Sensors & Actuators: A.

Physical 359 (2023) 114511

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Sensors and Actuators: A. Physical

journal homepage: www.journals.elsevier.com/sensors-and-actuators-a-physical

Exploiting the effect of inversion degree, phase, and size in nickel ferrite
nanoparticles: Implications for electrochemical behaviors and magnetic
hyperthermia properties
Van Manh Tien a, 1, Tuyet Nhung Pham a, *, 1, Van Hoang Ong a, c, Nguyen Le Nhat Trang a,
Ngo Xuan Dinh a, Nguyen Quang Hoa d, Duong Anh Tuan b, Anh-Tuan Le a, b, **
a
Phenikaa University Nano Institute (PHENA), PHENIKAA University, Hanoi 12116, Viet Nam
b
Faculty of Materials Science and Engineering, PHENIKAA University, Hanoi 12116, Viet Nam
c
University of Transport Technology, Trieu Khuc, Thanh Xuan District, Hanoi, Viet Nam
d
Faculty of Physics, VNU University of Science, Vietnam National University, Hanoi, 334 Nguyen Trai, Thanh Xuan, Hanoi, Viet Nam

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

Keywords: Nickel ferrite (NiFe2O4-NFO) nanoparticles with differences in crystal structure (phase, purity, and cation dis­
Spinel Nanomaterials tribution) and size, were effectively synthesized by a simple hydrothermal method at various treatment tem­
NiFe2O4 peratures (160, 180, and 200 ◦ C). NiFe2O4 nanoparticles were structurally investigated using XRD measurements
Cation Distribution
with Rietveld refinement and other measurements such as Raman and SEM. Among synthesized NFO samples,
Electrochemical Behaviors
Magnetic Hyperthermia
benefiting from possessing the smallest size, narrow size distribution, and partially inverted structure (δ = 0.54),
as well as the co-presence of the high ratio of the side phase of Ni(OH)2, NFO-180 sample exhibited many unique
features in terms of not only electrochemical properties (conductivity, active electrochemical surface area, and
charge/electron transfer kinetics) but also the magnetic hyperthermia properties with high saturation magne­
tization and large SAR coefficient. Some mechanisms and hypotheses were proposed to demonstrate the sig­
nificant impacts of the crystallite phase, size, purity, and particularly the cation distribution within NFO
nanoparticles on electrochemical behaviors and magnetic hyperthermia properties. According to that, the precise
control of the crystal structure (phase and purity), size, and cation distribution in NFO in general, and spinel
materials in particular, will be an ideal approach to improve efficiency according to the requirements related to
given applications.

1. Introduction
Nowadays, nickel ferrite NiFe2O4 (NFO) nanomaterials have attrac­
ted huge attention from the fundamental and applied points of view such
as magnetic data storage, energy storage devices, photocatalysis, sen­
sors, magnetic drug delivery, and anti-bacteria owing to their unique
chemical and physical properties in nanoscale size as well as low cost,
non-toxicity, ease of fabrication, and chemical stability compared to
their counterpart of bulk materials and various spinel ferrites [1,2]. It is
known that NiFe2O4 belongs to F3dm space group with the general
chemical formula:
[Ni2+ 3+ 2+ 3+
(1-δ)Feδ ]A[Niδ Fe(2-δ)]BO4
Depending on the cation distribution among the A and B sites, NFO
can be called the inverse spinel (δ = 1) or normal spinel (δ = 0). In a fully
inverse spinel structure, Ni2+ ions tend to occupy completely B sites
preferentially, while Fe3+ ions distribute equally between A and B sites.
Whereas, at a normal spinel, the fraction of A sites is occupied by
divalent metal (Ni2+) cations, and the fraction of B sites is occupied by
trivalent metal (Fe3+) cations. Recently, some reports displayed that the
magnetic, catalytic, and local physiochemical properties of the spinel
ferrite have been critically size-dependent, structure, chemical compo­
sition, and the degree of inversion (δ) [3–9]. For example, M. Harada
et al. [6] found that quantitative determination of cation distribution
(degree of inversion) in the tetrahedral and octahedral sites of the spinel

* Corresponding author.
** Corresponding author at: Phenikaa University Nano Institute (PHENA), PHENIKAA University, Hanoi 12116, Viet Nam.
E-mail addresses: nhung.phamthituyet@phenikaa-uni.edu.vn (T.N. Pham), tuan.leanh@phenikaa-uni.edu.vn (A.-T. Le).
1
V.M. Tien and T.N. Pham contributed equally to this work

https://doi.org/10.1016/j.sna.2023.114511
Received 21 April 2023; Received in revised form 14 June 2023; Accepted 20 June 2023
Available online 21 June 2023
0924-4247/© 2023 Elsevier B.V. All rights reserved.
V.M. Tien et al.
structures offered a deep insight into the influence of the cation distri­
bution on their magnetic properties such as saturation magnetization,
coercitivity field, and blocking temperature. In addition, the magnetic
properties were demonstrated to be strongly affected by particle size,
crystallinity, the direction of magnetization, and surface environments.
In which, the inversion degrees affected the saturation magnetization as
opposed to the particle size and the surface coordination impacted
spin-exchange interactions. A. Monohar and co-worker [2] also
demonstrated the remarkable influence of crystallite size of NFO nano­
particles on dielectric, ac-conductivity, magnetic, and magnetic hyper­
thermia properties. In another research, the magnetic behaviors of NFO
particles showed a close dependence on the particle size and shape as
well as cation distribution [10]. This report pointed out that the mag­
netic behaviors of the NFO was dominated more by the effect of spin
canting than the cation distribution in the surface shell of nanoparticles.
Hence, increasing particle size led to an increase in the saturation
magnetization and a decrease of coercivity.
It is interesting to note that the development of new applications in
the electrochemical sensor or magnetic hyperthermia fields of NFO still
requires versatile synthesized materials which allow for the fine-tuning
of electrochemical behaviors and magnetic hyperthermia properties
according to the specifications related to a given application. Moreover,
the fundamental understanding of the comprehensive mechanism and
effect of size, component, and cation distribution, can serve as a basis for
exploring the critical proofs of the changes in their electrochemical
behaviors and magnetic hyperthermia properties. However, to the best
of the author’s knowledge, the understanding of impact mechanisms of
size, phase purity, and the degree of inversion over electrochemical
behaviors and magnetic hyperthermia properties within NFO nano­
materials is still limited. Therefore, the main objective of the present
work is to explore in detail the influence of inherent side phase (Ni
(OH)2, size, and particularly the cation distribution within NFO nano­
particles on electrochemical behaviors and magnetic hyperthermia
properties. A series of systematic electrochemical measurements with
the presence of a redox probe ([Fe(CN)6]3-/4-) and magnetic hyper­
thermia measurements on the MSI automation system was underway.
Based on the obtained results, some mechanisms and hypotheses were
proposed to demonstrate the significant impacts of these parameters.
2. Experimental section
2.1. Chemicals
Sodium hydroxide (NaOH, Sigma Aldric, > 98%), NiCl2•6 H2O, and
FeCl3•6 H2O (> 98%) were purchased from Xilong Scientific Co., Ltd
(China) and Guangdong Guanghua Sci-Tech Co., Ltd. K3(Fe(CN)6), K4(Fe
(CN)6⋅3 H2O, chloramphenicol (CAP), and ethanol were provided from
Sigma-Aldrich (USA) and Merck KGaA, Germany. Phosphate buffered
saline solution (PBS, pH 7.4) was prepared by using different salts such
as NaCl, KCl Na2HPO4, and KH2PO4. Besides, the pH of the buffer so­
lution was adjusted by NaOH and H3PO4 solutions. Further, the screen-
printed electrode (SPE) was provided by DS Dropsens, Spain.
2.2. Methods
2.2.1. Preparation of NiFe2O4 nanoparticles
NiFe2O4 nanoparticles were successfully prepared using the hydro­
thermal method. Firstly, dissolved solutions of 0.3 M NiCl2 and 0.3 M
FeCl3 were mixed under magnetic stirring for 30 min. Next, 200 mmol of
0.2 M NaOH was slowly added to the prepared saline solution until the
pH reached 9. The obtained solutions were continually stirred for 1 h.
Then, this homogeneous solution was transferred into a hydrothermal
autoclave reactor and heated at a temperature of 160 ◦ C, 180 ◦ C, and
200 ◦ C for 20 h, respectively. After that, the resulting precipitations
were filtered and washed several times with double distilled water and
dried in air for 6 h at T = 80 ◦ C. The final products were labeled as NFO-
2
Sensors and Actuators: A. Physical 359 (2023) 114511
160, NFO-180, and NFO-200, corresponding to different hydrothermal
temperatures.
2.2.2. Preparation of NFO-modified SPEs
To study the electrochemical behaviours of electrodes modified with
different NFO samples, the screen-printed electrodes (SPE) were modi­
fied with the proposed materials. The modified SPEs were prepared by
dropping homogeneous solutions of various NFO samples at a concen­
tration of 1 mg mL− 1, respectively. According to that, the concentration
of 1 mg mL− 1 for NFO samples was prepared as following steps: In step
one, 5 mg of each proposed NFO sample was dispersed into 5 mL
distilled water and sonicated for 30 min to get homogeneous solutions;
In step two, these homogeneous solutions were dropped on the working
electrode surface of bare SPE and dried at 45 ◦ C. After that, the obtained
NFO/SPEs were stored in the air for the following electrochemical
measurements.
2.3. Apparatus
2.3.1. Physical measurements: XRD, Raman, VSM, and SEM
In this study, scanning electron microscopy (SEM) was used to
observe the morphology, size, as well as distribution of the prepared
NFO samples. By using Bruker D5005 X-ray diffractometer attached Cu
Ka radiation (λ = 0.154056 nm), the crystalline structure was analyzed
to obtain the lattice parameters and crystallographic phase of NFO
samples. Furthermore, to fully understand the XRD analysis, the soft­
ware FullProf for Rietveld analysis of the structure was used. Raman
spectroscopy (Horiba MacroRAM™) with 785 nm laser excitation was
also employed to study physicochemical characteristics. Additionally,
the magnetic characteristics of the proposed materials were determined
using a vibrating sample magnetometer (VSM, EV9. MicroSense) at
room temperature. To evaluate the hyperthermia performance of NFO
materials as hyperthermic agents, specific absorption rate (SAR) was
calculated. A magnetic hyperthermia system (MSI automation) was
employed to measure the heating capability of the magnetic fluid when
subjected to an AC magnetic field of 300 kHz and 5 kW of power. The
change of temperature was recorded to assess the heat-generating ca­
pacity of the fluid.
2.3.2. Evaluation of electrochemical characterizations
The electrochemical characteristics of bare SPE and SPEs modified
different NFO samples were performed on a Palmsens 4 electrochemical
workstation (PS Trace-Netherlands), a three-electrode system, at a
temperature around 298 K, by measuring cyclic voltammetry (CV) and
electrochemical impedance spectroscopy (EIS) measurements at various
setup conditions. First of all, cyclic voltammetry (CV) measurements
were performed on the synthesized samples in the potential range from
− 0.3–0.6 V at different scan rates from 20 to 70 mV s− 1 in 0.1 M KCl
solution containing 5 mM K3[Fe(CN)6]/K4[Fe(CN)6)], as a redox probe.
Following the CV measurement, electrochemical impedance spectros­
copy (EIS) was carried out on the electrodes in the frequency range of
0.01–50000 Hz.
3. Results and discussion
3.1. Microstructure and physical characterizations
Fig. 1 displays the powder XRD diffractions of NFO-160, NFO-180,
and NFO-200 in the range of 2θ from 5◦ to 70◦ . As can see, the diffraction
peaks for all samples were detected at 19.5, 30.1, 35.5, 38.7, 43.2, 53.7,
57.3, and 62.8º, corresponding to the crystallographic planes of (111),
(220), (311), (222), (400), (422), (511), and (440) of NFO (trevorite
phase) (JCPDS card No. 23–00295 [11], respectively. While some other
weak peaks were located at 19.2◦ , 33◦ , 38.5◦ , 52.1◦ , and 59◦ fitting with
(001), (100), (101), (102), and (110) planes, matching well with Ni
(OH)2 phase (theophrastite phase) (JCPDS card No 14–0117).
V.M. Tien et al.
Fig. 1. XRD patterns and Rietveld refined X-ray diffraction patterns of synthesized materials (NFO-160, NFO-180, and NFO-200), respectively.
Consequently, the X-ray diffraction patterns reveal the co-presence of
two phases in all synthesized samples, including the trevorite phase
(NiFe2O4) and theophrastite phase (Ni(OH)2). As described in Fig. 1, it is
apparent that the peak intensity of the NiFe2O4 (trevorite) phase was
higher than that of the Ni(OH)2 (theophrastite) phase in both three
samples. Namely, the NFO-180 sample has the highest peak intensity of
Ni(OH)2 phase with approximately 27.8% (Table 1). Furthermore, the
XRD patterns show that the NFO phase became clear as the temperature
rises from 160 to 200 ℃. Herein, the formation of the Ni(OH)2 phase is
probably due to the excess Ni atoms in the reaction [12–14]. The broad
peaks in the XRD patterns also indicate that the proposed samples have
ionic distances from the core to their surface, suggesting size in the
nanoscale range [6]. To determine the particle size, the cosθ value was
recorded through 2θ = 35.5◦ and then used to calculate by Scherrer’s
formula: d = ksλCu/βcosθ (with ks as Scherrer constant and β is full width
at half maximum of peak 2θ = 35.5º). According to that, the calculated
size of NFO-160, NFO-180, and NFO-200 was about 186.56, 153.24, and
164.52 Å, respectively. Clearly, these results show that the NFO-180
sample was the smallest size. We recognize that the ratio of Ni:Fe in
the precursor materials (NiCl2 and FeCl3) affects remarkably the for­
mation of NiFe2O4 phase. If this ratio is low, the formation of the NFO
phase does not occur, furthermore, only the presence of the hematite
phase or Ni-doped α-Fe2O3 material is observed as demonstrated in some
previous reports. Namely, these studies have consistently reported that
the formation of the NFO phase occurred within a specific ratio range of
20–30% [12,15–19] in hydrothermal techniques and co-precipitation
3
Sensors and Actuators: A. Physical 359 (2023) 114511
methods [17]. In contrast, the high Ni:Fe ratio results in the predomi­
nance of the Ni(OH)2 phase along with the initial NFO phase [13]. The
co-formation mechanism of the Ni(OH)2 phase in the synthesis of NFO
nanoparticles involves several steps. Initially, NFO nanoparticles are
formed as the starting material. Excess Ni atoms present in the system
act as nuclei for the growth of Ni(OH)2, binding to the exposed Ni atoms
on the surface of NFO nanoparticles. The atomic distance between
specific facets of Ni(OH)2 and NFO enables epitaxial growth and het­
erogeneous nucleation, resulting in a coherent interface between the
two phases. This mechanism highlights the role of excess Ni atoms and
epitaxial growth in the co-formation of the Ni(OH)2 phase on NFO
nanoparticles [20–23]. In addition to the Ni:Fe precursor ratio, the
co-formation of both NFO and Ni(OH)2 phases is also influenced by pH
and calcination temperature [21,22]. In hydrothermal process, the
forming reaction of Ni(OH)2 and NiFe2O4 as follows [20]:
Ni + NO−3 + H2 O→Ni(OH)2 + NO−2 (1)
2Fe3+ +4Ni(OH)2 →NiFe2 O4 +3Ni2+ +4H2 O (2)
Therefore, in this study, we maintained a fixed Ni:Fe ratio and varied
the synthesis temperature condition in order to investigate the co-
evolution of NiFe2O4 and Ni(OH)2 phases, as well as the particle size
variations of the samples. The decrease in crystallite size with increasing
Ni(OH)2 phase has also been observed in some previous studies and was
attributed to the fast nucleation process, which hinders the
V.M. Tien et al. Sensors and Actuators: A. Physical 359 (2023) 114511

Fig. 2. SEM images of the synthesized materials: (a): NFO-160; (b): NFO-180; and (c): NFO-200, corresponding to the distribution of particle size, respectively.

Table 1
Variation with the temperature of the relative lattice parameter, conventional statistical parameters χ2, Rwp, and Rexp of NiFe2O4.
Sample Ni (OH)2 NiFe2O4 (wt%) a (Å) (NiFe2O4) Rwp Rexp χ2 δ (Ni)tetrahedral (Ni)octahedral (Fe)tetrahedral (Fe)octahedral
(wt%) (%) (%) (%) (%) (%) (%)

NFO-160 23.3 76.7 8.339 9.333 9.337 1.00 1 93.269 6.731 1.188 98.812
NFO-180 27.8 72.2 8.371 7.538 9.477 0.79 0.54 74.881 25.119 24.421 75.579
NFO-200 23.5 76.5 8.354 7.010 5.327 1.31 0 99.867 0.133 4.6 95.4

agglomeration process, resulting in smaller crystallite size [13,24]. Hill et al. [27], and combined with Sickafus’s equation [26,28] of the
To further exploit the XRD results, the software FullProf was used for average radius on A and B sites:
Rietveld analysis as illustrated in Fig. 1. Table 1 shows the results of the ath = a0 + n δ (1)
analysis, including the lattice parameter (a), weight profile R-factor
8 [ √̅̅̅ ( √̅̅̅ ) ]
(Rwp), expected R-Factor (Rexp), and the goodness of fit (χ2). It is a0 = √̅̅̅ rNi2+ + 3 r3+ FeB + 1 + 3 R0 ≈ 8.371Å (2)
important to note that when the fit model is the χ2 value, which would
3 3 A

be close to 1 if the data of experimental matched the fitting data. The [ √̅̅̅ √̅̅̅ ]
8 3 3 3+
strain broadening was determined using the Williamson-Hall equation, n = √̅̅̅ − rNi2+ + r2+ Ni + r3+
Fe − rFeB ≈ − 0.032Å (3)
3 3 2 B A
2
which utilized a function of 2θ:β.cosθ = Kλ/d + 4δ. sin θ. The strain (δ)
A

can be quantified by evaluating the intercept (Kλ/d) of the line on the y- 2+

axis [25]. The acquired strain coefficients were − 0.0037, − 0.0014, and
− 0.0029, denoting the magnitude of strain in the respective samples.
The negative slope observed in the analysis further substantiates the
existence of compressive strain within the proposed samples in Fig. 1d. It
is apparent from Table 1 that the theophrastite phase (Ni(OH)2) in the
NFO-180 was dominant, which relates to the change in the parameter of
lattice and ratio of Ni to Fe ions. Since the Ni2+ ion has a smaller radius
(0.55 Å) than the Fe3+ ion (0.65 Å) [26], an increase in the concentra­
tion of Ni ion in NFO-180 resulted in changes in lattice parameter a (Å)
and the distribution of Fe3+ and Ni2+ ions on A (tetrahedral) and B
(octahedral) sites within NFO crystal structure. As known, spinel ferrites
have the general formula: [M2+ 3+ 2+ 3+
(1-δ)Feδ ]A[Mδ Fe(2-δ)]BO4, where δ is
3+
inversion degree, which is occupied by Fe on A sites or occupied on B
sites by M2+ cation. Depending on the percentage of Ni2+ ions occupying
B sites, one can call the compound to be normal spinel (δ = 0) or inverse
spinel (δ = 1). Some recent reports demonstrated that the properties
such as electrochemical and magnetic properties were a close relation­
ship to the ratio between A and B sites [6]. The theoretical lattice
parameter of the unit cell (ath) could be calculated using the equation of
where rNi2+ = 0.55 and r2+
NiB = 0.69 for Ni cations, r3+
FeA = 0.49 and
A
3+
r3+
FeB = 0.65 for Fe cations on tetrahedral A and octahedral B sites. It
should be noted that the numerical values assigned constants (a0 and n)
are critical in determining the potential range of values for the theo­
retical lattice parameter (ath) in NiFe2O4. Fig. 3c was generated using
Eqs. (1–3), with incremental changes to the value of δ in steps of 0.01,
resulting in the corresponding change of ath (red line in Fig. 3c). The
experimental lattice parameters for NFO-160, NFO-180, and NFO-200
were found to be 8.339, 8.371, and 8.354, respectively. The value of δ
being equal to 1 for the NFO-160 sample indicates that its theoretical
lattice parameter matches that of an inverse spinel structure, suggesting
the NFO-160 sample was an inverse spinel structure. Thus, for the NFO-
160 sample, the distribution was reversed with the trivalent cations
(Fe3+) and the divalent cations (Ni2+). In contrast, according to the
theoretical lattice parameter (red line in Fig. 3c), the δ value being equal
to 0 for the NFO-200 sample indicates that the NFO-200 sample was a
normal spinel structure, which means the Ni2+ cations only occupied at
the tetrahedral sites while the Fe3+ cations occupied the octahedral sites.
For the NFO-180 sample, the experimental lattice parameter was

4
V.M. Tien et al.
Fig. 3. (a): Raman spectra; (b): VSM data of the synthesized materials (NFO-160, NFO-180, and NFO-200); and (c): NiFe2O4 lattice parameter as a function of
inversion degree (red line). The blue line indicates the experimental lattice parameter (aexp) derived from the Rietveld refinement of s X-ray of NiFe2O4 pattern.
determined around 8.354 Å, corresponding to a degree of inversion (δ)
of 0.54. This suggests that both tetrahedral and octahedral sites within
the NFO-180 structure were occupied by both Ni2+ and Fe3+ cations.
SEM images of the different NFO samples can provide information
about the size, form, microstructures, and surface morphology. In this
case, both three images show the presence of particles with well-defined
octahedral structures, along with that the appearance of hexagonal disk-
shaped particles. All of them show good control of particle size with
average diameters lower than 160 nm, narrow size distribution, and
good dispersion. Namely, the size distribution was determined in the
range from 140 to 220 nm for NFO-160, from 140 to 180 nm for NFO-
180, and from 140 to 200 nm for NFO-200 by using ImageJ software.
As observed, the NFO-180 sample possessed the smallest particle size,
leading to increase surface area, exposure area, and interactability, and
providing many unique advantages of a nanomaterial at a smaller
nanoscale.
Fig. 3a shows the Raman spectra of the proposed samples (NFO-160,
NFO-180, and NFO-200). NiFe2O4 nanoparticles showed three peak
maxima at 332, 482, and 702 cm− 1, most of which are the typical
Raman modes of the cubic spinel ferrite structure [4,29] and corre­
sponding to the Raman active modes as Eg, T2 g, and A1 g [11,30]. The
Raman modes above 600 cm− 1 were considered due to A1 g symmetry
involving symmetric stretching of oxygen atoms with respect to the
metal ions in tetrahedral voids. Details, Raman peak at 702 cm− 1 (A1 g
mode) presented symmetric stretching of the Ni-O bonds at the tetra­
hedral voids, and a prominent peak at 482 cm− 1 (T2 g mode) was
considered as the asymmetric bending and stretching at the octahedral
sites [14,30–33]. Also, the Eg mode (332 cm− 1) was related to the
symmetric bending of the Ni-O bonds at the octahedral sites. More
5
Sensors and Actuators: A. Physical 359 (2023) 114511
interestingly, the appearance of the extra A1 g sub-band at around
660 cm− 1 for NFO-180 and NFO-160 samples was considered the
important direct proof of the tetrahedral-octahedral cationic site
inversion as mentioned in our previous report [34]. It is explained via
the difference in possible configurations of cations at
tetrahedral-octahedral voids. Thus, it also might provide value infor­
mative in directly recognizing whether the spinel material is an inverse
one and the degree of inversion (high-low) via the further investigation
of the peak intensity. In this case, the relative intensity ratio (Iv) between
702 and 660 cm− 1 of phonon modes, Iv is equal to 3.31 and 1.49 for
NFO-160 and NFO-180 samples, respectively (inserted in Fig. 3a). Ac­
cording to that, it can be inferred that the inverse degree for NFO-160
was higher than that of NFO-180, which agrees well with the XRD re­
sults and Rietveld analysis. The Raman modes of the NFO nanoparticles
annealed at lower temperatures were very broad and shifted to low
frequency, compared with that of nanoparticles annealed at higher
temperatures. This feature was related to a consequence of the phonon
confinement effect in nanocrystals [4,35]. It is worth noting that as the
annealing temperature increases, the Raman peaks became smaller and
sharper arising from the increase in size and crystallinity of NFO [11].
Moreover, it is worth noting that the magnetic properties of these
NFO samples were also influenced considerably by the crystallite size
and morphology, as well as the cation distribution of Fe3+ and Ni2+
between the A and B sites within the spinel structure. Many reports
exhibited that the change in particle size to nanoscale dimensions led to
decreased surface energy [36–38]. However, this energy was still suf­
ficient to retain the cation redistribution in a spinel structure. Therefore
cation redistribution might affect the magnetization at A and B sites as
explained using Neel’s two sub-lattice model [36]. According to that, the
V.M. Tien et al.
saturation magnetization (Ms) of spinel ferrite depended on the cation
distribution between A and B sites. The net magnetization per formula
unit was calculated by M = MB − MA, where MB and MA reflect the
sublattice magnetization values of the B and A sites, respectively. For
example, for the NFO-160 sample, it was inverse spinel
[M2+ 3+ 2+ 3+
(1-δ)Feδ ]A[Mδ Fe(2-δ)]BO4, with δ = 1. In this case, the Ni
2+
ions
occupied B sites and the Fe3+ ions were evenly divided between the A
and B sites. Hence, the magnetic moments of the Fe3+ ions (5µB) cancel,
and the net magnetic moment was simply that of the Ni2+ ion (2µB),
which was 2µB. Similarly, the net magnetic moment of NFO-180 was
determined at about 4.76µB. The predicted results were in agreement
with experimental measurements, which tend to decrease with particle
size. Additionally, the magnetization was strongly dependent on the
non-collinear structure of spins on the surface. Indeed, benefiting from
small particle size and good distribution of cation of NFO-180 could lead
to a higher surface area, which could remarkably enhance the super­
exchange interaction to reach a higher Ms value of 37.32 emu/g
compared with that of 32.49 emu/g for NFO-160 and 33.61 emu/g for
NFO-200. The facts show that the above hypothesis was correct when
observing and analyzing the obtained magnetic hysteresis (M-H) curves
at room temperature as in Fig. 3b. From the M-H data, we obtained the
value of saturation magnetization (Ms), and magnetic coercivity (HC) as
listed in Table 2. These results were also consistent with the findings of
previous studies [25,39,40]. The behaviours of all three curves at
various NFO samples were typical of ferromagnetic materials, corre­
sponding to saturation magnetization (Ms) at high field and coercivity
(HC) at low field. Overall, the magnetic properties of the NFO samples
were closely related to their cation distribution and particle size.
3.2. Electrochemical investigations
One of the most important potential applications of NFO nano­
material is mentioned most in electrochemical sensors. Herein, to study
more in detail the strong influence of phase components and cationic
distribution within NFO structure on the electrochemical behaviors,
including electrical conductivity and charge transport, cyclic voltam­
metry (CV) and electrochemical impedance spectroscopy (EIS) mea­
surements were carried out to evaluate and compare the electrochemical
characteristics of the bare SPE and NFO-modified SPEs (NFO-160/SPE,
NFO-180/SPE, and NFO-200/SPE).
Fig. 4 (a-b) displays the cyclic voltammetry (CV) curves obtained
from NFO-160/SPE, NFO-180/SPE, and NFO-200/SPE at various scan
rates in the range from 20 mV s− 1 to 70 mV s− 1. On the other hand,
Fig. 4d presents a correlative comparison of all three modified electrodes
at a scan rate of 50 mV s− 1. As can see, the CV curves for all electrodes
exhibited a pair of reversible redox peaks at 0.1 V and 0.3 V. These
peaks were associated with the electron transfer reaction of [Fe(CN)6]4−
reversibly into [Fe(CN)6]3− and at the same time [Fe(CN)6]3− reversibly
into [Fe(CN)6]2− . One can see at a scan rate of 50 mV s− 1, the peak
current (Ip) values observed on the three NFO-modified electrodes were
around 103 µA for NFO-160/SPE, 125 µA for NFO-180/SPE, and 122 µA
for NFO-200/SPE, respectively. The results indicate that NFO-180/SPE
had the highest electrochemical response, followed by NFO-200/SPE
and NFO-160/SPE. To explain this, we calculated and evaluated
several kinetic parameters related to the electron transfer reaction of the
redox probes. In this case, the peak-to-peak separation potential (ΔEp =
Epa-Epc) was determined from the recorded CV curves. This parameter is
a key indication that shows the limits of electrical conductivity and
charge transfer kinetics. The following sequence was used to arrange the
Table 2
Variation with the temperature of the relative magnetic parameters.
Samples NFO-160 NFO-180 NFO-200
Ms (emu/g) 32.49 37.32 33.61
HC (Oe) 147.74 131.18 127.28
6
Sensors and Actuators: A. Physical 359 (2023) 114511
ΔEp values of the NFO samples: NFO-180/SPE (0.190 V) < NFO-160/
SPE (0.199 V) < NFO-200/SPE (0.210 V). According to that, NFO-180/
SPE had the lowest potential separation, followed by NFO-160/SPE and
NFO-200/SPE. This suggests that NFO-180 had the highest electrical
conductivity and charge transfer kinetics, enabling the redox probes to
transfer electrons more efficiently. In contrast, NFO-200/SPE possessed
the highest potential separation, indicating that it exhibited the lowest
electrical conductivity and charge transfer kinetics, resulting in a less
efficient electron transfer reaction.
In the detail, Fig. 5 displays that the redox peak current response
increased linearly as the square root of the scan rate (ν1/2), in accordance
with the regression equations:
Ipa (µA)= 8.757 ν1/2 (mV s− 1) + 41.083 (R2 =0.9861) for NFO-160/
SPE;.
Ipa (µA)= 14.597ν 1/2 (mV s− 1) + 20.615 (R2 =0.9882) for NFO-180/
SPE;.
Ipa (µA)= 14.381ν1/2 (mV s− 1) + 21.821 (R2 =0.9959) for NFO-200/
SPE;;.
And:
Ipc (µA)= − 9.125 ν1/2 (mV s− 1) - 40.163R2 = 0.9743) for NFO-160/
SPE;.
Ipc (µA)= − 14.786 ν 1/2 (mV s− 1) - 18.932 (R2 =0.9982) for NFO-
180/SPE;.
Ipc (µA)= − 14.865 ν1/2 (mV s− 1) - 18.567 (R2 =0.9979) for NFO-
200/SPE;.
The linear relationship between Ip and ν1/2 indicates that the electron
transfer reaction of probe molecules occurred through a diffusion-
controlled process. The slopes of these linear equations were used to
calculate the active electrochemical surface area (EASA) by using the
Randles-Sevcik formula (Eq. 4). According to that, the Randles-Sevcik
equation relates the peak current (Ip) in cyclic voltammetry to various
electrochemical parameters, including the number of electrons trans­
ferred (n), diffusion coefficient (D), EASA, scan rate (ν), and concen­
tration of the electroactive species (C0) [41]:
Ip = (2⋅69×105) n3/2D1/2Aν1/2C0 (4)
As a result, the EASA value was calculated to be approximately
0.135, 0.161, and 0.161 for NFO-160/SPE, NFO-180/SPE, and NFO-
200/SPE, respectively.
To further verify the enhancement in electrical conductivity, charge
transport, and charge transfer kinetics at different NFO-modified elec­
trodes, EIS measurement was considered as a direct and effective
method to evaluate these properties on the electrode surface (Fig. 6).
Moreover, the electron transfer rate constant (ket) could be also calcu­
lated from the value of charge transfer resistance (Rct) and EASE (A)
values obtained as described above:
ket = RT/n2F2AC0Rct (5)
where, R is the gas constant, T is temperature, F is Faraday’s con­
stant, and the value of n is number of electrons transferred. The term C0
denotes the concentration of [Fe(CN)6]3-/4- in the bulk solution, while
Rct represents the resistance for electron transfer. As a result, the Rct
value could be obtained as 296.1 Ω for NFO-160/SPE, 266.9 Ω for NFO-
180/SPE, and 287.2 Ω for NFO-200/SPE. According to that, the ket value
was determined for these modified electrodes to be around 1.11 × 10− 3,
1.24 × 10− 3, and 1.15 × 10− 3. The results indicate that NFO-180/SPE
owned the highest ket value, which can be attributed to its high EASA
value, low separation potential (ΔEp) value, and small Rct value.
From a series of differences in recorded ΔEp, EASA, Rct, and ket
values, the remarkable influence of the NFO’s structure, morphology,
phase component, and cationic distribution on their electrochemical
properties is undeniable. To claire that, some hypotheses were proposed
as follows:
Firstly, benefiting from the small particle size, narrow size distribu­
tion range, and uniform dispersibility of both the two NFO-180 and
V.M. Tien et al.
Fig. 4. CV curves on different NFO-modified electrodes in presence of 0.1 M KCl containing 5 mM Fe(CN)3-/4-
NFO-200 samples, such NFOs-modified electrodes displayed larger
EASA values compared with NFO-160/SPE. Such properties facilitated
providing more active sites and better exposure areas as well as creating
an effective interaction between the electrode surface and electrolyte,
resulting in the formation of the higher AESA.
Second, the high crystallinity and co-presence of the high ratio of the
side phase of Ni(OH)2 within the NFO-180 structure arising from the
epitaxial growth of a-Ni(OH)2 on the cubic NiFe2O4 could be a major
factor, leading to the effective charge transport and high electrical
conductivity owing to the synergistic effect of NFO and Ni(OH)2 [42].
Thirdly, some reports believed that the distribution of Fe3+ and Ni2+
ions on the A and B sites within the spinel structure considerably
7
Sensors and Actuators: A. Physical 359 (2023) 114511
6 at different scan rates from 20 to 70 mV s− 1.
affected the electron transfer between the electrode and the electrolyte
[6,13,43,44]. This is because the Fe3+ and Ni2+ ions have different
electronic configurations and redox potentials, which can affect the
mechanism of the redox reaction and the kinetics of electron transfer.
Indeed, for NFO-180, the existence of different valence states (Ni2+/Ni3+
and Fe2+/Fe3+) and the hopping of charge carriers taking place among
ions on the octahedral sites within inversed structural lattices are
beneficial to conductivity, electron transfer reaction, and charge transfer
process [34,45]. Furthermore, the close correlation between the geo­
metrical/lattice defects and electronic properties was also explored and
discussed in many previous reports. For these reasons, it is easy to
further understand why the significant decrease of Rct and the increase
V.M. Tien et al.
Fig. 5. The linear plots of Ip versus ν1/2 in presence of 0.1 M KCl containing 5 mM Fe(CN)3-/4-
Fig. 6. EIS plots of various NFO/SPEs in 0.1 M KCl containing 2.5 mM Fe
(CN)3-/4-.
6
of ket value at NFO-180/SPE could be observed, compared with
NFO-200/SPE and even NFO-200/SPE. As a result, the Ip value of
NFO-180/SPE achieved the largest level than NFO-200/SPE and
NFO-160/SPE.
One other important characteristic of NFO samples that need to be
mentioned in this case is the magnetic hyperthermia property. The
specific absorption rate (SAR), which is a measure of how efficiently a
material can convert electromagnetic energy into heat, was analyzed by
measuring the initial rate of variation of temperature of the NFO
samples in a water medium with different concentrations. All experi­
ments involving AC magnetic field thermal activation were conducted
magnetic hyperthermia system (MSI automation) in the temperature
range from 15 to 50 ◦ C and suspension concentration of 5 mg mL− 1. As
shown in Fig. 7a, the temperature versus time curves were recorded for
NFO-160, NFO-180, and NFO-200 samples, respectively. From the
observation, there was not much difference between NFO-180 and NFO-
200 samples when the temperature of samples reached up to 45 ◦ C,
while both were significantly different from NFO-160. The mathemat­
ical description of these curves was achieved using Eq. (6). The heating
rate was defined as follows:
dT k ( t)
= exp − (6)
dt τ τ
The time constant, τ, is the parameter that describes the response to a
step input in a first-order dynamic system. According to that, the SAR
coefficient was calculated and used to evaluate this difference.
8
Sensors and Actuators: A. Physical 359 (2023) 114511
6 at different scan rates from 20 to 70 mV s− 1.
Cp dT
SAR = (7)
ϕ dt
where Cp represents the specific heat capacity of the samples (4.18 J/g
◦
C), and dT/dt represents the initial slope of the temperature change
over time. As displayed in Fig. 7b, the SAR values for each sample were
estimated at varying magnetic fields applied. It can be further observed
that the specific absorption rate (SAR) increased with the increase of
field amplitudes at all modified electrodes which were also found to be
in good agreement with other reports [39,46,47]. The trend of
increasing SAR with higher field amplitudes was attributed to the
greater amount of energy transferred to the material at stronger field
strengths. The obtained results indicate that there was a difference in the
heating efficiency at three synthesized NFO samples. The SAR values of
NFO-180 at all applied magnetic fields were higher than that of NFO-160
and NFO-200, suggesting that NFO-180 has better heating capacity than
others. Particularly, at high magnetic fields (H = 39.86 kA/m), a large
difference in SAR values of all NFO samples was observed. The high SAR
value of NFO-180 still exhibited better potential as a hyperthermic agent
for magnetic hyperthermia and biomedical applications. In addition, we
also investigated the thermal value of the specific absorption rate (SAR)
for the NFO-180 sample at various concentrations under the same
magnetic field (33.22 kA/m), as shown in Fig. 7c. These results
demonstrated there was a gradual decrease in SAR value with
decreasing concentration. This implies that as the concentration of the
NFO-180 sample decreased, the rate of energy absorption also
decreased. Indeed, at higher concentrations, the high density of
NFO-180 particles within the solution enhanced remarkably the inter­
action and exposure among the particles, resulting in more effective
energy absorption.
As known, the magnetic properties of the NFO samples directly
depend on their crystallite size [39]. Thus, possessing a small crystal size
is beneficial to get a better specific absorption rate (SAR) value. This is
due to the fact that smaller particles have a larger surface area per unit
mass, leading to more efficient energy absorption and transfer [47,48].
Additionally, the uniform distribution and higher density of NFO-180
per volume unit of solution lead to an increased heating capacity. As
described, the high magnetic moment per unit mass of NFO-180 owing
to their higher surface area-to-volume ratio, small particle size, good
distribution of cation and lower magnetization losses arising from sur­
face spin fluctuations exhibiting via the highest Ms value among the
three proposed samples was an important factor, which contributed to
the higher SAR value. The unique synergistic of small particle size, high
density, and high magnetic moment in NFO-180 makes it a promising
candidate for magnetic hyperthermia applications in biomedical fields,
such as cancer therapy and drug delivery [49].
V.M. Tien et al.
Fig. 7. (a) Temperature versus time plots of aqueous suspension of NFO-160, NFO-180, and NFO-200 samples at concentration of 5 mg mL−
360 kHz; (b) SAR values of different NFO samples; and (c) SAR values of NFO-180 sample at the different concentrations.
4. Conclusions
In this study, NFO nanoparticles with the changes in crystallite
phase, size, and cation distribution, were synthesized by a simple hy­
drothermal method at various treatment temperatures (160, 180, and
200 ◦ C). The XRD analysis with Rietveld refinement and Raman results
confirmed the formation of crystallite phase, purity, and the degree of
inversion of NFO nanostructures. The SEM images showed the
morphology, size, and particle distribution of different NFO samples.
From the electrochemical measurements, VSM data, and magnetic hy­
perthermia study it was found that electrochemical behaviors and
magnetic hyperthermia properties were closely associated with the
crystallite phase, size, and particularly the cation distribution within
NFO nanoparticles. Namely, benefiting from the small size, narrow size
distribution, and partially inverted structure (δ = 0.54), as well as the
co-presence of the high ratio of the side phase of Ni(OH)2, NFO-180
sample exhibited many unique features in terms of not only electro­
chemical properties (conductivity, active electrochemical surface area,
and charge/electron transfer kinetics) but also the magnetic hyper­
thermia properties with high saturation magnetization and large SAR
coefficient. Consequently, the precise control of the crystal structure
(phase and purity), size, and cation distribution in NFO in general, and
spinel materials in particular, will be an ideal approach to improve ef­
ficiency according to the requirements related to given applications.
9
Sensors and Actuators: A. Physical 359 (2023) 114511
1
and a frequency of
CRediT authorship contribution statement
V.M. Tien: Validation, Methodology, Formal Analysis, Writing –
original draft. T.N. Pham: Conceptualization, Methodology, Validation,
Investigation, Writing – original draft. O.V. Hoang: Validation, Inves­
tigation. N.L.N. Trang: Validation, Investigation. N.X. Dinh: Valida­
tion, Investigation. N.Q. Hoa: Methodology, Formal Analysis. D.A.
Tuan: Methodology, Validation. A.-T. Le: Conceptualization, Method­
ology, Supervision, Project administration, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
This research was supported in full with Kurita Asia Research Grant
(22Pvn015-T5) provided by Kurita Water and Environment Foundation.
V.M. Tien et al.
The authors would like to acknowledge the support for Raman & Elec­
trochemical measurements from NEB Lab; Hyperthermia measurements
from NERE Lab in the Phenikaa University; XRD, SEM and VSM supports
from HUS-VNU-Hanoi, IOP-VAST and ITIMS-HUST.
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Van Manh Tien: From 2008–2012: Student at Faculty of Physics, Hanoi University of
Science, Vietnam National University. From 2013–2020: Student at the Department of
Physics, Chungbuk National University. From 2021–2022, he joined as a Post-doctoral
Researcher at the School of Natural Science, Department of Physics, Ulsan National
Institute of Science and Technology (UNIST), Ulsan, South Korea. In April 2022, he joined
a Post-doctoral Researcher at Phenikaa University Nano Institute, Phenikaa University,
V.M. Tien et al. Sensors and Actuators: A. Physical 359 (2023) 114511

Vietnam. His interests are magnetic nanomaterials, nano-chemistry, energy storage, and Anh-Tuan Le obtained Ph.D degree at the Department of Materials Science and Engi­
environmental. neering, Chungnam National University (CNU), South Korea, in 2007. In 2019, he was
appointed as a Full Professor in Materials Science. He is currently a Director of Phenikaa
University Nano Institute (PHENA), Phenikaa University. His research interests are in a
Tuyet Nhung Pham received the Degree of Engineer in Chemical Engineering Technol­
wide range of soft magnetic materials, functional nanomaterials for biomedical and
ogy, Ha Noi University of Mining and Geology, Viet Nam in 2017. From 2017–2019, she
environmental applications, advanced chemo/bio sensing technologies, nanomedicine,
studied and received a Master degree in Nanomaterials at Gachon University, Korea. Dec
nano-formulations for sustainable agriculture.
2019, she has joined as a researcher at Phenikaa University Nano Institute, Phenikaa
University, Viet Nam. Her research interests are nanomaterials for environmental, energy
storage, and cosmetics applications.

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