.org/0000-0002-8548-271X

14 of 14
MOLAEI ET AL.
[
[
[
[
[
[
[
[
[
[
[
[
25] S. Molaei, T. Tamoradi, M. Ghadermazi, A. Ghorbani‐
[42] K. Wang, L. Yang, W. Zhao, L. Cao, Z. Sun, F. Zhang, Green
Chem. 2017, 19, 1949.
Choghamarani, Catal. Lett. 2018, 148, 1834.
26] M. Nikoorazm, A. Ghorbani‐Choghamarani, N. Noori, Res.
Chem. Intermed. 2016, 42, 4621.
[43] F. Rajabi, F. Fayyaz, R. Luque, Micropor. Mesopor. Mater. 2017,
253, 64.
27] S. Molaei, T. Tamoradi, M. Ghadermazi, A. Ghorbani‐
Choghamarani, Micropor. Mesopor. Mater. 2018, 272, 241.
[44] M. Zare, Z. Moradi‐Shoeili, P. Esmailpour, S. Akbayrak, S.
Özkar, Micropor. Mesopor. Mater. 2017, 251, 173.
28] M. Cheng, H. Zhao, J. Yang, J. Zhao, L. Yan, H. Song, L. Chou,
[45] V. Rama, K. Kanagaraj, K. Pitchumani, J. Org. Chem. 2011, 76,
Micropor. Mesopor. Mater. 2018, 266, 117.
9090.
29] T. Tamoradi, M. Ghadermazi, A. Ghorbani‐Choghamarani,
Catal. Lett. 2018, 148, 857.
[46] S. Rezaei, A. Ghorbani‐Choghamarani, R. Badri, A. Nikseresht,
Appl. Organometal. Chem. 2017, 32, e3948.
30] M. A. E. A. A. A. El Remaily, S. K. Mohamed, Tetrahedron
[47] M. Hajjami, Z. Yousofvand, Catal. Lett. 2015, 145, 1733.
2
014, 70, 270.
[48] M. Hajjami, S. Rahmani, J. Porous Mater. 2015, 22, 1265.
31] F. Abrishami, M. Ebrahimikia, F. Rafiee, Appl. Organometal.
Chem. 2015, 29, 730.
[49] A. Ghorbani‐Choghamarani, Z. Darvishnejad, M. Norouzi,
Appl. Organometal. Chem. 2015, 29, 170.
32] A. Ghorbani‐Choghamarani, P. Moradi, B. Tahmasbi, RSC Adv.
[
[
[
[
[
50] M. Nikoorazm, A. Ghorbani‐Choghamarani, H. Mahdavi, S. M.
Esmaeili, Micropor. Mesopor. Mater. 2015, 211, 174.
2
016, 6, 56638.
33] T. Tamoradi, A. Ghorbani‐Choghamarani, M. Ghadermazi,
Chem. 2017, 41, 11714.
51] G. Azadi, A. Ghorbani‐Choghamarani, L. Shiri, Transit. Met.
Chem. 2017, 42, 131.
34] D. Habibi, M. A. Zolfigol, M. Safaiee, A. Shamsian, A.
52] M. Nikoorazm, A. Ghorbani‐Choghamarani, M. Ghobadi, S.
Massahi, Appl. Organometal. Chem. 2017, 31, e3848.
Ghorbani‐Choghamarani, Catal. Commun. 2009, 10, 1257.
35] L. Shiri, A. Ghorbani‐Choghamarani, M. Kazemi, Res. Chem.
Intermed. 2017, 43, 2707.
53] A. Jabbari, B. Tahmasbi, M. Nikoorazm, A. Ghorbani‐
Choghamarani, Appl. Organometal. Chem. 2018, 32, e4295.
36] M. A. Zolfigol, K. Amani, A. Ghorbani‐Choghamarani, M.
Hajjami, R. Ayazi‐Nasrabadi, S. Jafari, Catal. Commun. 2008,
54] A. Ghorbani‐Choghamarani, Z. Moradi, G. Azadi, J. Sulfur
Chem. 2018, 39, 237.
9, 1739.
[
37] T. Tamoradi, B. Mehraban‐Esfandiari, M. Ghadermazi, A.
Ghorbani‐Choghamarani, Res. Chem. Intermed. 2018, 44,
How to cite this article: Molaei S, Tamoradi T,
Ghadermazi M, Ghorbani‐Choghamarani A.
Ordered mesoporous SBA‐15 functionalized with
yttrium(III) and cerium(III) complexes: Towards
active heterogeneous catalysts for oxidation of
sulfides and preparation of 5‐substituted 1H‐
tetrazoles. Appl Organometal Chem. 2018;e4649.
https://doi.org/10.1002/aoc.4649
1
363.
[
38] J. Davarpanah, A. R. Kiasat, Catal. Commun. 2014, 46, 75.
39] B. Lei, B. Li, H. Zhang, L. Zhang, W. Li, J. Phys. Chem. C 2007,
[
1
11, 11291.
40] F. Wang, L. Jiang, J. Wang, Z. Zhang, Energy Fuels 2016, 30,
885.
[
[
5
41] J. N. Appaturi, M. R. Johan, R. J. Ramalingam, H. A.
Al‐Lohedan, Micropor. Mesopor. Mater. 2018, 256, 67.