Phys. Scr. 98 (2023) 055922 https://doi.org/10.

1088/1402-4896/acc9ea

PAPER

Microstructures, optical and electrochemical properties of advanced

RECEIVED
25 December 2022
Fe0.8Se0.14Si0.06MoO4 nanocrystalline for energy storage
REVISED
26 March 2023
applications
ACCEPTED FOR PUBLICATION
3 April 2023
PUBLISHED
A M Mansour1 , A M Fathi2, Ali B Abou Hammad1,∗ and Amany M El Nahrawy1
11 April 2023 1
Solid State Physics Department, Physics Research Division, National Research Centre, 33 El Bohouth St., Dokki, Giza 12622, Egypt
2
Physical Chemistry Department, National Research Centre, 33 ElBohouth, Dokki,Giza, P.O.12622, Egypt
∗
Author to whom any correspondence should be addressed.
E-mail: abohmad2@yahoo.com

Keywords: optical, electrochemical, Fe0.8Se0.14Si0.06MoO4, electrochemical properties, pseudo-capacitive, catalytic applications

Abstract
Technological progress has raised expectations regarding the growth of energy storage structures.
Enhancing the energy density and surface area and producing a high specific capacitance super-
capacitor is urgently demanded. The microstructural and optical properties of Fe0.8Se0.14Si0.06MoO4
nanocrystallites produced by the advanced sol-gel technique are investigated. XRD and TEM show
that the nanocrystallites have a crystallite nanosize of 15.6 nm and a mean diameter of 14–23.6 nm for
the formed monoclinic structure. The diffuse reflectance spectra of the synthesized
Fe0.8Se0.14Si0.06MoO4 calcined at 650 °C for 2 h were measured in the range of 200 to 2500 nm. The
type and value of the energy band gap were obtained from the diffuse reflectance spectra. Enhancing
the energy density and surface area and producing a high specific capacitance of the supercapacitor is
urgently required to develop unique positive and negative electroactive nanostructures. The formation
of advanced Fe0.8Se0.14Si0.06MoO4 mesoporous structures with large surface areas and adjusted energy
band gap could expand more electroactive locations, which supported the contact of the electrode-
electrolyte and improved the ion and electron passage through the chemical reactions. The good
electrochemical performance of Fe0.8Se0.14Si0.06MoO4 was exhibited with a high specific capacitance
of 681.6 F g−1 at 1.0 A g−1. The specific capacitance decreased to 396.8 F g−1 after 1000 charge-
discharge cycles at 1.0 A g−1. Therefore, Fe0.8Se0.14Si0.06MoO4 was suggested as a promising positive
electrode material for energy storage applications.

1. Introduction

Semiconductors memory and capacitors devices, storage systems, and metallic nanoparticles are getting
substantial attention to overcome the limitations of conventional electronic devices. Semiconductors metallic
nanoparticles introduce compelling advantages such as wide bandgap, higher transport of electrons, and density
of states around their Fermi level, which increases their ability. Also, embedded dopants consider a significant
choice of various functions that offer better performance and flexibility for semiconductors engineering
systems.
The market demand for energy storage devices is on the rise due to the swift expansion of electric vehicles,
wearable electronics, and smartphones [1]. Electrochemical capacitors have high-power energy storage that can
fit the gap between using conventional batteries and capacitors [2]. They divided according to their mechanisms
in storing energy into two types: (1) electrical double layer capacitor (EDLC) in which non-faradic charge
separations occur at the interface between the solid electrode and the electrolyte; (2) pseudo-capacitor (PSC) in
which redox reactions occurred at/near the surface of the solid electrode [3]. Low energy density storage of
supercapacitors can hinder their use on a larger scale. Therefore, it is important to concern intensive approaches
in the development of new electrode materials for supercapacitors.

© 2023 IOP Publishing Ltd

Phys. Scr. 98 (2023) 055922 A M Mansour et al

The discovery of novel materials, synthesis processes, and the development of new theoretical and
experimental techniques for research provides opportunities for developing innovative nanodevices and
nanomaterials. To design nanodevices for the next generation, it is requisite to understand their intrinsic
features [4]. Several researchers are working worldwide towards developing nanomaterials that are intended to
perform more complex and efficient tasks. Thus, the development of entirely new technologies and
nanomaterials with desirable functional properties may lead to a generation of new products that will enhance
the quality of the living environment shortly [4].
Transition metal oxides (nanoceramic or semiconductors) are the main constituents of advanced
engineering nanomaterials. Further, they are insulators with high electrical resistivity, saturation magnetization,
permeability, low values of eddy current, dielectric losses, and moderate permittivity [5]. No material with such
wide-ranging properties exists, and hence ferrites find applications in almost all fields.
Binary metal oxides, such as NiCo2O4, CoMoO4, CuCo2O4, etc have been considered pseudocapacitor
materials [6–8]. Due to their exceptional electronic, optical, mechanical, and thermal characteristics, two-
dimensional (2D) materials have garnered significant research attention in diverse fields owing to their vast
potential applications. Several 2D materials, such as transition metal-carbon disulfide (TMDC), boron nitride,
layered double hydroxide, black phosphorus, graphene, and graphite carbonitride, have been effectively
fabricated [9, 10]. Among them, molybdenum ions are typical two-dimensional (2D) transition metal that has
an adjustable indirect band gap in their systems [11]. Recently, transition metal molybdates (MMoO4, M = Fe,
Cu, Ni, Mn, and Co) have concerned as energy storage material because of their semiconducting nature and
their pseudocapacitive behavior that results from the electrochemical activity of the metal ions in the stable
molybdate structure[12–16].
FeMoO4, which contains two redox ions (Fe &Mo), is considered the most significant transition metal
molybdates to be used as electrode materials for Li-ion batteries and negative electrodes for supercapacitors
[17–20]. The nanostructure for the FeMoO4 phase has a higher catalysis activity due to its wide band gap, higher
active sites, stronger light absorption, and environmental friendliness, which promote the separation of photo-
induced electrons and holes [21].
However, little research is concerned about its use as a positive electrode for supercapacitor applications.
Herein, to optimize the synthesis temperature, optical, and catalytic reactions and particularly promote the
efficiency of FeMoO4 systems, both SiO2 and SeO2 were added. We investigated the microstructures and optical
properties of Fe0.8Se0.14Si0.06MoO4 nanocrystallites capacitors synthesized using the advanced sol-gel method
and calcined at 650 °C. Herein, the motivation of support Fe0.8Se0.14Si0.06MoO4 with a lower concentration of
SiO2 to increase their ability toward a higher crystallinity at lower calcination temperature, suit functional and
trapped charges that offer an interesting property. The nanocrystalline is examined by X-ray diffraction and
Transmission Electron Microscopy (XRD/TEM). Their spectroscopic property was examined by FTIR and
diffused reflectance analysis and the electrochemical performance of the prepared material was explored.

2. Experimental work

2.1. Synthesis of Fe0.8Se0.14Si0.06MoO4 nanocrystallites

The sol-gel method was used to synthesize Fe0.8Se0.14Si0.06MoO4 nanocrystallites. In this method, molybdenum
(V) chloride (MoCl5, Sigma-Aldrich) and iron nitrate (Fe(NO3)3.9H2O) were dissolved in ethylene glycol, and
3 ml of HNO3 (68%). Tetraethoxysilane (Aldrich)/ ethanol was added to (0.2 M HNO3 (68%)/H2O) and left to
react for 40 min for the nitric acid hydrolysis of TEOS. Dissolving selenium oxide (SeO2; PubChem; 98%) in
(0.2 M HNO3 (68%)/H2O) according to the required stoichiometric proportions. Then mix the four
components’ solutions and vigorously stir for 1 h at 45 °C. Then the solution was aged in a dryer at 150 °C for
8 h. Finally, the sample was calcined at 650 °C.

2.2. Characterization
XRD record of the Fe0.8Se0.14Si0.06MoO4 nanocrystalline was collected at ambient conditions and filtered using
CuKα radiation; tube operated at 30 mA and 45 kV, with Ni filter to eliminate Kβ on Empyrean diffractometer
by Panalytical (Almelo; The Netherlands) in (2θ) 20–80°. Morphological properties were deliberate by using a
Transmission Electron Microscope (TEM). In addition, the sample was further examined by scanning electron
microscopy and energy Dispersive Spectroscope (SEM/EDS) using a TESCAN-VEGA3 electron microscope
operated at 20.0 kV. FTIR studies were carried out with JASCO 460 PLUS, FTIR spectrometer range from 400 to
2000 cm−1. Diffuse reflectance was measured in the wavelength range of 200–2500 nm through a double-beam
spectrophotometer (JASCO: V-570 model).

2
Phys. Scr. 98 (2023) 055922 A M Mansour et al

Figure 1. XRD pattern of Fe0.8Se0.14Si0.06MoO4nanocrystalline.

2.3. Electrochemical measurements

The working electrode for studying the electrochemical performance was prepared by mixing the active
material, carbon black, PVDF (polyvinylidene fluoride) in the weight ratio of 80:10:10 using DMF (N,
N-Dimethyl formamide) as a solvent to form a slurry and mixed by ultra-sonication for 30 min. Then 10 μl of
the suspension was dropped onto the surface of nickel foam with a micropipette, and then it dried at 60 °C for
40 min and then at room temperature overnight. Before that, the Ni foam was cleaned by degreasing in acetone,
etching in 1 M HCl for 15 min, and subsequently washing in water and ethanol for 5 min each. The
electrochemical investigations, such as cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD),
were carried out in a three-electrode conventional glass cell containing the electrolyte solution, which is 1.0 M
KOH aqueous solution. The measurement was done at 25 °C using Origalys OGS 200 potentiostat/galvanostat.
The potential of the working electrode was measured against an Ag/AgCl reference electrode (E° = 0.203 V
versus SHE), while pure Pt-wire was used as a counter electrode. Cyclic voltammetry curves were used to
characterize the electrochemical behavior of our electrodes at different scan rates from 0.01–0.2 V s−1, covering
a potential window (0–0.6 V) (versus Ag/AgCl). Galvanostatic charge/discharge measurements were run from
the potential window (−0.3 to 0.5 V) at current densities of 1, 3, 5, 8, and 10 A g−1.

3. Results and discussion

3.1. Crystalline phase (XRD)

The XRD pattern of Fe0.8Se0.14Si0.06MoO4 is displayed in Figure 1. Well-defined peaks were observed in the XRD
pattern. The peaks are high in intensity and sharp in broadening. Therefore, the sample is well crystallized. The
reflection peaks were indexed with (hkl) according to the JCPDS card no. 89–2367, which proves the monoclinic
structure (β-FeMoO4) of the sample. The XRD pattern doesn’t show any other peaks besides the peaks of the
monoclinic phase [11, 22, 23]. Therefore, the Fe0.8Se0.14Si0.06MoO4 sample has no other phases inside the
structure. This data confirms that the small amounts of selenium and silica are completely soluble inside the
monoclinic structure. Also, some peaks in the obtained XRD can be matched with the iron silicate (Fe2SiO4)
(Card No. 01-087-0320), suggesting that the incorporation of SiO2 in Fe0.8Se0.14Si0.06MoO4 nanostructure.
Additionally, the characteristic diffraction peaks at (021), (201), (220), and (−221) in Fe0.8Se0.14Si0.06MoO4 show
that SiO2 nanoparticles have effectively distributed within the inner structure.
The crystallite size of the sample is in the range of 15.6 nm and it was estimated from the Scherer formula
[24];
0.89l
G=
b cos q
where β and λ are the FWHM of the most intense peak and the XRD wavelength, respectively.
The lattice parameters, a, b, and c, were estimated from the following equation [24];
1 1 ⎡ h2 k 2 sin2 b l2 2hl cos q ⎤
= + + -
d 2 sin b ⎣
2 ⎢a 2 b 2 c 2 ac ⎥
⎦

3
Phys. Scr. 98 (2023) 055922 A M Mansour et al

Figure 2. HR-TEM results of Fe0.8Se0.14Si0.06MoO4 nanocrystallites electrode.

The obtained lattice parameters are a = 9.9658 Å, b = 9.53096 Å, & c = 6.6306 Å. The XRD data can be assigned
for determining the theoretical density (Dx) of the sample according to the following relations [25]:

8M
Dx =
Na V

where M, V, and Na are the molecular weight of the sample, the volume of the crystal and the Avogadro’s
number, respectively. The molecular weight of the sample (Fe0.8Se0.14Si0.06MoO4) is given by:

M = 0.8MFe + 0.14M Se + 0.06M Si + MMo + 4M O = 217.3531 g mol-1

The volume of the sample is given by V = a * b * c = 629.798 Å3, therefore the theoretical density will be
4.58 g cm−1.

3.2. TEM
The nanoparticles behavior of the prepared Fe0.8Se0.14Si0.06MoO4 nanocrystallites electrode was examined by
HR-TEM as shown in figure 2. Figure 2 presents the TEM images of Fe0.8Se0.14Si0.06MoO4 nanocrystallites,
revealing this advanced electrode nanomaterials’ successful adherence formation. It is clearly observed from
Figures 2(a), (b) that nanometer, two-dimensional (2D) Mo, and submicrometer particles accumulated for the
synthesized sample. Particle size changes could increase their electrochemical activity. The Fe0.8Se0.14Si0.06MoO4
nanocrystallites electrode has a diameter nanosize from 3 nm up to 43 nm as seemed from the particle size
distribution in Figure 2(d).
This nano-dimensional (2D) Mo and nanocrystallite Fe0.8Se0.14Si0.06MoO4 have a higher specific surface
area and yield profuse electroactive sites that can contribute to the electrochemical redox reactions. Also, the

4
Phys. Scr. 98 (2023) 055922 A M Mansour et al

Figure 3. SEM-EDS results of Fe0.8Se0.14Si0.06MoO4 nanocrystallites electrode.

changes in the particle size between the interconnected nanoparticles can assist as an ion holder, which endorses
the electrochemical reactions.

3.3. SEM and EDS analysis

The morphology of Fe0.8Se0.14Si0.06MoO4 nanocrystallites in the resultant powder was observed using an SEM.
The SEM images of the calcined Fe0.8Se0.14Si0.06MoO4 nanocrystallites at 650 °C at different ranges (5 μm and
2 μm) are shown in Figure 3. As perceived, the nanocrystalline sample is arranged as fine and coarse
nanoparticles. The sample possesses finer particles with a dense structure. The elemental composition of
Fe0.8Se0.14Si0.06MoO4 was inveterate by EDS (Figure 3(c)). Figure 3(c) approves that the atomic ratio of Fe and
MO is around 1:2.8 which supports the two main constituents with the designed structure.
From Figure 3(c) the EDS spectrum of the Fe0.8Se0.14Si0.06MoO4 nanocrystallites electrode in which the
presence of elements such as Mo, Fe, O, Si, and Se are confirmed [26].
It’s noted that their signals couldn’t have the same value as those that originated from the specimen required
stoichiometric during data acquisition [27]. Where EDX depends on the x-ray emission peaks, which are
emitted in all directions (isotropically), so they may not all escape the sample and can be generated by any atom
in the sample sufficiently excited by the incoming beam. EDX provides the spatial distribution of elements
through mapping for the spot where the beam interacted. So, maybe a big difference between the chemical
formula and the elemental components of the sample [27].

5
Phys. Scr. 98 (2023) 055922 A M Mansour et al

Figure 4. FTIR spectrum of Fe0.8Se0.14Si0.06MoO4 nanocrystallites electrode.

3.4. FTIR analysis

The FTIR spectrum analysis of the Fe0.8Se0.14Si0.06MoO4 nanocrystallites, presented in Figure 4, attends to agree
with the chemical composition of nanocrystallites. The FTIR spectrum performed the bending connection at
460–611 cm−1 of (Si–O–Si and O–Si–O) and symmetric stretching bonds of the Si–O–, respectively [28–30].
The obtained band at 611 cm−1 is attributed to the molybdate structure (Mo–O–Mo). The two characteristic
weak bands obtained for SiO-molybdate in the region of 830–968 cm−1 were owing to The Si–O–Mo, Si–O–Fe,
and Mo–O [24]. The absorption band at 1639 cm−1, corresponds to the characteristic stretching vibrations of
Fe–O– and Mo–O– bonds, respectively [11]. The absorption peak position of SiO2 of Fe0.8Se0.14Si0.06MoO4
nanocomposite is significantly consistent with the peaks of FeMoO4. So, the absorption bands in the spectral
part of (400–1100 cm−1) correspond to the bending and the stretching of MoO4 tetrahedral, Si–O–Fe, and Mo–
O–Si bonds [31]. The characteristic broad absorption band at 3299 cm−1 is attributed to the stretching mode of
adsorbed water on the sample surface.
The FTIR result displays that the Fe0.8Se0.14Si0.06MoO4 nanocrystalline has good chemical stability.

3.5. DRS spectral study

Figure 5 shows the diffuse reflectance spectra of synthesized Fe0.8Se0.14Si0.06MoO4 calcined at 650 °C for 2 h in
the range of 200 to 2500 nm. The figure demonstrates a sudden increase of reflectance at about 350 nm and then
shows a slight decrease with wavelength increase. The inset in Figure 5 represents the corresponding scattering
and absorbance. The scattering takes the same behavior as the reflectance, where it is responsible for the
behavior of reflectance. The absorbance shows an opposite behavior to the reflectance and the scattering.
According to the spectra, the predominant absorption band exists at the wavelength of 300 nm ascribed to
octahedral coordination of isolated molybdenum ions and/or molybdenum loading on the surface [32]. The
band at 1900 nm belongs to a d–d transition of Mo2+ ions in a distorted octahedral structure, however, it might
also be ascribed to Fe-Mo interaction. The bands that belong to iron oxides exist at 530, 590, 755, 800, and
870 nm [32].
The direct and indirect band gaps were calculated for the synthesized Fe0.8Se0.14Si0.06MoO4. The optical
band gap of the sample was evaluated using energy Tauc’s plots [28, 33] (Figure 6). The direct and indirect band
gaps for the synthesized Fe0.8Se0.14Si0.06MoO4 are found to be 2.51 eV and 3.06 eV respectively. Hence, the
synthesis of advanced Fe0.8Se0.14Si0.06MoO4 with a wide bandgap can direct the growth of the electroactive sites,
reduce the dead mass, and thus enhances the electron transportations. They are shown in Figure 6. The material
is suitable for application in electronic industries, computer chip substrates, solar cells, and smaller band gap
energy-boosted photocatalytic activity [34, 35].
There were empirical and semiempirical relations that were used for the refractive index calculations from
the energy gap of semiconductors. Some of them are the Moss relation, Ravindra relation, Herve-Vandamme
relation, Reddy relation, Kumar and Singh relation, and Anani relation [36, 37]. The mean value of all calculated
refractive indices is tabulated in Table 1 for both direct and indirect cases.

6
Phys. Scr. 98 (2023) 055922 A M Mansour et al

Figure 5. The diffuse reflectance spectra of synthesized Fe0.8Se0.14Si0.06MoO4 calcined at 650 °C for 2 h in the range of 200 to 2500 nm,
and the inset represents the corresponding scattering and absorbance.

Figure 6. Tauc’s plots of synthesized MoFe doped with Se/Si calcined at 650 °C for 2 h in the range of 200 to 2500 nm for direct and
indirect cases.

Table 1. Energy gap, refractive index, dielectric constant, and optical

electronegativity of synthesized Fe0.8Se0.14Si0.06MoO4 calcined at 650 °C for 2 h for
direct and indirect cases.

Eg(eV) n epsilon Δχ* Duffy Δχ* Reddy

Direct 2.51 2.6 6.78 0.674688 0.916559977

Indirect 3.06 2.42 5.92 0.822528 1.068770511

7
Phys. Scr. 98 (2023) 055922 A M Mansour et al

Figure 7. (a) Cyclic voltammetry for Fe0.8Se0.14Si0.06MoO4 in 1.0 M KOH aqueous solution at different scan rates (0.01–0.2 V s−1), (b)
the relation between logυ and log current of the peak, and (c) the relation between the scan rate and the specific capacitance.

The material dielectric constant is calculated also from the obtained refractive index[36] and tabulated in
Table 1 for both direct and indirect cases:
Duffy [38] and Reddy [39] demonstrated the optical electronegativity (Δχ*) from the energy gap and
refractive index, respectively. The optical electronegativity values were calculated by both methods and
tabulated in Table 1 for both direct and indirect cases.

3.6. The electrochemical behavior of Fe0.8Se0.14Si0.06MoO4

The electrochemical behavior of the Fe0.8Se0.14Si0.06MoO4 sample was determined by cyclic voltammetry (CV)
in 1.0 M KOH aqueous solution using Ag/AgCl as a reference electrode. Figure 7(a) shows the CV curves of the
Fe0.8Se0.14Si0.06MoO4 sample over the potential window (0–0.6 V) at different scan rates (0.01–0.2 V s−1). The
CV curves show one oxidation peak at 0.42–0.55 V, and the corresponding reduction peak at 0.06–0.20 V which
are attributed to the intercalation and deintercalation of the OH ions into the electrode surface [40, 41]. The
presence of a redox peak in the voltammogram of Fe0.8Se0.14Si0.06MoO4 demonstrates the pseudo-capacitive
behavior of the material. It is noted that the oxidation peak is shifted to a more positive potential and the
reduction peak is shifted to more negative potential values with increasing the scan rate which indicates low
resistance of the material that accelerates ion diffusion[42]. Furthermore, the current of the oxidation and
reduction peaks (ip) increased with increasing the scan rate (u ), and consequently, the CV area enlarged
indicating improved electron transfer through the material.
To investigate the mechanism of the ion transfer, the relation between log ip and log u for both the anodic
and cathodic peak was plotted according to the following relation:

log i p = log a + b log u

The relation was represented by a straight line with slope = b (figure 7(b)), when the value of b close to or equal
0.5, the reaction of the electrode was suggested to be diffusion controlled and like battery type-one, and when it
equal to or close to unity the mechanism was controlled by surface process and the material showed capacitive

8
Phys. Scr. 98 (2023) 055922 A M Mansour et al

Figure 8. (a) Galvanostatic charge–discharge curves for Fe0.8Se0.14Si0.06MoO4 in 1.0 M KOH at different applied current densities (b)
the relation between the applied current density and the specific capacitance, and (c) the relation between the number of cycles and the
specific capacitance at 1 A g−1.

type nature, for Fe0.8Se0.14Si0.06MoO4 sample the value of b is close to 0.5 indicating diffusion controlled
mechanism and battery type-one nature of the material [43, 44].
From the CV curve, the specific capacitance (Cs) of the material can be calculated by the following relation,

Cs =
ò IdV
2muDV
Where ∫IdVis the area under the CV curve, ΔV is the potential window (0–0.6 V), m is the active mass of the
material in gm, and u is the scan rate (V/s).
Figure 7(c) shows the change of the specific capacitance with increasing the scan rate, where there is a
decrease in the specific capacitance value with increasing the scan rate. At a low scan rate, the active sites decrease
where the ions have a long time to reach and interact with the electrode surface, whereas, at high scan rates, the
time is not enough for the ions to reach and interact with the electrode subsequently the specific capacitance is
decreased [45, 46].
Figure 8(a) shows the galvanostatic charge-discharge curves for Fe0.8Se0.14Si0.06MoO4 in the potential range
of −0.3 to 0.5 V (versus Ag/AgCl) in 1.0 M KOH at different current densities (1–10 A g−1). Nonlinear behavior
for the charge-discharge of Fe0.8Se0.14Si0.06MoO4 was observed indicating pseudocapacitive behavior (faradic) as
shown previously from CV measurement. The specific capacitances at different current densities for
Fe0.8Se0.14Si0.06MoO4 were calculated via the following equation [47, 48]:

Cs =
ò
I V (t ) dt
m (DV )2
The relation between the calculated specific capacitance and the applied current densities was conducted in
Figure 8(b), where it decreases with increasing the current because the time for high current density is not
enough for the electrolyte to reach the active sites of the surface [46]. The highest specific capacitance value

9
Phys. Scr. 98 (2023) 055922 A M Mansour et al

Table 2. Comparison between the reported specific capacitance of FeMoO4 in literature and the current work.

Material Cs, F g−1 Condition References

Fe0.8Se0.14Si0.06MoO4 681.60 1.0 A g−1, 1.0 M KOH Our work

FeMoO4/graphene 135.00 1.0 A g−1, 1.0 Na2SO3 [20]
FeMoO4 110.00 1.0 A g−1, 6.0 M KOH [26]
Calcined FeMoO4 493.00 1.0 A g−1, 6.0 M KOH [41]
FeMoO4 nanosheet arrays 477.47 2.0 A g−1, 3.0 M KOH [48]
FeMoO4 nanofibers/rGO 135.50 2.0 A g−1, 1.0 Na2SO3 [55]

approaching 681.6 F g−1 was observed at a current density of 1.0 A g−1. The specific capacitance of the studied
material derived from CV (100 F g−1 at scan rate 0.01 V s−1) is much lower than that of GCD results; it is nearly
equal to the specific capacitance measured at an applied current of 8 mA g−1. This may be explained by the
difference in the applied potential and the scales during the two techniques, as the CV method depends on the
scan rate which can be used to determine the time of the experiment, however, the GCD method depends on the
applied current and the time is resultant from the experiment where the longer time of the discharge indicates a
higher stored charge [49].
The value of the specific capacitance of Fe0.8Se0.14Si0.06MoO4 derived from GCD is superior when compared
with the previous works that used FeMoO4 material as an electrode (table 2). FeMoO4 is highly stable and has fast
redox processes, as well as its low cost, therefore it represents the most encouraging material used for
supercapacitors application. However, it has low specific capacitance due to its poor electrical conductivity;
therefore, modifying its electrical conductivity by doping it with Se and Si increased their specific capacitance as
seen in Table 2. Also, this decrease in the specific capacitance of Fe0.8Se0.14Si0.06MoO4 may be due to the metal–
O–Si bonds influencing the functionality of the Fe0.8Se0.14Si0.06MoO4 electrode and the presence of asymmetric
cell configuration [50, 51].
This behavior indicates that the doping of Se and Si in FeMoO4 plays a role in increasing the specific
capacitance of FeMoO4 nanostructured. It’s known that SiO2 can increase the specific capacitance of the
electrode materials for storage systems and supercapacitors. The presence of Se and Si made a nonidentical bond
between Fe and O resulting in the presence of an inductive effect that redistributes the electron around the metal
center and facilitates the charge transfer [52]. In addition, the less electronegativity of Se than oxygen results in
increasing the covalency in the bond between metal and oxygen which faster the charge transfer [53].
Furthermore, the high ionic diffusion of Se and the large anionic polarizability of metal selenides leads to
excellent electrochemical properties.
To reveal the stability of Fe0.8Se0.14Si0.06MoO4, long-term cycling of charge-discharge at 1 A g−1 for 1000
cycles was performed, and the relation between the specific capacitance and the number of cycles was plotted in
Figure 8(c). It was noted that the specific capacitance decreases as the number of cycles increases and it retains
about 73% due to the degradation of the material from the surface to the electrolyte with long-term cycling [54].
Accordingly, increasing the electron conductivity and high ionic in the Fe0.8Se0.14Si0.06MoO4
nanocrystalline may be achieved by increasing the Se ratio, which will lead to improved energy storage
performance. The presence of nanospheres and two dimensions-shaped Fe0.8Se0.14Si0.06MoO4 nanocrystalline
exhibited higher expressively specific capacitance value, which attributed to their mesoporous structure with the
larger surface area and synergistic outcome between the internal compositions of Fe0.8Se0.14Si0.06MoO4
nanocrystalline. The obtained results encourage to modification of this electrode with various dopants that
support their higher ability in storage energy systems and supercapacitor applications.

4. Conclusion

The nanocrystalline Fe0.8Se0.14Si0.06MoO4 electrode was obtained using a sol-gel process at 600 °C. Various
physicochemical techniques characterized the electrode nanocrystallites’ microstructural and energy bandgap
behaviors. The Fe0.8Se0.14Si0.06MoO4 nanocrystallites exhibited higher connected mesoporous structure
applicably for advanced catalytic applications.
The material exhibits both direct and indirect transition with values of transition gap of 2.51 and 3.06 eV,
respectively. The corresponding refractive indices were 2.6 and 2.42 for direct and indirect cases, respectively.
The cyclic voltammetry of Fe0.8Se0.14Si0.06MoO4 shows one redox couple that demonstrates the pseudo-
capacitive behavior of the material. The reaction through Fe0.8Se0.14Si0.06MoO4 was diffusion controlled, and
the material exhibited battery type-one in nature. The value of the specific capacitance of Fe0.8Se0.14Si0.06MoO4

10
Phys. Scr. 98 (2023) 055922 A M Mansour et al

is 681.6 F g−1 at 1.0 A g−1 and the initial specific capacitance is retained about 73% after 1000 cycles of charge-
discharge.

Data availability statement

The data cannot be made publicly available upon publication due to legal restrictions preventing unrestricted
public distribution. The data that support the findings of this study are available upon reasonable request from
the authors.

Declaration of competing interest

The authors declare no competing financial interest.

Consent to participate

Authors confirm their participation.

Consent for publication

The authors confirm their acceptance for Publication.

Conflict of interest

The authors announce that they have no conflict of interest.

ORCID iDs

A M Mansour https://orcid.org/0000-0001-5886-0650
Ali B Abou Hammad https://orcid.org/0000-0003-4467-7059
Amany M El Nahrawy https://orcid.org/0000-0002-3501-2541

References
[1] Sun Y, Shi X L, Yang Y L, Suo G, Zhang L, Lu S and Chen Z G 2022 Biomass-derived carbon for high-performance batteries: from
structure to properties Adv. Funct. Mater. 32 2201584
[2] Mukkabla R, Meduri P, Deepa M and Ghosal P 2016 Durable Li-S batteries with nano-sulfur/graphite nanoplatelets composites Chem.
Eng. J. 303 369–83
[3] Liang P, Wang F and Hu Z A 2018 Controlled synthesis of ordered sandwich CuCo2O4/reduced graphene oxide composites via layer-
by-layer heteroassembly for high-performance supercapacitors Chem. Eng. J. 350 627–36
[4] El Nahrawy A M, Hemdan B A, Mansour A M, Elzwawy A and Abou Hammad A B 2021 Integrated use of nickel cobalt aluminoferrite/
Ni2 + nano-crystallites supported with SiO2 for optomagnetic and biomedical applications Mater. Sci. Eng. B 274 115491
[5] Dionne G F 1975 A review of ferrites for microwave applications Proc. IEEE 63 777–89
[6] Veerasubramani G K, Krishnamoorthy K and Kim S J 2016 Improved electrochemical performances of binder-free CoMoO4
nanoplate arrays@Ni foam electrode using redox additive electrolyte J. Power Sources 306 378–86
[7] He X, Liu Q, Liu J, Li R, Zhang H, Chen R and Wang J 2017 Hierarchical NiCo2O4@NiCoAl-layered double hydroxide core/shell
nanoforest arrays as advanced electrodes for high-performance asymmetric supercapacitors J. Alloys Compd. 724 130–8
[8] Wen S, Liu Y, Bai H, Shao R, Xu W and Shi W 2018 Full synergistic effect of hydrothermal NiCo2O4 nanosheets/CuCo2O4 nanocones
supported on Ni foam for high-performance asymmetric supercapacitors J. Solid State Chem. 262 327–34
[9] Li M, Hong M, Dargusch M, Zou J and Chen Z G 2021 High-efficiency thermocells driven by thermo-electrochemical processes Trends
Chem. 3 561–74
[10] Meng W, Liu X, Song H, Xie Y, Shi X, Dargusch M, Chen Z G, Tang Z and Lu S 2021 Advances and challenges in 2D MXenes: From
structures to energy storage and conversions Nano Today 40 101273
[11] Guo X, Jia J, Gao P, Zhang T, Zha F, Tang X, Tian H and Zuo Z 2022 Flower-like FeMoO4@1T-MoS2 micro-sphere for effectively
cleaning binary dyes via photo-Fenton oxidation J. Colloid Interface Sci. 622 284–97
[12] Mai L Q, Yang F, Zhao Y L, Xu X, Xu L and Luo Y Z 2011 Hierarchical MnMoO4/CoMoO4 heterostructured nanowires with enhanced
supercapacitor performance Nat. Commun. 2011 21 2 1–5
[13] Xu Z, Li Z, Tan X, Holt C M B, Zhang L, Amirkhiz B S and Mitlin D 2012 Supercapacitive carbon nanotube-cobalt molybdate
nanocomposites prepared via solvent-free microwave synthesis RSC Adv. 2 2753–5
[14] Baskar S, Meyrick D, Ramakrishnan K S and Minakshi M 2014 Facile and large scale combustion synthesis of α-CoMoO4: Mimics the
redox behavior of a battery in aqueous hybrid device Chem. Eng. J. 253 502–7
[15] Senthilkumar B, Vijaya Sankar K, Kalai Selvan R, Danielle M and Manickam M 2013 Nano α-NiMoO 4 as a new electrode for
electrochemical supercapacitors RSC Adv. 3 352–7

11
Phys. Scr. 98 (2023) 055922 A M Mansour et al

[16] Purushothaman K K, Cuba M and Muralidharan G 2012 Supercapacitor behavior of α-MnMoO4 nanorods on different electrolytes
Mater. Res. Bull. 47 3348–51
[17] Zhang Z, Li W, Ng T W, Kang W, Lee C S and Zhang W 2015 Iron(II) molybdate (FeMoO4) nanorods as a high-performance anode for
lithium ion batteries: Structural and chemical evolution upon cycling J. Mater. Chem. A 3 20527–34
[18] Ju Z, Zhang E, Zhao Y, Xing Z, Zhuang Q, Qiang Y and Qian Y 2015 One-pot hydrothermal synthesis of FeMoO 4 nanocubes as an
anode material for lithium-ion batteries with excellent electrochemical performance Small 11 4753–61
[19] Senthilkumar B and Kalai Selvan R 2014 Hydrothermal synthesis and electrochemical performances of 1.7 V NiMoO4 ·
xH2O||FeMoO4 aqueous hybrid supercapacitor J. Colloid Interface Sci. 426 280–6
[20] Wang Y, He P, Lei W, Dong F and Zhang T 2014 Novel FeMoO4/graphene composites based electrode materials for supercapacitors
Compos. Sci. Technol. 103 16–21
[21] Butler S Z et al 2013 Progress, challenges, and opportunities in two-dimensional materials beyond graphene ACS Nano 7 2898–926
[22] Liu H, Gu C, Li D and Zhang M 2015 Non-enzymatic hydrogen peroxide biosensor based on rose-shaped FeMoO4 nanostructures
produced by convenient microwave-hydrothermal method Mater. Res. Bull. 64 375–9
[23] El Sharkawy H M, Mohamed A M, Ramadan M and Allam N K 2022 FeMoO4 nanoparticles as functional negative electrode material
for high performance supercapacitor devices over a wide pH range J. Energy Storage 54 105272
[24] Jeseentharani V, Dayalan A and Nagaraja K S 2018 Nanocrystalline composites of transition metal molybdate (Ni1–xCoxMoO4; x = 0,
0.3, 0.5, 0.7, 1) synthesized by a co-precipitation method as humidity sensors and their photoluminescence properties J. Phys. Chem.
Solids 115 75–83
[25] Nahrawy A M E, Hammad A B A, Bakr A M and Wassel A R 2019 Adjustment of morphological and dielectric properties of ZnTiO3
nanocrystalline using Al2O3 nanoparticles Appl. Phys. A 125 54
[26] Deyab M A A, Stankulov T, Slavcheva E, Awadallah A E, ElSaeed S M and Zaki E G G 2020 Design and synthesis of FeMoO4/CuO for
electrochemical energy storage system J. Mol. Liq. 314 113693
[27] Dhas S S J, Suresh S, Rita A, Dhas S A M B, Gowri Shankar Rao R and Biju C S 2020 Effect of annealing on the photoluminescence and
thermoluminescence properties of Eu2 + doped BaSO4 microgravels J. Mater. Sci., Mater. Electron. 31 11113–22
[28] Mansour A M, Abou Hammad A B, Bakr A M and El Nahrawy A M 2022 Silica zinc titanate wide bandgap semiconductor
nanocrystallites: synthesis and characterization Silicon 14 11715–29
[29] El Nahrawy A M, Montaser A S, Abou Hammad A B, Ezzat M and El-shakankery M 2020 Copper lithium silicate/ZrO2 nanoparticles-
coated kevlar for improving UV–vis absorbance/ protection properties Silicon 12 1743–50
[30] El Nahrawy A M, Abou Hammad A B and Mansour A M 2021 Preparation and characterization of transparent semiconducting silica
nanocomposites doped with P2O5 and Al2O3 Silicon 13 3733–9
[31] Eda K, Kato Y, Ohshiro Y, Sugitani T and Whittingham M S 2010 Synthesis, crystal structure, and structural conversion of Ni
molybdate hydrate NiMoO4·nH2O J. Solid State Chem. 183 1334–9
[32] Mitran G, Chen S and Seo D K 2019 Molybdenum dopped copper ferrites as active catalysts for alcohols oxidative coupling Mater. 2019
12 1871
[33] El Nahrawy A M, Abou Hammad A B, Bakr A M, Shaheen T I and Mansour A M 2020 Sol–gel synthesis and physical characterization of
high impact polystyrene nanocomposites based on Fe2O3 doped with ZnO Appl. Phys. A 126 654
[34] ElNahrawy A M, Mansour A M, ElAttar H A, Sakr E M M, Soliman A A and Hammad A B A 2020 Impact of Mn-substitution on
structural, optical, and magnetic properties evolution of sodium–cobalt ferrite for opto-magnetic applications J. Mater. Sci., Mater.
Electron. 31 6224–32
[35] Ibrahim R S, Azab A A and Mansour A M 2021 Synthesis and structural, optical, and magnetic properties of Mn-doped CdS quantum
dots prepared by chemical precipitation method J. Mater. Sci., Mater. Electron. 32 19980–90
[36] Tripathy S K 2015 Refractive indices of semiconductors from energy gaps Opt. Mater. (Amst). 46 240–6
[37] Pal S, Kumar Tiwari R, Chandra Gupta D and Singh Verma A 2014 Simplistic theoretical model for optoelectronic properties of
compound semiconductors J. Mater. Phys. Chem. 2 20–7
[38] Duffy J A 2001 Ultraviolet transparency of glass: A chemical approach in terms of band theory, polarisability and electronegativity Phys.
Chem. Glas. 42 151–7
[39] Reddy R R, Rama Gopal K, Nazeer Ahammed Y, Narasimhulu K, Siva Sankar Reddy L and Krishna Reddy C V 2005 Correlation
between optical electronegativity, molar refraction, ionicity and density of binary oxides, silicates and minerals Solid State Ionics 176
401–7
[40] Aziz R A, Muzakir S K, Misnon I I, Ismail J and Jose R 2016 Hierarchical Mo9Se11 nanoneedles on nanosheet with enhanced
electrochemical properties as a battery-type electrode for asymmetric supercapacitors J. Alloys Compd. 673 390–8
[41] Sivakumar P, Kulandaivel L, Park J W, Raj C J, Ramesh R and Jung H 2022 Well-assembled nanosheets of nickel-cobalt double
hydroxide flower as a reversible faradic battery-type electrode material for high-performance hybrid supercapacitor Ceram. Int. 48
35578–85
[42] Yan J, Fan Z, Sun W, Ning G, Wei T, Zhang Q, Zhang R, Zhi L and Wei F 2012 Advanced asymmetric supercapacitors based on Ni(OH)
2/graphene and porous graphene electrodes with high energy density Adv. Funct. Mater. 22 2632–41
[43] Yang S, Han Z, Sun J, Yang X, Hu X, Li C and Cao B 2018 Controllable ZnFe2O4/reduced graphene oxide hybrid for high-performance
supercapacitor electrode Electrochim. Acta 268 20–6
[44] Amiri M, Saeed Hosseiny Davarani S, Ebrahim Moosavifard S and Fu Y Q 2022 Cobalt-molybdenum selenide double-shelled hollow
nanocages derived from metal-organic frameworks as high performance electrodes for hybrid supercapacitor J. Colloid Interface Sci.
616 141–51
[45] Vidhyadharan B, Misnon I I, Aziz R A, Padmasree K P, Yusoff M M and Jose R 2014 Superior supercapacitive performance in
electrospun copper oxide nanowire electrodes J. Mater. Chem. A 2 6578–88
[46] Fathi A M, Abdel-Hameed S A M, Margha F H and Ghany N A A 2016 Electrocatalytic oxygen evolution on nanoscale crednerite
(CuMnO2) composite electrode Zeitschrift fur Phys. Chemie 230 1519–30
[47] Patil A M, An X, Li S, Yue X, Du X, Yoshida A, Hao X, Abudula A and Guan G 2021 Fabrication of three-dimensionally
heterostructured rGO/WO3·0.5H2O@Cu2S electrodes for high-energy solid-state pouch-type asymmetric supercapacitor Chem. Eng.
J. 403 126411
[48] Handal H T, Mohamed W A A, Labib A A, Moustafa S A and Sery A A 2021 The influence of surface modification on the optical and
capacitive properties of NiO nanoparticles synthesized via surfactant-assisted coprecipitation J. Energy Storage 44 103321
[49] MOHD ABID M A ’A Z A M, Radzi M I, Mupit M, Osman H, Munawar R F, Samat K F, Mohd Suan M S, Isomura K and Islam M R
2020 Cyclic voltammetry and galvanostatic charge-discharge analyses of polyaniline/graphene oxide nanocomposite based
supercapacitor Malaysian J. Compos. Sci. Manuf. 3 14–26

12
Phys. Scr. 98 (2023) 055922 A M Mansour et al

[50] Li Y, Ma L, Fu Y, Zhang C, Shi Y, Xu Y and Li J 2022 Sulfurization enhancement of FeMoO4 for electrochemical ammonia synthesis
with high Faradaic efficiency in neutral media J. Electroanal. Chem. 905 115981
[51] Verma P, Maire P and Novák P 2010 A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries
Electrochim. Acta 55 6332–41
[52] Liu Q, Xie L, Liu Z, Du G, Asiri A M and Sun X 2017 A Zn-doped Ni3S2 nanosheet array as a high-performance electrochemical water
oxidation catalyst in alkaline solution Chem. Commun. 53 12446–9
[53] Rao A V R K, Dudhe P and Chelvam V 2021 Role of oxygen defects in basicity of Se doped ZnO nanocatalyst for enhanced triglyceride
transesterification in biodiesel production Catal. Commun. 149 106258
[54] Jin M, Lu S Y, Ma L, Gan M Y, Lei Y, Zhang X L, Fu G, Yang P S and Yan M F 2017 Different distribution of in situ thin carbon layer in
hollow cobalt sulfide nanocages and their application for supercapacitors J. Power Sources 341 294–301
[55] Ranjith K S, Raju G S R, Chodankar R N, Ghoreishian S M, Kwak C H, Huh Y S and Han Y-K 2020 Electroactive ultra-thin rGO-
enriched FeMoO4 nanotubes and MnO2 nanorods as electrodes for high-performance all-solid-state asymmetric supercapacitors
Nanomaterials 10 289

13