Journal of Porous Materials

https://doi.org/10.1007/s10934-022-01398-9

Synthesis, characterization and catalytic activity of copper deposited

on MCM‑41 in the synthesis of 5‑substituted 1H‑tetrazoles
Mohammad Ghadermazi1 · Somayeh Molaei1 · Shida Khorami1

Accepted: 18 November 2022

© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2022

Abstract
Cu-functionalized mesoporous MCM-41 materials were synthesized via two different types of post-functionalization modi-
fication of MCM-41, without the ligand (MCM-41@Cu) and with ligand (MCM-41@Histidine@Cu). Cu-functionalized
mesoporous MCM-41 sample was also prepared directly via co-condensation of ­CuCl2 and decyltrimethylammonium bromide
(DTAB) with tetraethyl orthosilicate (TEOS) (Cu-MCM-41). The textural properties of the samples were characterized by
powder X-ray diffraction (XRD), Fourier transforms infrared (FTIR) spectra, nitrogen adsorption–desorption, transmission
electron microscopy (TEM), and scanning electron microscopy (SEM). The results show that the structure of MCM-41
persisted after modification. These catalysts are efficient catalysts for the synthesis of 5-substituted 1H-tetrazoles in water.
Cu-functionalized mesoporous MCM-41 materials displayed high catalytic performance at low-temperature. Cu-function-
alized MCM-41 sample synthesized with direct co-condensation method displayed better catalytic activity compared to
Cu-functionalized mesoporous MCM-41 materials prepared with post-synthesis grafting methods. These catalysts can be
easily recovered.

Keywords  Cu-functionalized · Mesoporous MCM-41 · Synthesis of 5-substituted 1H-tetrazoles

1 Introduction with lower molecular weights appear to be more difficult to

Mesoporous silica materials have received considerable
attention in the field of catalysis and separation [1–4].
The acidity, reactivity, and ion exchange capacity of pure
mesoporous silica materials are weak due to the absence
of active sites in their structure [5–7]. The high concentra-
tion of the silanol groups on the pore walls of mesoporous
silica is helpful to the insertion of active sites [7–9]. MCM-
41 as mesoporous silica materials are ideal solid supports
for insertion of active sites due to their highly ordered pore
structure with diameters of 2–10 nm and large surface areas
[7, 10–13]. Ordered mesoporous silica may be synthesized
in the presence of different polymers and surfactants. Alkyl
trimethylammonium bromides (ATABs) were widely used as
surfactants [14]. The length of the ATAB alkyl chain affects
the pore size [15, 16]. Heavier surfactants were seldom used
because they were difficult to dissolve. ATAB surfactants
* Mohammad Ghadermazi
mghadermazi@yahoo.com
1
Department of Chemistry, Faculty of Science, University
of Kurdistan, Sanandaj, Iran
organize themselves, so they produce less ordered materials
with wider pore size distributions [17].
There are two overall methods for the modification or deri-
vatization of mesoporous silica: direct co-condensation and
post-synthesis grafting method [18–20]. Post-functionalization
modification of MCM-41 has gained considerable interest for
the fabrication of favorable catalysts [21]. In this method, after
the formation of the ordered mesoporous silica, the grafting of
functional groups occurred. The post-functionalization modi-
fication method uses the silanol groups present on the silica
surface [19, 22]. Specific parts of the ordered mesoporous
materials surface (pore entrances, pore surface, external sur-
face) can be modified and high functionalization degrees are
possible without destroying the mesoscopic order [19, 23] .
Functionalization of mesoporous silica with both inorganic
and organic materials is attractive because of the possibility of
conjoining the various groups with mesoporous materials [19,
24, 25]. Asefa et al. described the preparation of catalysts that
include organ amine and silanol groups for the Henry reac-
tion [26]. Cu-functionalized MCM-41 was synthesized with
DL-2-Pyrrodidone ligand for the synthesis of symmetrical
disulfides and thioether formation reaction by Molaei et al.

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 Journal of Porous Materials

[27]. An exciting choice is the presentation of active species

via direct co-condensation technique while the mesoporous
materials are being prepared [28]. Co-condensation is a one- DTAB + NaOH + TEOS

step approach in which the functional molecules are intro- H2O, 80 °C

duced into the materials during mesoporous development [29].
This quite simple and inexpensive approach may lead to the
completely homogenous distribution of active species in the
structure of silica [30].
Many studies have been recognized in the incorpora-
tion of transition metal elements in the silicate framework
for the preparation of catalysts. Copper is a very appeal-
ing element because of its polarizability and special redox
properties [31]. Therefore, copper-based catalysts have been
the focus of recent studies [27, 32–35]. The Cu/ZnO on the
PMS (periodic mesoporous silicates) has been synthesized
by Grunert et al. [35]. Zinc and copper-containing MCM-48
and MCM-41 materials were prepared by Hartmann et al.
[36]. Cu-Al MCM-41 was studied by Kevan et al. [37].
The aim of this report is to investigate the efficiency of
the grafting and co-condensation methods for the synthe-
sis of Cu-functionalized mesoporous MCM-41 materials.
In this way, Cu-functionalized mesoporous MCM-41 was Scheme 1  Schematic synthesis of MCM-41
synthesized by two different types of post-functionalization
modification methods including: with or without ligand
(MCM-41@Cu and MCM-41@Histidine@Cu). Cu-func- precipitate was collected with filter paper and washed with
tionalized MCM-41 sample was also synthesized directly water. The MCM-41@Histidine was dried in an oven at 60 °C.
by co-condensation of ­CuCl2 and decyltrimethylammonium
bromide (DTAB) with tetraethyl orthosilicate (TEOS) (Cu- 2.2.2 Cu‑functionalized MCM‑41 via post‑synthesis
MCM-41) for the synthesis of 5-substituted 1H-tetrazoles. grafting method (with ligand)

2 Experimental In this step, 1 g of the previous step precipitate (MCM-

2.1 Preparation of mesoporous MCM‑41
1 g of decyltrimethylammonium bromide (DTAB) was intro-
duced to 480 mL of distilled water with stirring to get a
homogeneous solution. 3.5 mL of sodium hydroxide (2 M)
was introduced to this solution and stirring was continued
for 5 min at 80 °C. After that, 5 mL of tetraethyl orthosili-
cate (TEOS) was introduced to the solution and stirred for
2 h at 80 °C. The obtained product was collected and washed
with distilled water after two hours. The MCM-41 was dried
at 60 °C and calcinated at 550 °C for 5 h to completely
remove the surfactant [5] (Scheme 1.)
2.2 Synthesis of Cu‑functionalized mesoporous
MCM‑41
41@Histidine) with 2.5 mmol of ­CuCl2. in ethanol solvent
(40 mL) was refluxed for 16 h. After that, the resulting
precipitate was collected and washed several times with
ethanol, and finally dried in an oven at 50 °C. The obtained
Cu-functionalized MCM-41 were designated as MCM-41@
Histidine@Cu (Scheme 2).
2.2.3 Cu‑functionalized mesoporous MCM‑41
via post‑synthesis grafting method (without ligand)
Afterward, the obtained MCM-41 (1 g) with 2.5 mmol of
­CuCl2 in 30 mL of ethanol solvent was refluxed for 16 h.
After that, the resulting precipitate was collected and washed
several times with ethanol, and finally dried in an oven at
50 °C. The obtained Cu-functionalized MCM-41 was des-
ignated as MCM-41@Cu (Scheme 3).

2.2.1 Post‑synthetic modification of MCM‑41 with Histidine 2.2.4 Cu‑functionalized mesoporous MCM‑41 via direct

co‑condensation method
1 g of MCM-41 mesoporous silica and 1.5 g of Histidine
ligand in deionized water (40 mL) were completely dispersed. The method for preparation of Cu-functionalized
The resulting mixture was refluxed for 48 h. After that, the mesoporous MCM-41 by direct co-condensation technique

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Scheme 4  Schematic synthesis of Cu-MCM-41 catalyst

the product was dried at 50 °C and calcinated at 550 °C

for 24 h to completely remove the surfactant. The obtained
Cu-functionalized mesoporous MCM-41 were designated
as Cu-MCM-41(Cu:Si = 1:50) (Scheme 4).

Scheme 2  Schematic synthesis of MCM-41@Histidine@Cu catalyst

was reported previously [38]. 5 g of decyltrimethylam-

monium bromide (DTAB) was introduced to 66 mL of
a solution containing 1.0 g of NaOH. After that, TEOS
(20 mL) was introduced to the solution and stirred until
a clear gel was obtained. Then the solution of C
­ uCl2 was
added slowly and stirred for 2 h. Then the final mixture
was transferred to a Teflon bottle and subjected to autog-
enous pressure for 7 days at 90 °C. The resulting precipi-
tate was collected and rinsed with distilled water. Then,

Scheme 5  The applications of Cu-functionalized mesoporous MCM-

Scheme 3  Schematic synthesis of MCM-41@Cu catalyst 41 catalysts towards the synthesis of 5-substituted 1H-tetrazoles

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Scheme 6  A plausible mecha-

nism for MCM-41/Cu catalyzed
synthesis of 5-substituted
1H-tetrazoles [53]

2.3 General process for the synthesis of 1H‑
tetrazoles
1 mmol of nitrile, 1.2 mmol of sodium azide, and 70 mg of cat-
alyst were weighed separately and poured into a 25 mL flask.
3 mL of H­ 2O was added to the reaction mixture and placed at
80 °C. Progression of the reaction was followed by TLC with a
suitable ratio of n-hexane and ethyl acetate solvent (3:2). After
the end of the reaction, the catalyst was filtered and the reac-
tion mixture was treated with ethyl acetate and acidified with
10 mL of HCl (5 N). After cooling the reaction solution, the
precipitate (tetrazole) formed with 2–5 mL of cold water was
washed and the yield of the product was determined using the
weight of the precipitate obtained (Scheme 5, 6).

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Fig. 1  FT-IR spectra of MCM-

41, Cu-MCM-41, MCM-41@ MCM-41
Cu, Histidine and MCM-41@
Histidine@Cu

Cu-MCM-41

MCM-41@Cu
Transmittance (%)

Histidine

MCM-41@Histidine@Cu

4400 3900 3400 2900 2400 1900 1400 900 400

-1
Wavenumber (cm )

2.4 Spectral data 5-(4-Nitrophenyl)-1H-tetrazole

1
HNMR (400 MHz, DMSO, ppm): δ 8.35–8.40 (d, 2H),
5-(3-Nitrophenyl)-1H-tetrazole 8.47–8.49 (d, 2H) (Table 3, Entry 2).
1
HNMR (400 MHz, DMSO, ppm): δ 7.93–7.95 (m, 1H), 5-(4-Bromophenyl))-1H-tetrazole
1
8.45–8.50 (m, 2H), 8.85 (s, 1H) (Table 3, Entry1). HNMR (400 MHz, DMSO, ppm): δ 7.83–7.86 (m, 4H)
(Table 3, Entry 14).

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Fig. 2  SXRD pattern of Cu- 30000

MCM-41, MCM-41@Cu,
MCM-41@Histidine@Cu MCM-41@Histidine@Cu
25000

Intensity (a. u.)

20000 MCM-41

15000

MCM-41@Cu
10000
Cu-MCM-41
5000

0
0.5 1.5 2.5 3.5 4.5 5.5 6.5 7.5 8.5 9.5 10.5

2θ (°)

Fig. 3  WXRD pattern of 3000

Cu-MCM-41, MCM-41@Cu,
MCM-41@Histidine@Cu 2500

2000
Intensity (a. u.)

1500

1000
Cu-MCM-41

500 MCM-41@Cu

MCM-41@Histidine@Cu
0
0 10 20 30 40 50 60 70 80 90

2θ (°)

Fig. 4  Nitrogen adsorp- 400

tion–desorption analysis of
(a) Cu-MCM-41, MCM-41@ 350
Histidine@Cu

300
Volume adsorbed, cm /g STP

250 MCM-41@Histidine@Cu
3

200

150
Cu-MCM-41
100

50

0
0 0.2 0.4 0.6 0.8 1 1.2
Relative pressure, (p/p0)

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Journal of Porous Materials

3 Results and discussion 2920 ­cm−1, which are associated with the symmetric and
asymmetric stretching of –CH2–, respectively. The band
3.1 Characterization around 3740 ­cm−1 is associated with the stretching vibra-
tion of –OH from terminal silanol groups (Si–OH), which
3.1.1 FT‑IR is invisible after the coordination with cupric ions or con-
densation of silanol groups with the organic group.
The FT-IR analysis of MCM-41, Cu-MCM-41, MCM-41@ For as-synthesized Cu-MCM-41, The vibration bands at
Cu, and MCM-41@Histidine@Cu are shown in Fig. 1. The 959–970 ­cm−1 are due to the incorporation of metal into the
FT-IR spectra of as-synthesized vibration bands of sam- silica framework. This band is due to the stretching vibra-
ples with MCM-41 support, including Si–O–Si asymmet- tions of Si–OH or Si–O–M (M = metal) [39, 40], indicat-
ric stretching vibration at 1076–1095 ­cm−1, Si–O–Si sym- ing the heteroatom incorporation into the framework of
metric stretching vibration at 796–810 ­cm−1, and Si–O–Si mesoporous materials [41]. This band is weak for parent
bending vibration at 460–470 ­cm−1 [39] were detected. MCM-41 [40].
The broad bands around 3450 ­cm−1 are associated with For as-synthesized MCM-41@Cu, there is a band
the –OH stretching vibration of the ­H2O molecule [31], observed at 958 ­cm−1, which corresponds to the vibration
and the band around 1630 ­cm−1 is associated with the –OH of Si–O–Cu+ in the MCM-41@Cu sample. These results
bending vibration from adsorbed water [31]. suggest that copper species have been effectively applied to
For MCM-41, the presence of decyltrimethylammonium the MCM-41 framework.
bromide (DTAB) lead to the bands appearing at 2850, and For the Histidine, the bands at 676–721 ­cm−1 are asso-
ciated with the bending vibration of the ­sp2 CH group,
1141 ­cm−1 is associated with the stretching vibration of CN
in the imidazole group, 1411 ­cm−1 is associated with sym-
Table 1  Textural parameters of the catalysts
metric COO group stretching vibration, 1452 ­cm−1 is due to
Sample BET surface Mean pore t-Plot external Pore symmetric NH bending vibration, 1613 ­cm−1 is associated to
area ­(m2/g) diameter surface area volume C=C stretching vibrations, 2034 ­cm−1 is associated to Ν–Η
(nm) ­(m2 /g) ­(cm3/g)
stretching vibrations, 3200–3500 ­cm−1 are associated with
MCM-41 767.6 4.6 671.2 0.87 the stretching vibrations of Ο–Η of ­H2O [42].
Cu-MCM-41 142.1 10.2 109.9 0.36 For as-synthesized MCM-41@Histidine@Cu, the specific
MCM-41@ 530.7 3.9 499.0 0.52 band at 1452 ­cm−1 in Histidine is absent in the spectrum
Histidine@ of MCM-41@Histidine@Cu, revealing that the binding of
Cu

Fig. 5  The TEM images Cu-

MCM-41

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 Journal of Porous Materials

a b c

3000
b
2000

a 1500
2500
c
SiK
1500
SiK
2000
SiK

1000
1500
1000

1000

500
500 500 OK
OK NK
OK
CuL CuK CuK keV
0
CuK 0 10.00 CK
CuL CuL CuK CuK
CuK keV 0 keV
0
0 10.00
0 10.00

Fig. 6  SEM images and EDS analysis of a Cu-MCM-41, b MCM-41@Cu, and c MCM-41@Histidine@Cu

Histidine with cupric ions occurred through the amine group
[42].
3.1.2 XRD
Figure 2 shows the small-angle XRD (SXRD) patterns cal-
cined MCM-41, Cu-MCM-41, MCM-41@Cu, and MCM-
41@Histidine@Cu. The X-ray diffraction of MCM-41
shows a strong peak at 2θ = 1.5° corresponding to the reflec-
tions of the (100) plane and two weak peaks at 2θ = 3.3°,
3.9° corresponding to the reflections of the (110) and (200)
plane, indicating a well-ordered two dimensional hexagonal
(p6mm) formation of channels [39, 43]. Therefore, after the
introduction of copper species, the structure of the MCM-
41 material remains unchanged. However, the intensity is
less than pure MCM-41. The reduction of the intensity of
the reflections of the (­ d100) plane (except for MCM-41@
Histidine@Cu) and the disappearance of d­ 110 and ­d200 plane
reflections can be attributed to the fall in the ordering of the
channels after impregnation of the copper particles [39, 44].
The SXRD pattern of Cu-MCM-41 presents only one peak
at 2 theta close to 1°. This result has been reported by Neeli
et al. for Cu(II)/γ-Fe2O3@SBA-15 [45]. The maxima usually
tend to shift toward lower angles with decreasing particle
size. The maximum approximately corresponds to that of the
original dispersion [46]. It has a good agreement with SEM.
The wide-angle XRD (WXRD) analysis of Cu-
MCM-41, MCM-41@Cu, and MCM-41@Histidine@Cu
samples are illustrated in Fig. 3. WXRD analysis of Cu-
MCM-41 displays peaks at 2θ = 36.2 and 39.1°, which cor-
respond to monoclinic CuO [47]. The diffraction peak at
2θ = 75.1° can be due to metallic copper species [48]. But
these diffraction peaks are absent in MCM-41@Cu, and
MCM-41@Histidine@Cu samples because of low copper
content. In addition, the feature at 2θ = 23° was due to
amorphous silica [48].
3.1.3 N2 adsorption–desorption isotherms
Figure 4 depicts the N­ 2 adsorption–desorption isotherms
of the Cu-MCM-41, and MCM-41@Histidine@Cu sam-
ples. All the copper-containing MCM-41 samples display
type IV isotherms, which are characteristic of mesoporous
materials with 2-dimensional cylindrical channels according
to the IUPAC nomenclature [49]. It can be concluded that
mesopores of the particles are retained even after functional-
ization. Textural parameters of the MCM-41, Cu-MCM-41,

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Table 2  Optimization of reaction parameters for the synthesis of 5-substituted 1H-tetrazoles

Entry Catalyst (mg) Solvent Catalyst (mg) Temperature (°C) Time (min) Yield (%)a

1 Cu-MCM-41 H2O/EtOH (1:1) 100 Refluxing conditions 24 h nil

2 Cu-MCM-41 H2O r/EtOH (2:1) 100 Refluxing conditions 24 h 80
3 Cu-MCM-41 EtOH 100 Refluxing conditions 24 h 25
4 Cu-MCM-41 DMF 100 Refluxing conditions 24 h 50
5 Cu-MCM-41 DMSO 100 Refluxing conditions 24 h 60
6 Cu-MCM-41 Hexane 100 Refluxing conditions 24 h nil
7 Cu-MCM-41 Toluene 100 Refluxing conditions 24 h 40
8 Cu-MCM-41 Acetonitrile 100 Refluxing conditions 24 h 60
9 Cu-MCM-41 H2O 100 Refluxing conditions 15 78
10 Cu-MCM-41 H2O 100 80 15 77
11 Cu-MCM-41 H2O 100 60 20 74
12 Cu-MCM-41 H2O 100 40 20 70
13 Cu-MCM-41 H2O 100 Room temperature 30 75
14 Cu-MCM-41 H2O 70 80 15 70
15 Cu-MCM-41 H2O 50 80 25 76
16 Cu-MCM-41 H2O 30 80 25 64
17 MCM-41@Cu H2O 100 80 45 75
18 MCM-41@Histidine@Cu H2O 100 80 60 70
19 Copper modified zeolites H2O 100 80 120 66
20 MCM-41 H2O 100 80 24 h 50
21 – H2O 100 80 24 h nil

Bold indicate the ideal reaction condition for the synthesis of 5-substituted 1H-tetrazoles
­ aN3, (1.2 mmol), catalyst, and solvent (3 mL) at temperature
Reactions conditions: Nitrile (1 mmol), N
a
 Isolated yield

and MCM-41@Histidine@Cu samples are summarized 3.1.4 TEM, SEM, and EDS

in Table  1. The incorporation of Cu species inside the
mesoporous channels reduced textural parameters. As can
be seen, a gradual reduction in the surface area of the modi-
fied samples was found. In other words, the addition groups
block the ­N2 adsorption by decreasing the available sites.
The decrease in pore volume and pore size in comparison
with pure MCM-41 is due to the dispersion of copper into
the silica walls [31]. The increase in pore size of the Cu-
MCM-41 sample in comparison with the parent MCM-41
material is due to the higher amount of copper species in the
former materials.
To characterize the array of mesoporous materials, TEM
images of Cu-MCM-41 are illustrated in Fig. 5. It can be
observed that the Cu-MCM-41 sample exhibits parallel one-
dimensional mesoporous channels, indicating copper species
do not affect the structure of MCM-41.
The SEM images of Cu-MCM-41, MCM-41@Cu, and
MCM-41@Histidine@Cu are illustrated in Fig. 6. It can be
observed that the particles are spherical with size ranges
from 17 to 42 nm for Cu-MCM-41, 80–118 nm for MCM-
41@Cu, and 87–113  nm for MCM-41@Histidine@Cu.
The difference between particle sizes can be attributed to
the different dispersion of particles in the catalysts. Better

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Table 3  Synthesis of 5-substituted 1H-tetrazoles derivatives in the Table 4  Synthesis of 5-substituted 1H-tetrazoles derivatives in the
presence of Cu-MCM-41 presence of MCM-41@Cu

Entry Substrate Product Time (min) Yield (%) Entry Substrate Product Time (min) Yield (%)

80 70 95 70
1 1

75 72 80 68
2 2

40 72 60 66
3 3

4 20 78 4 30 74

5 5
20 75 45 68

30 73 150 75
6 6

7 15 77 7 45 79

8 20 70 8 120 70

90 77
9 9 150 70

75 80 90 63
10 10

11 80 78 11 120 68

12 90 81 12 110 81

13 65 85 13 90 78

60 92 60 90
14 14

Reactions conditions: Nitrile (1  mmol), ­

NaN3 (1.2  mmol), H
­ 2O
(3 mL) and catalyst (100 mg) at 80 °C
Reactions conditions: Nitrile (1  mmol), ­
NaN3 (1.2  mmol), H
­ 2O
(3 mL) and catalyst (100 mg) at 80 °C

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Table 5  Synthesis of 5-substituted 1H-tetrazoles derivatives in the dispersion of particles in the Cu-MCM-41 compare to the
presence of MCM-41@Histidine@Cu MCM-41@Cu, and MCM-41@Histidine@Cu has resulted
in reduced particles.
The EDS spectra of Cu-MCM-41, MCM-41@Cu, and
MCM-41@Histidine@Cu confirmed the presence of Cu, O,
Entry Substrate Product Time (min) Yield (%)
Si, and N atoms in the structure of the catalysts. From EDS
spectra, the sample synthesized via the co-condensation
1
200 71
technique (Cu-MCM-41) displays a higher amount of cop-
per in the framework compared to samples synthesized via
the post-functionalization method.
160 73
2
3.2 Catalytic activity
125 66
3 The Cu-functionalized mesoporous MCM-41 samples were
tested for the synthesis of 5-substituted 1H-tetrazoles. To
optimize the experimental conditions, 4-chlorobenzonitrile
4 70 72 and ­NaN3 in the presence of the catalyst were selected as
trial substrates. The influence of several operating conditions
like catalyst content, solvent, the temperature was studied
and the results are summarized in Table 2.
5
90 69

200 67
3.2.1 Effect of solvent
6

The synthesis of 5-substituted 1H-tetrazoles was performed

7 60
8 175
70
using different solvents such as DMF, DMSO, acetonitrile,
dioxane, toluene, EtOH, EtOH/water, and water. The yield
of the product was increased in water. The solvent dielectric
constant shows an important role in stabilizing the inter-
mediate of the reaction. At a higher dielectric constant of
67

the solvent, the stronger ionic forces stabilize the interme-

diate of the reaction [41, 50]. Among the solvents, water
190 74
9 had the highest dielectric constant (80), after that DMSO
(47.2), DMF (38.3), acetonitrile (36.6), EtOH (24.3), and
hexane (2.0). The solvent influence can be described accord-
110 79 ing to the extent of the solubility of the reactants. Sodium
azide derivatives are better soluble in water. The overall
10

order of reactivity of all the solvents used in the synthesis

11 150 77 of 5-substituted 1H-tetrazoles using Cu-MCM41 is as fol-
lows: water > DMSO > DMF > acetonitrile > EtOH > hexane.

3.2.2 Effect of temperature
12 160 81

The product yield decreased with the decline of tempera-

13 120 85
ture from 100 °C to room temperature. According to the
Arrhenius equation, the increase of reaction rate with tem-
perature was expected [40]. For this reaction, the best result
90 88
was obtained at 80 °C.
14

Reactions conditions: Nitrile (1  mmol), ­

NaN3 (1.2  mmol), H
­ 2O
(3 mL) and catalyst (100 mg) at 80 °C

13

Fig. 7  Recyclability study of the Cu-MCM-41, MCM-41@Cu, and MCM-41@Histidine@Cu catalyst in the preparation of and
5-(4-bromophenyl)-1H-tetrazole
3.2.3 Effect of amounts of catalyst
The influence of catalyst amounts on the synthesis of 5-sub-
stituted 1H-tetrazoles was studied by using different amounts
of the Cu-MCM-41 as the catalyst (30 to 100 mg) at 80 °C
using water as solvent. From Table 2, the maximum yield
was taken when 100 mg of catalyst was utilized. The reason
for the maximum yield is the large number of active sites
available in the framework of the samples.
3.2.4 Effect of different catalysts
Parent MCM-41 and Cu-functionalized mesoporous MCM-
41 samples were tested for the synthesis of 5-substituted
1H-tetrazoles. Without any metal loading, provided no
1H-tetrazole yield. Cu-MCM-41 provided 77% 1H-tetrazole
yield in 15 min. In the case of MCM-41@Cu, 75% 1H-tetra-
zole yield was provided in 45 min. In the case of the MCM-
41@Histidine@Cu sample, 70% 1H-tetrazole yield was pro-
vided in 60 min. And in the case of copper-modified zeolites,
66% 1H-tetrazole yield was provided in 120 min. The highly
dispersed copper ions in the Cu-MCM-41 strongly adsorb
the more reactants [41].
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Journal of Porous Materials
Overall, the ideal reaction conditions for the synthesis
of 5-substituted 1H-tetrazoles were: ­H2O as the solvent,
and 100 mg of catalyst at 80 °C (Table 2, entry 10). To
generalize the scope of the Cu-MCM-41, MCM-41@
Cu, and MCM-41@Histidine@Cu for the synthesis of
5-substituted 1H-tetrazoles, under optimal conditions a
series of substituted nitriles were used, and the results
are shown in Tables  3, 4 and 5. As these Tables, the
favorable product was gained under mild conditions, and
in short reaction times, the 1H-tetrazoles were obtained
with good yields. Due to highly dispersed copper ions,
the Cu-MCM-41 shows better activity for the synthesis
of 5-substituted 1H-tetrazoles in comparison with MCM-
41@Cu, and MCM-41@Histidine@Cu samples.
In the study of azide-nitrile cycloaddition catalyzed by
­Cu2+, the coordination of the nitrile substrate to the Lewis
acidic iron is the source of the catalysis in the formation
of 1H-tetrazoles. ­Cu2+ coordinated to the nitrile, and this
is the dominant factor influencing [2 + 3] cycloaddition.
Subsequent nucleophilic attack by azide)intermediate
A + B includes mechanisms A [51] and B [52]) followed
by hydrolysis produces tetrazole as the end product, with
Journal of Porous Materials

Table 6  Comparative performance of MCM-41@3,4,5-tri hydroxyphenyl acetic acid @Fe and MCM-41@Fe with other literatures
Entry Catalyst and conditions Substrate Time (min) Yield (%) Recyclability Refs

1 CoY zeolite (20 mg), Nitrile (1 mmol), Sodium azide (2 mmol), Phenylacetonitrile 14 h 80 6 [54]
Solvent: DMF, Temp: (120 °C) 4-Chlorobenzonitrile 14 h 91
4-Nitrobenzonitrile 14 h 95
Benzonitrile 14 h 90
2 Pd‐isatin‐boehmite (30 mg); Nitrile (1 mmol), Sodium azide 2-Chlorobenzonitrile 4.2 h 93 5 [55]
(1.5 mmol), Solvent: PEG, Temp: (120 °C) 4-Chlorobenzonitrile 7.5 h 88
4-Nitrobenzonitrile 4 h 92
Benzonitrile 8 h 94
3 ZnO/Co3O4 (50 mg); Nitrile (1 mmol), Sodium azide (1.5 mmol), 4-Nitrobenzonitrile 12 h 84 4 [56]
Solvent: DMF, Temp: (120–130 °C) 4-Chlorobenzonitrile 12 h 94
4-methylbenzonitrile 12 h 92
Benzonitrile 12 h 90
4 CuFe204 (40 mol %); Nitrile (1 mmol), Sodium azide (1.5 mmol), 4-Borobenzonitrile 12 h 90 5 [57]
Solvent: DMF, Temp: (120 °C) 4-Chlorobenzonitrile 12 h 89
3-Chlorobenzonitrile 12 h 87
Benzonitrile 12 h 82
5 FeCl3–SiO2 (90 mg); Nitrile (2 mmol), Sodium azide (3 mmol), 3-Borobenzonitrile 12 h 79 3 [58]
Solvent: DMF, Temp: (120 °C) 4-Chlorobenzonitrile 12 h 77
4-Nitrobenzonitrile 12 h 81
Benzonitrile 12 h 79
6 Cu (II) immobilized on ­Fe3O4@SiO2@L-Histidine (50 mg); Nitrile 4-Borobenzonitrile 9 h 89 5 [59]
(1 mmol), Sodium azide (1 mmol), Solvent: PEG, Temp: (120 °C) 4-Chlorobenzonitrile 240 95
3-Nitrobenzonitrile 180 90
Benzonitrile 180 90

­C u 2+ catalyst being released for the next cycle of reac- 4 Conclusion

tions [53].
3.3 Recyclability study
The recyclability of the Cu-MCM-41, MCM-41@Cu, and
MCM-41@Histidine@Cu was considered in the synthesis
of 1H-tetrazole. 4-bromobenzonitrile was chosen as a model
substrate. At the end of the reaction, the catalyst was sepa-
rated, washed with EtOAc, and dried at 50 °C. Then, it was
spent in the synthesis of 1H-tetrazole with a fresh reaction
mixture. In the regenerated sample after six cycles, catalytic
activity was not significantly decreased (Fig. 7).
The comparison of catalyst and conditions, recyclability,
and conversion with reported catalysts in the literature for
the synthesis of 5-aryl tetrazoles are presented in Table 6.
The reported catalysts suffer from disadvantages such as the
use of organic solvents, longer times, higher temperatures,
and less recyclability. The MCM-41@3,4,5-tri hydroxyphe-
nyl acetic acid @Fe and MCM-41@Fe exhibit better reac-
tion time, and recyclability under mild conditions and are
more importantly green catalysts.
Cu-functionalized MCM-41 samples were synthesized.
FT-IR analysis proved the presence of copper species in the
framework of MCM-41. XRD pattern displays the hexago-
nal mesoporous structure of the MCM-41 material remains
unchanged after copper modification. The wide-angle XRD
analysis of Cu-MCM-41 shows peaks corresponding to mon-
oclinic CuO and metallic Cu species. The MCM-41@Cu
and MCM-41@Histidine@Cu samples displayed no diffrac-
tion peaks for copper species because of low copper content.
BET studies show that the incorporation of copper into the
silica walls decreased textural parameters. The SEM images
of samples show that the particles are spherical with size
ranges from 17 to 42 nm for Cu-MCM-41, 80–118 nm for
MCM-41@Cu, and 87–113 nm for MCM-41@Histidine@
Cu. From EDS spectra, the sample synthesized via the co-
condensation technique (Cu-MCM-41) displays a higher
amount of copper in the framework compared to samples
synthesized via the post-functionalization method. Due to
highly dispersed copper ions, the Cu-MCM-41 shows better
activity for the synthesis of 5-substituted 1H-tetrazoles in
comparison with MCM-41@Cu, and MCM-41@Histidine@
Cu samples.

13

Acknowledgements  The authors are deeply grateful to the University
of Kurdistan for the financial support on this research project.
Author contributions  MG: Conceptualization, Methodology, Valida-
tion, Formal analysis, Resources, Supervision, Project administration,
Funding acquisition. SM: Conceptualization, Methodology, Software,
Resources, Writing Original Draft, Writing Review and Editing, Visu-
alization. SK: Investigation, Data Curation.
Declarations  on SBA-15 as a very efficient nanocatalyst for green aerobic oxi-
Competing interests  The authors have no relevant financial or non-
financial interests to disclose.
References
1. S. Molaei, M. Ghadermazi, Synthesis and characterization of
indium and thallium immobilized on isonicotinamide-function-
alized mesoporous MCM-41: two novel and highly active hetero-
geneous catalysts for selective oxidation of sulfides and thiols to
their corresponding sulfoxides and disulfides. Appl. Organomet.
Chem. 33, e4972 (2019)
2. S. Molaei, M. Ghadermazi, Immobilization of cerium (IV) and
erbium (III) in mesoporous MCM-41: two novel and highly
active heterogeneous catalysts for the synthesis of 5-substituted
tetrazoles, and chemo- and homoselective oxidation of sulfides.
Appl. Organomet. Chem. 33, e4854 (2019)
3. S. Molaei, M. Ghadermazi, Selective and efficient oxidation
of sulfides and thiols to their corresponding sulfoxides and
disulfides catalyzed with praseodymium (III) and dysprosium
(III) isonicotinamide (INA) complexes grafted onto modified
mesoporous MCM-41. Solid State Sci. 100, 106091 (2020)
4. 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 CS cross-coupling reaction of aryl halides. Polyhedron 156,
35–47 (2018)
5. S. Molaei, T. Tamoradi, M. Ghadermazi, A. Ghorbani-Choghama-
rani, Synthesis and characterization of MCM-41@AMPD@Zn
as a novel and recoverable mesostructured catalyst for oxidation
of sulfur containing compounds and synthesis of 5-substituted
tetrazoles. Microporous Mesoporous Mater. 272, 241–250 (2018)
6. S. Molaei, T. Tamoradi, M. Ghadermazi, A. Ghorbani-
Choghamarani, Highly efficient oxidative coupling of thiols and
oxidation of sulfides in the presence of MCM-41@Tryptophan-
Cd and MCM-41@Tryptophan-Hg as novel and recoverable
nanocatalysts. Catal. Lett. 148, 1834–1847 (2018)
7. L. Song, T. Bu, L. Zhu, Y. Zhou, Y. Xiang, D. Xia, Synthesis of
organically–inorganically functionalized MCM-41 for adsorp-
tive desulfurization of C4 hydrocarbons. J. Phys. Chem. C 118,
9468–9476 (2014)
8. S. Molaei, T. Tamoradi, M. Ghadermazi, A. Ghorbani-
Choghamarani, Ordered mesoporous SBA-15 functionalized
with yttrium(III) and cerium(III) complexes: towards active het-
erogeneous catalysts for oxidation of sulfides and preparation of
5-substituted 1H-tetrazoles. Appl. Organomet. Chem. 33, e4649
(2019)
9. X.S. Zhao, G.Q. Lu, Modification of MCM-41 by surface silyla-
tion with trimethylchlorosilane and adsorption study. J. Phys.
Chem. B 102, 1556–1561 (1998)
10. T. Tamoradi, M. Ghadermazi, A. Ghorbani-Choghamarani, S.
Molaei, Synthesis and characterization of oxo-vanadium complex
13
Journal of Porous Materials
anchored onto SBA-15 as a green, novel and reusable nanocatalyst
for the oxidation of sulfides and oxidative coupling of thiols. Res.
Chem. Intermed. 44, 4259–4276 (2018)
11. S. Molaei, M. Ghadermazi, Heterogeneously catalyzed selective
aerobic oxidation of sulfides with supported Dy on SBA-15 as
recyclable catalyst under green condition. Solid State Sci. 101,
106148 (2020)
12. S. Molaei, M. Ghadermazi, Highly ordered mesoporous La(III)-
substituted 5-oxopyrrolidine-2-carboxylic acid (Glp) immobilized
dative coupling of thiols to disulfides. Appl. Organomet. Chem.
34, e5328 (2020)
13. K.M. Parida, S.K. Dash, Adsorption of C ­ u2+ on spherical Fe-
MCM-41 and its application for oxidation of adamantane. J. Haz-
ard Mater. 179, 642–649 (2010)
14. A. Sayari, Y. Yang, Highly ordered MCM-41 silica prepared in the
presence of decyltrimethylammonium bromide. J. Phys. Chem. B
104, 4835–4839 (2000)
15. P.I. Ravikovitch, D. Wei, W.T. Chueh, G.L. Haller, A.V. Neimark,
Evaluation of pore structure parameters of MCM-41 catalyst sup-
ports and catalysts by means of nitrogen and argon adsorption. J.
Phys. Chem. B 101, 3671–3679 (1997)
16. A. Sayari, Periodic mesoporous materials: synthesis, characteriza-
tion and potential applications. Stud. Surf. Sci. Catal. 102, 1–46
(1996)
17. M. Kruk, M. Jaroniec, A. Sayari, Adsorption study of surface and
structural properties of MCM-41 materials of different pore sizes.
J. Phys. Chem. B 101, 583–589 (1997)
18. A.M.B. Furtado, D. Barpaga, L.A. Mitchell, Y. Wang, J.B.
DeCoste, G.W. Peterson, M.D. LeVan, Organoalkoxysilane-
grafted silica composites for acidic and basic gas adsorption.
Langmuir 28, 17450–17456 (2012)
19. D. Brühwiler, Postsynthetic functionalization of mesoporous
silica. Nanoscale 2, 887–892 (2010)
20. T. Yokoi, H. Yoshitake, T. Tatsumi, Synthesis of amino-func-
tionalized MCM-41 via direct co-condensation and post-synthesis
grafting methods using mono-, di-and tri-amino-organoalkoxysi-
lanes. J. Mater. Chem. 14, 951–957 (2004)
21. H. Ritter, D. Brühwiler, Accessibility of amino groups in post-
synthetically modified mesoporous silica. J. Phys. Chem. C 113,
10667–10674 (2009)
22. J. Chen, Q. Li, R. Xu, F. Xiao, Distinguishing the silanol groups
in the mesoporous molecular sieve MCM-41. Angew. Chem. Int.
Ed. 34, 2694–2696 (1996)
23. M. Laghaei, M. Sadeghi, B. Ghalei, M. Dinari, The effect of
various types of post-synthetic modifications on the structure
and properties of MCM-41 mesoporous silica. Prog. Org. Coat.
90, 163–170 (2016)
24. S. Molaei, M. Ghadermazi, Anchoring of palladium onto the
surface of porous MCM-41 modified with DL-pyroglutamic
acid as a novel heterogeneous catalyst for Suzuki-Miyaura cou-
pling reactions. J. Organomet. Chem. 953, 122064 (2021)
25. M. Ghadermazi, S. Molaei, N. Ghadermazi, Introduction of
Fe into mesoporous MCM-41 for the synthesis of 5-substi-
tuted 1H-Tetrazoles from aryl nitriles in water. Microporous
Mesoporous Mater. 328, 111441 (2021)
26. K.K. Sharma, T. Asefa, Efficient bifunctional nanocatalysts by
simple postgrafting of spatially isolated catalytic groups on
mesoporous materials. Angew. Chem Int. Ed. 46, 2879–2882
(2007)
27. S. Molaei, M. Ghadermazi, A green methodology for thioether
formation reaction and synthesis of symmetrical disulfides over
new heterogeneous Cu attached to bifunctionalized mesoporous
MCM-41. Microporous Mesoporous Mater. 319, 110990 (2021)
28. Á. Szegedi, Z. Kónya, D. Méhn, E. Solymár, G. Pál-Borbély,
Z.E. Horváth, L.P. Biró, I. Kiricsi, Spherical mesoporous
Journal of Porous Materials
MCM-41 materials containing transition metals: synthesis and
characterization. Appl. Catal. A Gen. 272, 257–266 (2004)
29. J. Liu, Y. Shin, Z. Nie, J.H. Chang, L.-Q. Wang, G.E. Fryxell,
W.D. Samuels, G.J. Exarhos, Molecular assembly in ordered
mesoporosity: a new class of highly functional nanoscale mate-
rials. J. Phys. Chem. A 104, 8328–8339 (2000)
30. A. Jankowska, A. Chłopek, A. Kowalczyk, M. Rutkowska, M.
Michalik, S. Liu, L. Chmielarz, Catalytic performance of spheri-
cal MCM-41 modified with copper and iron as catalysts of
­NH3-SCR process. Molecules 25, 5651 (2020)
31. X.-Y. Hao, Y.-Q. Zhang, J.-W. Wang, W. Zhou, C. Zhang, S. Liu,
A novel approach to prepare MCM-41 supported CuO catalyst
with high metal loading and dispersion. Microporous Mesoporous
Mater. 88, 38–47 (2006)
32. S. Molaei, M. Ghadermazi, Cu attached functionalized
mesoporous MCM-41: a novel heterogeneous nanocatalyst for
eco-friendly one-step thioether formation reaction and synthesis
of 5-substituted 1H-tetrazoles. Res. Chem. Intermed. 47, 4557–
4581 (2021)
33. L. Wang, S. Velu, S. Tomura, F. Ohashi, K. Suzuki, M. Oka-
zaki, T. Osaki, M. Maeda, Synthesis and characterization of CuO
containing mesoporous silica spheres. J. Mater. Sci. 37, 801–806
(2002)
34. Z. Li, L. Gao, Synthesis and characterization of MCM-41 dec-
orated with CuO particles. J. Phys. Chem. Solids 64, 223–228
(2003)
35. R. Becker, H. Parala, F. Hipler, O.P. Tkachenko, K.V. Klementiev,
W. Grünert, H. Wilmer, O. Hinrichsen, M. Muhler, A. Birkner,
MOCVD-loading of mesoporous siliceous matrices with Cu/ZnO:
supported catalysts for methanol synthesis. Angew. Chem. Int. Ed.
43, 2839–2842 (2004)
36. M. Hartmann, S. Racouchot, C. Bischof, Characterization of
copper and zinc containing MCM-41 and MCM-48 mesoporous
molecular sieves by temperature programmed reduction and car-
bon monoxide adsorption. Microporous Mesoporous Mater. 27,
309–320 (1999)
37. A. Poppl, M. Hartmann, L. Kevan, Electron spin resonance and
electron spin echo modulation studies of Cu (II) ion coordina-
tion and adsorbate interaction in ion-exchanged AlMCM-41
mesoporous materials. J. Phys. Chem. 99, 17251–17258 (1995)
38. Y. Li, D. Duan, M. Wu, J. Li, Z. Yan, W. Wang, G. Zi, J. Wang,
One-step synthesis of 2, 5-dihydroxyterephthalic acid by the oxi-
dation of p-xylene over M-MCM-41 (M= Fe, Fe/Cu, Cu) cata-
lysts. Chem. Eng. J. 306, 777–783 (2016)
39. Y. Shu, Y. Shao, X. Wei, X. Wang, Q. Sun, Q. Zhang, L. Li,
Synthesis and characterization of Ni-MCM-41 for methyl blue
adsorption. Microporous Mesoporous Mater. 214, 88–94 (2015)
40. S.K. Roy, D. Dutta, A.K. Talukdar, Highly effective methylated
Ti MCM-41 catalyst for cyclohexene oxidation. Mater. Res. Bull.
103, 38–46 (2018)
41. D. Rath, K.M. Parida, Copper and nickel modified MCM-41 an
efficient catalyst for hydrodehalogenation of chlorobenzene at
room temperature. Ind. Eng. Chem. Res. 50, 2839–2849 (2011)
42. C.N. Iswarya, S.C.G.K. Daniel, M. Sivakumar, Studies on L-his-
tidine capped Ag and Au nanoparticles for dopamine detection.
Mater. Sci. Eng. C. 75, 393–401 (2017)
43. S. Bhunia, D. Saha, S. Koner, MCM-41-supported oxo-
vanadium(IV) complex: a highly selective heterogeneous catalyst
for the bromination of hydroxy aromatic compounds in water.
Langmuir 27, 15322–15329 (2011)
44. S.S. Bhoware, A.P. Singh, Characterization and catalytic activ-
ity of cobalt containing MCM-41 prepared by direct hydrother-
mal, grafting and immobilization methods. J. Mol. Catal. A 266,
118–130 (2007)
45. C.K.P. Neeli, H.P.R. Kannapu, V.N. Kalevaru, S.R.R. Kamaraju,
D.R. Burri, An efficient and selective benzylic oxidation of tetralin
to 1-tetralone on Cu (II) immobilized γ-Fe2O3@ SBA-15 magnetic
nanocatalyst in green water medium without base or additives.
Mol. Catal. 453, 74–84 (2018)
46. H. Bunjes, M.H.J. Koch, K. Westesen, Effect of particle size on
colloidal solid triglycerides. Langmuir 16, 5234–5241 (2000)
47. K.M. Parida, D. Rath, S.S. Dash, Synthesis, characterization
and catalytic activity of copper incorporated and immobilized
mesoporous MCM-41 in the single step amination of benzene. J.
Mol. Catal. A Chem. 318, 85–93 (2010)
48. X. Ma, H. Chi, H. Yue, Y. Zhao, Y. Xu, J. Lv, S. Wang, J. Gong,
Hydrogenation of dimethyl oxalate to ethylene glycol over
mesoporous Cu-MCM-41 catalysts. AIChE J. 59, 2530–2539
(2013)
49. F. Raji, M. Pakizeh, Study of Hg (II) species removal from aque-
ous solution using hybrid ­ZnCl2-MCM-41 adsorbent. Appl. Surf.
Sci. 282, 415–424 (2013)
50. S. Gómez-Quero, E. Díaz, F. Cárdenas-Lizana, M.A. Keane,
Solvent effects in the catalytic hydrotreament of haloaromatics
over Pd/Al2O3 in water+ organic mixtures. Chem. Eng. Sci. 65,
3786–3797 (2010)
51. J. Roh, K. Vávrová, A. Hrabálek, Synthesis and functionalization
of 5-substituted tetrazoles. Eur. J. Org. Chem. 2012, 6101–6118
(2012)
52. Z.P. Demko, K.B. Sharpless, Preparation of 5-substituted 1
H-tetrazoles from nitriles in water. J. Org. Chem. 66, 7945–7950
(2001)
53. V. Rama, K. Kanagaraj, K. Pitchumani, Syntheses of 5-substituted
1H-tetrazoles catalyzed by reusable CoY zeolite. J. Org. Chem.
76, 9090–9095 (2011)
54. V. Rama, K. Kanagaraj, K. Pitchumani, Syntheses of 5-substituted
1 H-tetrazoles catalyzed by reusable CoY zeolite. J. Org. Chem.
76, 9090–9095 (2011)
55. A. Jabbari, B. Tahmasbi, M. Nikoorazm, A. Ghorbani-Choghama-
rani, A new Pd-Schiff-base complex on boehmite nanoparticles:
Its application in Suzuki reaction and synthesis of tetrazoles.
Appl. Organomet. Chem. 32, e4295 (2018)
56. S.M. Agawane, J.M. Nagarkar, Synthesis of 5-substituted 1
H-tetrazoles using a nano ZnO/Co3O4 catalyst. Catal. Sci. Tech-
nol. 2, 1324–1327 (2012)
57. B. Sreedhar, A.S. Kumar, D. Yada, CuFe2O4 nanoparticles: a
magnetically recoverable and reusable catalyst for the synthesis
of 5-substituted 1H-tetrazoles. Tetrahedron Lett. 52, 3565–3569
(2011)
58. M. Nasrollahzadeh, Y. Bayat, D. Habibi, S. Moshaee, ­FeCl3–SiO2
as a reusable heterogeneous catalyst for the synthesis of 5-substi-
tuted 1H-tetrazoles via [2+ 3] cycloaddition of nitriles and sodium
azide. Tetrahedron Lett. 50, 4435–4438 (2009)
59. G. Azadi, A. Ghorbani-Choghamarani, L. Shiri, Copper (II)
immobilized on F ­ e3O4@ ­SiO2@ l-Histidine: a reusable nanocata-
lyst and its application in the synthesis of 5-substituted 1H-tetra-
zoles. Transit. Met. Chem. 42, 131–136 (2017)
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