CuCO3-CuO nanocomposite as a novel and environmentally friendly catalyst for triazole synthesis

Article abstract of DOI:10.1039/c5ra17224a

This paper focuses on the use of natural sources for the preparation of efficient and low cost catalysts. CaCO₃ is obtained from cuttlefish bone and was modified by the cation exchange of Ca²⁺ by Cu²⁺ in CaCO₃ u

Full text of DOI:10.1039/c5ra17224a

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1
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Nanocomposite CuCO -CuO as a novel and environmentally friendly catalyst for
3
triazole synthesis.
a,b
c,d*
c
Halima Hadj Mokhtar , Bouhadjar Boukoussa , Rachida Hamacha , Abdelkader
c
a
Bengueddach , Douniazad El Abed .
Laboratoire de Réactivité et Chimie Fine L.C.F, Université d’Oran 1 Ahmed Ben Bella, BP 1524 El
M’naouer, 31100 Oran, Algeria.
a
b
Centre de Recherche Scientifique et Technique en Analyses PhysicoꢀChimiques (C.R.A.P.C), BP 384,
BouꢀIsmail RP 42004 Tipaza, Algeria.
c
Laboratoire de Chimie des Matériaux L.C.M, Université d’Oran1 Ahmed Ben Bella, BP 1524 Elꢀ
Mnaouer, 31000 Oran, Algeria.
d
Centre Universitaire Ain Témouchent, Institut des Sciences et de la Technologies, BP 284, 46000
Ain Témouchent, Algeria
*Corresponding author. Tel: +213771663458.
Eꢀmail addresses: bbouhdjer@yahoo.fr
Abstract:
This paper focuses on the use of natural sources for the preparation of efficient and
low cost catalysts. The CaCO material is obtained from the bone of cuttlefish that
3
+
+
++
was modified by cation exchange of Ca by Cu in CaCO
copper (Cu(NO ) at different concentrations. The modification of solids was
investigated by Xꢀray diffraction (XRD), Fourier transform infrared spectroscopy
3
using a solution of
3 2
)
(
FTIR), scanning electronic microscopy (SEM), the energy dispersive spectrometry
EDS) and ultraviolet–visible (UV–vis) spectroscopy. The results show that the
(
3
copper exchanged materials contain nanoparticle composite CuCO ꢀCuO. The
obtained solids were used as catalysts for cycloaddition reaction of different azides
with activated alkenes at room temperature under liquidꢀphase conditions. The
different parameters which affect the reaction were investigated such as reaction time,
temperature reaction, effect of copper content, catalyst mass, effect of solvent and
nature of azide. High yields were obtained with the catalyst containing more amount
of copper. The best catalysts were calcined at different temperatures 200, 300, 400,
1

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5
3
00°C in order to determine the active phase CuCO or CuO in the catalytic reaction.
The XRD analysis of calcined composites show that the increase in calcination
temperature leads to the formation of the CuO phase. On the other hand, the use of
these calcined materials as catalysts shows that the active phase is copper carbonate.
Finally, a new method for preparing triazoles in short reaction times was developed
by the use of cheap environmentally friendly catalyst.
3
Keywords: CaCO , Copper carbonate, Cycloaddition reaction, Triazoles synthesis,
Catalyst reꢀuse.
1
. Introduction
During the last decades, the manufacturing of inorganic materials with specific size,
morphology and crystallinity are considered as the factor responsible for their
1ꢀ3
properties. To date, the scientists focused on the synthesis of ordered structures
with different morphologies and structures assembled by nanostructures 1D and 2D
which have a great interest to chemists and materials scientists for their new
4
properties and fundamental importance in the practical applications areas. Recently,
considerable effort has been devoted to investigate effective methods of synthesis of
porous materials including free procedures in one step and simple catalyst are highly
5
desirable.
CaCO
3
is the most abundant crystalline biomineral which has drawn the attention of
6
researchers because of its different morphologies such as needleꢀshaped, nanoꢀ
7
8
spheres, rhombohedralꢀshaped, lensꢀshaped and hexagonalꢀshaped, microspheres
9
with urchinꢀshaped structure. This material proved to be a suitable catalyst or
10
catalyst support for different reaction such as degradation of Acid Red B, propylene
1
1
5
12ꢀ14
epoxidation,
oxidation of 1,2ꢀdichlorobenzene, biodiesel production,
2

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15
16
homocoupling of aromatic halides, decomposition of acetylene, photoꢀcatalysis of
1
7
18
COD, Fischer–Tropsch synthesis.
The carbonateꢀbased materials involve a large variety of cations such as Ca, Mg, Fe,
Cu or Mn leading to different composition for examples CaCO , MgCO , CuCO ,
3
3
3
FeCO , MnCO . The proprieties of these materials allow them to be used in a large
3
3
applications in food and pharmaceutical industries, and also as filler in paper, plastic
materials, in catalysis, adsorption, medicine, electronics, ceramics, optic, energy,
18ꢀ25
magnetic, pigments and cosmetics.
The use of matrices containing copper in the
catalysis field has received much attention in the last decades, due to the important
26ꢀ28
basicity and potential redox of copper,
the synthesis of a hybrid material CuCO3ꢀ
CuO is much easy by using copper precipitation method in the medium containing the
2
9ꢀ31
CaCO
3
or Na
2
CO
3
,
and the use of heating promotes the transformation of CuCO
3
to CuO, this gives a perspective on the use of these solids in different fields mainly in
heterogeneous catalysis.
In the last years many publications were focused on the synthesis of triazoles, these
organic products have been interesting in the development of novel compounds with
anticonvulsant,
antidepressant,
antioxidant,
antiꢀinflammatory,
analgesic,
antinociceptive, antibacterial, antimycobacterial, antifungal, antiviral, anticancer, antiꢀ
32ꢀ35
parasitic, antiꢀurease and other activities.
There are many methods for preparing
3
6,37
triazole derivatives that have been developed,
the use of heterogeneous catalytic
system benefits from considerable synthetic advantages, easy availability of starting
materials, short durations of reaction, simplicity of the reaction procedure, efficient
38
catalyst for regeneration and separation. Heterogeneous catalysts based on copper
++
are considerably preferred for these type of reaction due to the presence of Cu . For
the purpose to obtain the best catalytic performance for cycloaddition reactions,
3

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different catalysts based on copper are described in the literature such as:
3
9,40
41
Cu/mesoporous materials,
copper nanoparticles (Cu NPs), zeolite supported
42
43
44
copper nanoparticles, Cu/chitosan, Cu/polymer catalysts and others….
This work focuses on the facile and low cost synthetic method that leads to the direct
3 3
transformation of CaCO to CuCO ꢀCuO nanostructured materials by precipitation of
CaCO in a solution containing Cu(NO ) . Furthermore, the cycloaddition reaction of
3
3 2
different azides catalyzed by CuCO
3
ꢀCuO was also discussed based on experimental
evidence. This contribution will also provide new insights into better understanding
the reaction kinetics for cycloaddition of azideꢀactivated alkenes.
2
. Experimental
2
.1. Preparation procedure for catalysts
The material CaCO was obtained from cuttlefish bone, it was recovered in the
3
seashore areas in Ain el turck Oran Algeria, see Fig.1. After grinding the solid and
washing with ethanol to remove all organic traces, the recovered powder was treated
3 2
by solutions containing different concentrations of Cu(NO ) . After a few minutes
stirring the product is formed as attested by the appearance of a blue precipitate. The
obtained materials were filtered, washed and dried at 353K. The concentrations of
copper nitrate solutions employed for the preparation of catalysts are : 1M, 0.8 M, 0.6
M, 0.4 M and 0.2 M, and the formed products are respectively named : MB1, MB0.8,
3
MB0.6, MB0.4, MB0.2 and MB0 (CaCO before treatment with copper solution).
Fig.1. Preparation of nanocomposite CuCO ꢀCuO using cuttlefish bone.
3
4

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2
.2. Catalytic test:
Scheme 1: Cycloaddition reaction of arylazides and activated alkenes using
nanocomposite CuCO ꢀCuO catalyst.
3
The catalytic reaction involves the preparation of solution containing arylazides
(1mmol) in DMF (1mL) (see scheme 1), then was firstly added activated alkenes
(
1mmol) and morpholine (1mmol) then the catalyst CuCO ꢀCuO (20mol%). The
3
mixture was stirred 1.5ꢀ4 h at room temperature. After completion of the reaction, the
precipitate formed upon addition of H O (10 mL) was filtrated, washed with H O and
2
2
dried. To remove the catalyst, the precipitate was extracted with ethylacetate. After
removal of the solvent, the crude product was recrystallized (by EtOH).
2
.3. Characterization
The XRD powder diffraction patterns of the CaCO
3
3
and CuCO ꢀCuO nanocomposite
materials were obtained with a Bruker D8 Advance XꢀRay diffractometer (40 kV, 30
mA) using CuKα radiation (λ= 0.154 nm) in the 2θ range of 5–70°. The surface
topography of the different solids was observed using SEM on a Hitachi Sꢀ4800
microscope. The energy dispersive spectrometer (EDS), SAMx Diode: SiLi, marque:
NORAN was used for the determination of the catalyst chemical composition. FTIR
−
1
spectra of the nanocomposite materials in the range 400–4000 cm were collected on
a BRUKER ALPHA PlatiniumꢀATR. Ultraviolet visible (UV–vis) absorbance
spectrum was recorded at room temperature on a Specord 210 Analytik Jena
spectrometer.
3
. Results and discussion
5

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3
.1. Catalyst characterization
The diffraction patterns of the CaCO
concentration of Cu(NO are given in Fig.2. The XRD pattern of CaCO
3
3
and CuCO
3
ꢀCuO obtained at different
obtained
3
)
2
from cuttlefish bone is assigned to the aragonite structure. In fact, the diffraction
peaks appearing in the range of 2θ=26.8–27.6°, 2θ=33.3–38.7°, 2θ=43.5–46.4°,
2
θ=49.1–51° and 2θ=53.3, are well matched with the standard pattern of the aragonite
4
5
structure according to the literature. For the case of cuttlefish bone (CaCO
modified with different concentrations of Cu(NO , we note that there was
appearance of two different phases, the first one diffraction peaks appear between
θ=12.9°, 2θ=21.6ꢀ24.7°, 2θ=32.4ꢀ33.7°, 2θ=36.8°, 2θ=40.1°, 2θ=42.4° and 2θ=44.1°
which correspond to a structure of copper carbonate CuCO , in agreement with the
3
)
3 2
)
2
3
4
6
literature. The second phase is related to the CuO structure and its diffraction peaks
appear between 2θ=35.8, 2θ=49.7°, 2θ=52.2 and 2θ=53.9° once again these results are
4
6,47
consistent with the literature.
The figure also shows that the peaks intensity of
CuO is much lower compared to peaks characteristic of CuCO phase.
3
6

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1
200
1
000
800
600
400
200
0
10
20
30
40
50
2
Theta
MB0
MB0,6
MB0,2
MB0,8
MB0,4
MB1
CuCO3
CuO
Fig.2. XRD patterns of CaCO
3
3
and CuCO ꢀCuO with different Cu concentration.
The appearance of CuO can be explained by the drying temperature (80°C) which as
demonstrated by Teo et al, plays a very important role on the decomposition of
CuCO
expected to be enhauced. We note also that the concentration of copper plays a very
important role on the structure of the material CuCO ꢀCuO, the highest peaks
intensity is obtained with average concentrations of Cu(NO ) (the case of materials
3
into CuO strucure, and when increasing temperature CuO formation is
3
1
3
3
2
MB0.4 and MB0.6).
UV–vis reflectance diffuse spectra were recorded to investigate the coordination
environment of Cu species. Fig.3 shows the UV–vis spectra of CaCO and CuCO
3
3
ꢀ
CuO with various Cu contents spanning from 200 nm to 1000 nm. All the materials
exhibited intensive absorption centering around 282 nm for the case of CaCO and
3
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2
3
57ꢀ326 nm for CuCO , evidencing ligandꢀtoꢀmetal charge transfer between oxygen
++ 48,49
ligand and isolated Cu .
3
,4
,2
,0
,8
,6
,4
,2
,0
,8
,6
,4
,2
,0
,8
,6
,4
,2
,0
3
3
2
2
2
2
2
1
1
1
1
1
0
0
0
0
0
200
400
600
800
1000
Wavelength (nm)
MB0
MB0,6
MB0,2
MB0,8
MB0,4
MB1
3 3
Fig.3.UV–vis spectra of CaCO and CuCO ꢀCuO with different Cu concentration.
The intensity of this last band increased proportionally with the Cu loading,
+
+
suggesting more isolated Cu present in the composite CuCO
3
ꢀCuO. Furthermore a
materials was
generally assigned to the d–d transition of Cu in pseudoꢀoctahedral coordination,
weak and broad absorption between 600 and 800 nm for all CuCO
3
++
4
9,50
indicating formation of segregated CuO particles.
The much higher intensity of the
peak between 230–300 nm, compared to the peak across the range 600–800 nm,
+
+
demonstrates that isolated Cu for CuCO
materials. These results are consistent with XRD data.
The FTIR data of CaCO aragonite and CuCO ꢀCuO composite obtained at different
Cu(NO ) concentration are given in Fig.4. For the case of CaCO aragonite we can
3
phase are the predominant species in these
3
3
3
2
3
8

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−1
observe bands at 1673–1504 cm (overtones and combinations bands) attributed to
5
1
−1
the C=O groups of the carbonate ions. The bands at 1423–1310 cm (antisymmetric
−1
−1
stretching mode), 1045 cm (symmetric stretching mode), 852–806 cm (out of
−1
plane bending mode) and 770–666 cm (in plane bending mode) are attributed to the
5
2
vibrations of carbonate internal group C–O corresponding to aragonite structure. If
−1
the adsorption band of O–H stretching vibration around 3542 cm can be assigned to
the presence of occluded water in CaCO aragonite, this adsorption peak with a
3
−1
shoulder at 3335 cm should be the O–H stretching vibration of crystal water and
interꢀparticle hydrogen bonds.
0,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
4
000 3500 3000 2500 2000 1500 1000 500
-1
Wavenumber (Cm )
MB0
MB0.6
MB0.2
MB0.8
MB0.4
MB1
3 3
Fig.4.FTꢀIR spectra of CaCO and CuCO ꢀCuO with different Cu concentration.
The copper modified materials show some significant differences, indicating that
physical and/or chemical changes occured after copper adsorption. First, new peaks
−1
−1
appear at 1538, 2342 and 2464 cm , whereas the one peak at 1495 cm disappears.
−1
Second, there is slight postꢀadsorption increase for peak strength at 1538, 2342 cm
(Fig.4). These IR spectra changes are most likely due to the ionꢀexchange between
9

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+
+
++
Cu and Ca . We also note that there was an increase in the band intensity between
360–3542 (the case of MB1 sample) due to the water absorbed in the surface of
solids. On the other hand, there was a slight displacement a few bands between 661
3
−1
and 1636 cm , suggesting that the conjugate action from the solids may be affected
by the ionꢀexchange or electrostatic attraction on the surfaces during the adsorption
process.
3 3
Fig.5. EDS of CaCO and composite CuCO ꢀCuO with different Copper
concentration ; (a) MB0, (b) MB0.2, (c) MB0.4, (d) MB0.6, (e) MB0.8, (f) MB1.
10

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The chemical composition of the solids was characterized by EDS measurements to
confirm the presence of CaCO and CuCO ꢀCuO. The corresponding EDS spectrum
3
3
of the different samples are shown on figure 5. Fig.5a presents the EDS spectra of
MB0 sample which confirms the presence of CaCO with no other impurities.
3
Concerning the CaCO modified by different concentrations of copper (MB0.4ꢀMB1)
3
Fig. 5cꢀf, we note that the increase in the copper concentration causes increased
copper content in the solid structure (Fig. 5cꢀf). The tested concentrations generate the
formation of a solid without any impurity, the resulting solids consisting essentially of
C, Cu and O, except in the case of the solid MB0.2 which is formed by Ca, Cu, C and
O, an obious explanation of this is that the formation of a solid which contains both
3 3 3
CaCO and CuCO ꢀCuO with the CuCO ꢀCuO being the predominant species (Fig.
5
c).
Scaning electronic microscopy was used for the study of the morphology of the
prepared materials. Fig.6 shows SEM images of MB0 (pure CaCO ) and modified
3
with different concentrations of copper, which was obtained following precipitation
method (see experimental part). There is a major difference in the morphology of the
MB0 (pure CaCO
3
) and the MB0.2ꢀMB1 (CuCO
3
ꢀCuO) materials as obtained by the
),
precipitation method. Fig.6a shows the image of cuttlefish bone (aragonite CaCO
3
we can see that the nanostructure looks as noodleꢀlike morphology, (Fig.6cꢀf) shows
the SEM images of CuCO ꢀCuO nanoplates with the thickness of platelets below 200
3
nm for MB0.6 (Fig.6d) and lateral dimensions much bigger in comparison with the
thickness (Fig.6cꢀf), these results are significantly similar to the literature, we also
note that the changes in the morphologies depends on the increasing of copper
concentration. As it can be seen from (Fig.6dꢀf) higher concentrations of copper
generates a spectacular morphologies in the case of MB1 (shape salad) and MB0.8
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(
shape desert rose). For the case of MB0.2 we observe that there is a mixture of
aggregates that is due to the presence of several structures such as CaCO and the
composite CuCO ꢀCuO (Fig.6b), these results were already confirmed by EDS
3
3
analysis. The obtained information indicates that the copper concentration has a
significant influence on the morphology, and the connectivity of differents nanoplates.
(
(
(
a)
c)
e)
(
b)
(d)
(f)
Fig.6. SEM image of CaCO
3
and CuCO
3
ꢀCuOfor different Copper concentration: (a)
MB 0, (b) MB 0.2, (c) MB 0.4, (d) MB 0.6, (e) MB 0.8, (f) MB 1.
12

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3
.2. Catalytic experiments
Based on the results obtained in Fig.7.a and b we note that all the catalysts have a
significant catalytic activity for the cycloaddition reaction except for the material
3
CaCO .
100
(a)
80
60
40
20
0
0
1
1
.5 hours
hours
.5 hours
0,0
0,2
0,4
0,6
0,8
1,0
Copper concentration
100
(b)
80
60
40
20
0
MB0
MB0.2
MB0.4
MB0.6
MB0.8
MB1
0,0
0,5
1,0
1,5
2,0
Reaction time (hours)
Fig.7. Optimization of parameters for cycloaddition reaction: (a) effect of copper
concentration – 20mol% of catalyst; (b) effect of reaction time.
The catalyst prepared at high concentrations of copper possesses the best catalytic
reactivity for cycloaddition reaction (case of MB1 and MB0,8), whereas when using
3
CuCO ꢀCuO solids interesting yields of about 96% are obtained for a reaction time
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3
between 0.5ꢀ1.5 hours. Whereas, when using CaCO no product has been obtained,
++
this difference in activity is thus probably due to the presence of Cu in composite
++
materials which has been obtained by cation exchange with Ca . We note that not
only we reduce the reaction time, but also we have developed a simple process for the
separation of final product by filtration.
We also studied the effect of solvent on the cycloaddition reaction, hence without the
additition of morpholine, no product was obtained with the composite materials (see
table S1 additional file) as catalysts which indicates that the presence of morpholine
plays a very important role for activated alkenes. It is well known that the nitrogen
bases are used to accelerate triazole formation, in particular by coordinating to the
catalytically active copper species, and promoting their liberation from the catalyst
5
3,54
matrix, thus as improving their thermodynamic stability.
Moreover, the basic
character of the amines can contribute to the deprotonation of the alkynes and alkenes
55,56
component.
If we compare our results with or without CuCO ꢀCuO catalysts, the composite
3
materials CuCO
Table.1). The addition of active methylene, arylazides and DMF in the presence of
morpholine without CuCO ꢀCuO materials leads to the formation of triazoles with
3
ꢀCuO gives the best catalystic performance for this reaction (see
3
interesting yields after 24 hours of reaction time. The different obtained structures of
+
heterocycles were characterized by NMR spectroscopic analysis (NMRꢀH and NMRꢀ
13
C ) and the fourier transform infrared spectroscopy (FTIR) (see additional file). In all
cases with or without catalysts composite we note that the halogenꢀsubstituted azides
(Cl or Br) give moderate yields for the products (3b and 3c), because of the lower
electroattractor nature of Cl and Br as compared to the nitro group.
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Table.1. Cycloaddition reaction of arylazide 1(aꢀc) with the activated alkenes 2(aꢀd)
performed at room temperature
Without
With
CuCO -CuO
a
b
CuCO
Yield(%)
3
c-CuO
3
c
Entry
1
R(1)
R’(2)
Product (3)
t(h) Yield(%)
t(h)
Me
4ꢀNO2
90
64
24
24
96
1.5
(
1a)
(2a)
Me
40
2
2
3
4
4ꢀBr (2b)
(
1a)
Me
61
90
24
24
60
90
4
4ꢀCl (2c)
(
1a)
Me
2ꢀCl,4ꢀ
1.5
(
1a)
2
NO (2d)
8
0
24
24
79
93
1.5
1.5
4
ꢀNO
2
5
6
Et (1b)
Ph (1c)
(
2a)
4
ꢀNO2
2a)
89
(
a
Reaction conditions: arylazide1(a-c) ( 1 mmol), activated alkene 2(a-d) ( 1 mmol), Morpholine
(
1 mmol), DMF (1 mL), room temperature,24 h (see procedure 1ꢀS3).
b
Reaction conditions: arylazide1(a-c) ( 1 mmol), activated alkene 2(a-d) ( 1 mmol), Morpholine
1 mmol), CuCO ꢀCuO (20mol%), DMF (1 mL), room temperature, (1,5ꢀ4) h (see procedure2ꢀ S3).
(
3
c
Isolated yields.
15

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1
00
9
0
8
0
7
0
6
0
5
0
4
3
0
0
2
1
0
0
0
5
%
mol
24h
1
%
0 mol
24h
2
%
0 mol
1,5h
2
%
5 mol
1,5h
30 mol
%
1,5h
Catalyst amount
Fig.8. Effect of the catalysts amount in the catalytic reaction: nitrophenylazides
1mmol) in DMF (1mL), Ethyl acetoꢀacetate (1mmol),morpholine (1mmol) and
CuCO ꢀCuO (20mol%).
(
3
In order to understand the influence of the heterogeneous catalysts on the
cycloaddition reaction, we have prepared a solution which contains nitrophenylazide
(1mmol) in DMF (1mL), Ethyl acetoꢀacetate (1mmol) and morpholine (1mmol) using
different amounts of composite catalysts CuCO ꢀCuO (MB1) (Fig.8). Using 5 and 10
3
mol% of composite materials led to medium yields between 65ꢀ79% for 24 h reaction
time. However we can notice in Fig. 8 that increasing the amount of catalyst has a
positive impact on the reaction yield, with an optimal value (96%) obtained after 1.5
hour in the presence of 20ꢀ30% of catalyst.
In order to understand what is the catalytic active phase CuCO or CuO, we proposed
3
to use the best catalyst MB1 at different temperature of calcination (200, 300, 400 and
5
00°C) to get different form of copper, the obtained solids were characterized by
XRD and FTIR as shown in Fig.9. and Fig.10.
The results obtained by XRD for MB1 material treated at different temperatures of
calcination shows that at 200 °C there is always the existence of two phases CuCO3
3
and CuO, with the appearance of all characteristic peaks of the CuCO phase (Fig.9),
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but beyond of this value, we see the appartition of a single phase corresponding to
31
CuO, these results are consistent with the literature. When can also deduce that a
temperature of 300°C is sufficient to transform all the copper carbonates to CuO.
Fig.10 represents the FTIR spectrum of CuCO ꢀCuO treated at different temperatures.
3
The FTIR analysis are in agreement with the XRD results, the material MB1 before
and after calicnation at 200 °C presents the same vibration (existence of CuCO
3
and
CuO), whereas for calcined materials between 300ꢀ500 °C, there has been a change in
−1
the vibration bands, we note the appearance of bands at 521 and 603 cm which
57
correspond to the stretching vibration of Cu–O bond in monoclinic CuO. The
−1
−1
vibration in the range of 600–1166 cm (at 800 and 875 cm ) is attributed to M–O
5
8
−1
stretching of CuO (M = Cu). Further, a small and wide band at 1418 and 3271 cm
is ascribed to the vibrational modes of O–H bond of the H O molecules physiosorbed
2
59
on the surface of the CuO.
The obtained material MB1 at different temperatures of calcination was used as
catalyst for the reaction of arylazide 1(a) with activated alkene 2(a), the main results
are listed in the table.2. From these results, we can conclude that the increase in the
calcination temperature causes the formation of CuO particles, which their presence in
the reaction medium has no effect on the reaction, thus the active phase in the reaction
is copper carbonate CuCO3.
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25000
CuCO3
CuO
20000
15000
10000
5
000
0
1
0
20
30
40
50
60
70
2
Theta
MB1ꢀ200
MB1
MB1ꢀ300
MB1ꢀ400
MB1ꢀ500
3
Fig.9. The XRD patterns of CuCO ꢀCuO calcined at differents temperatures.
1
0
0
0
0
0
0
0
0
0
0
,0
,9
,8
,7
,6
,5
,4
,3
,2
,1
,0
-
0,1
4
000 3500 3000 2500 2000 1500 1000
500
-
1
Wavenumber (Cm )
MB1
MB1ꢀ400°C
MB1ꢀ200°C
MB1ꢀ500°C
MB1ꢀ300°C
3
Fig.10. FTꢀIR spectra of CuCO ꢀCuO calcined at differents temperatures.
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Table.2. Effect of calcination temperature on the catalytic activity of the MB1
catalyst:
Catalysts
Temperature of
calcination
Phase
Yields
a
MB1
//
CuCO
CuCO
CuO
CuO
CuO
3
3
ꢀCuO
ꢀCuO
96
54
MB1-200
MB1-300
MB1-400
MB1-500
200 °C
300 °C
400 °C
500 °C
//
no product
no product
no product
no product
b
CuO
CuO
a
The catalysts were calcined for 2 hours.
CuO commercial SIGMAꢀALDRICH.
b
Reaction conditions: arylazide 1(a) (1mmol), activated alkene 2(a) (1mmol), Morpholine catalyst
20mol%), DMF (1mL), room temperature, 1,5 h.
(
Reusability of the catalysts has been studied in the cycloaddition of 4ꢀnitrophenyl
azide (1) under the following conditions: 4ꢀnitrophenyl azide (2 mmol), Ethyl acetoꢀ
3
acetate (2 mmol), CuCO ꢀCuO (MB1, 20 mol%), DMF (2 ml), room temperature, 1.5
h reaction time. The catalysts were filtered, washed with DMF and dried before use in
the following cycles, the results are represented in Fig.11 and as it can be seen the
catalyst could be reused up to three times with little loss of activity, the slight
3
decrease in yields may be due to the surface deactivation of nanocomposite CuCO ꢀ
CuO. We also note that the blue coloration of the catalyst before reaction, changed to
a green color after 3 cycles of reꢀuse due to the complexation of the catalysts with
organic ligands in the reaction medium, these results were confirmed by XRD and
FTIR analysis (see additional file Fig S1 and Fig S2). From the fourth cycle there was
a progressive decrease in yields, in this stage we noticed that there was leaching of
copper and the recovered catalyst lost its color due to the participation of copper in
the reaction medium (see additional file Fig S3).
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1
00
5
0
0
1
Cyle
2
Cyle
3
Cyle
4
Cycle
5
Cycle
Run of Cycle
Fig.11. Catalyst reusability. Reaction conditions 4ꢀnitrophenyl azide (2mmol), Ethyl
acetoꢀacetate (2mmol), catalyst (20mol %), DMF (2 mL), room temperature,reaction
time: 1.5 h (15 min) (at the end of the reaction, the catalyst is dried and reused).
Conclusion:
The composite materials CuCO ꢀCuO have been successfully prepared by direct
3
synthesis method using Cu(NO ) and bone of cuttlefish. The method involves the use
3 2
of natural source for the preparation of efficient and low cost catalysts.The
characterization methods show that the products formed by the precipitation have
nanocomposite structure consisting of copper carbonate and copper oxide. The
composites prepared at different copper concentrations show interesting results as
catalysts for cycloaddition reaction and the increase of the copper content in the
material leads to better results in the cycloaddition reaction, hence the MB1
nanocomposite material gives the best yield achieved in a short reaction time (1 hour).
We have confirmed that the increase of the calcination temperature causes the
formation of CuO, and a calcination about 300 °C is sufficient for the transformation
of all CuCO
3
to CuO phase. The use of MB1 at different temperatures of calcination
allowed us to determine the active phase which is CuCO
3
.
We showed that the reaction time, nature of used azide, and the catalyst mass play an
important role on the yields of the product, and these catalyst may be used for three
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cycles beyond of this value a decrease in yield has been obtained due to leaching of
copper in the reaction medium.
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