Diamond & Related Materials 143 (2024) 110881

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Diamond & Related Materials

journal homepage: www.elsevier.com/locate/diamond

The hydrothermal synthesis of d-Ti3CN/V2O5 hollow spheres for enhanced

supercapacitors applications
Iffat Ashraf a, Muhammad Asad Asghar a, Saba Ahmad a, Davoud Dastan b, Mudassir Iqbal a, *
a
Department of Chemistry, School of Natural Sciences (SNS), National University of Sciences and Technology (NUST), Islamabad 44000, Pakistan
b
Department of Materials Science and Engineering, Cornell University, Ithaca, NY 15850, USA

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

Keywords: In this work, d-Ti3CN MXene was obtained by selective etching of Al from Ti3AlCN by hydrofluoric acid, and a
D-Ti3CN hydrothermal method was employed to prepare d-Ti3CN/V2O5 hollow spheres. The prepared d-Ti3CN/V2O5
MXene hollow spheres showed enhanced electrochemical properties. V2O5 hollow spheres expanded the distance be­
V2O5
tween d-Ti3CN MXene sheets, leading to fast electron transport and improved electrochemical performance of d-
Nanocomposite
Supercapacitor
Ti3CN/V2O5 hollow spheres. A specific capacitance of 340 F g− 1 was achieved at 1 A g− 1 current density, which is
higher than that of d-Ti3CN MXene (321 F g− 1) and V2O5 hollow sphere (155 F g− 1). The initial capacitance
retention is 89 % after 6000 cycles of constant current charge and discharge at the current density of 10 A g− 1. In
short, d-Ti3CN/V2O5 hollow spheres show excellent supercapacitor performance regarding specific capacitance
and stability.

1. Introduction introduction of and conductive material such as graphene, MXene in

V2O5 can be done to improve its electrochemical performance [23,26].
Supercapacitors (SCs) are considered promising devices to electro­ To counter the mentioned challenges, scientists have aimed their
chemically store renewable energy due to their high charge/discharge research on 2D metal carbide, nitride/carbonitride, named MXenes.
rate and excellent cyclic stability [1–4]. Hence, they are useful for ap­ Their properties, such as metallic conductivity, fast ion intercalation,
plications such as portable electronics, etc. SCs are classified into elec­ and hydrophobic nature, make them suitable candidates for electro­
trical double-layer capacitors (EDLCs) and pseudo capacitors depending chemical energy storage applications.
upon different charge storage mechanisms [5,6]. In EDLC, the charge The discovery of MXenes has aroused broad interest in 2D materials.
storage principle is according to ion adsorption, whereas in pseudoca­ MXene, first reported in 2011, was synthesized by chemical etching and
pacitors surface redox reaction occurs [7]. Different energy storage de­ extracting the ‘A' layer using Hydrofluoric acid from the layered MAX
vices such as lithium-ion batteries, sodium-ion batteries, potassium-ion phase (Mn+1AXn, where n = 1, 2 or 3, M belongs to − 1the early transition
batteries and supercapacitors are most commonly used. In recent years, metal, A represents group IIIA or IV A elements and X indicate C or N)
efforts have been made to synthesize new electrode materials for [27]. 2D metal carbide/nitride or carbonitride are attractive materials
supercapacitors. Transition metal oxides (TMOs), dichalcogenides, for energy storage devices such as supercapacitors, lithium-ion batteries
graphene, and polymer-based materials have been used as super­ (LIBs), lithium‑sulfur (Li–S) batteries due to their high electrical con­
capacitors electrode materials [8–21]. The redox reaction usually occurs ductivity, superior metallic conductivity, outstanding chemical stability,
in metal oxides with multiple valence states. Among transition metal large surface area, high density and excellent capacitive performance
oxides, Vanadium pentoxide (V2O5) is considered as an electroactive [28–33]. 2D Ti3C2 was the first MXene studied, exhibiting excellent
electrode material for supercapacitors because of its mixed oxidation performance in various energy storage devices [34]. Ti3CN MXene
state, low toxicity, low cost, wide potential window, high energy density possesses both TiC and TiN groups and theoretically may show superior
as well as high capacitance [22,23]. The poor conductivity and physical, chemical, and mechanical properties [35]. The self-restacking
decreased cyclic stability have limited its use in supercapacitors [24,25]. of MXene causes a ruinous effect by reducing the movement of elec­
Several structural morphological modifications and doping/ trolyte ions, hence decreasing its electrochemical performance. The

* Corresponding author.
E-mail address: [email protected] (M. Iqbal).

https://doi.org/10.1016/j.diamond.2024.110881
Received 12 October 2023; Received in revised form 29 January 2024; Accepted 29 January 2024
Available online 30 January 2024
0925-9635/© 2024 Elsevier B.V. All rights reserved.
I. Ashraf et al. Diamond & Related Materials 143 (2024) 110881

introduction of nanostructures can improve the performance of elec­

trodes by providing shorter ion and electron transport distances
[17,36–43]. Different groups have reported MXene related super­
capacitors. For instance, Yang et al. fabricated nitrogen-doped delami­
nated MXene by two-step method and reported a specific capacitance of
266 F g− 1. Furthermore, PPy/Ti3C2 was synthesized with a specific
capacitance of 458 F g− 1.
In this work, we design a strategy to synthesize novel d-Ti3CN/V2O5
hollow spheres for supercapacitor applications. d-Ti3CN MXene was
prepared from its MAX phase precursor using HF acid, whereas V2O5
hollow spheres were fabricated hydrothermally using ammonium met­
avanadate. These newly fabricated d-Ti3CN/V2O5 hollow spheres
showed excellent electrochemical performance towards super­
capacitors. A specific capacitance of 340 F g− 1 at the current density of 1
A g− 1 was obtained with 89 % capacitance retention after 6000 cycles at
10 A g− 1 based on the merits of highly exposed active sites and improved
conductivity.

2. Materials and methods

2.1. Chemicals

Titanium aluminum carbonitride (Ti3AlCN) was purchased from

Carbon-Ukarine company. Ammonium metavanadate (NH4VO3), Hy­
drofluoric acid (HF, 48 %), Hydrochloric acid (HCl) tetrabutylammo­
nium hydroxide (TBAOH) and ethanol were purchased from Fischer
scientific company. Deionized water (DI) was used throughout the
synthesis process.

2.2. Synthesis

2.2.1. Synthesis of d-Ti3CN MXene

Ti3CN MXene was fabricated by adding Ti3AlCN MAX in 30 %
concentrated HF at 35 ◦ C for about 18 h. The HF-treated product was
washed multiple times with deionized water and ethanol to attain
neutral pH. The sample was dried in a vacuum oven at 60 ◦ C for 24 h.
TBAOH was added to HF-treated Ti3CN MXene and magnetically stirred Fig. 1. XRD pattern of a) Ti3AlCN, b) d-Ti3CN MXene, c) V2O5 hollow spheres
for about 3 h. The washing and drying of the solution was carried out as and d) d-Ti3CN/V2O5 hollow spheres.
that for Ti3CN MXene to collect black-colored d-Ti3CN MXene [44].
2.3. Material characterization
2.2.2. Synthesis of V2O5 hollow spheres
About 0.25 g (2.14 mmol) of ammonium metavanadate (NH4VO3) XRD analysis was performed on the Malven Analytical Empyrean
was added to the 50 mL deionized water (DI) and magnetically stirred instrument. The structural morphology of the prepared materials was
for half an hour at room temperature to obtain a yellow-colored solu­ confirmed by scanning electron microscopy (SEM) using VEGA2 TES­
tion. Then about 10 mL 1 M hydrochloric acid was added dropwise to CAN. X-ray Photoelectron Spectroscopy (XPS) was carried out on
the above solution and magnetically stirred for 15–20 min. The 2 mL of Thermo kα instrument with a monochromatic beam of Aluminum X-rays
hydrazine hydrate was added as a reducing agent and stirred for another and Scanning Transmission Electron Microscopy (STEM) was done by
45 min until a greyish-colored solution was attained. The mixture was Hitachi HD-2700 STEM/TEM using Cu grid.
washed using DI water and ethanol to remove acid and attain neutral
pH. After washing, the product was dried in a vacuum oven at 60̊ C for
24 h. This greyish-colored powder was annealed in a muffle furnace at 2.4. Electrochemical performance measurement
250̊ C for 2.5 h to collect yellowish-colored V2O5 hollow spheres.
All electrochemical measurements were performed using an Inter­
2.2.3. Synthesis of d-Ti3CN/V2O5 hollow spheres face 1000 E, potentiostat/galvanostat/ZRA, Gamry Instruments work­
0.25 mmol of d-Ti3CN MXene and V2O5 hollow spheres were added station with a three-electrode system in 2 M KOH solution. Ag/AgCl and
in DI water in separate beakers and stirred for about 25 min to form a Pt wire were used as a reference and counter electrode. For electrode
uniform suspension. The aqueous solution of d-Ti3CN MXene was slowly preparation, samples fabricated (active materials) were mixed with
transferred to V2O5 hollow spheres solution and magnetically stirred for carbon black and PVDF in N-methyl pyrrolidone (NMP) at a weight ratio
about 10–15 min. This green-colored solution mixture was transferred to of 85:10:5. The as-prepared slurry was coated on a piece of nickel foam
a Teflon-lined steel autoclave and kept at 120 ◦ C for 10 h. The mixture followed by pressing them into pieces and drying in a vacuum oven at 60
was cool down at room temperature, and then by washing and drying C for 24 h. The mass loading of the working electrode was 1.5 mg. Cyclic
̊
(60 ◦ C for 24 h) we collected black-colored d-Ti3CN/V2O5 hollow voltammetry (CV) curves were measured at different scan rates (2–100
spheres. mV s− 1) in a potential window of − 0.3 to 0.45 V. Galvanostatic charge/
discharge (GCD) was measured at various current densities (1, 2, 3, 5
and 10 A g− 1). Furthermore, electrochemical impedance spectroscopy
(EIS) was performed in 0.1–10 MHz. The specific capacitance was

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I. Ashraf et al. Diamond & Related Materials 143 (2024) 110881

Table 1 Furthermore, the formation of V2O5 hollow spheres was confirmed as its
Crystallinity and grain size of synthesized materials. XRD patterns matched with (200), (001), (101), (110), (301), (011),
Material Crystallinity (%) Grain size (nm) (310), (111), (002), (202), (411), (600) and (020) planes of V2O5 hollow
spheres (JCPDS# 41–1426) as shown in Fig. 1c. No signal of any im­
d-Ti3CN MXene 77 % 35 nm
V2O5 hollow spheres 65 % 25 nm purity phases was detected. In the XRD pattern of d-Ti3CN/V2O5 hollow
d-Ti3CN/V2O5 81 % 43 nm spheres all the corresponding peaks of d-Ti3CN MXene and V2O5 hollow
spheres indicate successful synthesis of our desired material as shown in
Fig. 1d. Crystallinity and grain size are important factors for super­
calculated from GCD curves by using Eq. (1) [45]. capacitor applications. The Scherrer formula, D = Kλ/(β cos θ) was used
Cs = IΔt/ (1) to calculate grain size by using origin software. Table 1 indicates d-
mΔV
Ti3CN/V2O5 hollow spheres have better crystallinity and grain size
where Cs (F g− 1) represents specific capacitance, I is for applied current, compared to other materials.
Δt indicates the discharge time, m (g) denotes the mass of active ma­ XPS was used to analyze the elemental composition and chemical
terial, and ΔV designates potential interval. states of d-Ti3CN/V2O5 hollow spheres. The XPS survey spectrum and
high-resolution XPS spectra of Ti2p, C1s, N1s, V2p, and O1s of d-Ti3CN/
3. Results and discussion V2O5 hollow spheres are shown in Fig. 2a-f. The survey spectra show
that Ti, C, N, V, and O elements are detected. In the Ti2p spectrum, the
3.1. Characterization characteristic peak at 459 and 465 eV correspond to Ti(IV) 2p3/2 and Ti
(IV) 2p1/2, as depicted in Fig. 2b. The largest signal at 285 eV corre­
The XRD pattern for Ti3AlCN, d-Ti3CN MXene, V2O5 hollow spheres, sponds to the adventitious carbon (C–C) from Ti3CN MXene (Fig. 2c).
and d-Ti3CN/V2O5 hollow spheres is shown in Fig. 1a-d. The XRD Fig. 2d represents the XPS spectra of N1s. The dominant N1s peak at 396
pattern of Fig. 1b suggests a conversion of Ti3AlCN to d-Ti3CN MXene, as eV corresponds to the C– –N of Ti3CN MXene. The peak at 401 is
a peak centering at 10◦ corresponding to (002) plane of Ti3AlCN is attributed to the pyridine-like nitrogen, as shown in Fig. 2d. In Fig. 2e,
shifted to a lower angle. Similarly, the peak at 39◦ which indicates the the two fitting peaks at 517.2 eV and 525 eV correspond to V2p3/2 and
presence of aluminum (Al) diminishes, which indicates Al has been V2p1/2, respectively. The O1s peak at 530 eV contributes to the oxygen
successfully removed from the Ti3AlCN MAX, forming d-Ti3CN MXene. ions linked with V–O bonds in V2O5 hollow spheres, as shown in Fig. 2f.

Fig. 2. a) XPS survey spectra of d-Ti3CN/V2O5 hollow nanospheres, XPS spectra of b) Ti2p, c) C1s, d) N1s, e) V2P and f) O1s.

Fig. 3. SEM images of a) d-Ti3CN MXene, b) V2O5 hollow spheres and c) d-Ti3CN/V2O5 hollow spheres.

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I. Ashraf et al. Diamond & Related Materials 143 (2024) 110881

Fig. 4. a-c) STEM images of d-Ti3CN/V2O5 hollow spheres at various magnifications, Elemental mapping images of d) Ti, e) C, f) N, g) V, and h) O.

The structure and morphology of d-Ti3CN MXene, V2O5 hollow 3.2. Electrochemical measurement
spheres, and d-Ti3CN/V2O5 hollow spheres were characterized by
scanning electron microscopy (SEM) at the resolution of 1 μm. Fig. 3a The electrochemical measurement of d-Ti3CN MXene, V2O5 hollow
shows SEM image of d-Ti3CN MXene with clear accordion-like layered spheres, and d-Ti3CN/V2O5 hollow spheres was carried out using 2 M
thin nanosheets. The SEM image clearly shows larger spacing between KOH as an electrolyte. The cyclic voltammetry (CV) curves were
layers, indicating that Al has been successfully removed. Similarly, measured at different scan rates (2–100 mV s− 1) in a potential window
Fig. 3b shows the SEM image of V2O5 hollow spheres, indicating that of − 0.3-0.45 V, as shown in Fig. 5a-d. Cathodic and anodic peaks indi­
hollow nanospheres have been prepared with great uniformity. The SEM cate that a faradic reaction takes place. The increase in scan rate shifts
image of d-Ti3CN/V2O5 hollow spheres is shown in Fig. 3c. d-Ti3CN/ the potential of anodic and cathodic peaks to more negative and positive
V2O5 comprises many round hollow nanospheres incorporated on d- values due to increased internal diffusion resistance. From the com­
Ti3CN nanosheets. This type of structure is more favorable for the parison curve, as shown in Fig. 5d, it is seen that d-Ti3CN/V2O5 hollow
application of supercapacitors because of the higher surface area and spheres exhibited the highest peak current density and the largest in­
increased interlayer spacing between MXene nanosheets, which has tegral area at the scan rate of 2 mV s− 1 compared to d-Ti3CN MXene and
increased the interaction of electrode and electrolyte ions. V2O5 hollow spheres. CV profile of bare Ni-foam indicates there is a
The sample was observed using STEM further to verify the structure small contribution in current density that can be neglected. This in­
of d-Ti3CN/V2O5 hollow spheres, as shown in Fig. 4. The lamellar dicates that d-Ti3CN/V2O5 electrode possesses a faster faradic process
structure of 2D d-Ti3CN and hollow spheres are seen in Fig. 4a-c. STEM and excellent rate capability because of enhanced surface area due to
of this newly synthesized material is in good agreement with SEM re­ successfully incorporating V2O5 hollow spheres in d-Ti3CN MXene.
sults. Fig. 4e-i shows the elemental mapping images of a selected area of The electrochemically active surface area of all the materials was
d-Ti3CN/V2O5 hollow spheres. It can be seen that hollow spheres are calculated from non-faradic region of CV curves (− 0.25 V to − 0.15 V).
evenly loaded on the d-Ti3CN MXene. The current difference (ΔJ) between anode and cathode at potential of
− 0.2 V was plotted against scan rate to get a linear line the slope of
which is equal to the electrochemical double layer (Cdl) as shown in

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I. Ashraf et al. Diamond & Related Materials 143 (2024) 110881

Fig. 5. CV curves of a) d-Ti3CN MXene, b)) V2O5 hollow spheres, c) d-Ti3CN MXene/ V2O5 hollow spheres at various scan rates, d) Comparison of CV curves at 2 mV
s− 1, e) EDLC calculated from non-faradic region of CV, and f) calculated electrochemically active surface area.

Fig. 5e [46]. The Cdl is then divided by specific capacitance (Cs) to get V2O5 hollow spheres at 1 A g− 1 is about 321 F g− 1, 155 F g− 1 and 340 F
the ECSA. For basic electrolytes, the Cs of 40 μF cm− 2 was universally g− 1. This increase in specific capacitance of d-Ti3CN/V2O5 hollow
applied to calculate the ECSA [47,48]. The d-Ti3CN/V2O5 hollow spheres is mainly due to the synergistic effect of d-Ti3CN MXene and
spheres showed highest ECSA of 2209.5 cm2 than 2084.25 and 1517 cm2 V2O5 hollow spheres in which MXene serves as a conductive material,
of V2O5 hollow spheres and d-Ti3CN MXene, respectively. This excep­ whereas V2O5 hollow spheres have increased specific surface area.
tionally high surface area of d-Ti3CN/V2O5 hollow spheres further Furthermore, good interaction between MXene nanosheets and V2O5
supports the excellent electrochemical activity of the composite. hollow spheres has increased the charge transportation rate, which has
To calculate the specific capacitance of prepared materials using increased specific capacitance. The GCD curves show a typical faradic
formula 1, galvanostatic charge-discharge (GCD) curves of d-Ti3CN behavior different from the “V” shaped curve of EDLC. Fig. 7a compares
MXene, V2O5 hollow spheres, and d-Ti3CN/V2O5 hollow spheres were specific capacitance for d-Ti3CN MXene, V2O5 hollow nanospheres, and
measured at different current densities (1, 2, 3, 5, & 10 A g− 1) are shown d-Ti3CN/V2O5 hollow nanospheres calculated at different current den­
in Fig. 6a-c. From the comparison curve at 1 A g− 1, the d-Ti3CN/V2O5 sities. The above GCD results indicate that metal oxides with hollow
hollow spheres showed the longest discharging time compared to d- spheric structures can intimately anchor on MXene nanosheets, and the
Ti3CN MXene and V2O5 hollow spheres, as shown in Fig. 6d. The specific synergistic effect of MXene and hollow spheres boost the electro­
capacitance of d-Ti3CN MXene, d-V2O5 hollow spheres, and d-Ti3CN/ chemical properties of this electrode material, which agrees with the CV

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I. Ashraf et al. Diamond & Related Materials 143 (2024) 110881

Fig. 6. GCD curves of a) d-Ti3CN/V2O5 hollow spheres, b) d-Ti3CN, c) V2O5 hollow spheres at different current densities, and d) comparison curve at current density
of 1 A g− 1.

Fig. 7. a) Specific capacitance calculated at various current densities, b) Nyquist plot of d-Ti3CN, V2O5 hollow spheres, and d-Ti3CN/V2O5 hollow spheres.

results.
Table 2
Similarly, the EIS of prepared materials was performed from 10 MHz
Rs, Rct values of prepared samples.
to 0.1 Hz. The EIS curve confirmed the better electrochemical perfor­
mance of d-Ti3CN/V2O5 hollow spheres. They all show a quasi- Sample Rs Rct

semicircle arc in the high-frequency region and a straight line at low d-Ti3CN 0.64 0.60
frequency which is an indication of capacitive behavior of electrodes. V2O5 hollow spheres 0.90 0.78
d-Ti3CN/V2O5 hollow spheres 0.18 Ω 0.72 Ω
The straight line displayed good capacitive property and low diffusion
impedance, which offers fast charge transfer transport in charge/
discharge process. The diameter of quasi semicircle arc is proportional to of all the materials and least diameter of semicircle was observed in case
the resistance in flow of charge [49]. From Nyquist plot, elements of the of the d-Ti3CN/V2O5 hollow spheres. Rs and Rct values of prepared
equivalent circuit are determined [50]. Fig. 7b shows the Nyquist plots samples are illustrated in Table 2.

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I. Ashraf et al. Diamond & Related Materials 143 (2024) 110881

Fig. 8. a) CV curves at scan rate of 5 mV s− 1 for total and capacitive current, b) Contribution ratio of diffusive and capacitive currents at different scan rates, c) the b-
values calculated at different potentials, and d) calculated diffusion coefficients.

To determine the mechanism of charge storage the kinetic analysis of

our best material was performed. The contribution of capacitive current
and diffusive current was determined using Dunn's method [51,52] as
describe in Eq. (2) [53–55].

i (V) = k1 v + k2 √v (2)
The Eq. (2) can be modified to get Eq. (3)

i (V)/√v = k1 √v + k2 v (3)

where i(V) is the current at any fixed potential, v represents the scan
rate, k1 is the slope and k2 is the intercept of linear line between i(V)/v1/
2
and v1/2, and k1v is capacitive current while k2v1/2 represents diffusive
current (k2v1/2). Fig. 8a shows the comparison of CV at scan rate of 5
mV s− 1 with the capacitive contribution of current towards the charge
storage mechanism. The scan rate dependence of capacitive and diffu­
sive currents of d-Ti3CN/V2O5 hollow spheres was shown in Fig. 8b. At
scan rate of 2 mV s− 1, ~79 % of the capacitance was diffusive while at
higher scan rate of 100 mV s− 1 the diffusion process was suppressed due
to increase in diffusion resistance while capacitive current was
dominant. 1
The b-value was determined by using Eq. (4) to further evaluate the Fig. 9. Cyclic stability of d-Ti3CN/V2O5 hollow spheres at 10 A g− cur­
rent density.
charge storage mechanism.

i = avb (4) different potentials. At potential below peak potential the b-value is in
range of 0.9–1.0 which indicates that the current in this region is pref­
The b-value can be determined from the slope of the graph of log of
erably capacitive in nature. While at peak potential and above peak
current against log of scan rate. The b-value has two well defined con­
potential the b-value ranges from 0.5 to 0.7 which is ascribed to the
ditions: b = 1.0 and b = 0.5. Fig. 8c shows the calculated b-values at

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I. Ashraf et al. Diamond & Related Materials 143 (2024) 110881

Table 3 Declaration of competing interest

Comparison table of MXene related work.
Material Specific Current Capacitance Ref The authors declare that they have no known competing financial
Capacitance density retention interests or personal relationships that could have appeared to influence
MoO3/MXene@CC 775 F g− 1 1 A g− 1
96.4 % [56] the work reported in this paper.
1
Ti3C2 352.4 mAh g 1 A g− 91.5 % [57]
MXene@Graphene − 1
Data availability
composite aerogel
1
V2O5/MXene 768 F g− 1 A g− 1 93.3 % [58]
Ag-doped V2O5/MXene 875 F g− 1
1 A g− 1 93 % [59]
No data was used for the research described in the article.
1
Ti3C2Tx 347 F g− 5 mV s− 1 – [60]
d-Ti3CN/V2O5 340 F g− 1
1 A g− 1 89 % This Acknowledgments
work
The authors acknowledge the support from the School of Natural
diffusion process dominating in this region. The diffusion coefficient was Sciences (SNS), NUST, Pakistan, and Georgia Institute of Technology,
determined by plotting cathodic peak current (Ip) against square root of Atlanta, USA.
scan rate to get a straight line (Fig. 8d) the slope of which gives diffusion
coefficient according to Randles-Sevcik Eq. (5) References
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CRediT authorship contribution statement
[17] I. Ashraf, S. Ahmad, D. Dastan, M.J.J.o.A. Iqbal, Compounds, Ni-doped CeO2
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