Journal of Alloys and Compounds 835 (2020) 155306

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Spectroscopic investigation of chitosan-supported Cu2O/CuO

nanocomposite; a separable catalyst for water-pollutants degradation
Mervat F. Zayed a, *, Wael H. Eisa b, **, Abd ElHameed M. Hosam b, Amira M. Abou Zeid c
a
Chemistry Department, Faculty of Science, Menoufia University, Egypt
b
Spectroscopy Department, Physics Division, National Research Centre (NRC), Dokki, Cairo, Egypt
c
Chemistry Department, Faculty of Science, Jazan University, Saudi Arabia

a r t i c l e i n f o a b s t r a c t

Article history: Designing nano-products using renewable/sustainable resources, while minimizing the use of hazardous
Received 29 November 2019 reagents, is a major challenge. A new solid-state preparation route of chitosan-supported copper oxide
Received in revised form using ascorbic acid (of biological origin) is developed. This method fulfills the environmental and eco-
18 March 2020
nomic requirements in terms of being a non-toxic, solvent-free, energy saving, and available for mass-
Accepted 20 April 2020
Available online 25 April 2020
production. The powder X-ray diffraction proves the formation of Cu2O/CuO nanoparticles. The scan-
ning and transmission microscopy show the narrow size-distribution of the copper oxide particles. The
Fourier transforms infrared and X-ray photoelectron spectroscopies provide evidence for the complex-
Keywords:
Ball-milling
ation of copper ions with hydroxyl and amino groups of chitosan. The catalytic activity of the chitosan-
Chitosan supported copper oxide nanocomposites is investigated toward a group of organic water-pollutants. The
Copper oxide heterogeneous catalyst shows high catalytic activity in reduction of 4-nitrophenol, cationic, anionic dyes,
Catalyst and reactive dyes. The recyclability and reusability issues are efficiently treated here.
Water pollutants © 2020 Elsevier B.V. All rights reserved.

1. Introduction performance of the catalytic reduction of organic pollutants [2].

The world is witnessing a large and continued increase in many
industrial activities that exert large quantities of liquid wastes.
These wastes cause serious environmental problems that nega-
tively affect the living systems in general and the human being in
particular. The organic pollutants (nitrophenols, dyes … etc) are
considered as the main source of water contamination. The organic
pollutants are relatively stable against the biodegradation pro-
cesses under aerobic conditions [1]. Researchers proposed several
approaches to degrade and/or remove these hazardous compounds
from wastewater. These approaches vary between physical, chem-
ical, and biological pathways. Among these methods, the catalytic
reduction has been proven as a simple and efficient route to com-
plete conversion of pollutant to non-harmful compounds. The
catalytic reduction is frequently used in degrading wide categories
of organic pollutants on a large scale, even at low concentrations.
Nanoscale catalysts take the leading role in improving the
* Corresponding author.
** Corresponding author.
E-mail addresses: mervat.zayed@yahoo.com (M.F. Zayed), waeleisa@yahoo.com
(W.H. Eisa).
This is attributed to their high specific surface area which allows a
large number of active centers to accelerate the reduction process
[3e5]. Metallic nanocomposites composed of two metals and/or
metals oxides display improved catalytic activity. This is due to the
synergistic effect of either geometric and electronic aspects, or the
so-called strain effect and ligand effect [6]. However, the applica-
tion of nanocatalyst faces three main obstacles; (1) the aggregation/
agglomeration of the particles due to their high surface energy lead
to reduce their activity, (2) the lake of applicable ways to reuse/
recycle of the nanocatalysts from the reaction medium, and (3) the
scarcity of eco-friendly, easy-to-operate, mass-production and
sustainable synthetic pathways.
To satisfy the conditions of environmental and sustainable
processes it is essential to develop new synthetic processes that are
economic, environmentally-friendly, as well as able to produce
highly reactive, stable, scalable and recyclable heterogeneous cat-
alysts [7]. The heterogeneous catalysis has benefitted immensely
from the recent developments of polymeric nanocomposites [8].
The importance of polymeric nanocomposite in catalysis is
based on [9]; (1) the ease of the preparation in different physical
shapes (granules, fibers, films, etc.), (2) retaining of the inherent
properties of both nanoparticles and the supporting polymer as

https://doi.org/10.1016/j.jallcom.2020.155306
0925-8388/© 2020 Elsevier B.V. All rights reserved.
2 M.F. Zayed et al. / Journal of Alloys and Compounds 835 (2020) 155306
well as some improved characteristics due to organic-inorganic
interactions, (3) their higher stability and processability, and (4)
the availability of wide category of functional groups on the poly-
meric backbone chain [10]. In this regard, polymeric nano-
composites emerge as efficient heterogeneous catalysts for
different catalytic transformations to achieve clean and sustainable
industrial processes creating environmentally-benign products.
Copper oxides (CuO and Cu2O) are widely applied catalysts in
organic synthesis. Copper oxides attract the researchers’ interests
on account of their low-cost and environmental characteristics as
compared with precious transition metal catalysts (silver, gold, and
platinum) [11]. Copper oxides have been prepared using thermal
[12] and chemical [13] decomposition, irradiation [14], sono-
chemical treatment [15], electrochemical method, and polyol
method [16]. However, it is still challenging to find a synthetic
pathway that is clean, simply-operated and produces narrow-size
distribution in large-scale production.
Chitosan (Cs) is the N-deacetylated derived form of abundant
naturally occurring chitin polymer [17]. Cs is considered an ideal
eco-friendly matrix in terms of its biocompatibility, biodegrad-
ability, antifungal, antioxidant, and antibacterial characteristics.
The water solubility, hydroxyl, and amino groups of Cs chains
enable and facilitate the interaction with different metals forming
stable complexes [18]. The role of Cs as a complexing agent inspired
the researchers to widely use it as a supporting matrix for stabi-
lizing different metal/metal oxide nanoparticles. For instance, Cs
matrix is used to support metal/metal oxide nanocatalysts, such as
copper [19], silver [20], gold and platinum [21], Fe3O4 [22], and TiO2
[23].
In this work, we put forward a convenient solid-state method to
prepare monodispersed copper oxide. The copper salt is grounded
with Cs powder to produce Cs/copper complex. Thereafter, Cs/
copper complex is further grounded with ascorbic acid (AA) at
room temperature and dry conditions to form Cs/Cu2O/CuO nano-
composite. Using the solid-state ball-milling method, it is possible
to produce gram-quantity of spherical nanoparticles with a narrow
size distribution. An interesting proof-of-concept for the applica-
tion of this nanocomposite is its potential in heterogeneous catal-
ysis toward different water pollutants (Scheme 1). The film-
forming ability of Cs presents a built-in property to Cs/Cu2O/CuO
nanocomposite which facilitates the recycling and reusing of the
nanocatalyst.
This synthetic pathway is carried out using the abundant Cs at
ambient conditions and avoids the use of hazardous precursors and
solvents fulfilling the demands of sustainable and environmental
concerns. This method turns on a motivating research line where
renewable/abundant resources can be coupled with the different
types of metal/metal oxide nanoparticles to solve many environ-
mental issues.
2. Experimental
2.1. Solid-state preparation of Cs/Cu2O/CuO
1 g of CuCl2.H2O (S.d. Fine-Chem. Ltd) and 2 g of Chitosan
powder (M.wt¼ (161)n, Bio Basic, Canada Inc.) were loaded into the
hardened chromium steel jar (100 mL). 45 g of zirconia milling balls
(diameter ¼ 3 mm) were added to the jar. A desktop vibrating ball
mill machine (Photon Scientific, Egypt) was used in the milling
process for 30 min. Thereafter, 0.5 g of ascorbic acid (Sigma-
Aldrich) was added to the above-mixed powder and the milling
process was continued for an additional 30 min. The whole process
was carried out in dry conditions i.e. no milling liquids are used. The
produced reddish-brown powder was collected, washed with
distilled water/ethanol and filtered to remove the un-reacted
chemicals. The filtered powder was dried at 40  C for 6 h and
then kept in a tight vial for further analysis.
2.2. Preparation of free-standing film of Cs/Cu2O/CuO
0.5 g of Cs/Cu2O/CuO nanocomposite powder was dispersed in
5 mL distilled water using an ultrasonic probe for 10 min. There-
after, 15 mL of 1% Cs solution was added to the Cs/Cu2O/CuO solu-
tion and the ultrasonic treatment was continued for an additional
10 min to achieve good dispersion. The solution was poured on a
Petri dish and the solvent was evaporated naturally at ambient
condition. The dry Cs/Cu2O/CuO film was exfoliated as a free-
standing film.
2.3. The catalytic experiment
The catalytic activity of the prepared Cs/Cu2O/CuO nano-
composite was evaluated for the degradation of different types of
water pollutants i.e. 4-nitrophenol (4-NP), methylene blue (MB)
(cationic dye), methyl orange (MO) (anionic dye), and reactive red
dye (RR). 10 mL of the stock solutions were prepared as follow: Cs/
Cu2O/CuO (25 mg), NaBH4 (0.1 M), 4-NP (102 M), MB (3  103 M),
MO (3  103 M), and RR (9  104 M). The catalytic experiments
were carried out at room temperature (z23  C) by adding the
following reagents to a quartz cuvette filled with 2.77 mL distilled
water: (1) 25 mL (4-NP)/200 mL (NaBH4)/10 mL nanocatalyst, (2)
25 mL (MB)/100 mL (NaBH4)/10 mL nanocatalyst, (3) 100 mL (MO)/
100 mL (NaBH4)/5 mL nanocatalyst, and (4) 200 mL (RR)/100 mL
(NaBH4)/10 mL nanocatalyst. The catalytic experiment of Cs/Cu2O/
CuO nanocomposite was followed by monitoring the UVevis
spectra.
2.4. Characterization and instrumentations
Crystalline structure of synthesized Cs/Cu2O/CuO nano-
composite was detected using an X-ray diffractometer (XRD)
(Schimadzu 6000DX device). The operating setup was Cu Ka
(l ¼ 1.5405 Å) as a radiation source; scanning range 2q ¼ 5e80 ;
operating voltage ¼ 40 kV; the scan speed ¼ 0.02 /min. To evaluate
the morphology, size, and distribution of the Cs/Cu2O/CuO nano-
composite, the scanning electron microscope (SEM, Quanta FEG
250) and transmission electron microscope (TEM, JEOL-JEM-1011)
were used. The elemental composition of nanocomposite was
identified using energy-dispersive X-ray spectroscopy (EDS) built in
the SEM device. The structural properties were studied using
Fourier transforms infrared spectrometer (FTIR, Jasco FT/IR 6100)
and X-Ray photoelectron spectrometer (XPS, Thermo Scientific K-
ALPHA instrument). The UVevisible (UVevis) spectra were
collected using Jasco V-630 UV-VIS spectrophotometer. The ther-
mal degradation was assessed using a thermogravimetric analyzer
(TGA, EXSTAR 6000 TG/DTA 6300 N, Seiko Instruments Inc) at a

heating rate of10 C/min. The surface charge of Cs/Cu2O/CuO
nanocomposite in aqueous solution was measured using Zetasizer
(Malvern Instruments).
3. Results and discussion
3.1. XRD analysis
Fig. 1a displays the typical XRD data of the as-prepared Cs/Cu2O/
CuO nanocomposite powder using ascorbic acid. The diffraction
pattern shows a halo around 2q ¼ 20 which is attributed to the Cs
[24]. The XRD pattern confirms the presence of Cu2O and CuO in the
as-prepared sample. It could be seen that the diffraction peaks at 2q
values of 29, 36, 43, and 62 which represent lattice planes (110),
 M.F. Zayed et al. / Journal of Alloys and Compounds 835 (2020) 155306
Scheme 1. The ball-milling preparation of Cs/Cu2O/CuO nanocomposite.
(111), (200), (220), and (311). These lattice planes are well-matched
with the cubic structure of Cu2O (JCPDS No. 05-0667). Also, the
presence of CuO is confirmed by the presence of the diffraction
peaks at 2q ¼ 32, 48, 58, and 65 which are related to the planes
(110), (20-2), (202), and (310), respectively. The lattice planes of
CuO nanoparticles coincide with the JCPDS No. 45-0937. The
broadening of the diffraction peaks is related to the nanosize of the
particles. The average crystallite size of the Cu2O and CuO nano-
particles is calculated from the FWHM of (220) and (202), which are
more intense reflection peaks. The calculated crystallite size of
Cu2O and CuO nanoparticles is 19 and 26 nm, respectively, using
Scherrer equation [25].
3.2. UVevis spectroscopic data
Fig. 1b displays the UVevis absorption spectrum of the as-
prepared Cs/Cu2O/CuO nanocomposite powder. The sample has
an absorption peak at ca. 432 nm which matches the reddish-
brown color of the sample [26]. The narrow absorption peak in-
dicates the formation of Cu2O/CuO nanoparticles with homogenous
size and shape [27]. The optical bandgap of Cs/Cu2O/CuO nano-
composite can be calculated from the UVevis spectrum using
Tauc’s relation:

1=n
ahn ¼ k hn  Eg
where a, h, n, k, and Eg are the absorption coefficient, Plank’s
3
constant, the photon frequency, an energy-independent constant,
and optical bandgap energy, respectively. The value of the constant
n determines the transition type i.e. n ¼ 2 for direct transition and
n ¼ 1/2 for indirect transition [25]. Fig. 1b (inset) shows that n ¼ 2
gives the best linear relation of (ahv)2 vs photon energy (hv) i.e. the
absorption is due to a direct transition. By extrapolating the straight
line to the abscissa i.e. (ahv)2 ¼ 0, the optical bandgap energy of
Cu2O/CuO can be determined as 1.85 eV.
3.3. FTIR spectroscopic data
Fig. 1c shows the FTIR spectra of naked Cs and Cs/copper oxide
nanocomposite. The spectrum of naked Cs displays thirteen IR
vibrational peaks in the range 4000e400 cm1. The IR peaks at
3347 and 3283 cm1 could be assigned to n(OeH) and n(NeH),
respectively. The nas(CH2) and ns(CH2) of Cs are located at 2923 and
2854, respectively. The sharp IR peak at 1622 cm1 aroused from
n(C]O) of NHCOCH3 group whereas the d(NH2) is located at
1594 cm1 [27]. The IR peaks at 1464, 1423, 1320, 1260 cm1 are
assigned as d(CH2) in CH2OH group, ds(CH3) in NHCOCH3 group,
d(CeH) in pyranose ring, and complex vibrations of NHCO group
(Amide III band), respectively [28]. The nas(CeOeC) and ns(CeOeC)
of glycosidic linkage are proved at 1155 and 1082 cm1, respec-
tively. The IR signal at 1036 cm1 is attributed to n(CeO) in the
primary OH group [29].
The FTIR spectrum of Cs/copper oxide exhibits remarkable
structural changes as compared with that of Cs. The position of the
4 M.F. Zayed et al. / Journal of Alloys and Compounds 835 (2020) 155306
Fig. 1. (a) The XRD, (b) the UVevis spectrum (the inset is the Tauc plot pattern), and (c)
FTIR spectra of the Cs/Cu2O/CuO nanocomposite.
broad band 3700-3100 cm1 is shifted to the lower frequencies and
its shape becomes more asymmetric indicating the complexation of
Cu ions with OH and NH2 groups. The n(C]O) and d(NH2) groups
undergo a shift to the higher frequency side. The intensity of the
NH2 peak becomes greater than that of C]O peak [30]. This may be
attributed to the deacetylation of Cs as a result of interaction with
Cu ions. These results accord well with the literature and indicate
the ability of these functionalities to react with Cu ions [29,31,32].
The spectral shape of IR peaks of glycosidic linkage (1155 and
1082 cm1) suffers from distortion due to the cross-coordination of
adjacent Cs chains with Cu ions [32]. The appearance of the three IR
peaks at 629, 558, and 507 cm1 is attributed to the formation of Cu
oxide; the IR peak at 629 cm1 is assigned to the n(CueO) in Cu2O
[33] whereas the peaks at 558 and 507 cm1 are attributed to
n(CueO) in CuO [34]. The FTIR spectrum confirmed the success in
producing Cs-stabilized Cu2O/CuO nanocomposite via solid-state
reaction.
3.4. XPS analysis
XPS analysis is used to determine the surface chemical structure
of naked Cs and Cs/Cu2O/CuO nanocomposite. The survey spectrum
of Cs shows the presence of three peaks at 285, 400, and 532 eV
which are related to C, N, and O, respectively (Fig. 2a). The fitting of
the C 1s peak reveals the presence of four components as given in
Fig. 2c. The peak at 284.7 eV could be attributed to the aliphatic
eCH2 group whereas the peak at 285.4 eV is assigned as CeNH2.
The binding peak at 286.5 eV is aroused from CeOH, and CeO while
the peak at 288.3 eV is attributed to OeCeO, and NeC]O [35,36].
The N 1s peak at 400 eV can be analyzed into two peaks (Fig. 2d).
The first peak at 399.8 eV is attributed to NH2 and NeC]O groups
and the second one at 401.8 eV is assigned to the protonated amino
groups NHþ3 [37]. The resolved spectrum of O 1s displays two
peaks (Fig. 2e). The peak at 532 eV is assigned to C]O group and
that at 533.2 eV is attributed to OeCeO group [35,38].
The survey spectrum of Cs/Cu2O/CuO nanocomposite shows the
presence of binding energy peaks of C, N, O as well as that of Cu. The
interaction of Cs with CuCl2 in presence of ascorbic acid induces
several structural changes in the shape of C 1s, N 1s, and O 1s as
compared with those of naked Cs. Regarding the C 1s spectrum of
Cs/Cu2O/CuO nanocomposite, the intensity of the peak at 285.3 eV
(CeNH2) decreases while that of the peak at 286.5 eV (CeOH/CeO)
increases. The peak at 288.3 eV (OeCeO/NeC]O) shifts to the
lower energy side (288 eV). For N 1s spectrum, the intensity of
protonated amino groups (NHþ3) peak at 401.8 eV increases
markedly in Cs/Cu2O/CuO nanocomposite. This may be due to the
acidic nature of the reaction in the presence of ascorbic acid during
the grinding process. The O 1s spectrum of Cs/Cu2O/CuO nano-
composite displays an additional peak at 530.1 eV which is attrib-
uted to OeCu of CuO and Cu2O [38,39]. The C]O peak at 532 eV is
intensified after the formation of copper oxide.
The XPS survey spectrum of Cs/Cu2O/CuO nanocomposite dis-
plays two main peaks at ~933.3 and 953.1 eV assigned to Cu 2p3/2
and 2p1/2, respectively. The high resolution spectrum of Cu 2p3/2
and 2p1/2 regions (Fig. 2b) indicates the presence of Cu in mono-
and divalent oxidation states. The peaks at 933.2 and 953.3 eV are
ascribed to the Cu2O while those at 935.1 and 955.9 eV are the
characteristic peaks of CuO [40,41]. In addition, four shake-up
satellite peaks are recorded at 940.7, 944.1, 960.5 and 963.3 eV
[42]. These satellite peaks are appeared as a result of electron
transfer from ligand (Cs) orbital to the 3d orbital of Cu, supporting
the presence of divalent oxidation states of Cu in the prepared
sample [43]. The results of XPS data reveal that the functional
groups eNH2 and eC]O groups suffered from structural distortion
in both shape and spectral position which reflect their role in the
complexation with Cu ions. XPS is considered a sensitive tool to
determine the oxidation state of Cu in compounds [44]. The high-
resolution of Cu 2p core-level XPS spectrum confirms the forma-
tion of both Cu2þ and Cu1þ. The ratio of Cu2O/CuO was calculated
from the deconvolution of Cu 2p3/2 and was found to equal 3.7. The
XPS results accorded well with the XRD and FTIR results.
3.5. Electron microscope imaging
The surface morphology of the as-prepared Cs/Cu2O/CuO
nanocomposite was studied using SEM imaging and displayed in
Fig. 3a. The SEM image clarifies that the chitosan particles were
 M.F. Zayed et al. / Journal of Alloys and Compounds 835 (2020) 155306
Fig. 2. (a) XPS survey spectra, (b) Cu 2p, (c) C 1s, (d) N 1s, and (e) O 1s of Cs and Cs/Cu2O/CuO nanocomposite.
decorated with Cu2O nanoparticles. The Cu2O nanoparticles
appeared as shiny clusters with semi-spherical shape. The average
size of Cu2O nanoparticles is found to be in the range of 11e28 nm.
Fig. 3b showed the EDX spectrum of Cs/Cu2O/CuO nano-
composite to determine its elemental composition and purity. The
EDX spectrum displayed the presence of eight peaks. The peak at
0.28 KeV is due to the binding energy of C K while that at 0.4 KeV
belongs N K. The peak at 0.53 KeV is the binding energy of O K. The
binding energies of 0.9, 8, and 8.9 KeV are assigned to Cu L, Cu Ka
and Cu Kb, respectively. The binding energies at 2.63 and 2.8 KeV
correspond to Cl Ka, and Cl Kb, respectively. The presence of C, O,
and N peaks verifies the role of Cs as a dispersant and stabilizing
agent for the solid-state synthesis of Cu2O/CuO nanoparticles. The
elemental analysis shows that the weight% of Cu is 26.79.
The shape and size of Cs/Cu2O/CuO nanocomposite were further
examined via TEM and displayed in Fig. 3c. The Cu2O/CuO nano-
particles are spherical-shaped and homogenously dispersed
throughout the image field. The Cu2O/CuO nanoparticles appear as
dispersed dark spots within the paler color sheet of Cs matrix. The
presence of Cs matrix makes the Cu2O/CuO nanoparticles, to a large
extent, free from aggregation/agglomeration. This confirms the role
of Cs matrix as a dispersant/stabilizer agent in the current solid-
state route. The histogram in Fig. 3d showed the size distribution
of Cu2O/CuO nanoparticles obtained by the examination of 300
particles. The Cu2O/CuO nanoparticles exhibit a narrow size
5
distribution ranging from 9 to 24 nm with a maximum at 18 nm.
Fig. 4 presented the HRTEM image of the Cs/Cu2O/CuO composite. It
could be seen that there are two different interplanar distances of
0.23 and 0.25 nm, correlated to the crystalline planes of Cu2O and
CuO, respectively. Furthermore, the fast Fourier transform (FFT)
patterns show two sets of diffraction spots that confirm the pres-
ence of the two crystalline structures of Cu2O and CuO within the
grain.
3.6. TGA of Cs and Cs/Cu2O/CuO nanocomposite
The TGA/DTG curves of naked Cs and Cs/Cu2O/CuO nano-
composite are displayed in Fig. 5. Two stages of weight loss% are
observed, as shown in two peaks in the DTG curves for both sam-
ples. The first weight loss% stage (z10%) is recorded at 115  C, for
both samples, is attributed to the evaporation of physisorbed water
molecules. The second weight loss% stage starts at 230 and 190  C
for Cs and Cs/Cu2O/CuO, respectively. This stage can be regarded as
two steps in terms of the thermal degradation rate. The first step
(190e340  C) has the faster rate showing the major weight loss% i.e.
43 and 25% for Cs and Cs/Cu2O/CuO, respectively. The second step
(340e650  C) has the slower rate with weight loss%z 23% for both
samples. These two steps are assigned to the thermal degradation
of the Cs chain resulting in depolymerization, saccharide rings
dehydration, and decomposition of acetylated and deacetylated Cs
6 M.F. Zayed et al. / Journal of Alloys and Compounds 835 (2020) 155306

Fig. 3. (a) SEM, (b) EDX, (c) TEM, and (d) size histogram of Cs/Cu2O/CuO nanocomposite.

Fig. 4. The HRTEM of Cs/Cu2O/CuO nanocomposite.

units [25]. It should be noted that the thermal degradation rate of

Cs is slower than that of Cs/Cu2O/CuO in the range of 190e305  C
and faster in the range of 305e650  C. This may be attributed to the
presence of copper oxide nanoparticles. It was reported that the
depolymerization of chitosan D-glucosamine units occurred in the
range of 200e300  C whereas the thermolysis of glycosidic linkages Fig. 5. (a) TGA, and (b) DTG thermograms of naked Cs and Cs/Cu2O/CuO.

occurred in the range of 330e500  C [45,46]. Hence, it could be

concluded that the presence of copper oxide nanoparticles (with
which accelerate the depolymerization of the Cs matrix in the
high surface energy) enhances the heat transfer to the Cs chains
temperature range of 190e305  C. The FTIR data indicates the
 M.F. Zayed et al. / Journal of Alloys and Compounds 835 (2020) 155306
probability of bonding between copper oxide nanoparticles and
glycosidic linkages. Therefore, the slow thermal degradation rate in
the temperature range of 305e650  C may be attributed to the need
for more thermal energy to break the bonds between Cu2O/CuO
and the Cs chains. At the end of the thermal treatment, the resul-
tant product is carbon and carbon/Cu2O/CuO for Cs and Cs/Cu2O/
CuO, respectively. The residual weight% is 20% for Cs sample which
is less than that of Cs/Cu2O/CuO (42%).
3.7. Mechanism of Cu2O/CuO growth via solid-state reaction
Powders subjected to the ball-milling process suffer from a se-
ries of complex changes. The successive collisions (between balls
and mixed powders) destroy the crystalline domain, break the
existing bonds and create new active surfaces for interactions. This
could result in the formation of nanoscale particles with narrow
dispersions and high yield [47]. Hence, the ball-milling process is
used to carry out a solid-state production of Cu2O/CuO nano-
particles supported on Cs matrix.
The structure of Cs polymer contains considerable functional
groups of (‒NH2) and (‒OH) having a strong ability for complexing
with metal ions. On milling of Cs and CuCl2 powders, the Cu2þ are
adsorbed and/or captured onto Cs surface using (‒NH2) and (‒OH)
groups. This is confirmed from the data collected by FTIR and XPS
which show a remarkable deformation and spectral shift to (‒NH2)
and (‒OH) groups. Two models are reported to describe the
complexation between metal and Cs. The first is the bridge model
in which Cu ions connect nitrogen atoms in the same chain and/or
from adjacent chains. The second is the pendent model in which
complexation occurs through one pendant-like bond of Cu to eNH2
groups [48]. The FTIR data confirm the presence of spectral changes
in the glycosidic linkage peaks (1155 and 1082 cm1) indicating the
presence of crosslinking between Cs chains by coordinated Cu ions
i.e. the bridge model controls the complexation reaction. The
spectral distortion of glycosidic linkages could be attributed to the
increase of their length by steric effect as a result of the presence of
metal ions within Cs interacting with adjacent Cs chains [49].
At this stage, there is no sign for the copper oxidation i.e. the
color of the mixed powder (Cs and CuCl2) retains its bluish-white
color for several days. Upon milling the mixed powder with
ascorbic acid, the color of the resultant powder turns into reddish
brown which is taken as an indication of Cu2O/CuO nanoparticles
formation. Recently, Cu2O and CuO have been prepared using
ascorbic acid (eco-friendly reagent) [50e52]. This process proceeds
via redox reaction i.e. the enediol group of ascorbic acid is oxidized
to a diketone to produce dehydroascorbic acid whereas the Cu2þ
are reduced to Cuþ ions yielding Cu2O. Thereafter, the surface layer
of Cu2O is oxidized to CuO particles due to the continuous exposure
to the atmospheric oxygen as well as the heat of the milling process.
XPS data shows the surfaces of Cu2O/CuO nanoparticles are
capped with Cs chains which prevent/minimize the aggregation
and agglomeration. The nanoparticles tend to aggregate by the
weak van der Waals forces and the Cs powder acts as a physical
barrier preventing their motion toward each other. This can be seen
through the TEM image which displayed a number of well-
dispersed and un-aggregated Cu2O/CuO nanoparticles.
3.8. Static catalytic performance of the Cs/Cu2O/CuO
nanocomposite
3.8.1. Catalytic activity of Cs/Cu2O/CuO nanocomposite for 4-NP
reduction
Fig. 6a displays the UVevis spectra of 4-NP solution with and
without the addition of NaBH4. After addition of NaBH4, the peak at
320 nm (the characteristic of 4-NP) is immediately red-shifted to
7
400 nm with the appearance of yellow color in the reacting solution
due to the formation of 4-nitrophenolate ions [53].
The catalytic reduction of 4-NP to 4-AP is routinely evaluated by
following the intensity changes of the electronic bands at 400 and
300 nm of the reactant 4-NP and the product 4-AP, respectively. In
the absence of catalyst, the reacting solution (4-NP þ NaBH4)
maintains its yellow color even for weeks i.e. no reduction occurs.
This is due to the considerable difference between the reducing
potentials of H3BO3/BH 4 (1.33 V) and 4-NP/4-AP (0.76 V) [54].
Upon the addition of Cs/Cu2O/CuO nanocomposite, the 4-
nitrophenolate peak (400 nm) decays gradually over reaction
time reaching its minimum value after 12 min (Fig. 6b). In a coin-
cidence, a new absorption peak emerges at 300 nm and increases
due to the formation of 4-AP. The reactants (4-NP and NaBH4) are
adsorbed onto the surface of catalyst (Cs/Cu2O/CuO). This will
reduce the energy required to activate the reduction reaction and
promotes the electron transfer from BH4 to 4-NP for the produc-
tion of the un-toxic 4-AP [55].
With a large excess of [NaBH4], the rate constant (k) of the
catalytic reduction reaction depends on the concentration of 4-NP
by the following relation which is first-order kinetic relation;
lnðCt = Co Þ ¼ lnðAt = Ao Þ ¼  kt
where the symbols C and A are the concentration and absorption of
4-NP, respectively. The subscripts o and t indicates the values of C
and A at the beginning and after time t of the reaction, respectively.
The inset of Fig. 6b displays the linear relation of ln(At/Ao) with the
reaction time (t). The graph shows a linear relation between ln(At/
A0) and the reaction time (t). The rate constant (k) of the catalytic
reaction equals the slope of the straight line that is z 0.275 min1.
3.8.2. Effect of reaction conditions on the rate constant of the
catalytic reaction
3.8.2.1. Effect of 4-NP concentration. Fig. 6c shows the linear rela-
tion of ln(At/A0) vs time for different 4-NP concentrations keeping
the other parameters constant ([NaBH4] ¼ 7 mM, [Cu2O/
CuO] ¼ 2 mg/L, pH ¼ 8). The reaction proceeds slowly with the
increase of the 4-NP concentration (Table 1). The presence of a large
number of 4-NP molecules in the reaction media leads to in-
equivalent adsorption of the reactants (4-NP and NaBH4) onto the
surface of the catalyst (Cu2O/CuO). Hence, the electron-rely pro-
cess, occurred at the catalyst surface, will be resisted and the re-
action rate will be minimized.
3.8.2.2. Effect of Cu2O/CuO dosage. The effect of the Cu2O/CuO
dosage on the rate constant of catalytic reduction of 4-NP
([NaBH4] ¼ 7 mM, [4-NP] ¼ 0.16 mM, pH ¼ 8) has been displayed
in Fig. 6d. Table 1 shows that the increased dosage of Cu2O/CuO
nanoparticles i.e. the reaction constant is increased from 0.21 to
0.62 min1 as the Cu2O/CuO dosage is increased from 1 to 3 mg/L.
The utilization of more Cu2O/CuO nanoparticles means there are a
large number of active sites available for the adsorption of the re-
actants, 4-NP and NaBH4, which facilitate the electron-rely process
and therefore effectively speed up the catalytic reaction [56]. Above
3 mg/L of Cu2O/CuO nanoparticles, it is too hard to record the
spectral decay of the absorption peak at 400 nm.
3.8.2.3. Effect of pH value. The efficiency of catalytic reduction of 4-
NP ([NaBH4] ¼ 7 mM, [4-NP] ¼ 0.16 mM, [Cu2O/CuO] ¼ 2 mg/L) has
been studied in the pH range 2e10 and the data is given in Fig. 6e
and Table 1. It is worth mentioning that for pH  5 the solution of 4-
NP is colorless due to the absence of the 4-nitrophenolate ions i.e.
the absorption peak at 400 nm does not appear. As the pH value
increases from 6 to 9, the reaction rate is drastically enhanced in the
8 M.F. Zayed et al. / Journal of Alloys and Compounds 835 (2020) 155306

Fig. 6. (a) The UVevis spectra of 4-NP solution before and after the addition of NaBH4, and (b) the time-evaluation of 4-NP reduction (the inset is the relation of ln(At/Ao) vs time).
The dependence of the rate constant of catalytic reduction of 4-NP to 4-AP on (c) 4-NP concentration, (d) Cu2O/CuO dosage, (e) pH value, and (f) The stability of the catalytic
performance of Cs/Cu2O/CuO nanocomposite in 20 cycles.

Table 1
The dependence of the rate constant (k) of the catalytic reduction of 4-NP on the operational parameters of the reaction.

[4-NP] (mM) Cu2O/CuO dosage (mg/L) pH value

0.08 0.16 0.25 1 2 3 6 7 8 8.5 10

k (min¡1) 0.56 0.27 0.17 0.21 0.27 0.62 0.09 0.15 0.27 0.33 0.22

pH range 6e8.5, and finally, the reaction rate is decreased again at
pH ¼ 10. The hydrolysis of NaBH4 is pH-dependent i.e. the higher
the pH, the slower the hydrolysis of NaBH4 [57].
The recyclability of Cs/Cu2O/CuO catalyst is of utmost impor-
tance in determining the real-use feasibility. Twenty repetitive
cycles of catalytic reaction were performed by centrifugation of Cs/
Cu2O/CuO nanocomposite between every cycle. Fig. 6f showed the
conversion and activity percentage of twenty repetitive catalytic
cycles. For each cycle, the activity % was calculated by computing
the ratio of each reduction rate to the initial reduction rate. It was
observed that even after the eighth cycle, 100% conversion with
98.4% activity was obtained. The conversion was reduced to 82%
with 62% activity after the twentieth cycle. Furthermore, the
powdery nature of Cs/Cu2O/CuO nanocomposite retards the ag-
gregation/agglomeration of the catalyst. This was further
confirmed by characterizing Cs/Cu2O/CuO nanocomposite after the
catalytic cycles using XRD and TEM (Fig. 7 a, b). The XRD pattern
showed some distortion in the chitosan peak at 2q ¼ 20 i.e. the
peak became weaker and broader. The XRD peaks related to the
copper oxide maintained their shape and intensity. The TEM image
also confirmed that the Cs/Cu2O/CuO nanocomposite maintained
their spherical shape with little aggregation/agglomeration
throughout the image field. This guarantees the prolonged shelf-
life or efficient storage capability of this nanocomposite system
which is an additional advantage comparing with colloidal nano-
composites. These findings are noteworthy in terms of the actual
applications of such systems.
3.8.3. Separation of the catalyst
The catalytic activity of the nanocomposites is correlated to the
 M.F. Zayed et al. / Journal of Alloys and Compounds 835 (2020) 155306 9

nanoparticles is guided by its chemical functionality, bio-

compatibility, and good film-forming ability which enable its use
as a recyclable heterogeneous catalyst.
The Cs/Cu2O/CuO powder is transformed into a free-standing
film and soaked in the reacting medium to start the catalytic re-
action. The reactants diffuse onto the film and get in contact with
the Cu2O/CuO nanoparticles where the electron-rely process can
occur. At the end of the catalytic process, the catalyst is easily
removed, just by handling. Fig. 7c shows the graphical represen-
tation of ln(At/Ao) against t for the catalytic reduction of 4-NP using
Cs/Cu2O/CuO composite film. The reaction exhaust more time as
compared with that required in case of using the powdery nano-
composite. The modulation of Cu2O/CuO nanoparticles within Cs
film hinders the reaching of the reactant to the nanoparticles as
well as occupies some reactive catalytic centers that result in
decreasing the reaction rate. After the reaction completion, the
working solution is tested for the released Cu species using an
atomic absorption spectrometer. The obtained results do not show
the presence of Cu species in the working solution i.e. Cu2O/CuO
nanoparticles are tightly bonded to the polymeric film matrix.
Table 2 showed the reported rate constant of the reduction of 4-
NP to 4-AP catalyzed by Copper-based catalysts. The previously
reported studies include the use of expensive metals (Pd, Au …etc.),
complicated fabrication processes, and the use of hazardous ma-
terials. In addition, these studies depend on the filtration and
centrifugation techniques in the separation of the catalyst which
are not favored in real applications.

3.8.4. The catalytic activity of Cs/Cu2O/CuO nanocomposite toward

the degradation of cationic, anionic, and reactive dyes
The catalytic performance of the prepared Cs/Cu2O/CuO powder
in the reduction of different types of dyes such as MB (cationic dye),
MO (anionic dye), and RR (reactive dye), is evaluated. The textile,
rubber, and paper industries widely use such types of dyes. It is
worth to mention that the reduction experiment of the three dyes
was performed once with dye þ NaBH4 (no catalyst) and once with
dye þ catalyst (absence of NaBH4). In both cases, the visual in-
spection, as well as the UVevis spectra, did not show considerable
color fading even after several hours of reaction.
Fig. 8a shows the time-dependent UVevis spectra of the cata-
lytic reduction of MB. In aqueous medium, MB displays two ab-
sorption peaks at 663 and 613 nm due to (p‒p *) transitions [72].
After Cs/Cu2O/CuO addition to the reaction mixture, the peak in-
tensities decrease gradually reaching its minimum value after
5 min. This occurs online with the color change from blue to
colorless giving evidence of the efficient catalytic activity of the
catalyst. The calculated rate constant (k) is found to be 0.59 min1.

Table 2
Catalytic reduction of 4-NP to 4-Ap with NaBH4 induced by Copper-based catalysts.

Catalyst k (min1) Ref

Fig. 7. (a) The XRD, (b) TEM of the Cs/Cu2O/CuO nanocomposite after 20 catalytic
Aglaiaelaeagnoidea/CuO 0.57 [58]
cycles, and (c) the relation of ln(At/Ao) vs time for 4-NP degradation using Cs/Cu2O/CuO
Gundeliatournefortii/CuO 2.7 [59]
nanocomposite film.
CuO 0.12 [60]
Cu2O 0.74 [61]
Cu2OeCueCuO 0.62 [62]
homogeneous nanoparticles dispersion which enables the acces- Cu/Cu2O/C 1.51 [63]
sibility of the reactants to the reactive catalytic sites. On the other Cu/Cu2O/graphene oxide 2.84 [64]
hand, the efficient isolation of the nanocatalyst from the reacting Cu2O@CuO/(AuePd) 0.52 [65]
Polyester fabric @CuOeSieN(OH)2 0.317 [66]
medium represents the major stumbling block in the way of their
N-doped Cu/C 1.602 [67]
actual application [4]. Catalysts with high activities but hardly Cu 0.182 [68]
isolated from the reacting medium are unfavored in the industrial Graphene/Ni foam/Cu 3.369 [69]
applications. Consequently, the development of easily separable Si nanowire/Cu 0.6306 [70]
catalyst is rather necessary. The choice of Cs support for Cu2O/CuO Cu 0.0953 [71]
Cs/Cu2O/CuO 0.62 This study
10 M.F. Zayed et al. / Journal of Alloys and Compounds 835 (2020) 155306
Fig. 8. The time-dependent UVevis spectra of the catalytic degradation of (a) MB, (b)
MO, and (c) RR using Cs/Cu2O/CuO nanocomposite in the presence of NaBH4. The inset
is the linear relation of ln(At/A0) vs time of the reaction.
Fig. 8b displays the time-dependent UVevis spectra of the cat-
alytic reduction of MO. Two absorption peaks at 470 and 282 nm
are detected for the MO solution. After the insertion of Cs/Cu2O/
CuO nanocomposite, the gradual decay of the peak at 470 nm is
started with the appearance and growth of a new absorption peak
at 251 nm is observed. The complete decolorization of the MO dye
exhausts 7.5 min with a rate constant equal to 0.51 min1. In
presence of an active catalyst, the azo site (eN]Ne) of MO mole-
cule can be reduced by strong reducing agent NaBH4 at and is
converted into amino groups eNH2 which are indicated by the
appearance of the new peak at 251 nm [73].
The catalytic activity of Cs/Cu2O/CuO nanocomposite in the
degradation of RR dye is evaluated using UVevis spectrometer and
is given in Fig. 8c. The two absorption peaks at 536 and 513 nm
show a swift decrease in intensity after the addition of the catalyst.
The absorption of these two peaks shows nearly zero-intensity
within 6 min indicating the completion of the reduction process.
The calculated rate constant is 0.46 min1.
The catalytic activity of Cs/Cu2O/CuO composites toward MB
(cationic dye) was attributed to the electrostatic attraction between
negatively charged Cs/Cu2O/CuO (z-potential ¼ 42 mV) and the
positively charged MB. This electrostatic attraction brings the MB
molecules at the surface of the catalyst close to NaBH4 where the
electron relay takes place. It was reported that MO (anionic dye)
could be adsorbed to Cs through eNH2, eOH functionalities
through hydrogen bonds, van der Waals force, etc. [2,74,75]. Hence,
the physical and/or chemical binding between MO and Cs at the
surface of Cu2O/CuO is responsible for the adsorption of anionic dye
molecule to the catalyst surface to facilitate the electron-rely pro-
cess. This might partially explain the catalytic mechanism.
4. Conclusion
A heterogeneous catalyst of Cs/Cu2O/CuO nanocomposite is
produced in gram-quantity using a solid-state ball-milling process.
The prepared nanoparticles are monodispersed with an average
particle size of 18 nm. The FTIR and XPS data show the ability of (‒
NH2) and (‒OH) groups to bind Cu ions and the presence of the two
oxidation states of Cu. The Cs/Cu2O/CuO nanocomposite shows
efficient catalytic behavior toward 4-NP, MB (cationic dye), MO
(anionic dye), and RR. The Cs/Cu2O/CuO nanocomposite was reused
for eight successive catalytic cycles without noticeable deteriora-
tion in the catalytic activity. The use of Cs in catalyst preparation
enables the making of a free-standing film of the catalyst that fa-
cilitates the recovery and reuse of the nanoparticles. The easy-
handling of the polymeric film of catalyst not only avoids the
catalyst filtration or centrifugation but also presents an efficient
and applicable method for recycling the nanocatalysts. This envi-
ronmentally benign protocol collects several advantages such as
low-cost, simple setup, elimination of hazardous reagents, and high
yields of catalyst. These specifications present the solid-state pro-
tocol as a promising technique for economic production and envi-
ronmental requirements.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
CRediT authorship contribution statement
Mervat F. Zayed: Conceptualization, Investigation, Methodol-
ogy, Writing - original draft, Writing - review & editing. Wael H.
Eisa: Conceptualization, Data curation, Funding acquisition, Inves-
tigation, Supervision, Writing - original draft, Writing - review &
editing. Abd ElHameed M. Hosam: Data curation, Formal analysis,
Methodology, Software, Validation, Writing - original draft. Amira
M. Abou Zeid: Data curation, Formal analysis, Methodology, Vali-
dation, Visualization, Writing - original draft.
 M.F. Zayed et al. / Journal of Alloys and Compounds 835 (2020) 155306
Acknowledgment
The authors appreciate the technical and financial support
provided by the National Research Centre, in-home project unit,
project No. 12020226.
References
[1] X. Liu, M. Qiu, C. Huang, Degradation of the reactive black 5 by fenton and
fenton-like system, Procedia Eng. 15 (2011) 4835e4840.
 Moln
[2] A. ar, The use of chitosan-based metal catalysts in organic trans-
formations, Coord. Chem. Rev. 388 (2019) 126e171.
[3] W.H. Eisa, A.M. Abdelgawad, O.J. Rojas, Solid-state synthesis of metal nano-
particles supported on cellulose nanocrystals and their catalytic activity, ACS
Sustain. Chem. Eng. 6 (2018) 3974e3983.
 Moln
[4] A. ar, A. Papp, Catalyst recyclingda survey of recent progress and current
status, Coord. Chem. Rev. 349 (2017) 1e65.
[5] P. Zhao, R. Zhang, J. Wang, Adsorption of methyl orange from aqueous solution
using chitosan/diatomite composite, Water science and technology, J. Int.
Assoc. Water Pollut. Res. 75 (2017) 1633e1642.
[6] Y. Dai, Y. Wang, B. Liu, Y. Yang, Metallic nanocatalysis: an accelerating
seamless integration with nanotechnology, Small 11 (2015) 268e289.
[7] F. Yang, D. Deng, X. Pan, Q. Fu, X. Bao, Understanding nano effects in catalysis,
Natl. Sci. Rev. 2 (2015) 183e201.
[8] W.H. Eisa, A.A. Shabaka, Ag seeds mediated growth of Au nanoparticles within
PVA matrix: an eco-friendly catalyst for degradation of 4-nitrophenol, React.
Funct. Polym. 73 (2013) 1510e1516.
[9] X. Zhao, L. Lv, B. Pan, W. Zhang, S. Zhang, Q. Zhang, Polymer-supported
nanocomposites for environmental application: a review, Chem. Eng. J. 170
(2011) 381e394.
[10] A.Z. Badruddoza, Z.B. Shawon, W.J. Tay, K. Hidajat, M.S. Uddin, Fe3O4/cyclo-
dextrin polymer nanocomposites for selective heavy metals removal from
industrial wastewater, Carbohydr. Polym. 91 (2013) 322e332.
[11] K. Mikami, Y. Kido, Y. Akaishi, A. Quitain, T. Kida, Synthesis of Cu(2)O/CuO
nanocrystals and their application to H(2)S sensing, Sensors 19 (2019).
[12] V.H. Luan, J.H. Han, H.W. Kang, W. Lee, Highly porous and capacitive copper
oxide nanowire/graphene hybrid carbon nanostructure for high-performance
supercapacitor electrodes, Compos. B Eng. 178 (2019) 107464.
[13] T.N.Q. Trang, L.T.N. Tu, T.V. Man, M. Mathesh, N.D. Nam, V.T.H. Thu, A high-
efficiency photoelectrochemistry of Cu2O/TiO2 nanotubes based composite
for hydrogen evolution under sunlight, Compos. B Eng. 174 (2019) 106969.
[14] E. Luevano-Hipo lito, L.M. Torres-Martínez, D. Sa nchez-Martínez, M.R. Alfaro
Cruz, Cu 2 O precipitation-assisted with ultrasound and microwave radiation
for photocatalytic hydrogen production, Int. J. Hydrogen Energy 42 (2017)
12997e13010.
[15] N. Silva, S. Ramirez, I. Diaz, A. Garcia, N. Hassan, Easy, quick, and reproducible
sonochemical synthesis of CuO nanoparticles, Materials 12 (2019).
[16] L. Tamayo, M. Azocar, M. Kogan, A. Riveros, M. Paez, Copper-polymer nano-
composites: an excellent and cost-effective biocide for use on antibacterial
surfaces, Materials science & engineering, Mater. Sci. Eng. C applications 69
(2016) 1391e1409.
[17] S.B. Marpu, E.N. Benton, Shining light on chitosan: a review on the usage of
chitosan for photonics and nanomaterials research, Int. J. Mol. Sci. 19 (2018).
[18] K. Ravishankar, K.M. Shelly, R.P. Desingh, R. Subramaniyam, A. Narayanan,
R. Dhamodharan, Green, solid-state synthesis of maleated chitosan and ion-
otropic gelation with chitosan, ACS Sustain. Chem. Eng. 6 (2018)
15191e15200.
[19] P. Kaur, B. Kumar, V. Kumar, R. Kumar, Chitosan-supported copper as an
efficient and recyclable heterogeneous catalyst for A3/decarboxylative A3-
coupling reaction, Tetrahedron Lett. 59 (2018) 1986e1991.
[20] N. Alhokbany, T. Ahama, Ruksana, M. Naushad, S.M. Alshehri, AgNPs
embedded N- doped highly porous carbon derived from chitosan based
hydrogel as catalysts for the reduction of 4-nitrophenol, Compos. B Eng. 173
(2019) 106950.
[21] M.J. Laudenslager, J.D. Schiffman, C.L. Schauer, Carboxymethyl chitosan as a
matrix material for platinum, gold, and silver nanoparticles, Bio-
macromolecules 9 (2008) 2682e2685.
[22] N.H. Abdullah, K. Shameli, E.C. Abdullah, L.C. Abdullah, Solid matrices for
fabrication of magnetic iron oxide nanocomposites: synthesis, properties, and
application for the adsorption of heavy metal ions and dyes, Compos. B Eng.
162 (2019) 538e568.
[23] L. Bergamonti, C. Bergonzi, C. Graiff, P.P. Lottici, R. Bettini, L. Elviri, 3D printed
chitosan scaffolds: a new TiO2 support for the photocatalytic degradation of
amoxicillin in water, Water Res. 163 (2019) 114841.
[24] S. Logpriya, V. Bhuvaneshwari, D. Vaidehi, R.P. SenthilKumar, R.S. Nithya
Malar, B. Pavithra Sheetal, R. Amsaveni, M. Kalaiselvi, Preparation and char-
acterization of ascorbic acid-mediated chitosanecopper oxide nanocomposite
for anti-microbial, sporicidal and biofilm-inhibitory activity, J. Nanostruct.
Chem.y 8 (2018) 301e309.
[25] S.S.M. Ali, W.H. Eisa, A. Abouelsayed, Solvent-free and large-scale preparation
of silver@polypyrrole core@shell nanocomposites; structural properties and
terahertz spectroscopic studies, Compos. B Eng. 176 (2019) 107289.
11
[26] Y. Yang, D. Xu, Q. Wu, P. Diao, Cu2O/CuO bilayered composite as a high-
efficiency photocathode for photoelectrochemical hydrogen evolution reac-
tion, Sci. Rep. 6 (2016) 35158.
[27] W.H. Eisa, T. Abdelnaby, S. Mostafa, M.Y. Elzayat, In situ preparation of chi-
tosan/gold nanocomposite: structural and catalytic properties, Adv. Polym.
Technol. 37 (2018) 2095e2101.
[28] Y. Shigemassa, H. Matsuura, H. Sashiwa, H. Saimoto, Heavy metal contami-
nation, Int. J. Biol. Macromol. 18 (2006) 237.
[29] L. Gritsch, C. Lovell, W.H. Goldmann, A.R. Boccaccini, Fabrication and charac-
terization of copper(II)-chitosan complexes as antibiotic-free antibacterial
biomaterial, Carbohydr. Polym. 179 (2018) 370e378.
[30] S.M. Pourmortazavi, H. Sahebi, H. Zandavar, S. Mirsadeghi, Fabrication of
Fe3O4 nanoparticles coated by extracted shrimp peels chitosan as sustainable
adsorbents for removal of chromium contaminates from wastewater: the
design of experiment, Compos. B Eng. 175 (2019) 107130.
[31] S. Mekahlia, B. Bouzid, Chitosan-Copper (II) complex as antibacterial agent:
synthesis, characterization and coordinating bond- activity correlation study,
Physics Procedia 2 (2009) 1045e1053.
[32] J. Qu, Q. Hu, K. Shen, K. Zhang, Y. Li, H. Li, Q. Zhang, J. Wang, W. Quan, The
preparation and characterization of chitosan rods modified with Fe3þ by a
chelation mechanism, Carbohydr. Res. 346 (2011) 822e827.
[33] I. Prakash, P. Muralidharan, N. Nallamuthu, M. Venkateswarlu,
N. Satyanarayana, Preparation and characterization of nanocrystallite size
cuprous oxide, Mater. Res. Bull. 42 (2007) 1619e1624.
[34] A. Singhal, M.R. Pai, R. Rao, K.T. Pillai, I. Lieberwirth, A.K. Tyagi, Copper(I) oxide
nanocrystals - one step synthesis, characterization, formation mechanism,
and photocatalytic properties, Eur. J. Inorg. Chem. 2013 (2013) 2640e2651.
[35] I.F. Amaral, P.L. Granja, M.A. Barbosa, Chemical modification of chitosan by
phosphorylation: an XPS, FT-IR and SEM study, J. Biomater. Sci. Polym. Ed. 16
(2012) 1575e1593.
[36] R.S. Vieira, M.L.M. Oliveira, E. Guibal, E. Rodríguez-Castello n, M.M. Beppu,
Copper, mercury and chromium adsorption on natural and crosslinked chi-
tosan films: an XPS investigation of mechanism, Colloid. Surface. Phys-
icochem. Eng. Aspect. 374 (2011) 108e114.
[37] S. Bensalem, B. Hamdi, S. Del Confetto, M. Iguer-Ouada, A. Chamayou,
H. Balard, R. Calvet, Characterization of chitosan/montmorillonite bio-
nanocomposites by inverse gas chromatography, Colloid. Surface. Phys-
icochem. Eng. Aspect. 516 (2017) 336e344.
[38] M.C. Sportelli, A. Volpe, R.A. Picca, A. Trapani, C. Palazzo, A. Ancona,
P.M. Lugara, G. Trapani, N. Cioffi, Spectroscopic characterization of copper-
chitosan nanoantimicrobials prepared by laser ablation synthesis in aqueous
solutions, Nanomaterials 7 (2016).
[39] J.F. Xu, W. Ji, Z.X. Shen, S.H. Tang, X.R. Ye, D.Z. Jia, X.Q. Xin, Preparation and
characterization of CuO nanocrystals, J. Solid State Chem. 147 (1999)
516e519.
[40] X. Liu, J. Chen, P. Liu, H. Zhang, G. Li, T. An, H. Zhao, Controlled growth of CuO/
Cu 2 O hollow microsphere composites as efficient visible-light-active pho-
tocatalysts, Appl. Catal. Gen. 521 (2016) 34e41.
[41] Y.C. Zhang, J.Y. Tang, G.L. Wang, M. Zhang, X.Y. Hu, Facile synthesis of sub-
micron Cu2O and CuO crystallites from a solid metallorganic molecular pre-
cursor, J. Cryst. Growth 294 (2006) 278e282.
[42] N. Cioffi, N. Ditaranto, L. Torsi, R.A. Picca, L. Sabbatini, A. Valentini, L. Novello,
G. Tantillo, T. Bleve-Zacheo, P.G. Zambonin, Analytical characterization of
bioactive fluoropolymer ultra-thin coatings modified by copper nanoparticles,
Anal. Bioanal. Chem. 381 (2005) 607e616.
[43] B. Li, X. Luo, Y. Zhu, X. Wang, Immobilization of Cu(II) in KIT-6 supported Co 3
O 4 and catalytic performance for epoxidation of styrene, Appl. Surf. Sci. 359
(2015) 609e620.
[44] M. Younas, J. Shen, M. He, R. Lortz, F. Azad, M.J. Akhtar, A. Maqsood, F.C.C. Ling,
Role of multivalent Cu, oxygen vacancies and CuO nanophase in the ferro-
magnetic properties of ZnO:Cu thin films, RSC Adv. 5 (2015) 55648e55657.
[45] M.A. Gamiz-Gonzalez, D.M. Correia, S. Lanceros-Mendez, V. Sencadas,
J.L. Gomez Ribelles, A. Vidaurre, Kinetic study of thermal degradation of chi-
tosan as a function of deacetylation degree, Carbohydr. Polym. 167 (2017)
52e58.
[46] Y.S. Nam, W.H. Park, D. Ihm, S.M. Hudson, Effect of the degree of deacetylation
on the thermal decomposition of chitin and chitosan nanofibers, Carbohydr.
Polym. 80 (2010) 291e295.
[47] T. Prasad Yadav, R. Manohar Yadav, D. Pratap Singh, Mechanical milling: a top
down approach for the synthesis of nanomaterials and nanocomposites,
Nanosci. Nanotechnol. 2 (2012) 22e48.
[48] L. Gritsch, C. Lovell, W.H. Goldmann, A.R. Boccaccini, Fabrication and charac-
terization of copper(II)-chitosan complexes as antibiotic-free antibacterial
biomaterial, Carbohydr. Polym. 179 (2018) 370e378.
[49] J. Qu, Q. Hu, K. Shen, K. Zhang, Y. Li, H. Li, Q. Zhang, J. Wang, W. Quan, The
preparation and characterization of chitosan rods modified with Fe3þ by a
chelation mechanism, Carbohydr. Res. 346 (2011) 822e827.
[50] E. Aguilera-Ruiz, M. de la Garza-Galv an, P. Zambrano-Robledo, J.C. Ballesteros-
Pacheco, J. Vazquez-Arenas, J. Peral, U.M. García-Pe rez, Facile synthesis of
visible-light-driven Cu2O/BiVO4 composites for the photomineralization of
recalcitrant pesticides, RSC Adv. 7 (2017) 45885e45895.
[51] G.S. Theja, R.C. Lowrence, V. Ravi, S. Nagarajan, S.P. Anthony, Synthesis of
Cu2O micro/nanocrystals with tunable morphologies using coordinating li-
gands as structure controlling agents and antimicrobial studies, Crys-
tEngComm 16 (2014) 9866e9872.
12 M.F. Zayed et al. / Journal of Alloys and Compounds 835 (2020) 155306
[52] A. Tahira, A. Nafady, M. Arain, Sirajuddin, S.T.H. Sherazi, T. Shaikh, Q. Baloach,
M. Willander, Z.H. Ibupoto, The synthesis of new nanostructures of CuO using
ascorbic acid as growth directing agent and their sensitive electrochemical
detection of hydrazine, Sens. Lett. 14 (2016) 611e615.
[53] M.F. Zayed, W.H. Eisa, Phoenix dactylifera L. leaf extract phytosynthesized
gold nanoparticles; controlled synthesis and catalytic activity, Spectrochim.
Acta Mol. Biomol. Spectrosc. 121 (2014) 238e244.
[54] W.H. Eisa, M.F. Zayed, B. Anis, L.M. Abbas, S.S.M. Ali, A.M. Mostafa, Clean
production of powdery silver nanoparticles using Zingiber officinale: the
structural and catalytic properties, J. Clean. Prod. 241 (2019) 118398.
[55] M. Li, G. Chen, Revisiting catalytic model reaction p-nitrophenol/NaBH4 using
metallic nanoparticles coated on polymeric spheres, Nanoscale 5 (2013)
11919e11927.
[56] A. Mondal, A. Mondal, B. Adhikary, D.K. Mukherjee, Cobalt nanoparticles as
reusable catalysts for reduction of 4-nitrophenol under mild conditions, Bull.
Mater. Sci. 40 (2017) 321e328.
[57] S. Choi, Y. Jeong, J. Yu, Spontaneous hydrolysis of borohydride required before
its catalytic activation by metal nanoparticles, Catal. Commun. 84 (2016)
80e84.
[58] G. Manjari, S. Saran, T. Arun, A. Vijaya Bhaskara Rao, S.P. Devipriya, Catalytic
and recyclability properties of phytogenic copper oxide nanoparticles derived
from Aglaia elaeagnoidea flower extract, J. Saudi Chemical Soc. 21 (2017)
610e618.
[59] M. Nasrollahzadeh, M. Maham, S.M. Sajadi, Green synthesis of CuO nano-
particles by aqueous extract of Gundelia tournefortii and evaluation of their
catalytic activity for the synthesis of N-monosubstituted ureas and reduction
of 4-nitrophenol, J. Colloid Interface Sci. 455 (2015) 245e253.
[60] S. Konar, H. Kalita, N. Puvvada, S. Tantubay, M.K. Mahto, S. Biswas, A. Pathak,
Shape-dependent catalytic activity of CuO nanostructures, J. Catal. 336 (2016)
11e22.
[61] T. Aditya, J. Jana, N.K. Singh, A. Pal, T. Pal, Remarkable facet selective reduction
of 4-nitrophenol by morphologically tailored (111) faceted Cu2O nano-
catalyst, ACS Omega 2 (2017) 1968e1984.
[62] A.K. Sasmal, S. Dutta, T. Pal, A ternary Cu2O-Cu-CuO nanocomposite: a catalyst
with intriguing activity, Dalton Trans. 45 (2016) 3139e3150.
[63] H. Niu, S. Liu, Y. Cai, F. Wu, X. Zhao, MOF derived porous carbon supported Cu/
Cu 2 O composite as high performance non-noble catalyst, Microporous
Mesoporous Mater. 219 (2016) 48e53.
[64] K. Yang, Y. Yan, H. Wang, Z. Sun, W. Chen, H. Kang, Y. Han, W. Zahng, X. Sun,
Z. Li, Monodisperse Cu/Cu2O@C core-shell nanocomposite supported on rGO
layers as an efficient catalyst derived from a Cu-based MOF/GO structure,
Nanoscale 10 (2018) 17647e17655.
[65] W. Yao, F.-L. Li, H.-X. Li, J.-P. Lang, Fabrication of hollow Cu2O@CuO-supported
AuePd alloy nanoparticles with high catalytic activity through the galvanic
replacement reaction, J. Mater. Chem. 3 (2015) 4578e4585.
[66] N. Bouazizi, A. El achari, C. Campagne, J. Vieillard, A. Azzouz, Copper oxide
coated polyester fabrics with enhanced catalytic properties towards the
reduction of 4-nitrophenol, J. Mater. Sci. Mater. Electron. 29 (2018)
10802e10813.
[67] Y. Bai, Q. Wang, C. Du, T. Bu, Y. Liu, X. Sun, W. Luo, R. Li, Y. Zhao, X. Zheng,
L. Wang, Three-dimensional Cu/C porous composite: facile fabrication and
efficient catalytic reduction of 4-nitrophenol, J. Colloid Interface Sci. 553
(2019) 768e777.
[68] Y. Zhang, P. Zhu, L. Chen, G. Li, F. Zhou, D. Lu, R. Sun, F. Zhou, C.-p. Wong,
Hierarchical architectures of monodisperse porous Cu microspheres: syn-
thesis, growth mechanism, high-efficiency and recyclable catalytic perfor-
mance, J. Mater. Chem. 2 (2014) 11966.
[69] L. Zhu, X. Guo, Y. Liu, Z. Chen, W. Zhang, K. Yin, L. Li, Y. Zhang, Z. Wang, L. Sun,
Y. Zhao, High-performance Cu nanoparticles/three-dimensional graphene/Ni
foam hybrid for catalytic and sensing applications, Nanotechnology 29 (2018)
145703.
[70] X. Yang, H. Zhong, Y. Zhu, H. Jiang, J. Shen, J. Huang, C. Li, Highly efficient
reusable catalyst based on silicon nanowire arrays decorated with copper
nanoparticles, J. Mater. Chem. 2 (2014) 9040.
[71] P. Deka, R.C. Deka, P. Bharali, In situ generated copper nanoparticle catalyzed
reduction of 4-nitrophenol, New J. Chem. 38 (2014) 1789.
[72] M.F. Zayed, W.H. Eisa, B. Anis, Removal of methylene blue usingPhoenix
dactylifera/PVA composite; an eco-friendly adsorbent, Desalination Water
Treat. 57 (2015) 18861e18867.
[73] M. Ismail, S. Gul, M.I. Khan, M.A. Khan, A.M. Asiri, S.B. Khan, Medicago
polymorpha-mediated antibacterial silver nanoparticles in the reduction of
methyl orange, Green Process. Synth. 8 (2019) 118e127.
[74] B. Zhao, X. Zhang, C. Dou, R. Han, Adsorption property of methyl orange by
chitosan coated on quartz sand in batch mode, Desalination Water Treat. 55
(2014) 1598e1608.
[75] F.-N. Allouche, N. Yassaa, H. Lounici, Sorption of methyl orange from aqueous
solution on chitosan biomass, Procedia Earth Planet Sci. 15 (2015) 596e601.