Colloids and Surfaces A: Physicochemical and Engineering Aspects 623 (2021) 126729

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Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

CuNPs-loaded amines-functionalized-SBA-15 as effective catalysts for

catalytic reduction of cationic and anionic dyes
Mohammed Hachemaoui a, Bouhadjar Boukoussa a, b, *, Issam Ismail c, Adel Mokhtar a, d,
Inas Taha e, Jibran Iqbal f, Salih Hacini g, Abdelkader Bengueddach a, Rachida Hamacha a
a
Laboratoire de Chimie des Matériaux L.C.M, Université Oran1 Ahmed Ben Bella, BP 1524, El-Mnaouer, 31000 Oran, Algeria
b
Département de Génie des Matériaux, Faculté de Chimie, Université des Sciences et de la Technologie Mohamed Boudiaf, BP 1505, El-Mnaouer, 31000 Oran, Algeria
c
Department of Chemical Engineering, Khalifa University of Science and Technology, P.O. Box 127788, Abu Dhabi, United Arab Emirates
d
Département Génie des Procédés, Institut des Sciences et Technologies, Université Ahmed Zabana, 4800 Relizane, Algeria
e
Department of Mechanical Engineering, Khalifa University of Science and Technology, P.O. Box 127788, Abu Dhabi, United Arab Emirates
f
College of Natural and Health Sciences, Zayed University, P.O. Box 144534, Abu Dhabi, United Arab Emirates
g
Laboratoire de Chimie Fine LCF, Université Oran1 Ahmed Ben Bella, BP‑1524, El‑Mnaouer, 31000 Oran, Algeria

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Stabilization of Cu-NPs on mesoporous

silica SBA-15 functionalized by different
amines.
• Reduction of MB and OG dye in a simple
and binary system under low concen­
tration of NaBH4.
• A strong catalytic property and selec­
tivity via MB dye was obtained.
• The Cu@SBA-3 catalyst was stable and
reusable with high conversion of MB
dye during five consecutive cycles.

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

Keywords: This work involves the preparation of mesoporous silica SBA-15 functionalized by different amines in order to
SBA-15 stabilize the copper nanoparticles and using the obtained materials as catalysts for the catalytic reduction of
CuNPs methylene blue (MB) and Orange G (OG) dyes in simple and binary systems. The obtained results clearly show
Reduction reaction
that the nature of the functionalized amines significantly influences the size, dispersion and content of copper
MB dye
OG dye
nanoparticles (CuNPs). Ultrafine nanoparticles were obtained by mesoporous silica SBA-15 functionalized by
Degradation triamine (Cu@SBA-3). Several parameters which influence the reduction reaction such as the mass of catalyst,
the nature of catalyst, the concentration of NaBH4 and the concentration of MB were investigated. The results
showed that the material containing higher content and finer sizes of CuNPs was the best catalyst (Cu@SBA-3)
for the reduction of MB dye. This catalyst showed a complete conversion of MB to Leuco-MB in a reaction time
which does not exceed 3 min. The application of the catalyst Cu@SBA-3 for the reduction of OG dye in a simple
and binary system (OG + MB) has shown encouraging results with selectivity via the MB dye. Lastly, the reuse of
this catalytic system has shown interesting results during five successive cycles thus, confirming its stability.

* Corresponding author at: Laboratoire de Chimie des Matériaux L.C.M, Université Oran1 Ahmed Ben Bella, BP 1524, El-Mnaouer, 31000 Oran, Algerie.
E-mail address: bbouhdjer@yahoo.fr (B. Boukoussa).

https://doi.org/10.1016/j.colsurfa.2021.126729
Received 9 March 2021; Received in revised form 22 April 2021; Accepted 24 April 2021
Available online 30 April 2021
0927-7757/© 2021 Elsevier B.V. All rights reserved.
M. Hachemaoui et al.
1. Introduction
Environmental pollution problems are still relevant today due to the
various industrial activities that continue to generate various pollutants,
including organic substances and heavy metals. One of the main con­
sequences of the human impact on the environment is water pollution
from certain textile industries. The use of dyes, products that are
extremely harmful to living beings, results in the dissemination of these
substances in aquatic, underground or surface environments, and causes
the death of certain animal species [1–3].
To date, several processes have been used in this field to reduce this
pollution. Adsorption on solid supports, photocatalysis and redox re­
actions are the most widely used methods [4–21]. Among these
methods, catalytic reduction using nanoparticles is the most widely used
method and the most promising due to its simplicity and speed of pro­
cessing [15–18]. It has been shown in several studies that metallic
nanoparticles exhibit remarkable catalytic properties via the reduction
of organic pollutants due to their small size and high surface/volume
ratio [15–18]. However, nanoparticles present a major problem which
lies in their aggregation when they are in solution, due to the in­
teractions that exist between them.
To prevent this aggregation, the presence of a stabilizing agent
located on their surface is therefore necessary [15–18]. The stabilizing
agent can be present from the initial step in which the nanoparticles are
first formed, in order to control their size and shape. The choice of
stabilizing agents is a crucial issue: in fact, not only does it give the
system the colloidal stability required for most applications, but it can
also confer new properties to the system [15–18]. Thus, the stabilizing
agent affects the size, shape and distribution of nanoparticles [18].
Several supports have been tested on metallic nanoparticles such as
clays [22], zeolites [16], mesoporous materials [23], graphene oxide
[24], porous metal oxides [25] and polymers [15–17]. Recently, mes­
oporous materials have been of particular interest due to their large
specific surfaces and their larger pore diameters [4,10–12,26]. In
particular, the mesoporous silica SBA-15 has known wide applications,
mainly in catalysis and as a catalytic support [27–30]. This material has
a greater wall thickness, giving it significant thermal stability and wider
pore diameter than zeolites and mesoporous materials (M41S type).
Several methods have been used in literature to stabilize nanoparticles
on the surface of SBA-15.
Impregnation and functionalization are the most promising and
widely used methods to effectively disperse nanoparticles. Recently,
functionalization with organic ligands containing chelating groups has
shown good potential for the stabilization of nanoparticles [28,31]. The
presence of amine, thiol or hydroxyl groups can generate strong
ligand-metal interactions [31]. It has also been shown in several studies
that the modification of these metal complexes by a reducing agent leads
to the formation of well-dispersed nanoparticles.
Based on our previously published studies [27,28,31], we propose
the use of SBA-15 as a support for copper nanoparticles. Several catalysts
have been prepared based on calcined SBA-15 using three different
aminosilanes (mono-, di- and tri-amine). This catalytic system is used for
the first time in this study for the degradation of organic pollutants. To
determine the role of functionalization on the stability and activity of
this catalytic system, SBA-15 impregnated only with copper was pre­
pared. The results of this work were used to better understand the cor­
relation between the nature of the amines used, the content of copper
NPs and the catalytic performance via the reduction of organic pollut­
ants both in simple and binary dye-containing systems.
2. Experimental
2.1. Materials
Pluronic P123, Hydrochloric acid, (HCl,36.5–38%), Tetraethyl
orthosilicate, (TEOS 99%), (3-Aminopropyle) trimethoxysilane, (3-
2
Colloids and Surfaces A: Physicochemical and Engineering Aspects 623 (2021) 126729
Aminopropyle) triethoxysilane, N-(3-Trimethoxysilylpropyl) ethyl­
enediamine, N-(3Trimethoxysilylpropyl) diethylenetriamine, Copper(II)
nitrate (Cu(NO3)2.3H2O,99%), Sodium tetrahydridoborate (NaBH4,
98%), were obtained from Sigma-Aldrich.
2.2. Synthesis of mesoporous silica SBA-15
The mesoporous silica SBA-15 was prepared following the procedure
mentioned in the literature [10,11,27,28,32,33]. Firstly, 2 g of Pluronic
(P123) was dissolved in a solution containing 15 mL of H2O and 60 g of
2 M HCl solution: The mixture was stirred at 40 ◦ C for 20 min and then
4.3 g of TEOS was added by dropping to the mixture under stirring at
40 ◦ C for 20 h. The obtained gel was then transferred to a Teflon-coated
steel autoclave and heated at 100 ◦ C for 48 h. After cooling at room
temperature, the resulting suspension was filtered, washed several
times, dried at 60 ◦ C for 24 h, and ultimately the final product was
calcined at 550 ◦ C for 6 h.
2.3. Amine-functionalized mesoporous silica SBA-15
The functionalization of mesoporous silica SBA-15 by different
amines (APTES) was realized according to the literature [27,28,34].
Briefly, 0.6 g of the mesoporous silica SAB-15 was dispersed in 150 mL of
toluene and then 3 g of aminosilane was added. The reaction mixture
was placed under reflux at a temperature of 60 ◦ C during 24 h. The final
product was filtered, washed several times with toluene and ethanol,
and then dried for 24 h at a temperature of 60 ◦ C. In this study, three
types of aminosilane were functionalized on the surface of mesoporous
silica which are: (3-Aminopropyle) trimethoxysilane, N-(3-Trimethox­
ysilylpropyl) ethylenediamine and N-(3-Trimethoxysilylpropyl) dieth­
ylenetriamine, designated as SBA-1, SBA-2 and SBA-3, respectively.
2.4. CuNPs loaded mesoporous silica SBA-15
The mesoporous silica SBA-15 and its amine-modified counterparts
were modified by Cu0 nanoparticles. In a typical preparation, 2 g of
mesoporous material was dispersed in 100 mL of solution of copper
nitrate (0.1 M) and stirred for 2 h at room temperature. The final product
was filtered, washed several times with distilled water and then dried at
60 ◦ C for 24 h. This step is similar to our previously published work
except modifications were made after copper complexation using a
NaBH4 solution to reduce Cu+2 to Cu0 [28,34]. To reduce the Cu+2
species to Cu0 NPs, the obtained materials were treated with 100 mL
solution of NaBH4 (1 M) and stirred for 2 h at room temperature. The
final products were filtered, washed with distilled water and then dried
at 60 ◦ C for 24 h. The final products are named Cu@SBA-0, Cu@SBA-1,
Cu@SBA-2, and Cu@SBA-3. Cu@SBA-0 presents the parent material
SBA-15 not functionalized but modified by Cu NPs.
2.5. Catalytic test
The obtained mesoporous materials were used as catalysts for cata­
lytic reduction of methylene blue (MB) and orange G (OG) in a simple
and binary system. For the simple system, 2 mL of the OG or MB dye
solution (0.6 mM) was placed in a quartz cuvette, and then 3 mg of
catalyst was added followed by the addition of 1.5 mL of a freshly-
prepared NaBH4 solution (6.8 mM). The reaction mixture was placed
in a UV-Vis spectrometer (UV–vis Specord 210 Analytik Jena) using a
program in which a scan is made in every minute. Several parameters
affecting the reduction of dyes have been studied by varying the dye
concentration between 0.3 and 0.6 mM, the NaBH4 concentration be­
tween 1.7 and 6.8 mM and the catalyst mass between 1 and 3 mg. For the
binary system, the same protocol was followed using a dye mixture (MB
+ OG) having a concentration of 0.3 mM. The mass of catalyst used was
3 mg and the concentration of NaBH4 was 6.8 mM.
M. Hachemaoui et al.
2.6. Catalyst characterization
The surface composition and chemical state of all materials modified
by Cu0NPs was measured by XPS using Kratos Axis Ultra radiation (AlKα
1486.6 eV). The functionalization of amines on the surface of SBA-15
was studied by infrared spectroscopy in the range of 4000–500 cm− 1
using a BRUKER ALPHA Platinum-ATR model. The thermal stability of
mesoporous silica functionalized by amines and doped by Cu0NPs was
studied by a thermobalance (TGA DISCOVERY SDT-650) under nitrogen
flow. An XRF spectrometer (X-MET 8000 by Oxford Instruments) was
used to gather raw spectra from samples. The morphology of all modi­
fied materials was observed by SEM using HITASHI TM-1000 electron
microscopy and TEM measurements were conducted using the Tecnai
TEM at a voltage of 200 kV. The copper content in each sample was
determined SEM-EDAX measurements using a quanta 3D dual-beam
SEM instrument.
3. Results and discussion
FTIR spectroscopy was used to gain qualitative insight into the na­
ture of the functional groups on the surface of the mesoporous silica
SBA-15. Fig. 1 shows the FTIR spectra of the obtained samples. The
parent material and the modified materials have the following vibration
modes: A broad band observed between 1231 and 1034 cm–1 and a low
band at 790 cm–1 both of which are attributed to the asymmetric and
symmetric elongation modes of the Si–O–Si [10,11,27,28,32,33]. The
stretching vibration of the Si–O of the free silanol groups is observed at
966 cm–1 [10,11,27,28,32,33]. The broad band between 3400 and 3100
cm–1 and the low band at 1645 cm–1 are characteristic of the water
molecules physisorbed on the surface of these samples. The intensity of
these two bands increased as a result of the amine modification by
amines and CuNPs loading. This could be due to the existence of several
interactions between the water molecules and amines or CuNPs that
subsequently lead to the improvement of the hydrophilic character of
the resulting composites. The materials modified by amines and CuNPs
showed the presence of two weak bands at 2936 and 2874 cm–1 which
are characteristic of –CH stretching of methyl groups containing ami­
nosilanes [27,28,34]. Characteristic bands of the N–H bond are also
observed in the range of 1600–1585 cm–1 and 3280–3370 cm–1 of the
–NH2 bond which overlap with the characteristic bands of physisorbed
water molecules [27,28,34].
The thermal properties of mesoporous silica functionalized by
various aminosilanes and doped with CuNPs are shown in Fig. 2(a and
b). From this figure, it is clear that the three materials have different
curves and mass losses due to the variation in the nature of aminosilane.
As demonstrated in the FTIR results, these materials have a hydrophilic
character due to several interactions between amines or CuNPs with
Fig. 1. FTIR spectra of obtained catalysts.
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Colloids and Surfaces A: Physicochemical and Engineering Aspects 623 (2021) 126729
water molecules. According to the dTG and TGA curves, there are
several degradation steps: the first step starts in the range 53–82 ◦ C due
to the water physisorbed on the surface of these solids. Desorption of
water molecules starts from 53 ◦ C, 57 ◦ C and 82 ◦ C for the Cu@SBA-1,
Cu@SBA-2 and Cu@SBA-3 samples, respectively [27,28,34]. This is
strongly related to the amine groups contained within each sample,
suggesting that the presence of tri-amine on the surface of SBA-15 causes
more interactions with water molecules than di- and mono-amines. It
should also be taken into consideration that the presence of copper on
the surface of the SBA-15 can improve the hydrophilic character. The
loss of water over this temperature interval is as follows: 6%, 8%, 11% of
mass losses were recorded for Cu@SBA-1, Cu@SBA-2 and Cu@SBA-3,
respectively. There are also two other mass losses which take place
over the range 170–225 ◦ C and also over the range 366–475 ◦ C, most
likely caused by the organic molecules existing in each sample under­
going several degradation steps. The mass losses recorded over the range
170–550 ◦ C are 13%, 17% and 20% for Cu@SBA-1, Cu@SBA-2 and
Cu@SBA-3, respectively. Beyond this temperature, the solids can un­
dergo slight mass losses due to the dehydroxilation of the free silanol
groups.
XPS was used to gather quantitative information about the surface
composition as well as the copper oxidation state. As shown in the
spectrum survey, all samples (Fig. 3a) have characteristic peaks of Si 2p,
C 1s, N 1s, and Cu 2p. The presence of low amounts of carbon in the
sample Cu@SBA-0 is due to residual carbon formed during the removal
of the surfactant P123 by calcination [35].
The Cu 2p spectrum (Fig. 3b) for all samples shows two intense peaks
at 932.38 eV and 952.41 eV which are attributed to Cu 2p3/2 and Cu
2p5/2, respectively. These two peaks can be attributed to Cu(0) and/or
Cu(I) [36]. It is known that it is difficult to distinguish between Cu(0)
and Cu(I) because their separation in binding energy is only about
0.3 eV [36]. No characteristic peak of Cu(II) was observed (around
937 eV or 957 eV) showing the total conversion of Cu(II) to Cu(0) or Cu
(I).
It is clearly visible that the peaks of Cu 2p3/2 and Cu 2p5/2 are intense
for Cu@SBA-1, Cu@SBA-2, Cu@SBA-3. The high intensity of the two
peaks for the functionalized materials confirms the high Cu content in
these samples due to the multiple interactions between amines and
copper species; while Cu@SBA-0 exhibited the weakest peaks due to the
lower copper content in this sample.
The O 1s spectra of all materials are shown in Fig. 3c. As shown in
this figure, an intense peak was observed for the sample Cu@SBA-
0 which refers to the Si–O–Si bond. This material also showed a weak
peak at 537 eV due to the interaction of CuNPs with the Si–O–Si of SBA-
15 [37,38]. On the other hand, the amine-functionalized and doped
materials exhibited less intense peaks which shifted from 532.14 eV to
531 eV due to surface functionalization by aminosilanes. This slight shift
was also observed in the spectra of Si 2p (see additional file, Fig. 1S).
These results are in agreement with those obtained elsewhere in the
literature [39]. It is also possible that this shift is related to the depo­
sition of CuNPs on the surface of the mesoporous silica.
The spectra of N 1s for the functionalized materials are shown in
Fig. 3d. It is known that the characteristic peak of –NH2 is around
400 eV, however, in our case a slight displacement of this peak was
observed around 399.39 eV, 399.42 eV and 399.49 eV for catalysts
Cu@SBA-1, Cu@SBA-2 and Cu@SBA-3, respectively. This shift is prob­
ably due to the several interactions between amines and copper species
[40].
The SEM, TEM and EDX mapping images are shown in Fig. 4. The
SEM images of all samples show a similar morphology in the form of
elongated aggregates (rod-like shape) with particle size of 400–800 nm.
It is observed that the functionalized materials also exhibit other parti­
cles in the form of aggregates, probably due to the functionalization by
aminosilanes. The TEM images of all materials showed black spots due
to the formation of CuNPs on the surfaces of the mesoporous silica SBA-
15. The nanoparticle size varies from one material to another in the
M. Hachemaoui et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 623 (2021) 126729

Fig. 2. (a) TGA and,(b) dTG curves of obtained samples.

Fig. 3. XPS spectra of obtained catalysis, (a) survey, (b) Cu 2p, (c) O 1s and (d) N 1s.

range of 4–15 nm for the catalysts Cu@SBA-0, Cu@SBA-1 and Cu@SBA-
2. The catalyst Cu@SBA-3 showed the finest particles having sizes less
than 4 nm, this is probably related to several sites (triamine) which can
stabilize CuNPs nanoparticles. The CuNPs were well-dispersed in all the
materials which were also confirmed by EDX mapping. For the Cu@SBA-
0 sample, the spots which corresponded to copper are unidentified due
to its low content in this sample. The EDX mapping images also showed
the formation of silica aggregates in materials functionalized by ami­
nosilanes, which is in agreement with the observations obtained by the
SEM images. As shown in Fig. 4, the copper content increases in the
following sequence 2.43%, 5.57% and 6.13% for the samples Cu@SBA-
1, Cu@SBA-2 and Cu@SBA-3, respectively. However, the sample
Cu@SBA-0 showed a small amount which was not determined by this
analysis (see Fig. 2S). From these analyses (SEM, TEM and EDAX map­
ping), it is clear that the nature of the amine groups used plays a very
important role in capturing and stabilizing the copper nanoparticles.
The best results in terms of the CuNPs content and dispersion were ob­
tained by the material functionalized by the triamines (Cu@SBA-3)
suggesting more interactions with the copper species.
4. Catalytic reduction of MB dye
4.1. Effect of catalyst dose
Fig. 5, shows the UV–vis spectra of MB dye during catalytic reduc­
tion. To understand the effect of the catalyst on the reduction of MB dye,

4
M. Hachemaoui et al.
Fig. 4. SEM, TEM and EDAX mapping images (from left to right) of obtained samples.
an adsorption test and a blank test without catalyst were performed
using the catalyst Cu@SBA-1. As shown in Fig. 5(a and b) the adsorption
test shows negligible adsorption during 15 min. The result of the blank
test without catalyst under the presence of NaBH4 (6.8 mM) showed an
almost negligible degradation confirming that the presence of NaBH4
(6.8 mM) does not influence the catalytic reduction of MB dye. How­
ever, it was observed that the addition of lower amounts of catalyst
produces a better degradation of MB dye (Fig. 5(d-f)). The conversion of
MB dye increases with increasing catalyst mass loading, and the best
results were obtained upon using 3 mg of catalyst (Fig. 5(d-f)). This mass
is much lower compared to other works carried out in the literature,
confirming the power of this catalyst to activate the reduction of MB dye
at lower catalyst masses. The role of the catalyst Cu@SBA-1 in the
reduction of MB dye is to transfer electrons coming from the donor
NaBH4 to the acceptor MB dye molecules [15,17,18]. It must also be
taken into account that the increase in the mass loading of catalyst leads
to an increase in the number of sites available to reduce the MB dye to
leuco-MB [15,17,18].
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Colloids and Surfaces A: Physicochemical and Engineering Aspects 623 (2021) 126729
4.2. Effect of support nature
To understand the effect of the functionalization of mesoporous silica
SBA-15 by amine on the reduction of MB dye, several catalytic tests were
carried out using the same operating conditions and only the catalysts
were changed. According to the Fig. 6(a-f), it is clearly seen that the
nature of the catalyst plays a very important role in the degradation of
MB dye, the degradation time of MB dye varies in the following
sequence: Cu@SBA-3> Cu@SBA-2 Cu@SBA-1 and Cu@SBA-0. In all
cases, the catalyst Cu@SBA-3 gave the best results in terms of rate
constant and reaction time (Fig. 6(e-f)), while the catalyst Cu@SBA-
0 showed poor MB degradation. From this result it was observed that
the degradation time varies as a function of the copper content deposited
on the surface of the SBA-15. As we have explained in the character­
ization section, the Cu retention was generally observed to be higher in
the materials functionalized by the amines and was best in the material
containing triamine. Thus, the presence of large content of copper in this
catalyst is the key factor to reduce MB dye. The calculated rate constant
M. Hachemaoui et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 623 (2021) 126729

Fig. 5. UV–vis spectra of MB dye during its degradation (a-e), (a) adsorption test, (b) blank test without catalyst, (c-e) catalytic tests using 1 mg, 2 mg and 3 mg
catalyst Cu@SBA-1, respectively. (f) Correlation between catalysts mass, reaction time and MB dye conversion.

(kapp) of Cu@SBA-3, Cu@SBA-2 and Cu@SBA-1 was 2.944, 1.495 and
0.494 min–1, respectively. It should also be noted that the size of CuNPs
can also influence the reduction of MB dye. According to the TEM im­
ages, the Cu@SBA-3 sample exhibited the finest size of CuNPs which
explains its performance compared to other catalysts.
4.3. Effect of concentration of NaBH4
The effect of the concentration of NaBH4 can significantly influence
the reaction time. Fig. 7(a-d) shows the UV–vis spectra of MB dye during
the degradation process. As shown in this figure, it is clear that the
concentration of NaBH4 significantly influences the reduction of MB
dye. The use of a concentration of 1.7 mM of NaBH4 in the presence of

6
M. Hachemaoui et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 623 (2021) 126729

Fig. 6. UV–vis spectra of MB dye during its degradation using: (a) Cu@SBA-0, (b) Cu@SBA-1, (c) Cu@SBA-2 and (d) Cu@SBA-3. (e) Correlation between catalyst
nature, reaction time and MB dye conversion. (f) Plot of ln(Ct/C0) as a function of reaction time.

the catalyst Cu@SBA-3 does not lead to any transformation. However, it
was shown that a concentration of 3.4 mM and 6.8 mM of NaBH4 leads
to total degradation during 4 min and 3 min, respectively. Increasing the
concentration of NaBH4 increases the density of electrons on the surface
of CuNPs, making the surface negative, which can easily attract the
cationic MB dye to the surface of the catalyst, and then it can easily
transfer these electrons to the MB dye by reducing them to leuco-MB.
These results are in agreement with the literature [41,42].
4.4. Effect of MB dye concentration
Fig. 8(a-d) shows the UV–vis spectra of reduction of MB dye at
different concentrations. In this experiment, all the conditions were kept
constant except for the concentration of MB dye which was changed
from 0.6 to 1 mM. As shown in this figure, the concentration of MB dye
influences the reaction time. The reduction time was 3, 26 and 50 min
upon using MB concentrations 0.6, 0.8 and 1 mM, respectively. There

7
M. Hachemaoui et al.
Fig. 7. UV–vis spectra of MB dye during its degradation using different concentrations of NaBH4, (a) 1.7 mM, (b) 3.4 mM and (c) 6.8 mM. (d) Effect of concentration
of NaBH4 in MB dye conversion and the reaction time.
are more than sufficient number of free sites on the catalyst surface to
reduce the MB dye at lower concentrations, but not as many sites are
available when using a higher MB concentration, which makes diffusion
and adsorption difficult for these dyes’ molecules. These results are in
agreement with the literature [18].
4.5. Catalytic reduction of OG dye in simple and binary system
The reduction of OG dye in the presence of Cu@SBA-3 catalyst was
carried out according to the conditions optimized above. As shown in
Fig. 9a, the dye reduction OG was complete during a time that does not
exceed 9 min. These results show the capacity of this catalyst to catalyze
the degradation of other types of dye having an anionic character.
However, the reduction time recorded for this catalyst for the reduction
of the MB dye was faster compared to that recorded for the OG dye in
simple systems. To study the selectivity of this catalytic system, a binary
mixture of MB and OG dyes was prepared and studied. As shown in
Fig. 9b, the reduction of MB dye was faster compared to OG, whereby 4
mins were sufficient to reduce all of the molecules of MB dye, while the
reduction of the OG dye took 10 min. This selectivity via the MB dye is
strongly linked to the several interactions between the dye and the
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Colloids and Surfaces A: Physicochemical and Engineering Aspects 623 (2021) 126729
catalyst surface. As we explained previously, the adsorption of NaBH4 on
catalyst Cu@SBA-3 leads to the formation of hydrides and electron
layers on its surface. This causes strong interactions between the elec­
tron rich catalytic surface and the cationic MB dye, as opposed to the
anionic OG dye, where the presence of two similar negative charges both
on adsorbent and adsorbate leads to electrostatic repulsions, reducing
the reaction rate compared to that of the cationic dye [16]. As shown in
Table 1, this catalytic system exhibits an interesting catalytic activity via
the reduction of MB dye, using only a low mass of catalyst with a high
concentration of MB dye under low concentration of NaBH4. The cata­
lysts mentioned in Table 1 have shown encouraging results but the
concentration of NaBH4 was higher which influences on the reaction
rate. Based on the calculation of the rate constant normalized by the
mass of catalyst, our system presented the most important value
showing its efficiency.
4.6. Catalyst reuse
The reuse of the best catalyst Cu@SBA-3 was carried out in order to
study its stability. The experiments were performed using the same
conditions optimized previously via the reduction of MB dye. At the end
M. Hachemaoui et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 623 (2021) 126729

Fig. 8. UV–vis spectra of MB dye during its degradation using different concentrations of MB dye, (a) 0.6 mM, (b) 0.8 mM and (c) 1 mM. (d) Effect of concentration
of MB dye on the reaction time and MB dye conversion.

of each reaction, the catalyst was recovered and then washed only with catalytic system has the power to catalyze the reduction reaction at low
water and then reused in a new cycle. As shown in Fig. 10, the con­ mass loadings of the catalyst and low concentration of NaBH4. The
version of MB dye was complete in each cycle confirming its stability reduction of OG in the simple and binary system showed a weak
and performance. However, it was observed that the reaction time in­ reduction compared to the MB dye confirming the selectivity of our
creases during each cycle. This is strongly linked to the loss of catalyst catalytic system via cationic dye. Finally, the reuse of Cu@SBA-3 during
mass during reuse and also to the saturation of some sites by MB dye, five successive cycles showed good stability.
subsequently leading to a decrease in the number of sites.
Funding
5. Conclusion
This research was supported by DGRSDT (Algeria).
Mesoporous silica SBA-15 was prepared and functionalized with
three different aminosilanes. These hybrid solids were subsequently
CRediT authorship contribution statement
used to stabilize copper nanoparticles. The modified materials were
tested as catalysts for the catalytic reduction of simple and binary dye
Mohammed Hachemaoui: Conceptualization, Validation, Writing-
systems consisting of MB and/or OG dyes. The different characterization
original draft, Software, Investigation, Data Curation. Bouhadjar Bou­
methods used in this study clearly confirmed the loading of CuNPs on
koussa: Formal analysis, Writing-review & editing, Funding acquisition,
the different supports, the content of CuNPs varies from one support to
Methodology, Visualization,. Issam Ismail: Formal analysis, Writing -
another. The catalyst named Cu@SBA-3 showed the best catalytic ac­
review & editing. Adel Mokhtar: Writing-review & Editing. Inas Taha:
tivity due to the higher content of CuNPs and ultrafine sizes which are
Formal analysis, Writing - review & editing. Jibran Iqbal: Formal
well-dispersed in the organic-inorganic matrix. Several parameters
analysis, Writing - review & editing. Salih Hacini: Formal analysis,
influencing the reaction of reduction were studied, showing that this
Writing - review & editing. Abdelkader Bengueddach: Funding

9
M. Hachemaoui et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects 623 (2021) 126729

Fig. 9. UV–vis spectra of degradation of OG dye in: (a) simple system and, (b) binary system.

Table 1
Comparative study with other work carried out in the literature via the reduction of MB dye in the presence of NaBH4.
Catalyst [MB] [NaBH4] Catalyst (mg) Time (min) kapp (min− 1) Ka (min− 1
mg− 1) Ref

Poly(GMA)@Ru/TiO2@Fe3O4 0.5 mM 0.2 M 3 4 0.55 0.183 [15]

Aerogel MC@CA(1) 0.6 mM 0.6 M 4.8 5 0.17 0.035 [17]
MC-PDA-Ag 40 mg/L 5.3 mM 10 5 0.87 0.087 [43]
Fe3O4-p(AN)-AU 50 mg/L 35.24 mM 10 6 0.8 0.08 [44]
Ag/PSNM-3 0.03 mM 60 mM 2 11 0.13 0.065 [45]
CuO-SDS 0.6 mM 6.8 mM 3 10 0.345 0.115 [18]
Silver/reduced graphene oxide 20 mg/L 30 mg 10 40 0.1551 0.015 [24]
Cu/SBA-15(12.5) 0.09 mM 0.2 M 1 8 0.51 0.51 [23]
1.0PdAS 25 mg/L 0.2 M 1 8 0.626 0.51 [46]
Cu@SBA-3 0.6 mM 6.8 mM 3 3 2.944 0.981 This study
a
The normalized rate constant by the weights of the catalyst.

acquisition, Writing-Review & Editing, Resources. Rachida Hamacha:

Project administration, Resources, Writing - Review & Editing.

Conflict of interest

The authors declare that they have no conflict of interest.

Appendix A. Supporting information

Supplementary data associated with this article can be found in the

online version at doi:10.1016/j.colsurfa.2021.126729.

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