Materials Today Communications 33 (2022) 104574

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Materials Today Communications

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Exploring the structural and electrochemical sensing of wide bandgap

calcium phosphate/CuxFe3-xO4 core-shell nanoceramics for H2O2 detection
Amir Elzwawy a, A.M. Mansour b, Hend S. Magar c, Ali B. Abou Hammad b, Rabeay Y.A. Hassan d,
Amany M. El Nahrawy b, *
a
Ceramics Department, National Research Centre (NRC), 33 El-Bohouth St., Dokki, Cairo 12622, Egypt
b
Solid State Physics Department, Physics Research Institute, National Research Centre (NRC), 33 El-Bohouth St., Dokki, Cairo 12622, Egypt
c
Applied Organic Chemistry Department, National Research Centre (NRC), 33 El-Bohouth St., Dokki, Cairo 12622, Egypt
d
Nanoscience Program, University of Science and Technology (UST), Zewail City of Science and Technology, Giza 12578, Egypt

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

Keywords: Calcium phosphate/ CuxFe3-xO4 core-shell nanoceramics have been synthesized using the organic sol-gel process
Magnetic nanosystems and calcined at 600 oC. The nanoceramics were explored by X-ray powder diffractometry (XRD), transmission
Copper ferrites electron microscopy (TEM)), Fourier transform infrared spectroscopy (FT-IR), UV–visible Diffuse Reflectance
Calcium phosphate
spectra (DRS), and electrochemical techniques including cyclic voltammetry (CV), and electrochemical imped­
Core-shell
Sol-gel
ance spectroscopy (EIS). The FTIR results confirmed the presence of calcium phosphate (CP) and CP coated with
Optical Cu-ferrite (0–30 mol% Cu:Fe3O4) core-shell nanoceramics. TEM analysis displayed nanospheres of calcium
Electrochemical sensing and biosensing phosphate shielded with a porous spheres-like morphology with internal nanoparticles of about 33 nm. The
reflectance spectra increase for all samples with increasing wavelength. Both direct and indirect gap transitions
were detected with lower values of the direct case than the indirect type. The dielectric constant, refractive
index, and optical electronegativity of all samples were calculated. When the ferricyanide was applied as the
standard redox probe for the electrochemical characterization, CV and EIS results revealed a remarkable
enhancement in the generated electrochemical signals. Moreover, modified screen-printed electrodes with the 20
Cu-CPF produced the highest redox current (0.198 mA) towards the direct oxidation of hydrogen peroxide. The
obtained interesting features nominate the newly developed core-shell calcium phosphate/CuxFe3-xO4 nano­
ceramics as promising candidates for talented magneto-optical and peroxide sensor applications.

1. Introduction
Ferrites are among the most exciting nanomagnetic materials. Fer­
rites are oxides of transition metal ions, thus, the magnetic properties of
these materials depend on the interaction between the metal ion and
oxygen situated in a different environment [1]. Inherently, ferrites are
classified according to the crystal structure of their corresponding
minerals namely, magnetoplumbite, garnet, and spinel. Spinel ferrites
are denoted as materials with a normal chemical formula MFe2O4 with
space group fd-3 m while M is a divalent metal ion like Co, Cu, Mg, Mn,
Ni, Zn, etc [2]. They are mixed metal oxides with iron oxide as the main
component. MFe2O4 crystallizes into a structure similar to the crystal
structure of the mineral, spinel (MgAl2O4). Hence they are called spinel
ferrites. Since the radius of oxygen ions is much higher than that of other
metal cations, the layer-by-layer arrangement of oxygen ions forms a
face-centered cubic lattice with two types of interstices known as the “A”
site and the “B” site [3]. Among the types of ferrites, spinel ferrites offer
versatile applications in diverse scientific and technological fields. Apart
from the favorable properties of spinel ferrites like significant electrical
characteristics, superparamagnetism, catalytic and optical properties,
CuFe2O4 possesses a few more fascinating merits namely phase transi­
tion, modified semiconducting specifications, thermal stability, and so
forth [4,5]. Copper ferrite usually exists in tetragonal and cubic phases.
The transition from cubic to tetragonal phase is due to the reduced
crystal symmetry associated with the presence of the Jahn-Teller
Cu2+(3d9) ion present in the crystal structure [6]. In equilibrium,
Cu2+ occupies the octahedral position leading to cooperative distortion
of tetragonal symmetry. The formation of either cubic or tetragonal
phases depends on the synthesis conditions [7]. The different applica­
tions of nano copper ferrites include the contrasting agent in magnetic

* Corresponding author.
E-mail addresses: am.elnahrawy@nrc.sci.eg, amany_physics_1980@yahoo.com (A.M. El Nahrawy).

https://doi.org/10.1016/j.mtcomm.2022.104574
Received 2 July 2022; Received in revised form 23 September 2022; Accepted 27 September 2022
Available online 29 September 2022
2352-4928/© 2022 Published by Elsevier Ltd.
A. Elzwawy et al.
resonance imaging [8], ferrofluids, catalytic uses [9], magnetic refrig­
eration [10], biomedical application [11,12], etc.
The core-shell nanostructures provide tunable properties which
illustrate improved optical and other characteristics compared to the
bare nanoparticles. The surface properties of a bare nanoparticle are
modified by coating a thin shell of a suitable material such as metal,
dielectric, or polymer on the particle surface. Therefore, a different class
of core-shell particles can be designed as per our requirement, applica­
tion, and necessity. A few examples of such nanostructures are metal
core@metal shell, metal core dielectric shell, dielectric core @ dielectric
shell, metal core@polymer shell, and metal core@ semiconductor shell,
etc [13]. Based on the composition and surface engineering, this class of
particles can be utilized for various biomedical purposes. These include
new diagnostic methods, contrast agents, a vehicle for targeted drug
delivery, thermal ablation therapy for cancer treatment, etc.
Hydroxyapatite is a naturally existing mineral formulated of calcium
phosphate with the chemical formula of Ca10(PO4)6(OH)2. It comprises
70% inorganic components and 30% organic components of bone
marrow and collagen with a 1.67 ratio for Ca/P [14]. Hydroxyapatite
(HA) exists as a mineral phase in shells as well as the teeth and bones of
mammals [15–17]. From one side, HA grasps a few desired merits, such
as raised osteoconductive characteristics, stability, and biocompati­
bility. In contrast, on the other side, it possesses a few unwanted spec­
ifications that hinder its wider applicability, such as reduced mechanical
strength [18]. The magnitudes of the compressive, tensile, and bending
strengths are ~ 1.5 × 108 Pa, 0.4–3 × 108 Pa, and 0.4–2.5 × 108 Pa
consecutively [19]. It is employed in different forms for various appli­
cations, mainly in the medical field as dental implants, a network for
drug delivery, and as a coating in metal prostheses [20]. The function­
alization of hydroxyapatite structure in sensing areas is reported. HA
nanorods for gas detection [21,22], humidity sensors [23], and elec­
trochemical detections [24]. Up to date, there are few reports about
adding HA particles into the magnetic systems and their effect on the
optical and electrochemical properties of these systems in the published
literature [25,26]. Various combinations of the core-shell structure for
electrochemical detection are introduced. The detection of hydrogen
peroxide based on ferrites was reported in the few preceding years using
various combinations and routes. The hydrothermal and sol-gel pro­
cedures with MFe2O4 (while M =Fe, Ni, Zn, Sn) was introduced [25,26].
MnFe2O4 decorated graphene nanosheets were reported either using a
one-pot solvothermal process or a solid-state reaction method for
enabling the electrochemical detection of hydrogen peroxide [27–29].
Despite these recent efforts, as far as the authors know, no reports
highlight the incorporation of HA as a core material with the Fe-doped
Cu composites. Based on the quantified implications of these initial
constituents, they are expected to be employed in electrochemical
sensing.
The tunability of calcium phosphate with magnetic nanoparticles for
a specific application is highly indebted to the physicochemical envi­
ronment during the synthesis. The preparation method and the calci­
nation of the prepared material affect its properties. The application of
nano-spinels in electrochemical, optoelectronic, and biomedical fields
requires superparamagnetic materials. All the aspects point out that the
study of synthesized complex nanoparticles is convenient for diverse
applications. Recently, the formation of core-shell structure (i.e., surface
modification), easiness to prepare nanoparticles, and chemical stability,
has been extended to the inorganic magnetic systems. In this regard,
little work is carried out to investigate the impact of Cu content on the
physical specifications of Ca-P2O5/Cu-Fe2O4 core-shell synthesized
nanoparticles. Studies in the core-shell field of adding HA particles into
the magnetic nanoparticles have mainly focused on the catalytic,
physical, and optical behavior of these complex nanocomposites.
Herein, we report the formation, characterization, and investigation
of the talented calcium phosphate coated with nano-ferrites nano­
ceramics calcined at a low temperature.
In the present work, we selected calcium phosphate nanospheres as
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Materials Today Communications 33 (2022) 104574
cores and CuxFe3-xO4 as shells to prepare calcium phosphate/ CuxFe3-
xO4core-shell nanoceramics using the combination of the co-
precipitation and sol-gel processes, and characterized their structure,
morphology, optical and electrochemical properties in detail. The pre­
pared nanoceramics were employed for the H2O2 detection via an
electrochemical approach. These nanoceramics’ interesting structural,
optical, and electrochemical properties are mainly controlled by cation
redistribution. This nanostructure might provide possibilities for sensing
and nanotechnology fields.
2. Experimental
2.1. Synthesis of hydroxyapatite nanoparticles (core)
Two precursors were employed as the Ca and P sources, calcium
nitrate for the former and diammonium hydrogen phosphate for the
latter. For the preparation of desired calcium phosphate with a 1.67 Ca/
P molar ratio, 0.298 M of Ca (NO3).4 H2O and 0.497 M of (NH4)2HPO4
were introduced. Separately, the mentioned molar ratios were dissolved
in 1 L of distilled water on a magnetic stirrer keeping the temperature at
60 oC for Ca and 80 ºC for the P for 5–15 min. The pH of the P solution is
adjusted at 10 by adding ammonium hydroxide droplets. Remarkably,
the calcium precursor solution dissolves much faster than the phos­
phorous precursor. Afterward, the P precursor is added to the Ca one
drop-wise under continuous stirring sustaining the pH at the 10 values
until complete mixing. The mixture temperature is adjusted at 100 ºC
with further stirring for 2 h. The delivered slurry was removed from the
stirrer for cooling down and aging overnight. Resulted precipitated HA
was obtained using filter paper and a Buchner funnel. Finally rinsed
repetitively with distilled water and then dried at 100 ºC for 24 h. The
reaction of the starting precursor to delivering the desired calcium
phosphate is noted as [30–32]:
10Ca(NO3)2.4H2O + 6(NH4)2HPO4 + 8NH4OH → Ca10(PO4)6(OH)2 +
20NH4NO3 + 20H2O (1)
Finally, the targeted hydroxyapatite is acquired and ready for the
subsequent stage.
2.2. Synthesis of calcium phosphate/ CuxFe3-xO4 nanoceramics
CuxFe3-xO4 (x = 0–30 mol% copper) was prepared using ethylene
glycol (CH2OHCH2OH) as an organic precursor and Fe, and Cu nitrates
as starting reagents. Firstly, ethylene glycol (as a chelating agent) was
placed in a beaker with Fe(NO3)20.9 H2O to 5 ml of distilled water under
constant stirring until forming a clear brown solution at a heating
temperature of 40 oC [33,34]. Then, different concentrations (0–30 mol
%) of Cu(NO3)20.3 H2O were added to Fe solution/30 ml ethylene gly­
col, and the blend was stirred for 1 h at 40 oC. The resulting copper
ferrite solutions were mixed well and stirred for another 30 min to form
a lower viscosity gel before loading the previously synthesized calcium
phosphate nanoparticles (Section 2.1). Secondly, the calcium phosphate
nanoparticles as core were introduced for Fe3O4 solution during the
stirring process at 40 oC. The heating temperature was raised to
approximately 100 oC and kept under stirring until a viscous brown and
dark green gel was formed. The calcium phosphate/ (0—30 mol%)
copper ferrite core-shell structure is formed by partially substituting iron
with copper during the sol-gel process with a continuous chemical
growth of copper ferrite on the calcium phosphate surface. In the sol-gel
process, the polycondensation eliminates OH and uses solvents as a re­
action medium.The wet sols obtained were allowed to gel at 40 oC for 7
h, where hydroxyl groups and the (Fe-O- and Fe-O-Cu) groups could
accelerate and catalyze the poly-condensation process. The gels (cal­
cium phosphate/ Fe3O4 and calcium phosphate/copper ferrites) were
calcined at 300 oC for 80 min to remove the -OH and organic molecules
at a heating rate of 15 oC/min. The resulting powders were calcined for
A. Elzwawy et al.
3 h at 600 oC to produce the copper ferrite spinel phase/calcium phos­
phate core-shell nanoceramics. The nanoceramics samples labeled with
calcium phosphate (CP), calcium phosphate Fe3O4 (0 Cu-CPF), calcium
phosphate Fe3O4/10 Cu (10 Cu-CPF), calcium phosphate Fe3O4/ (20,
30) Cu (20 Cu-CPF and 30 Cu-CPF).
2.3. Characterization techniques
X-ray diffraction was achieved with a Diano X-ray diffractometer,
using the CuKα-radiation and diffraction angles (2θ) range (10–70o).
The core-shell samples were pictured using transmission electron
microscopy (TEM-JEOL: CCD).
FTIR spectra of calcium phosphate and Fe3O4 doped with copper,
core-shell nanocomposites, were recorded with an FT-IR spectrometer
(Nicolet Impact:400 FTIR spectrophotometer) in the range of 400–4000
cm− 1.
2.4. Electrochemical measurements
Electrochemical measurements were performed using a Palmsens-4
electrochemical workstation. The commercial disposable screen-
printed carbon electrodes were purchased from Zensor Canadian com­
pany with the following specifications: Ag is the reference electrode, and
carbon is used as a working as well as a counter electrode. The area of
the working electrode is 3 mm.
Cyclic voltammetry (CV), and electrochemical impedance spectros­
copy (EIS) investigations were conducted in triplicates using the stan­
dard redox mediator of ferricyanide [Fe (CN)6]3 − /4 − (5 mM), while
0.1 M KCl solution was used as the supporting electrolyte. The CV pa­
rameters were recorded by sweeping the potential within − 0.4 to + 0.7
V, with a 50 mV/s scanning rate. The impedimetric evaluation was
executed within a frequency range from 10 kHz to 0.1 Hz at an open
circuit potential, under a 10 mV potential magnitude. For realizing the
structure of the surface, impedance information was fitted to an equiv­
alent circuit model. The electrochemical assessments were performed at
conventional temperature (25 ± 2 ◦ C).
Experimentally, a homogeneous aqueous suspension (5 mg) of each
of the chemically synthesized nanomaterials was prepared. 30 μL of
different suspension solutions were uniformly mounted on SPEs and
dried in the air. Scheme 1 represents the fabrication of modified/screen-
printed electrodes (SPEs). OCP, 10Cu-CPF, 20Cu-CPF, or 30Cu-CPF
materials were dropped onto the SPEs surface and left to dry in the
air, followed by gently washing with doubled distilled water to remove
excess material. The electrochemical activities of the nanomaterials-
based-SPEs are ready to be evaluated.
Scheme 1. Electrochemical setup and steps of electrode modification using the nanomaterials.
3
Materials Today Communications 33 (2022) 104574
2.4.1. H2O2 detection and chronoamperometric measurements
Electrochemical direct oxidation of H2O2 was examined using the
modified screen-printed electrodes with the newly developed nano­
materials. In this regard, a single concentration of hydrogen peroxide
was introduced into the electrochemical cell, and then the cyclic vol­
tammetric experiments were carried out in order to determine the vol­
tammetric character of the peroxide. Accordingly, chronoamperometric
readouts were recorded at a 1.2 V against Ag/AgCl. A convenient route
is introduced by adding a standard concentration of H2O2 within a 30 s
as a fixed time interval. Then, a standard calibration curve was con­
structed with a wide linear range of peroxide concentration
(2.5–200 μM). All hydrogen peroxide electrochemical measurements
were conducted in the PBS as the supporting electrolyte.
3. Results and discussion
3.1. XRD evaluation
The X-ray diffraction profile of the synthesized nanoceramics is
represented in Fig. 1(a &b). The plotted calcined powders’ patterns
reflect a crystalline multiphase structure of the initial constituents. The
calcium phosphate sample (core) is crystalline at 600 oC (Fig. 1a). The
crystallization of calcium phosphate shows Bragg peaks at diffraction
planes (200), (111), (210), (211), (112), (202), (130), (222), (213), and
(004) corresponding to the hexagonal calcium phosphate oxide phase
Ca10P6O25 (JCPDS No. 89–6495). Typically, this phase arises from the
higher crystallization in calcium phosphate systems [35–37].
Generally, three samples were prepared as a core-shell structure,
while the core is the calcium-phosphate nanoparticles and the shell is
the Cu co-doped iron oxide. Fig. 1b shows the XRD structure of the core-
shell composite samples. The XRD pattern confirms the presence of both
the calcium phosphate and the ferrite, the core, and the shell, respec­
tively. The peaks related to the calcium phosphate are represented in the
XRD pattern by (•). The XRD pattern of CPF shows the formation of iron
oxide Fe2O3 in the orthorhombic structure according to the JCPDS No.
89–7047, the peaks of the Fe2O3are represented in the XRD pattern by
(◆). The XRD pattern of 20Cu and 30 Cu shows the formation of spinel
ferrite by introducing Cu ions into the ferrite. The peaks of the spinel
copper ferrite (CuFe2O4) are indexed according to the JCPDS No.
72–1174 with a tetragonal structure and represented by (*) in the XRD
pattern.
3.2. TEM images
Calcium phosphate as core nanoparticles exhibited regular nano­
spheres particles in the range of 21 nm (Fig. 2a). After coating with
copper ferrites (10, 30 mol% Cu) over CaO: P2O5, accumulated spherical
A. Elzwawy et al.
Fig. 1. The XRD profile of; a) the core materials calcium phosphate with the
clear crystalline peaks, & b) the core-shell structure of calcium phosphate and
ferrite nanoceramics.
nanoparticles were observed holding 34 nm for the mean particle size,
which can be discovered in the corresponding TEM images (Fig. 2(b, c)).
Also, the distributions of particle size of calcium phosphate as a core and
coated with copper ferrites supported the noted average particle size
from TEM (Fig. 2d). The TEM image (Fig. 2(b, c)) unveiled the calcium
phosphate formation (core), and TEM proves the nanoparticles are
embedded inside the copper ferrites layers.
TEM images provided evidence for the successful sol-gel function­
alization of the copper ferrites nanoparticles by polymerization to pro­
duce copper ferrites/calcium phosphate core-shell.
3.3. FTIR analysis
FTIR analysis is a convenient technique to realize the nanomaterials’
chemical adsorption or functionalization within the complex. Herein the
FTIR determines the resultant functional groups for the synthesized
core-shell nanoceramics. Initially, the core material (i.e., the hydroxy­
apatite (HA)) is plotted (Fig. 3(a)) to reveal the successful formation of
the material using the co-precipitation process. The broad peak span­
ning from 3700 to 2900 cm-1 and peaking at 3433 cm-1 is indexed to the
OH- stretching mode with other smaller peaks at 632 cm-1 for OH-, while
at 1654, and 2929 cm-1 an adsorbed water peaks exist [38,39]. Typi­
cally, the hydroxyl band arises at a higher value of wavenumber
(~3500–3600 cm-1), this band tends to decline, which reflects that the
apatite possesses a higher content of CO2-3 per the unit cell [40]. Further,
the peaks of a phosphate group (PO3- 4 ) are of higher intensity and persist
at their relevant values as ν1 stretching vibrational mode (962 cm-1), ν2
vibrational mode (478 cm-1), ν3 vibrational mode (1032, and
1095 cm-1), and ν4 bending vibrational mode at (603, and 565 cm-1)
[41–43]. The apparent band residing at 874 cm− 1 is accredited to the
carbonate group (CO2- 3 ), which replaces the phosphate position in the
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Materials Today Communications 33 (2022) 104574
hydroxyapatite matrix [44,45]. Additionally, this carbonate might be
allocated to the residual from the co-precipitation synthesis approach.
Other peaks defining the CO2- -1
3 are located at 1423 and 1457 cm . Besides
-1
these, a small peak at 1542 cm could be noticed at higher magnifica­
tion. Referring to the listed figure, the characteristic bands of the hy­
droxyapatite are matched with the reported literature unveiling the
affirmation of the synthesis [38,46]. Moreover, peaks at around
550–600 cm-1 and 1000–1100 cm-1 shed light on the crystallinity of the
prepared apatite. High crystallinity for sharp and splitting peaks while
lower degree for wide unresolved peaks around the preceding
mentioned values [44,47]. Fig. 3(b) for the coated samples reveals the
peaks of the core-shell structure. Noticeably the characteristic peaks of
the phosphate vanish, affirming the successful formation of the targeted
HA/Fe core-shell structure. The gradual increase of the apparent peaks
of the composites around 1380 cm-1 might reflect the excess carbonate
residence as the heat treatment was moderately applied to the com­
posite. Noteworthy to mention that the continuous arrangement and
rearrangement of the composite promotes the alteration of the peaks
around 600 cm-1. The peak around 609 cm-1corresponds to Fe-O
bending vibration [48], and overlaps the adsorbed water peak. The
FTIR provides a perspective for the validity of the synthesis procedure to
acquire the desired core-shell matrices.
3.4. Optical properties
UV–VIS spectroscopy is a convenient device, that highlights the
bandgap type delivered by the absorption spectra. The electronic
structure of the material possesses a significant effect on the materials’
optical absorption in the visible as well as the ultra-violet region. It
comprises the received radiation interaction with the electronic states of
the targeted material [35,49,50]. The nature of the semiconducting
nanoceramics and their employment in optoelectronic areas might be
inferred by bandgap exploration. The transfer of electrons from the
lower energy (valence band) to the higher energy (conduction band) is
initiated by the incident electromagnetic rays that interact with the
valence band electrons, subsequently creating the bandgap region [36,
51,52]. The strength of the bonding between the electrons controls the
absorption value. Inherently, the absorption spectrum is separated into
three distinct regions, identified as the interband absorption region,
residual absorption, and Urbach tails [53,54].
The reflectance spectra for CP, CPF, and Cu-CPF nanoceramics are
displayed in Fig. 4a. Upon increasing the wavelength, the reflectance
increases for all samples. The reflectance is decreased by the addition of
Fe3O4 and also by Cu addition. The absorptances of the prepared core-
shell nanoceramics are represented in Fig. 4b. The absorbance in­
creases with the addition of CuxFe3-xO4. Two absorption peaks exist for
all samples. The first peak is located at about 255 nm for all samples
(inset (i), Fig. 4b); this absorption peak is related to CaO absorption
[55]. The second peak is located at about 306, 374, 395, and 414 nm
corresponding to CP, CPF, 20 Cu/CPF, and 30 Cu/CPF samples,
respectively (as seen in inset (ii), Fig. 4b). This peak is related to the
excitation and transition of the charge carriers between valance and
conduction bands [35,36,54,56]. The addition of Fe2O3 leads to the
shifting of the 2nd peak to 274 nm, and then by CuxFe3-xO4 addition, the
peak continues shifting to 414 nm as represented in inset ii in Fig. 4b.
The coefficient of absorption is expressed in terms of photon energy
by the familiar Mott and Davis equation as [12,57,58]:
F(R)hν = Con. (hν − Eopt )n (2)
herein, hν is the photon energy and Eopt is the optical bandgap. The
direct and indirect Eopt amounts are specified from (F(R) hν)2 and (F(R)
hν)1/2 curves, respectively, against hν (the photon energy). The
extrapolating of the plots linear section, where (F(R)hν)2 = 0 and (F(R)
hν)1/2 = 0) as drawn in Fig. 5a and b, correspondingly. The extrapolated
magnitudes of direct and indirect optical bandgaps are represented in
A. Elzwawy et al.
Fig. 2. TEM images of (a) calcium phosphate core coated with (b) 10 Cu and (c) 30 Cu ferrites.
Fig. 5c. The alteration in optical bandgap is accredited to the variation in
the local configuration of the composite structure due to several cations.
Remarkably, both the direct and indirect bandgap decreased dramati­
cally by Fe2O3 addition and nearly did not change by Cu addition. Be­
sides, with the growing content of Fe2O3, the value of Eopt declines
progressively from 3 or 3.39 eV to 1.70 or 2.13 eV, for direct and indi­
rect transition, respectively, as shown in Fig. 5c. The change of the
conduction and valence bands reduces the energy of the optical
bandgap. This might be referred to as the nanocomposite network’s
gradual increase in non-bridging oxygen (NBO) content [12,59].
For all the samples, indirect bandgaps are larger than direct bandg­
aps making the occurrence of the direct transition more probable than
the indirect transition.
The refractive index of a substance is believed to reduce when the
energy gap widens. Consequently, both of these frequent variables are
assumed to be related somehow. Various attempts were made to find an
adequate (empirical and semiempirical) link. Ravindra relation, Moss
relation, Herve-Vandamme relation, Kumar and Singh relation, Reddy
relation, and Anani relation are some of these efforts [60,61]. The mean
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Materials Today Communications 33 (2022) 104574
value of refractive indices calculated by all attempts in both cases (direct
and indirect transitions) are represented in Fig. 6a. The figure shows an
increase in refractive index in both cases (direct and indirect transition)
by the addition of Fe3O4 as a result of bandgap narrowing. Also, a small
rise in Cu addition.
The dielectric constant (ε) of the material is empirically considered
by squaring the refractive index (ε∞ = n2 ) [60]. As shown in Fig. 6 also,
the dielectric constant of the prepared sample shows the same behavior
as the refractive indices due to bandgap narrowing.
Duffy and Reddy [62,63] suggested two different empirical equa­
tions for the relationship between a refractive index and the optical
electronegativity of solids (Δχ *) as follows:
Δχ ∗ = 0.2688 Eg (Duffy)
Δχ ∗ = 9.8 e− n (Reddy)
The mean value of the two formulas (Duffy and Reddy) values were
calculated for the direct and indirect transition cases and were repre­
sented in Fig. 6b. The optical electronegativity of the prepared
A. Elzwawy et al. Materials Today Communications 33 (2022) 104574

Fig. 3. The resulting FTIR for the synthesized nanoceramics. (a) Hydroxyapa­
tite, and (b) core-shell nanoceramics.

nanocomposites lies in the range of (0.93–0.53) and (1.03–0.66) for

direct and indirect transition cases, respectively.
It was indicated by Pauling [64] that the value of optical electro­ Fig. 4. (a) Reflectance spectra and (b) the absorptances of calcium phosphate
negativity (Δχ*) tells the bonding properties of the material, where it (core) and samples coated with (10, 30) Cu ferrites.
will possess an ionic behavior if Δχ* is high and it will possess covalent
behavior if Δχ* is low. So, as shown in Fig. 6b and following the Pauling respectively. For more electrochemical information, several electro­
suggestion [64], the nanocomposite samples under consideration tend chemical parameters for the bare and modified SPEs are tabulated in
to covalently by Fe3O4 addition and Cu addition. Table 1.
Worth mentioning here that the decrease in the charge transfer re­
sistances indicates the redox reaction taking place at the electrode sur­
3.5. Electrochemical properties
faces is strongly enhanced and was supported by the catalytic actions of
the nanomaterials. Thus, the lower the Rct value the higher the elec­
CV and EIS methods afford admirable insights into the redox speci­
trocatalytic function, hence, 20Cu-CPF modified electrode is the highest
fications of the established film onto the electrode’s surface. Therefore,
electrocatalytic among the tested nanomaterials. On the other hand, the
electrochemical characterization of the bare (unmodified) and
increase in the voltammetric signals is referring to the higher conduc­
CPF,10Cu-CPF, 20 Cu-CPF or 30Cu-CPF modified screen printed elec­
tivity alongside the larger surface area of the modified electrode which is
trodes (SPE) was accomplished using CV and EIS tests in 5.0 mM of Fe
attributed to the physicochemical properties of the nanomaterials. In
(CN)3-/4- and 0.1 M of KCl solution. As a result, (shown in Fig. 7A),
terms of the capacitive current generation, electrochemical measure­
oxidation peaks of all modified electrode surfaces including CPF/SPE
ments were performed in a mediator-free condition, i.e. no redox probe
(0.203 mA), 10Cu-CPF (0.184 mA), 20Cu-CPF (0.198 mA), and 30Cu-
was used. To that end, the highest capacitive current and lowest
CPF (0.168 mA) were higher than that obtained by the bare electrode
capacitive impedance were achieved by the modification of the elec­
(0.133 mA). Accordingly, a high Faradaic current was conceived by
trodes with the 2 F-based nanocomposite, as shown in Fig. 8, and
CPF,10Cu-CPF, or 30Cu-CPF nanoceramics-based electrodes. The 20Cu-
Table 2.
CPF nanoceramic presented the highest redox current.
As a confirmation of the CV results, EIS experiments were conducted
in parallel with the CV. Fig. 7B revealed that the charge transfer re­ 3.6. The application of 20Cu-CPF-based nanoceramic for H2O2 detection
sistances (Rct) of all modified electrodes with the nanomaterials were
lower than that obtained by the bare (unmodified) -electrode (873.8 Ω). In this section, we explored the possibilities of the H2O2 detection
Whereas the calculated Rct values were 186.1 Ω, 111.9 Ω, 99.4 Ω, and using modified electrodes with the newly developed nanomaterials,
123.5 Ω for the CPF,10Cu-CPF, 20Cu-CPF or 30Cu-CPF modified SPE, while the possibility of direct oxidation followed by the direct electron

6
A. Elzwawy et al. Materials Today Communications 33 (2022) 104574

Fig. 5. (a) (F(R) hν)1/2 versus hv, (b) (F(R) hν)2 versus hv, and (c) the change of bandgap with Cu content.

Fig. 6. The change of (a) the refractive index, dielectric constant, and (b) optical electronegativity with sample content.

transfer was examined. In this regard, a single concentration of
hydrogen peroxide was inserted into the electrochemical cell, then the
direct oxidation was monitored by the CV. As illustrated in Fig. 9, the
modified electrodes with the 20Cu-CPF-based materials provided the
highest Faradaic current and lowest Faradaic impedance as compared
with the responses of other modified electrodes (Table 3). Therefore, the
use of 20Cu-CPF-based material is providing a strong electrocatalytic
activity to detect peroxide directly without the need for exogenous
electron mediators.
3.7. Chronoamperometric estimation of peroxide
CV measurements confirmed the occurring direct oxidation of
peroxide by employing the 20Cu-CPF/SPE. Concurrently, the intended

7
A. Elzwawy et al. Materials Today Communications 33 (2022) 104574

Fig. 7. Electrochemical nanomaterial characterizations using the cyclic voltammetry (A), and electrochemical impedance spectroscopy (B) for the Bare (unmodified
electrode), and modified electrodes with CPF,10Cu-CPF, 20Cu-CPF, or 30Cu-CPF nanoceramics. Experiments were conducted in standard redox probes ([Fe (CN) 3-/ 6]
4-
/ and the supporting electrolyte was KCl solution; Ag/AgCl is used as a reference electrode.

Table 1
Electrochemical information resulted from the electrochemical characterizations of all electrodes including the Bare (unmodified electrode), and modified electrodes
with the CPF,10Cu-CPF, 20Cu-CPF, or 30Cu-CPF. Eoxd., Ered., ΔE, Ia, Ic, and EIS fitting values in a solution of 5 mM [Fe (CN)6]3-/4- and 0.1 M KCl. These data are
extracted from Fig. 7.
Electrode type Ia (mA) Ic (mA) E oxd. .. (V) Ered. (V) ΔE (V) Rs (Ω) Rct (Ω) C (µF) Rct (Ω) CPE W (Ω)
(µF) n

Bare /SPE 0.133 -0.147 0.390 0.040 0.215 108.2 873.88 7.387 0.955 373.7
CPF/SPE 0.203 -0.197 0.290 0.160 0.225 39.04 22.29 0.112 186.1 572 0.405 312
10Cu-CPF/SPE 0.184 -0.184 0.300 0.130 0.215 39.55 34.10 0.109 111.9 498 0.418 354.9
20Cu-CPF /SPE 0.198 -0.196 0.290 0.160 0.225 40.45 28.2 0.125 99.4 521 0.504 295.1
30Cu-CPF /SPE 0.168 -0.178 0.300 0.160 0.23 40.81 45.25 0. 980 123.5 421 0.512 398.2

Ia: anodic current, Ic: Cathodic current, Eoxd.: Oxidation Potential, Ered.: reduction potential, ΔE: half of potential, Rs: resistance of the solution Rct: charge transfer
resistance CPE: constant Phase element, W: Warburg resistance.

Fig. 8. Voltammetric (A), and impedimetric measurements (B) for the modified electrodes with the nanocomposites. Measurements were conducted in a redox
probe-free electrolyte (PBS/KCl (pH=7.4)). Ag/AgCl is used as a reference electrode.

chronoamperometric measurements were conducted at a 1.2 V against

Table 2
Ag/AgCl. A convenient route is introduced by adding a certain amount
EIS fitting data for the modified SPEs in a solution of PBS/KCl (pH=7.4). These
of H2O2 within a 30 s time interval. Fig. 10 (a) represents the concen­
data are extracted from Fig. 8.
tration vs. current curve where the fast response is remarked, reflecting
Electrode type Rs (Ω) Rct (Ω) CPE the speedy transfer of electrons besides the electrocatalytic power of the
(µF) n
established 20Cu-CPF/SPE. Accordingly, Fig. 10 (b) demonstrates the
CPF/SPE 28.209 6934.2 130.7 0.785 merits of the proposed sensor. The corresponding calibration curve re­
10Cu-CPF/SPE 38.44 4624.1 183.4 0.8206
flects a wide span of linear response (2.5–200 μM). The sensitivity rea­
20Cu-CPF /SPE 29.26 2848.9 308.4 0.8128
30Cu-CPF /SPE 32.9 3511.1 210.3 0.8137 ches (0.88 µA⋅µM), while the limit of detection is 0.8 μM (S/N = 3). This
is a validation that the subjected material could be employed success­
fully for the direct detection of such a significant target in the biological

8
A. Elzwawy et al. Materials Today Communications 33 (2022) 104574

Fig. 9. Voltammetric (A), and impedimetric direct detection of hydrogen peroxides oxidation using the modified electrodes with the newly prepared nano­
composites. Measurements were conducted at a single concentration of hydrogen peroxide, while PBS was used as the supporting electrolyte. Ag/AgCl is used as a
reference electrode.

increase by the addition of CuxFe3-xO4 as a result of bandgap narrowing.

Table 3
This calcium phosphate/ CuxFe3-xO4 electrode has been used as a
Electrochemical parameters (CV and EIS fitting data) for CPF,10Cu-CPF, 20Cu-
sensing material for H2O2 detection. The electrochemical results
CPF, or 30Cu-CPF/SPEs in a solution of PBS_KCl (pH=7.4) containing
0.01 M H2O2.
confirmed that the new calcium phosphate/ CuxFe3-xO4nanoceramics
can be used effectively to directly detect such an important target in
Electrode type Ia (mA) E oxd. (V) Rs (Ω) Rct (Ω) CPE
..
biological analysis.
(µF) n

CPF/SPE 0.747 1.339 27.77 1460 312.7 0.703

10Cu-CPF/SPE 0.865 1.339 39.44 1454 389.1 0.730 CRediT authorship contribution statement
20Cu-CPF /SPE 0.495 1.159 32.03 1080 445.9 0.808
30Cu-CPF /SPE 0.981 1.359 34.50 1187 455.7 0.718 Amir Elzwawy: Conceptualization, Validation, Investigation,
Writing – original draft. A. M. Mansour: Conceptualization, Validation,
Investigation, Writing – original draft. Hend S. Magar: Formal analysis,
examination [65–68].
Validation, Writing – review & editing. Ali B. Abou Hammad:
Conceptualization, Validation, Investigation, Writing – review & edit­
4. Conclusion
ing. Rabeay Y.A. Hassan: Formal analysis, Validation, Writing – review
& editing. Amany M. El Nahrawy: Conceptualization, Validation,
Nanosized calcium phosphate has been uniformly cored into a cop­
Investigation, Writing – original draft.
per ferrite nanocomposite to fabricate core-shell calcium phosphate/
CuxFe3-xO4 nanoceramics. With the addition of CuxFe3-xO4 addition, the
reflectance spectra are decreased, and the absorbance increases. The
Declaration of Competing Interest
direct and the indirect bandgap decreased dramatically by CuxFe3-xO4
addition and then nearly did not change by Cu addition. The variation in
The authors declare the following financial interests/personal re­
the optical bandgap is ascribed to the discrepancy in the local configu­
lationships which may be considered as potential competing interests:
ration of the composite structure due to various cations. Refractive index
The authors declare that they have no conflict of interest. Also, there
and dielectric constant in both cases (direct and indirect transition)
isn’t any funding to support this work.

Fig. 10. (a) The chronoamperometric response of the 20Cu-CPF /SPE upon addition of H2O2 at 1.2 V. (b) The corresponding curve of calibration between the H2O2
concentration and the resultant current response. Ag/AgCl is used as a reference electrode.

9
A. Elzwawy et al.
Data availability
Data will be made available on request.
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