Cu (II) and Cd (II) anchored functionalized mesoporous SBA-15 as novel, highly efficient and recoverable heterogeneous catalysts for green oxidative coupling of thiols and C–S cross-coupling reaction of aryl halides

Article abstract of DOI:10.1016/j.poly.2018.09.014

Two novel heterogeneous catalysts have been synthesized by anchoring Cu and Cd Creatinine complexes onto the surface of mesochannels of SBA-15 for highly efficient oxidative coupling of thiols to disulfides using hydrogen peroxide and synthesis of sulfides using S₈ and KOH. The structure of the prepared catalysts was determined using SEM, FT-IR, X-ray diffraction, elemental analysis, N₂ adsorption–desorption analysis and TGA. The catalysts significantly enhanced the reaction rate of the oxidative coupling of thiols and C–S bond formations. The catalysts were reused several times without appreciable loss in their activity.

Full text of DOI:10.1016/j.poly.2018.09.014

Accepted Manuscript
Cu (II) and Cd (II) anchored functionalized mesoporous SBA-15 as novel, high-
ly efficient and recoverable heterogeneous catalysts for greenoxidative coupling
of thiols and C-S cross-coupling reaction of aryl halides
Somayeh Molaei, Taiebeh Tamoradi, Mohammad Ghadermazi, Arash
Ghorbani-Choghamarani
PII:
S0277-5387(18)30564-3
https://doi.org/10.1016/j.poly.2018.09.014
POLY 13412
DOI:
Reference:
Polyhedron
To appear in:
Received Date:
Revised Date:
Accepted Date:
2 July 2018
30 August 2018
6 September 2018
Please cite this article as: S. Molaei, T. Tamoradi, M. Ghadermazi, A. Ghorbani-Choghamarani, Cu (II) and Cd (II)
anchored functionalized mesoporous SBA-15 as novel, highly efficient and recoverable heterogeneous catalysts for
green oxidative coupling of thiols and C-S cross-coupling reaction of aryl halides, Polyhedron (2018), doi: https://
doi.org/10.1016/j.poly.2018.09.014
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Cu (II) and Cd (II) anchored functionalized mesoporous SBA-15 as novel,
highly efficient and recoverable heterogeneous catalysts for green oxidative
coupling of thiols and C-S cross-coupling reaction of aryl halides
Somayeh Molaei,a Taiebeh Tamoradi,a Mohammad Ghadermazi,a, Arash Ghorbani-
Choghamaranib
a University of Kurdistan, Department of Chemistry, Faculty of Science, Sanandaj, Iran
e-mail: mghadermazi@yahoo.com
b Department of Chemistry, Faculty of Science, Ilam University, P.O. Box, 69315516, Ilam, Iran
Abstract
Two novel heterogeneous catalysts have been synthesized by anchoring Cu and Cd creatinine
complexes onto the surface of mesochannels of SBA-15 for highly efficient oxidative coupling
of thiols to disulfides using hydrogen peroxide and synthesis of sulfides using S8 and KOH. The
structure of the prepared catalysts was determined using SEM, FT-IR, X-ray diffraction, elemental
analysis, N2 adsorption-desorption analysis and TGA. The catalysts significantly enhanced the
reaction rate of the oxidative coupling of thiols and C-S bond formations. The catalysts were
reused several times without appreciable loss in their activity.
Keywords Heterogeneous catalysts, Cu and Cd complexes, Creatinine, SBA‒15, Oxidative
coupling of thiols, C-S cross-coupling reaction.

Address correspondence to University of Kurdistan, Department of Chemistry, Faculty of Science,
Sanandaj, Iran.; e-mail: mghadermazi@yahoo.com (M. Ghadermazi).

1. Introduction
Separation and recovery of homogeneous catalysis systems may pose some challenges. So,
immobilization of catalytic metals on solid supports has attracted interest in recent years [1-3].
Large surface area with abundant Si-OH active bonds, tunable pore size, high chemical and thermal
stability, acceptable biological safety, wide possibilities for functionalization and high porosity of
silicate mesoporous materials make them useful in a number of applications like adsorbents and
supports for catalysis. The design and functionalization of surface of the silica mesoporous have
gained a lot of attention in heterogeneous catalysis in recent years [4-13]. Mesoporous SBA-15
which consists of 2D hexagonally ordered and long 1D channels was first synthesized by Zhao et
al. SBA-15 has gained increased attention due to its interesting properties including large pore
size, high surface areas > 1000 m2· g−1, thick walls, good hydrothermal stability and parallel pore
structure. Pure silica SBA-15 is poor in catalytic activity but introducing guests into the framework
of SBA-15 makes this material a very interesting heterogeneous catalyst for driving reactions [14-
20]. Oxidation of thiols to disulfides has been the subject of extensive studies because they have
been employed in chemical and biological processes. Oxidation in presence of heterogenized
catalysts with green oxidants such as H2O2 represents a rapidly growing field in industry [21-25].
Also, sulfides are important reagents and intermediates in the synthesis of organic, medicinal and
heterocyclic compounds, and they are valuable in the formation of other sulfur compounds.
Sulfides have been also used in different drugs such as anti-diabetes, anti-inflammatory, anti-
Alzheimer’s, anti-Parkinson’s, anti-cancer, and anti-HIV. [26-29]. Various catalytic systems are
now available for synthesis of sulfides [26, 29, 30]. The target is to develop novel, efficient and
selective catalytic systems for driving reactions in mild conditions. In our research, we report two
more active and recyclable heterogeneous catalysts with excellent activity and selectivity in green

condition for oxidations of thiols to disulfides and C-S cross-coupling reaction of aryl halides, by
grafting of Cu and Cd Creatinine complexes on the SBA-15 support.
2. Experimental
2.1. General remarks:
The non-ionic surfactant Pluronic Triblock copolymer P123, tetraethylorthosilicate (TEOS), 3-
chloropropyltrimethoxy silane (CPTMS) and all other available chemicals used in the study were
purchased from Aldrich and Merck. All chemicals were used as received without further
purification. The metal loadings were determined on ICP-OES in 730-ES Varian. FTIR spectra
were obtained by VRTEX 70 model BRUKER between 400 and 4000 cm-1 with an average of 25
scans for each sample. Thermogravimetric analysis (TGA) data was recorded on a Shimadzu DTG-
60 instrument. XRD patterns were carried out with MPD diffractometer of X’pert with Cu Kα
radiation at 45 kV and 40 mA. Morphologies of materials were observed by FESEM-TESCAN
MIRA3.
2.2. Preparation of SBA-15
The pure SBA-15 was firstly prepared according to the report [31]. As follows, P123 (4.0 g) were
added to mixture of water (30 mL) and HCl (2 M, 90 mL) and stirred for 5 h at 35 ºC. Next,
tetraethylorthosilicate (9.04 mL) was added gradually under stirring and stirred (20 hours) at 35
ºC. The resulting product was collected and washed with distilled water then dried at 60 ºC. Finally,
the sample was calcined at 823 K (5 h).

2.3. Preparation of of SBA-15- CPTMS
SBA-15(1g) and 3-chloropropyltrimethoxysilane (CPTMS) (1.5 ml) was added to toluene (30 ml).
The mixture was refluxed (24 h), filtered, and washed with n-hexane then dried at 60 ºC.
2.4. Preparation of of SBA-15@Creatinine
Organic modification of SBA-15- CPTMS with Creatinine has been carried out. SBA-15-Cl (1 g),
Creatinine (2 mmol) and of triethylamine (3 ml) was added to toluene (30 ml). The mixture was
refluxed (48 h), filtered, and washed thoroughly with distilled water then dried at 60 ºC.
2.5. Preparation of of SBA-15@Creatinine@M
SBA-15@Creatinine@M (M= Cu and Cd) was synthesized by stirring mixture of SBA-15
@Creatinine (1g) and Cu(NO3)2.3H2O(0.604g) and Cd(NO3)2 .4H2O (0.771g) in absolute ethanol
(30 mL). The mixture was refluxed (16 h), filtered, and washed with absolute ethanol then dried
at 60 ºC.
2.6. Typical procedures for the oxidative coupling of thiols
Typically, thiol (1 mmol), H2O2 (0.5 mL) and 0.005 g of catalyst was mixed with stirring. Upon
completion of the reaction (monitored by TLC), the catalyst was collected by simple filtration and

the resulting product was extracted, washed and the solvent evaporated over anhydrous Na2SO4
(Scheme 1a).
2.7. Typical procedures for the C-S bond formations reaction
Catalyst (0.05 g), aryl halide (1 mmol), and S8 (1 mmol) with KOH (0.7 g) in DMSO was stirred
at 130 ºC. Upon completion of the reaction (The reaction process was monitored by TLC), the
catalyst was collected by simple filtration and the product was separated, washed and the solvent
evaporated over anhydrous Na2SO4 (Scheme 1b).
2.8. Selected spectral data
2.8.1. Dibenzyl disulfide (Table 3, entry 3). 1H NMR (400 MHz, DMSO, ppm): δH= 3.18 (s, 2H),
3.67 (s, 2H), 7.38–7.43 (m, 4H), 7.50–7.54 (m, 4H), 7.62–7.66 (m, 2H).
2.8.2. 1,2-Di-p-tolyldisulfane (Table 3, entry 9). 1H NMR (400 MHz, DMSO, ppm): δH= 2.26 (s,
6H), 7.15- 7.17 (d, 4H), 7.54-7.56 (d, 4H).
2.8.3. Diphenyl Sulfide (Table 5, entry 1). 1H NMR (400 MHz, DMSO, ppm): δH = 7.31–7.34
(m, 6H), 7.37–7.40 (m, 4H).
2.8.4. Bis(4-hydroxyphenyl) sulfide (Table 5, entry 9). 1H NMR (400 MHz, DMSO, ppm): δH =
6.74–6.77 (d, 4H), 7.13–7.17 (d, 4H), 9.65 (s, OH).
3. Results and discussion

The preparation protocol of the SBA-15@Creatinine@M (M=Cu and Cd) samples is illustrated in
Scheme 2. The pure SBA-15 was firstly prepared according to the report [31]. Next, modification
of SBA-15 was performed with 3-chloropropyltrimethoxysilane (CPTMS). Creatinine was then
subjected to a SBA-15-CPTMS. Finally, SBA-15@Creatinine was reacted with M(NO3)2 (M= Cu
and Cd) to yield the final catalysts (Scheme 2).
Scheme 1 (a) The oxidative coupling of thiols into disulfides; (b) The C-S bond formations reaction.

Scheme 2 Synthesis of SBA-15@Creatinine@M (M=Cu and Cd).

3.1. Characterization of SBA-15@Creatinine@M (M=Cu and Cd)
The pure silica material (Figure1a), the SBA-15-CPTMS compound (Figure1b), the SBA-15@
Creatinine sample (Figure1c), and the SBA-15@Creatinine@M (M= Cu and Cd) (Figure1d and
1e) characterized by FT- IR technology. In Figure1a, the broad band observed at 3421 cm-1 can be
assigned to the O-H vibrations of the silica SBA-15 [32]. The intense band observed at 1082 cm-
1(νas, Si-O), the vibrational band at 806 cm-1 (νs, Si-O), and the band at 463 cm-1 (δ, Si-O-Si)
substantiate the formation of the silica framework [33]. The bands (in Figure1b) appeared at 2922
and 2852 cm-1, corresponding to the stretching vibrations of C-H bonds of the CPTMS chains,
reflect the presence of the 3-choloropropyltrimethoxysilane in mesoporous SiO2. In Figure1c,
some weak peaks in the region of 1662–1332cm−1 could be owing to the presence of ligand in the
hybrid materials and proving that Creatinine was successfully grafted onto the SBA-15. As shown
in SBA-15@Creatinine@M (M= Cu and Cd) spectra (Figure1d and 1e), the appearance of bands
around 1082, 806 and 463 cm-1 shows that with functionalization of SBA-15, the phase has not
been changed.

Fig. 1 FT-IR spectra of a) SBA-15, b) SBA-15- CPTMS, c) SBA-15@Creatinine, d) SBA-15@Creatinine@Cu and
e) SBA-15@Creatinine@Cd.

Low-angle X-ray measurements of SBA-15 depicted in Figure 2, exhibit one prominent peak at
1.05 and two weaker peaks at 1.74 and 1.98 in 2θ region, which correspond to (1 0 0), (1 1 0) and
(2 0 0) diffraction respectively, attributed to the ordered 2D-hexagonal mesoporous structure [34].
Loading metals Creatinine complexes into SBA-15 lowers the intensity of the (1 0 0) reflection,
and it leads to disappearance of the (110) and (200) reflections, which implied that the introduction
of metal complexes might slightly disturb the order of SBA-15. Retaining the (100) diffraction
after the anchoring of Cu and Cd Creatinine indicates that the well-ordered hexagonal structure of
SBA-15 has not been destroyed with the modifications.
Fig. 2 XRD patterns of SBA-15, SBA-15@Creatinine@Cu and SBA-15@Creatinine@Cd.

The N2 adsorption-desorption diagrams for SBA-15, SBA-15@Creatinine@Cu, and SBA-
15@Creatinine@Cd samples is illustrated in Figure 3. All materials present type IV isotherm,
which corroborated that these samples had a mesoporous structure [35]. From the Figure 3, it is
observed that the adsorption amount of the SBA-15@Creatinine@Cu, and SBA-
15@Creatinine@Cd materials decreased, which originated from the grafting of the guest at the
surface of the SBA-15. The textural parameters derived from adsorption data are listed in Table 1.
The decreases in structural parameters of modified SBA-15 were corresponding to the occupation
of the mesochannels of SBA-15 [36], suggested the successful loading of metal Creatinine groups
in the SBA-15.
Fig. 3 Nitrogen adsorption–desorption isotherms of SBA-15, SBA-15@Creatinine@Cu and SBA-
15@Creatinine@Cd.

Table 1 Texture parameters obtained from nitrogen adsorption studies.
SBET
Pore diameter
by BJH
method (nm)
2.4
2. 1
1.6
Pore
Sample
(m2/g)
volume
(cm3/g)
0.554
0.400
0.221
SBA-15
SBA-15@Creatinine@Cu
SBA-15@Creatinine@Cd
556.2
369.2
210.8
Thermogravimetric analysis (TGA) of SBA-15, SBA-15@Creatinine@Cu and SBA-
15@Creatinine@Cd are shown in Figure 4. For SBA-15, one major decomposition event below
200 ºC is corresponding to the loss of weakly adsorbed water in silica channels [37]. Two distinct
weight losses are evident in the TGA profiles of the SBA-15@Creatinine@Cu and SBA-
15@Creatinine@Cd. The thermal decomposition in a temperature range between 25 and 100 ºC
can be corresponding to the existence of interatomic water [37]. The second decomposition regions
for the SBA-15@Creatinine@Cu and SBA-15@Creatinine@Cd materials are assigned to the
decomposition of the structure of organic ingredients used during the synthesis procedure from the
silica surface (in the temperature range of 200–600 ºC). All these corroborated that the Creatinine
has taken place onto the surface of SBA-15.
Furthermore, the morphology of the SBA-15, the SBA-15@Creatinine@Cu and the SBA-
15@Creatinine@Cd were analyzed by FESEM techniques. The FESEM images (Figure 5) show
that the samples have a regular morphology. The morphology of the SBA-15 particles was retained
after the reaction with metals Creatinine complexes.
EDS elemental analysis (Figure 6) confirm the presence of Cu and Cd into the mesoporous silica
matrix. Inductively coupled plasma (ICP) analysis determined the copper and cadmium content
within the mesoporous silica samples, which was found to be 6.7% (w/w %) and 7.68% (w/w %)
respectively.

Fig. 4 TGA curves of SBA-15, SBA-15@Creatinine@Cu and SBA-15@Creatinine@Cd
.

Fig. 5 SEM images of (a) SBA-15, (b) SBA-15@Creatinine@Cu and (c) SBA-15@Creatinine@Cd, the scale
bar is 500 nm.

Fig. 6 EDS pattern of (a) SBA-15, (b) SBA-15@Creatinine@Cu and (c) SBA-15@Creatinine@Cd.

3.2. Catalytic Studies
The oxidative coupling thiols to disulfide was first carried out in the presence of the SBA-
15@Creatinine@M catalysts. To get optimum catalytic activity for S‒S bond formation reaction,
the coupling reaction of 2-Mercaptobenzoic acid as a model compound in presence of SBA-
15@Creatinine@Cu, as a highly efficient catalyst was tested. Different parameters including the
catalyst amount and the oxidant and solvent screening were evaluated on the performance of the
SBA-15@Creatinine@Cu catalyst. The results are included in Table 2. To evaluate the influences
of the solvents on the catalytic activity, 2-Mercaptobenzoic acid was oxidized in various solvents
like ethyl acetate, acetonitrile, ethanol and finally without solvent and the results are shown in
Table 2. Ethanol with the highest yield in the lowest time was found to be the most suitable. Then,
the coupling reactions were optimized by the study of different amounts of the catalyst. With an
increase in catalyst dosage from 5 up to 7 mg, no substantial change in reaction results was
achieved. So, 5 mg of the catalyst is sufficient. Subsequently, the effect of H2O2 amount on the
catalyst activity was tested. Finally, to show the high activity of the SBA-15@Creatinine@M
(M=Cu and Cd) as heterogeneous catalysts, other substrates with diverse functional groups was
tested (Table 3). From Table 3, these catalysts can provide a good activity for the oxidative
coupling thiols. As shown in scheme 3, a reaction mechanism for the oxidative coupling thiols is
illustrated [38].

Table 2 Optimization of the reaction conditions for the oxidative coupling of thiol using 2-Mercaptobenzoic acid
with H2O2 by SBA-15@Creatinine@Cu catalyst.a
Solvent
Catalyst
(mg)
Entry
H2O2 (mL) Time (min) Yield (%) b
1
2
3
4
5
6
7
Solvent free
Ethyl acetate
Acetonitrile
ETOH
5
5
5
5
3
7
5
0.5
0.5
0.5
0.5
0.5
0.5
0.4
15
15
12
10
15
10
20
85
88
90
94
90
95
90
ETOH
ETOH
ETOH
aReaction conditions: thiol (1 mmol), H2O2 (0.5 mL) and 0.005 g of catalyst and solvent
(3 mL) at room temperature.
bIsolated yield.

Table 3 Oxidative coupling of thiols into disulfides in the presence of SBA-15@Creatinine@M (M=Cu
and Cd).
Time (min)
Yield %
Entry
1
Substrate
Product
Cu
Cd
Cu
Cd
10
1
5
1
94
94
96
94
2
3
1
8
1
4
91
91
92
93
4
5
6
2
8
1
6
92
90
93
94
7
8
20
15
5
90
90
94
11
93
9
3
7
3
3
91
91
91
95
10

Scheme 3 Proposed mechanism for oxidative coupling of thiols in presence of SBA-15@Creatinine@M (M=Cu and
Cd) as catalyst.

In other part of our experiment, SBA-15@Creatinine@Cu and SBA-15@Creatinine@Cd
mesoporous catalysts has been employed in the C–S coupling reaction. The effect of various
solvents and bases, reaction temperature and catalyst dosage for SBA-15@Creatinine@Cu were
studied (Table 4). The coupling of Iodobenzene (1 mmol) was selected as test process. First, the
C-S coupling reaction was carried out without catalyst; blank runs gave negligible product (Table
4, entry 1). To study the effect of solvents on the catalytic activity of the SBA-15@Creatinine@Cu
catalyst, several solvents e.g. DMSO, PEG, H2O, ETOH, DMF and toluene was tested. Among
different solvents investigated, DMSO provided the highest yield (Table 4, entry 2). Then, effect
of temperature was evaluated. Lower yield (60 %) was observed at 80 ºC (Table 4, entry 8), with
increase from 80 to 100 ºC, no substantial change in the product was observed, but increasing from
100 to 130 ºC results an increase in catalytic activity and product yield. To determine the effect of
catalyst dosage in the reaction, different quantities of catalyst (30, 50 and 70 mg) was tested. By
reducing the quantity of catalyst from 50 to 30 mg, lower sulfide yield was obtained, but by
increasing catalyst dosage from 50 up to 70 mg no change in reaction results was achieved. So, 5
mg of the catalyst is suitable amount. To find out the suitable base, a series of bases e.g. KOH,
K2CO3, Na2CO3 and NaOH was examined. Notably, when KOH was used, excellent yield was
obtained. Finally, SBA-15@Creatinine@M (Cu and Cd) activity towards other substrates with
diverse functional groups was examined (Table 5). From Table 5, SBA-15@Creatinine@M (Cu
and Cd) provide a good activity for the C-S couplings reaction. As shown in scheme 4, a reaction
mechanism for the C-S couplings reaction is illustrated [38].

Table 4 Optimization of the reaction conditions for the C-S coupling reaction using Iodobenzene and S8 as sulfur
transfer agent in the presence SBA-15@Creatinine@Cu catalyst. a
Catalyst
(mg)
-
Time
(min)
15
15
15
15
15
15
15
15
15
15
15
15
15
15
Entry
Solvent
Base
Temp.(℃)
Yield (%) b
DMSO
DMSO
PEG
H2O
ETOH
DMF
Toluene
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
KOH
K2CO3
NaOH
Na2CO3
1
2
3
4
5
6
7
8
9
10
11
12
13
14
130
130
130
130
130
130
130
80
100
130
130
130
130
130
N.R
85
35
30
N.R
12
45
60
65
85
50
50
50
50
50
50
50
50
70
30
50
50
75
N.R
20
50
N.R
aReaction conditions: Catalyst (0.05 g), aryl halide (1 mmol), and S8 (1 mmol), base (0.7 g) solvent (3 mL) at
130 ºC.
bIsolated yield

Table 5 The C-S couplings reaction in the presence of SBA-15@Creatinine@M (M=Cu and Cd).
Time (min)
Yield%
Cu Cd
Entry
1
Substrate
Product
Cu
15
Cd
10
85
89
64
2
3
4
50
45
40
45
40
35
61
68
73
72
78
5
6
40
35
90
62
64
60
100
57
7
8
55
95
50
85
60
62
63
61
9
80
40
70
35
65
71
69
73
10

Scheme 4 Proposed mechanism for the C-S couplings reaction in the presence of SBA-15@Creatinine@M (M=Cu
and Cd).
Finally, the recyclability of the SBA-15@Creatinine@Cu and SBA-15@Creatinine@Cd catalysts
was investigated. Figure 7 shows the recyclability of the SBA-15@Creatinine@Cu and SBA-
15@Creatinine@Cd catalysts in the synthesis of Dibenzyl disulfide and Diphenyl sulfide as a
model reaction with maintaining the optimized reaction conditions. No significant reduce was
found in the yields after simple separation of the catalysts and being used repetitively eight times.
After every cycle, the catalysts were filtered, washed with ethyl acetate and reused. Also, by
inductively coupled plasma (ICP) analysis, the copper and cadmium content of recovered SBA-
15@Creatinine@Cu and SBA-15@Creatinine@Cd was determined, which was found to be 5.9 %
(w/w %) and 6.5 (w/w %) respectively.
The recovered catalysts were further characterized by FT-IR (Figure 8). FT-IR spectra pattern of
reused catalysts suggests that the structure of silicate parent of catalysts has been retained after the
catalysis (after eight cycles).

Fig. 7 Reusability of SBA-15@Creatinine@M catalysts in the synthesis of (a) Dibenzyl disulfide and (b) Diphenyl
sulfide.
Fig. 8 FT-IR spectra of recovered (a) SBA-15@Creatinine@Cu and (b) SBA-15@Creatinine@Cd
To compare the catalytic performance of the SBA-15@Creatinine@Cu and SBA-
15@Creatinine@Cd with the previous results, the preparation of 2,2′-Disulfanediyldiethanol and
Diphenyl sulfide as representative examples was compared with previous data in the literatures.
From Table 6, catalytic activity of SBA-15@Creatinine@Cu and SBA-15@Creatinine@Cd led to
better results.

4. Conclusion
In summary, we have developed two novel, efficient and reusable heterogeneous catalysts (SBA-
15@Creatinine@Cu and SBA-15@Creatinine@Cd) for oxidation of thiols to disulfides and C-S
bond formations. Some features of this work are facile approach to prepare the catalysts, and
encompassing broad range of functional groups in the preparation of disulfides and sulfides to run
faster and produce high yields in the presence of the catalysts. Moreover, these catalysts were able
to be recycled eight times without appreciable loss in their activity.
Table 6 Comparison of SBA-15@Creatinine@M (M=Cu and Cd) catalysts for the preparation of 2,2′-
Disulfanediyldiethanol and Diphenyl sulfide with previous reported procedure.
Time
(min)
Yield (%)
Ref.
Entry
Substrate
Catalyst
1
2
3
4
5
6
7
8
9
10
11
12
13
14
2-Mercaptoethanol
2-Mercaptoethanol
2-Mercaptoethanol
2-Mercaptoethanol
2-Mercaptoethanol
2-Mercaptoethanol
2-Mercaptoethanol
Iodobenzene
Iodobenzene
Iodobenzene
Iodobenzene
Iodobenzene
SBA-15@Creatinine@Cu
SBA-15@Creatinine@Cd
Ni-complex-boehmite
VO(IV)–MCM-41
Fe3O4-Adenine-Zn
Ni-salen-MCM-41
8
6
25
24
40
40
35
15
10
45
240
120
120
210
90
94
96
93
95
93
95
85
89
90
66
90
90
65
This work
This work
[39]
[21]
[40]
[41]
[41]
This work
This work
[42]
Cd-salen-MCM-41
SBA-15@Creatinine@Cu
SBA-15@Creatinine@Cd
Cu(II) - Vanillin-MCM-41
MCM-41-Adenine-Zr
ZrONP-PN
[38]
[30]
[43]
[27]
Iodobenzene
Iodobenzene
PdNP–PNF
MCM-41@Serine@Cu(II)

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