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Synthesis of spinel ferrites and application in the photodegradation of

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DOI: 10.1016/j.optmat.2022.113043

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Optical Materials
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Research Article

F
Synthesis of spinel ferrites and application in the photodegradation of
Rhodamine in water via pH control assistance

OO
M.C.M. Ferreira a, c, F.R. Praxedes a, c, M.A.L. Nobre b, c, S. Lanfredi a, c, *
a Department of Chemistry and Biochemistry, São Paulo State University (Unesp), School of Technology and Sciences, R. Roberto Simonsen – 305, CEP: 19060–900,
Presidente Prudente- SP, Brazil
b Department of Physics, São Paulo State University (Unesp), School of Technology and Sciences, R. Roberto Simonsen – 305, CEP: 19060–900, Presidente Prudente- SP,

Brazil
c São Paulo State University (Unesp), Institute of Biosciences, Humanities and Exact Sciences, São José do Rio Preto, SP, 15054–000, Brazil

ARTICLE INFO

Keywords:
Ferrites
Spinel structure
Rhodamine 6G
ABSTRACT

PR
Nanostructured powders of cobalt ferrite with stoichiometry CoxFe3-xO 4, where 0.4 ≤ x ≤ 1.2, were synthesized
by the wet chemical route from the Co-precipitation method. Single-phase and crystalline nanopowders of spinel
type structure with cubic symmetry and space group were characterized by X-ray diffraction. The struc-
tural refinement was carried out by the Rietveld Method showing a transition of normal spinel to an inverse
D
Photocatalysis
spinel, as a function of Co2+concentration. Both spectra, Infrared Spectroscopy and Diffuse reflectance spec-
troscopy were used to characterize chemical bonds Co2+ in tetrahedral coordination, for higher cobalt concentra-
tion, and band gap analysis, respectively. The photoactivity of powders was evaluated from the photodegrada-
TE

tion of the Rhodamine 6G dye under UV light. CoFe2O4 nanoparticles showed the best photocatalytic degradation
with 90.9% in an alkaline medium, which obeys a pseudo-first order kinetic reaction, being the maximum appar-
ent rate constant equal to 10.23 × 10−3. Effects of the occupation of tetrahedral and octahedral sites in the spinel
structure in the photoactivity parameter are discussed.
EC

1. Introduction absorption and catalytic properties, binary ferrites compositions have

Advanced oxidation processes as heterogeneous photocatalysis have
received special attention for environmental and industrial application,
as well as for clean energy generation [1,2]. Semiconductors, with mul-
tifunctional properties, are potential photocatalysts due to the coupled
principle of solar photon absorption [2–5]. Spinel ferrite-
RR
been proposed via the partial substitution of iron (III) by metal cations
as Co2+, Zn2+, and Ni2+ in the spinel structure [5–7,9]. Cobalt ferrite
CoFe2O4 is a classical n-type semiconductor with a narrow type band
gap of 1.76 eV [10]. The magnetic property of ferrite-based materials
has scored these materials as promising photocatalysts due to the possi-
bility of easy recuperation from the aqueous medium by applying a

semiconductor is a class of multifunctional materials with intrinsic
magnetic feature, which combined with the solar photo-absorption and
the adsorbent properties [5–8], enables its use in environmental reme-
diation with easy retrieval of photocatalyst from the medium by using
an applied magnetic field.
In recent years, ferrites with spinel structure have been investigated
CO
magnetic field [11–14]. However, some aspects related to the photoac-
tivity of cobalt ferrite with A:B different from 1:2 and its structure is
still unclear; since cobalt ferrite can be stabilized in two distinct cubic
structures called spinel and spinel inverse [15].
In a broad sense, if A = B = Fe, the cobalt ferrite is transformed in
Fe3O4. As a matter of fact, the ferrite Fe3O4 can be further considered a

for their photocatalytic properties [8]. The spinel structure has been
represented by formula AB2O4, where A and B represent sites of metal-
lic cation exhibiting tetrahedral octahedral coordination with oxygen
atoms, respectively. The small band gap-covering photon absorption at
visible light region of electromagnetic spectra makes A:B with a ratio of
1:2 mono-ferrite a poor photocatalyst. In order to improve the photo-
prototype of other new functional or polyfunctional phases. In this
study, binary cobalt ferrite nanoparticles with stoichiometry CoxFe3-xO4
(0.4 ≤ x ≤ 1.2) were prepared by the wet chemical, from the Co-
precipitation method. The Co-precipitation was chosen due to several
advantages, such as facile and rapid preparation, cost-effectiveness, and
high mass production [16]. Detailed structural characterization was

* Corresponding author. Department of Chemistry and Biochemistry, São Paulo State University (Unesp), School of Technology and Sciences, R. Roberto Simonsen

– 305, CEP: 19060–900, Presidente Prudente- SP, Brazil.

E-mail address: silvania.lanfredi@unesp.br (S. Lanfredi).

https://doi.org/10.1016/j.optmat.2022.113043
Received 30 May 2022; Received in revised form 6 September 2022; Accepted 22 September 2022
0925-3467/© 20XX

Note: Low-resolution images were used to create this PDF. The original images will be used in the final composition.
M.C.M. Ferreira et al.
carried out and the photocatalytic activity on the structural and physic-
ochemical properties of cobalt ferrites was established.
2. Experimental procedure
2.1. Synthesis of cobalt ferrite by the wet chemical reaction
A set of cobalt doped ferrite powders with formula Co0.4Fe2.6O4
(CFO-0.4), Co0.8Fe2.2O4 (CFO-0.8), CoFe2O4 (CFO-1.0) and Co1.2Fe1.8O4
(CFO-1.2) were synthesized via wet chemical using the Co-precipitation
method. Precursor solutions of the CFO-0.4, CFO-0.8, CFO-1.0 and
CFO-1.2 were prepared using cobalt nitrate, Co(NO3)2·6H2O (98%,
Synth), and iron nitrate, Fe(NO3)3·9H2O (98%, Synth) in deionized wa-
ter. The solution prepared, with concentration equal to 0.14 mol L−1,
was heated at 80 °C under continuous stirring. Cobalt ferrites were ob-
tained via alkali precipitation with NaOH solution (2 mol L−1). A
change in the solution's color from brown to dark was observed when
the precipitates were formed. The pH of the solution was equal to 9.0.
The system was kept under heating and stirring for 2 h until complete
precipitation of the powders. According to Zhao et al. [17], the synthe-
PR
sis of cobalt ferrite by the Co-precipitation method can be represented
by the following equations:
Co(NO3)2·6H2O → Co(H2O)62+ + 2NO3− (1)
Fe(NO3)3·9H2O → Fe(H2O)63+ + 3NO3− + 3H2O (2)
Co(H2O)62+ + NaOH → Co(OH)x2−x → Co(OH)2↓ → Co(OH)3− (3)
D
Fe(H2O)63+ + NaOH → Fe(OH)y3−y → Fe(OH)3↓ → Fe(OH)4− (4)
(5)
Co(OH)3− + 2Fe(OH)4− → CoFe2O4↓ + 4H2O + 3OH−
TE
The hydroxy metal complex (reaction 5) is the main path to gener-
ate the cobalt ferrite particles by the Co-precipitation method.
The precipitate was centrifuged (6000 rpm for 40 min) and washed
thrice with deionized water and ethanol. Then, precipitates were dried
at 80 °C for 24h.
EC
2.2. Characterization
The morphology of the particles was investigated by Scanning Elec-
tron Microscopy (SEM) using Carl Zeiss equipment, model EVO LS15.
The structural characterization of Co-doped ferrite powders was an-
alyzed by X-ray diffraction (XRD). The patterns were recorded in the re-
RR
gion of 5o ≤ 2θ ≤ 80o with a 0.02° scanning step using a Shimadzu dif-
fractometer (XRD-6000 model) with Cu-Kα radiation (λ = 1.54 Å) and
a monochromator of graphite. Crystalline structures of Co-doped fer-
rites powders were refined by the Rietveld method using FullProf soft-
ware [18,19]. The set of parameters and variables refined are summa-
rized, as follows: background coefficients using a polynomial of 5-order
with a pseudo-Voigt function; scale factor; lattice parameter; and
CO
atomic coordination for three atoms (Fe, Co, O). The crystalline struc-
tures were built using Vesta software [20] from atomic positions de-
rived by the refinement.
The chemical bonds of the powders were analyzed by Fourier-
transform infrared spectroscopy (FTIR) using a PerkinElmer spec-
trophotometer (Frontier model), equipped with a diamond-crystal for
the attenuated total reflection (ATR). The measurements were carried
out with an instrument resolution of 2 cm−1 in the range of
4000–250 cm− 1 for 60 scans.
The energy band gap of the samples was determined from the
Kubelka-Munk theory based on the Tauc method. The band gap was de-
termined by plotting (F(R)hν)1/α = B (hν – Eg) considering α = 1/2 for
a direct transition [21]. The UV–vis analysis was carried out in the
range of 220–1400 nm using a Shimadzu UV2600 spectrophotometer
2
Optical Materials xxx (xxxx) 113043
with sphere integration ISR-2600Plus model equipped with a diffuse re-
flectance module.
2.3. Adsorption and photocatalytic tests
The photocatalytic activity of the CFO-0.4, CFO-0.8, CFO-1.0, and
CFO-1.2 samples was evaluated following the kinetics of degradation of
Rhodamine 6G (C28H31N2O3Cl, 99%, Sigma-Aldrich) called Rhd6G. Ex-
periments were carried out in polyvinyl chloride (PVC) homemade re-
actor (250 mL) equipped with a mercury lamp (Osram, 15 W, maxi-
F
mum emission at ca. 254 nm) and a water pump (5W) operating at a
flow rate of 180 L h−1 [22]. The total volume of Rhd6G solution was
1 L, while the volume of irradiated solution in the photoreactor was ca.
OO
250 mL. The initial concentration of Rhd6G and the amount of the cata-
lysts used in all photocatalytic tests were 10.4 μmol L−1 and 100 mg, re-
spectively. Therefore, the loading of samples was maintained keep con-
stant at ca. 0.1 g L−1. The equilibrium of adsorption of Rhd6G in the
dark was achieved after 1 h under constant stirring. After this time, UV
irradiation was performed for the 4 h of reaction. Several aliquots were
taken each 15 min for the first hour of irradiation and each 30 min for
the next 3 h. Aliquots were centrifuged at 3000 rpm before analysis by
UV–Vis spectroscopy in a Genesis model spectrophotometer with a sin-
gle bean. The samples were measured at 525 nm as the wavelength of
maximal absorption for Rhodamine Rhd6G dye. Experiments were car-
ried out at neutral (7.0), acid (3.0), and alkaline pH (9.0). Thus, the in-
fluence of the pH of the solution upon adsorption and photocatalytic ac-
tivity was verified. For the tests in neutral and alkaline medium, the so-
lution was adjusted to 7.0, or 9.0 using NaOH solution ca. 2 mol L−1,
while for the experiments under acidic conditions were not necessary to
adjust the pH.
3. Results and discussion
3.1. Morphological analysis of cobalt ferrite
The set of SEM micrographs of the cobalt ferrite powders are shown
in Fig. 1a–d. The results indicate that the samples prepared using the
Co-precipitation method are nanoparticulate in a spherical shape. How-
ever, the cobalt ferrite particles present a tendency to form clusters, as
shown in the scheme in Fig. 1e. According to Zhao et al. [17], the syn-
thesis of cobalt ferrite by the Co-precipitation method follows equations
(1)–(5)(see section 2.1). The average particle size parameter decreases
as a function of Co amount in crystalline lattice, as observed in the his-
tograms of Fig. 1a–d. The particle size was estimated using Euler's theo-
rem [22], where the average particle size <P> is obtained from the
particle size distribution ρ(n) by means of the n range of the particles,
according to equation (6):
<P ≥ Σn.ρ(n) (6)
The average particle size of cobalt ferrite from the histograms in Fig.
1a–d were ca. 133.5 nm, 132 nm, 74.5 nm, and 102.3 nm for CFO-0.4,
CFO-0.8, CFO-1.0, and CFO-1.2, respectively. In addition, the particle
clusters formation is affected with a tendency to be less agglomerated,
as shown in Fig. 1a–d and schematized in Fig. 1e. Thus, considering the
experimental conditions studied here, NaOH solution (2 mol L−1) drop-
wise increase rapidly the local concentration in the cationic precursor
solution (0.14 mol L−1). Momentaneous supersaturation produces the
primary particles or nuclei, which Ostwald-ripening governs the crystal
growth. The Ostwald ripening is schematized in Fig. 1f.
The mass of these primary particles is available to grow larger parti-
cles and coarsen the size distribution [23,24]. Therefore, a metastable
supersaturated phase will not only generate primarily particles [23] but
will also cause deposition of the generated primary particles and conse-
quent growth of the clusters [24]. The growth and nucleation paths fol-
low the Gibbs–Thomson effect, where smaller clusters dissolve and
M.C.M. Ferreira et al.
PR
D
TE
Fig. 1. SEM micrographs of the powders of: a) CFO-0.4, b) CFO-0.8, c) CFO-1.0, and d) CFO-1.2. e) Schematic representation of cobalt ferrite particles pro-
duced via wet chemical, according to cobalt-doping. f) Schematic representation of the Ostwald-ripening process in the formation of cobalt ferrite particle.
transfer their mass to larger clusters. Therefore, the increase in cobalt-
doping can influence the thermodynamical stability and/or modifying
EC
mass transport mechanism of primary particles, generating more stable
smaller particles and clusters in CFO-1.0 and CFO-1.2 than in CFO-0.4
and CFO-0.8.
3.2. Structural analysis
RR
Fig. 2a shows diffractograms of CFO-0.4, CFO-0.8 CFO-1.0 and
CFO-1.2 powders synthesized using the Co-precipitation method. Dif-
fraction patterns of all powders were assigned to spinel structure with
cubic symmetry and space group (227) according to JCPDS card
number #22–1086 [25]. Diffraction lines of another phases are not evi-
denced, what confirms the Co2+-doping in the spinel structure and the
reaching of single-phase powders.
CO
Fig. 2b shows that the line hkl (311) exhibits a shifting of line of ca.
0.23° and an increase in the intensity as cobalt-doping increases. The
shifting of diffraction line to a high degree can be associated with a
shortening of the interatomic distance and some degree of uniform ten-
sion [26]. The tensile strain due to an internal compressive micro-stress
[27] causes a decreasing in unit cell volume as discussed further. How-
ever, an increase in the intensity of the cobalt-doping can be related to
a change in the atomic positions in the spinel structure with cubic sym-
metry [26].
In order to investigate the structural correlation with cobalt-doping,
the structural refinement was performed using the Rietveld method
[22]. In addition, the crystallite size and anisotropic shape were mod-
eled by the Rietveld refinement using the spherical harmonic approach
[22,28]. Fig. 2c shows the structural refinement of CFO-1.0 as a model,
and the crystalline structure representation is shown in Fig. 2d. Accord-
3
Optical Materials xxx (xxxx) 113043
F
OO
ing to Fig. 2d, the spinel structure is arranged in a close-packed cubic
lattice formed by oxygen atoms (red sphere) and with the iron and
cobalt ions distributed at two different crystallographic sites, tetrahe-
dral A-site (pink sphere) and octahedral B-site (purple sphere). The
crystallite anisotropic shape of cobalt ferrite powders is shown in Fig.
2e, and the average crystallite size (D) is listed in Table 1. The crystal-
lite shape, size and symmetry are influenced by cobalt-doping, assum-
ing a more cubic shape at the higher Co2+ concentration. The cubic
crystallite shape agrees with the TEM data reported by Karthickraja et
al. [29], Maaz et al. [30], and Zhang et al. [31]. In addition, the average
crystallite size (Table 1) increases from 4.6 to 8.8 nm in the range of
CFO-0.4 to CFO-1.0 and decreases to 3.9 nm for the CFO-1.2. As men-
tioned in the SEM discussion, the crystallization of cobalt ferrite is gov-
erned by the Gibbs–Thomson effect [23,24]. In this sense, the growth
and nucleation paths of cobalt ferrite crystallization change according
to cobalt-doping, where at low Co2+ concentration, the mass transfer is
favorable, allowing the development of larger crystallites. Furthermore,
the concentration of Co2+ higher than CFO-1.0 has an inverse effect re-
stricting the crystal growth. Therefore, the cobalt diffusion process in
the spinel structure is thermodynamically favorable up to the CFO-1.0
composition. According to Muhich et al. [32], cobalt and iron have sim-
ilar activation energies when they diffuse with +2 oxidation state. Ac-
cordingly, the range of CFO-0.4 to CFO-1.0 exhibits an increase in crys-
tallite size from 4.6 to 8.8 nm, as shown in Table 1. However, the excess
of cobalt-doped in the CFO-1.2 ferrite hampers the growth of crystal-
lites (3.9 nm). The main reason is the difference in activation energy in
the diffusion of cobalt and iron with +2 and + 3 oxidation states, re-
spectively [32]. In this sense, the diffusion of Co2+ governs the crystal-
lite growth mechanism in cobalt ferrites. Furthermore, smaller crystal-
lites benefit the formation of clusters, as in CFO-0.4 as in CFO-1.2.
M.C.M. Ferreira et al. Optical Materials xxx (xxxx) 113043

F
OO
PR
D
TE
EC

Fig. 2. a X-ray diffraction of cobalt ferrite powders. b Expansion of the 2θ region between 34° and 38°. c Structural refinement by the Rietveld method for CFO-1.0
as a model, with cubic symmetry (227). d Spinel structure representation of cobalt ferrite, where pink tetrahedron correspond to atomic A-sites and purple oc-
tahedron are related to atomic B-sites. e Crystallite anisotropic shape of cobalt ferrite samples modeled from spherical harmonic approach via Rietveld refinement.
RR

Table 1 tutional solid solution [26,33]. The non-isovalent substitution and the
Lattice parameters and unit cell volumes for the cobalt ferrite powders. difference in ionic radii between Co2+ (0.78 Å) and Fe3+ (0.67 Å) can
Powder Lattice Parameter Unit cell Volume Rp Rwp Rexp χ2 D lead to the lattice distortion in the cubic spinel structure of the ferrite
(Å) (Å3) (nm) [26,27,33,34]. Thus, the correlation between structure distortion and
atomic substitution can be related to the bond length and bond angle
a=b=c
measurements. The interatomic lengths are listed in Table 2.
According to Table 2, an expansion of the tetrahedral site from the
CO

CFO- 8.375(4) 587.43(50) 17.7 23.0 15.0 2.33 4.6

0.4 CFO-0.4 to CFO-1.0 sample is observed. The Fe(1)–O bond length in-
CFO- 8.347(5) 581.56(60) 12.0 15.5 12.0 1.66 5.7
0.8
Table 2
CFO- 8.364(3) 585.12(40) 13.1 17.5 14.9 1.38 8.8
1.0 Interatomic lengths of Fe–O and Co–O bonds of cobalt ferrite powders in
CFO- 8.341(6) 580.30(70) 13.9 17.8 15.1 1.38 3.9 Fe(1)O4 tetrahedron and Fe(2)O6 octahedron.
1.2 Bond Site CFO-0.4 CFO-0.8 CFO-1.0 CFO-1.2

Therefore, the cluster formation by smaller crystallite size of CFO-1.2, Length (Å)

controlled by Co2+ diffusion, favors the formation of large particles Fe(1)–O (x4) Tetrahedron 1.8742 1.8954 1.9137 1.8203
(102.3 nm) compared to CFO-1.0 (74.5 nm). Fe(2)–O (x6) Octahedron 2.0592 2.0371 2.0334 2.0769
The lattice parameters and unit cell volume of cobalt ferrite pow- Valence (v.u.)
ders obtained via structural refinement are listed in Table 1. Fe3+–O Tetrahedron 2.93 2.77 2.63 3.39
The lattice parameter a varies at ca. 0.033 Å as a function of cobalt- Fe3+–O Octahedron 2.67 2.83 2.86 2.54
doping and it can be correlated with a decrease in the unit cell volume. Co2+–O Tetrahedron 2.44 2.31 2.20 2.83

A reduction in the unit cell volume indicates the formation of a substi- Co2+–O Octahedron 2.22 2.36 2.38 2.12

4
M.C.M. Ferreira et al. Optical Materials xxx (xxxx) 113043

creases at about 0.0395 Å, while the octahedral site in the CFO-0.4 to
CFO-1.0 samples contracts at ca. 0.0258 Å for the Fe(2)–O bond length.
On the other hand, is worth noting that the CFO-1.2 sample presents a
contraction of the tetrahedral site at about 0.0934 Å and an expansion
of the octahedral site at around 0.0435 Å compared with the CFO-1.0
sample. The preference of occupation of the Co2+ was analyzed in
terms of bond valence. According to Brown [35], a bond valence theory
can be described in terms of the following equation (7):
(7)
hedral site. The results are listed in Table 3. The bond angle variance for
the octahedral site increases linearly from CFO-0.4 to CFO-1.0 at about
8.32°, while it decreases at about 12.33° for CFO-1.2 compared to CFO-
1.0. On the other hand, the tetrahedral site is still unchanged in relation
to Co2+-doping. According to Boxall et al. [36], the photoactivity in
magnetite (Fe3O4) is due to the efficient electron exchange between
Fe2+ and Fe3+ in the octahedral sites.
In addition, electronic transitions from ions tetrahedrally and octa-
hedrally coordinated, as in magnetite and spinel cobalt ferrites, gener-
ate a set of intermediate gap states, which can extend its light absorp-

F
tion. Since, both conduction and valence bands are formed from the 3 d
where s is the bond valence, r0 and r are the standard and experi- state of Fe and the 2p state of oxygen, a shifting of the electrons to the
mental bond length, respectively, and b is an empirical parameter with 3 d state of Fe reduces the crystal field sufficiently and gives the forma-

a value equal to 0.37. The r0 value reported by Brown [35] for Fe3+–O
and Co2+–O standards were 1.759 Å and 1.692 Å, respectively. In addi-
tion, the oxidation state (Vi) in each crystallographic site of the spinel
structure was obtained by the summation of the bond valence (sij) ac-
cording to equation (8) [35].
(8)
OO
tion of extended 3 d gap states [39]. Therefore, in this work, the major
contribution to the photoactivity of cobalt ferrite can be assigned to the
octahedron site distortion and Co2+ distribution between spinel atomic
sites.
3.3. Chemical bonds and optical analysis

PR
The valence at the octahedron and tetrahedron sites of the spinel
structure is listed in Table 2. The tetrahedral site assumes a valence
close to +2.0 as Co2+-doped increases up to CFO-1.0. On the other
hand, the octahedron site assumes a valence of ca. +3.0 as cobalt-
doped increases in the same way. Thus, Fe3+ prefers octahedral coordi-
nation, while Co2+ should occupies the tetrahedral coordination. These
results are in agreement with Sharma and coworkers [34]. However,
D
the difference in the valence of the octahedron site from the formal
charge +3.0 indicates that the preference of occupancy is not restricted
only to Fe3+, but also some Co2+ have occupancy at the octahedron site
TE
The FTIR spectra of the cobalt ferrite powders are shown in Fig. 3a
and FTIR and UV–vis spectroscopy results are listed in Table 4.
All the samples showed similar bands at 3370 cm−1 and 1584 cm−1
assigned to O–H stretching (νOH) and O–H deforming (δOH), respectively
[40,41]. These bands indicate water molecules chemically adsorbed, in
the powders. A third band observed at around 1338 cm−1 is assigned to
nitrate vibration [41], which can be derived from precursor reagents
adsorbed in the powders. The region between 1000 cm−1 and 250 cm−1
corresponds to the metal-oxygen (Me–O) bond. A band at around
961 cm−1 is attributed to the Fe-Co alloy system [41]. Another band at
around 554 cm−1 is assigned to Co–O stretching vibration mode from
the octahedral site [40–42]. The last band at 350 cm−1 is related to the

[36]. Therefore, there is some degree of inversion in the spinel struc-

ture. Above CFO-1.0, the spinel structure is preferentially inversed with
the octahedral and tetrahedral sites having +2.12 and + 3.39 valences
for the Co2+ and Fe3+ occupancy, respectively. These results indicate
that in the range of CFO-0.4 – CFO-1.0 a normal spinel structure is fa-
vored with slight inversion, while above CFO-1.0 the spinel structure
EC
Fe–O stretching vibration mode associated with the tetrahedral site
[40,42]. These bands indicate the formation of the spinel CoFe2O4.
The optical absorption spectra from diffuse reflectance measure-
ments for the cobalt ferrite powders are shown in Fig. 3b. A broad band
of cobalt ferrite powders is shown in the range of 220–800 nm, in the

shows a major degree of inversion [15,37]. Based on the variance angle
of the octahedral and tetrahedral sites [38], the distortion in both
atomic sites in the spinel structure of cobalt ferrite powders was mea-
sured. The bond angles are listed in Table 3.
(9)
RR
UV–Visible spectral region. This band is assigned to the overlapping 4A2
→ 4T1 (4P) transition of the tetrahedral Co2+ and the Co2+ + Fe3+ →
Co3+ + Fe2+ metal–metal charge transfer transition (MMCT) [43].
Also, it can be seen from the CFO-1.0 and CFO-1.2 bands in the region
of 700–1300 nm (inset of Fig. 3b), related to the 4A2 → 4T1 (4F) crystal
field transition of the Co2+ ions in tetrahedral symmetry [43]. The ap-
pearance of this band is in agreement with the results obtained from the

structural refinement (section 3.2). Therefore, the lack of a vibrational

The variance angle (σ2) depends on the number of bonds (n), ith
bond angles (θi), and ideal bond angle (θ0) of the atomic site. The ideal
bond angle assumes 90° for the octahedral site and 109.47° for the tetra-
Table 3
CO
band in the region of 700–1300 nm for the CFO-0.4 and CFO-0.8 pow-
ders can be correlated with a spinel structure with some degree of in-
version. For CFO-1.0, the Co2+ concentration is sufficient to create an
intense band in the region of 700–1300 nm, suggesting that the normal
spinel structure is favored. CFO-1.2 powder also presents an intense vi-

brational band in the region of 700–1300 nm, suggesting a normal

Bond angles (θ) of Fe(1)O4 tetrahedron and Fe(2)O6 octahedron of cobalt fer-
spinel structure with cobalt occupying the tetrahedral site. However,
rites.
according to rule of the valence sum for CFO-1.2, see section 3.2 discus-
Bond CFO-0.4 CFO-0.8 CFO-1.0 CFO-1.2
sion, Co2+ has a preference to occupy octahedral site with a valence of
θ (°) +2.12. In this sense, part of the Co2+ may migrate from tetrahedral to
the octahedral site in CFO-1.2, and the normal spinel structure becomes
O-Fe(1)-O (x6) 109.5 109.5 109.5 109.5 small inversion degree. Thus, these results can be correlate with a
O-Fe(2)-O (x6) 91.97 92.89 93.40 90.46
mixed spinel structure, i.e., CFO-1.2 can present both normal and in-
O-Fe(2)-O (x6) 88.03 87.10 86.61 89.54
O-Fe(2)-O (x3) 180.0 180.0 180.0 180.0 verted spinel with Co2+ occupying both tetrahedral and octahedral
Fe(1)-O-Fe(2) (x3) 123.9 123.2 122.9 124.9 sites.
Fe(2)-O-Fe(2) (x3) 91.94 92.83 93.30 90.46 Based on a direct transition (α = 1/2) [42,43], the energy gap of
σ2(oct) (°) 4.251 9.168 12.57 0.239 the cobalt ferrite powders was obtained from the Tauc plot method
σ2(tet) (.10−6 °) 1.200 1.200 1.200 1.200 (Fig. 3c). Considering values of energy gap derived from the best linear
range (2.25–3.25 eV), the intercept of the linear regression of the Tauc
The distortion measurement was calculated from equation (9) considering the plot with the energy axis determines the position of Eg Ref. [20] as
bond angles listed in Table 3.

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M.C.M. Ferreira et al. Optical Materials xxx (xxxx) 113043

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Fig. 3. a Infrared spectra of cobalt ferrites. b DR/UV–vis spectra in terms of the Kubelka-Munk theory. c Tauc plot according to a direct transition. d Linear regression
of Tauc plot in the range (2.25–3.25 eV).
D
Table 4 parameter photocatalytic efficiency (ζ) of the cobalt ferrite powders for
Attribution and wavenumber assignments of the Fe–O and Co–O vibration the oxidation of Rhd6G in water can be represented by equation (10)
bands obtained from FTIR spectra, and optical properties of samples, includ-
TE

[44].
ing maxima absorption wavelength (λabs-photon) and optical energy band gap
(Eg) obtained from DR/UV–vis spectra.
(10)
Powder Wavenumber (cm−1) λabs-photon (nm) Eg (eV)

Fe–O Co–O where C0 is the initial concentration of Rhd6G and Ct is the real-time
concentration of Rhd6G under UV light irradiation. A representative
EC

CFO-0.4 352 552 633 1.956

CFO-0.8 292 527 728 1.701 graphic of the photocatalytic efficiency of cobalt ferrites is shown in
CFO-1.0 310 550 633 1.958 Fig. 4f. The photocatalytic efficiency of cobalt ferrites seems to be re-
CFO-1.2 336 541 656 1.890 lated to the Co2+-doping. At alkaline pH, the CFO-0.8 powder has a
higher efficiency equal to 92.2%. However, the CFO-1.0 powder ex-
shown in Fig. 3d. The set of band gap values is listed in Table 4. The en- hibits an efficiency of 74.5% in acidic pH, 88.9% in neutral pH, and
ergy gap of cobalt ferrite synthesized by the Co-precipitation method 90.9% in alkaline pH. The increase in photoactivity under acidic condi-
RR

agrees with values of the literature [42,43]. The lower energy gap of
cobalt ferrite powders indicates that the Co2+-doping gives rise a new
level to the conduction band of ferrite and the electrons can be pro-
moted more easily from the valence band to these ions' levels, favoring
the cobalt ferrite powders’ response in the visible region.
CO
tions can be associated with the increase of Co2+-doping: 65.7%,
68.8%, 74.5%, and 76.2% for the CFO-0.4, CFO-0.8, CFO-1.0, and CFO-
1.2, respectively. On the other hand, the efficiency in the Co2+-doping
higher than CFO-1.0 decreases in neutral and alkaline pH. The kinetics
of Rhd6G degradation reaction over cobalt ferrite catalysts was investi-
gated in terms of the Langmuir-Hinshelwood mechanism [1]. In this

3.4. Photocatalysis mechanism, the rate of reaction (r) is proportional to the surface loaded
with pollutants (θ) according to equation (11).
The photocatalytic activity of cobalt ferrites was evaluated by the
(11)
photodegradation of Rhd6G as a pollutant model. According to diffuse
reflectance data, cobalt ferrite has a large absorption band in the
where kr is the reaction-rate constant, Kads the adsorption constant
UV–Vis region. The photodegradation of Rhd6G (1 L, 10.4 μmol L−1)
according to the Langmuir model, and Ceq is the concentration of the
under irradiation and in the absence of catalyst is shown in Fig. 4a. The
pollutant in the equilibrium conditions. As the Ceq value is lower
Rhd6G has a minimum degradation in the absence of catalyst, being
(≤10−3 mol L−1) for diluted systems, a simplification is made consider-
more susceptible to degradation in neutral (pH 7.0) to alkaline (pH 9.0)
ing . Thus, equation (11) is simplified to first-order kinet-
conditions. Fig. 4b–e shows the adsorption of the series of Rhd6G solu-
ics described by equation (12).
tions in the presence of the cobalt ferrite powders (100 mg) under light
irradiation for 240 min. (12)
In the presence of cobalt ferrites, Rhd6G concentration decreases
gradually with the irradiation time. The kinetics of degradation be-
comes more pronounced when the reaction occurs at alkaline pH. The

6
M.C.M. Ferreira et al. Optical Materials xxx (xxxx) 113043

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Fig. 4. Kinetics of Rh6G degradation under UV-irradiation: a Direct photolysis, b CFO-0.4, c CFO-0.8, d CFO-1.0, e CFO-1.2. f Photodegradation efficiency of cobalt
ferrite powders.
CO

where kapp is the first-order apparent rate constant which can be ob-
tained from the linear regression of the kinetic data of degradation, as a
function of the irradiation time, according to equation (13).
(13)
where Ceq is the initial concentration after achieving the equilibrium
of adsorption in the absence of light, and Ct is the concentration at the
time t of irradiation.
Fig. 5 shows the linear regressions of the kinetic data from Fig. 4b–e,
and a set of the kinetic parameters obtained for the Rhd6G photodegra-
dation is listed in Table 5.
According to Fig. 5, Rhd6G photodegradation follows a pseudo-first-
order reaction with good linear fitting. From the first-order apparent
rate constant (kapp), the cobalt plays a crucial role in the photoactivity
of cobalt ferrite powders. In a broad sense, the increase in the degrada-
tion can be derived from aspects such as particle size, structure, and re-
active sites [1], as well as surface characteristics.
The higher photoactivity level of cobalt ferrite powders can be due
to the intrinsic characteristics and surface area of nanoparticle clusters.
In this way, cobalt in tetrahedral coordination, as pointed out by the va-
lence shown in Table 2, favors the photoactivity of CFO-0.4, CFO-0.8,
and CFO-1.0 powders in neutral and alkaline media. However, the octa-
hedral coordination cobalt, as in CFO-1.2, benefits the photo activity in
the acidic medium. In this context, the higher CFO-0.8 photoactivity
over CFO-1.0 can be understood by means of cobalt occupation in the
tetrahedral site and its control of the Rhd6 adsorption over different pH

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M.C.M. Ferreira et al. Optical Materials xxx (xxxx) 113043

F
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Fig. 5. Linear regression from the kinetic data in Fig. 4: a CFO-0.4. b CFO-0.8. c CFO-1.0. d CFO-1.2.
D
Table 5 both tetrahedral and octahedral sites. For this reason, as shown in Fig.
List of kinetics parameters of Rhd6G photodegradation, in distinct pH values. 3b for CFO-1.0 and CFO-1.2, the octahedral site loses its distortion and
becomes more symmetrical with angles close to 90°.
TE

Powder pH kapp (min−1) x10−3 R2

CFO-0.4 Acidic 3.99 0.9562 4. Conclusions

Neutral 6.04 0.9705
Alkaline 9.49 0.9977 Cobalt ferrite nanoparticles with stoichiometry Co0.4Fe2.6O4,
CFO-0.8 Acidic 4.76 0.9832 Co0.8Fe2.2O4, CoFe2O4, and Co1.2Fe1.8O4 have been synthesized by the
Neutral 6.87 0.9313
wet chemical route, a Co-precipitation method, at 80 °C. The nanoparti-
EC

Alkaline 11.1 0.9931

cles show spherical morphology arranged in cluster form. Structural
CFO-1.0 Acidic 6.15 0.9759
Neutral 9.07 0.9977 analysis from XRD confirmed the synthesis of a cobalt ferrite single-
Alkaline 10.23 0.9991 phase with a spinel structure of cubic symmetry . Structural re-
CFO-1.2 Acidic 5.65 0.9661 finement by the Rietveld method showed an inverse spinel structure for
Neutral 6.93 0.9702 CFO-0.4, while for CFO-0.8 and CFO-1.0 a normal structure was more
Alkaline 9.30 0.9940
favorable. However, for CFO-1.2, the inverse spinel structure is again
RR

predominant. Both FTIR and UV–visible spectroscopies showed that the

conditions. Accordingly, the photoactivity of cobalt ferrites has an inti-
mate relationship with the cobalt tetrahedrally coordinated.
As highlighted in the structural characterization, the octahedral site
becomes more distorted with cobalt concentration increase in this site
and makes Fe3+ migrate to the tetrahedral site, in according to Table
data and discussion. From this point, the reaction rate increases at a
CO
Co2+ is tetrahedral coordination in the spinel structure for CFO-1.0 and
CFO-1.2 samples. The CFO-1.0 sample showed the best photoactivity
correlation in the degradation of the RhD6G in acidic (74.5%), neutral
(88.9%), and alkaline media (90.9%). The electronic excitation and mi-
gration on the surface of nanoparticles have an intrinsic correlation to
octahedral site distortion and Co2+ occupation at both octahedron and

neutral pH from 6.04 × 10−3 min−1 (CFO-0.4) to 9.07 × 10−3 min−1
(CFO-1.0); and at alkaline pH from 9.49 × 10−3 min−1 (CFO-0.4) to
11.1 × 10−3 min−1 (CFO-0.8), and 10.23 × 10−3 min−1 (CFO-1.0). This
behavior indicates a narrow correlation with the octahedral site activity
as it becomes more distorted (see Table 3). Earlier, similar effects in fer-
roelectric perovskites [22] and tetragonal tungsten bronze structures
[45] have been reported. Formation of reactive species can be derived
from apical oxygen atoms in octahedral sites, which is not as efficient in
the acid medium as in the alkaline medium [46], and thus, a decrease in
photoactivity is expected. On the other hand, the tetrahedral site con-
trols the photoactivity of cobalt ferrites in the acidic medium.
The rate constant of CFO-1.2 shows a slight change in the degrada-
tion reaction of Rhd6G in the acidic medium compared to the neutral
and alkaline medium. The structural and optical analysis of CFO-1.2
shows that Co2+ at higher concentrations has a preference to occupy
tetrahedron sites. According to the results, superficial reactions in an al-
kaline medium are favorably catalyzed by cobalt ferrite with a predom-
inant normal spinel structure. On the other hand, reactions under acidic
conditions are best catalyzed with cobalt ferrites of inverse spinel type
structure. These finds could be beneficial for designing new ferrite cata-
lysts for different waste water environment treatments.
CRediT authorship contribution statement
M.C.M. Ferreira : Investigation. F.R. Praxedes : Investiga-
tion. M.A.L. Nobre : Conceptualization, Investigation. S. Lanfredi :
Conceptualization, Investigation.

8
M.C.M. Ferreira et al.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Data availability
No data was used for the research described in the article.
Acknowledgment
F.R. Praxedes thanks “Coordenação de Aperfeiçoamento de Pessoal
de Nível Superior (CAPES)” - Finance Code 001. S. Lanfredi acknowl-
edges the Brazilian projects: Grant# 2002/05997-9, 2007/03510-9,
2014/11189-0, 2019/06623-6, 2020/00781-6 from São Paulo Re-
search Foundation (FAPESP) and CNPq for financial support. V.P. Car-
valho-Jr for DR/UV–vis measurements.
References
PR
[1] J.M. Herrmann, Photocatalysis fundamentals revisited to avoid several
misconceptions, Appl. Catal. B Environ. 99 (2010) 461–468, https://doi.org/
10.1016/j.apcatb.2010.05.012.
[2] Y. Zhang, Z.R. Tang, X. Fu, Y.J. Xu, TiO2 Graphene nanocomposites for gas-phase
photocatalytic degradation of volatile aromatic pollutant: is TiO2-graphene truly
different from other TiO2-carbon composite materials, ACS Nano 4 (12) (2014)
7303–7314, https://doi.org/10.1021/nn1024219.
[3] J. Li, C. Yu W. Fang, W. Zhou, L. Zhu, Y. Xie, Ag-based semiconductor
photocatalysts in environmental purification, Appl. Surf. Sci. 358 (A) (2015)
D
46–56, https://doi.org/10.1016/j.apsusc.2015.07.139.
[4] P. Dong, G. Hou, X. Xi, R. Shao, F. Dong, WO3-based photocatalysts: morphology
control, activity enhancement and multifunctional applications, Environ. Sci. Nano
4 (3) (2017) 539–557, https://doi.org/10.1039/c6en00478d.
[5] Y. Liu, Y. Song, Y. You, X. Fu, J. Wen, X. Zheng, NiFe2O4/g-C3N4 heterojunction
TE
composite with enhanced visible-light photocatalytic activity, J. Saudi Chem. Soc.
22 (4) (2018) 439–448, https://doi.org/10.1016/j.jscs.2017.08.002.
[6] Y. Lu, B. Ren, S. Chang, W. Mi, J. He, W. Wang, Achieving effective control of the
photocatalytic performance for CoFe2O4/MoS2 heterojunction via exerting external
magnetic fields, Mater. Lett. 260 (2020) 126979, https://doi.org/10.1016/
j.matlet.2019.126979.
[7] A. Sudhaik, P. Raizada, P. Shandilya, P. Singh, Magnetically recoverable
graphitic carbon nitride and NiFe2O4 based magnetic photocatalyst for degradation
EC
of oxytetracycline antibiotic in simulated wastewater under solar light, J. Environ.
Chem. Eng. 6 (2018) 3874–3883, https://doi.org/10.1016/j.jece.2018.05.039.
[8] K.K. Kefeni, B.B. Mamba, T.A. Msagati, Application of spinel ferrite nanoparticles
in water and wastewater treatment: a review, Separ. Purif. Technol. 188 (2017)
399–422, https://doi.org/10.1016/j.seppur.2017.07.015.
[9] A. Al-Anazi, W.H. Abdelraheem, K. Scheckel, M.N. Nadagouda, K. O’Shea, D.D.
Dionysiou, Novel franklinite-like synthetic zinc-ferrite redox nanomaterial:
synthesis, and evaluation for degradation of diclofenac in water, Appl. Catal. B
RR
Environ. 275 (2020) 119098, https://doi.org/10.1016/j.apcatb.2020.119098.
[10] E. Ferdosi, H. Bahiraei, D. Ghanbari, Investigation the photocatalytic activity of
CoFe2O4/ZnO and CoFe2O4/ZnO/Ag nanocomposites for purification of dye
pollutants, Separ. Purif. Technol. 211 (2019) 35–39, https://doi.org/10.1016/
j.seppur.2018.09.054.
[11] Z. Jia, D. Ren, Y. Liang, R. Zhu, A new strategy for the preparation of porous zinc
ferrite nanorods with subsequently light-driven photocatalytic activity, Mater. Lett.
65 (2011) 3116–3119, https://doi.org/10.1016/j.matlet.2011.06.101.
CO
[12] J.K. Rajput, G. Kaur, Synthesis and applications of CoFe2O4 nanoparticles for
multicomponent reactions, Catal. Sci. Technol. 4 (2014) 142–151, https://doi.org/
10.1039/c3cy00594a.
[13] G. El-Shobaky, A. Turky, N. Mostafa, S. Mohamed, Effect of preparation
conditions on physicochemical, surface and catalytic properties of cobalt ferrite
prepared by coprecipitation, J. Alloys Compd. 493 (2010) 415–422, https://
doi.org/10.1016/j.jallcom.2009.12.115.
[14] V. Pillai, D. Shah, Synthesis of high-coercivity cobalt ferrite particles using water-
in-oil microemulsions, J. Magn. Magn Mater. 163 (1996) 243–248, https://doi.org/
10.1016/S0304-8853(96)00280-6.
[15] K.E. Sickafus, J.M. Wills, N.W. Grimes, Structure of spinel, J. Am. Ceram. Soc. 82
(1999) 3279–3292, https://doi.org/10.1111/j.1151-2916.1999.tb02241.x.
[16] I. Safarik, K. Horska, K. Pospiskova, Z. Maderova, M. Safarikova, Microwave
assisted synthesis of magnetically responsive composite materials, IEEE Trans.
Magn. 49 (2012) 213–218, https://doi.org/10.1109/TMAG.2012.2221686.
[17] D. Zhao, X. Wu, H. Guan, E. Han, Study on supercritical hydrothermal synthesis
of CoFe2O4 nanoparticles, J. Supercrit. Fluids 42 (2) (2007) 226–233, https://
doi.org/10.1016/j.supflu.2007.03.004.
[18] J. Rodríguez-Carvajal, Recent advances in magnetic structure determination by
neutron powder diffraction, Phys. B: Phys. Condens. Matter 192 (1993) 55–69,
9
Optical Materials xxx (xxxx) 113043
https://doi.org/10.1016/0921-4526(93)90108-I.
[19] J. Rodríguez-Carvajal, An Introduction to the Program FullProff 2000
(Laboratorie Léon Brillouin, CEACNRS, Saclay), 2001 France.
[20] K. Momma, F. Izumi, VESTA 3 for three-dimensional visualization of crystal,
volumetric and morphology data, J. Appl. Crystallogr. 44 (2011) 1272–1276,
https://doi.org/10.1107/S0021889811038970.
[21] P. Makuła, M. Pacia, W. Macyk, How to correctly determine the band gap energy
of modified semiconductor photocatalysts based on UV-Vis spectra, J. Phys. Chem.
Lett. 9 (2018) 6814–6817, https://doi.org/10.1021/acs.jpclett.8b02892.
[22] F.R. Praxedes, M.A.L. Nobre, P.S. Poon, J. Matos, S. Lanfredi, Nanostructured
KxNa1-xNbO3 hollow spheres as potential materials for the photocatalytic treatment
of polluted water, Appl. Catal. B Environ. 298 (2021) 120502, https://doi.org/
10.1016/j.apcatb.2021.120502.
F
[23] R.B. McClurg, R.C. Flagan, Critical comparison of droplet models in
homogeneous nucleation theory, J. Colloid Interface Sci. 201 (2) (1998) 194–199,
https://doi.org/10.1006/jcis.1997.5379.
[24] B.J. McCoy, Distribution kinetics modeling of nucleation, growth, and
OO
aggregation processes, Ind. Eng. Chem. Res. 40 (2001) 5147–5154, https://
doi.org/10.1021/ie001034i.
[25] M. Sedlacik, V. Pavlinek, P. Peer, P. Filip, Tailoring the magnetic properties and
magnetorheological behavior of spinel nanocrystalline cobalt ferrite by varying
annealing temperature, Dalton Trans. 43 (2014) 6919–6924, https://doi.org/
10.1039/c4dt00166d.
[26] B.G. Toksha, S.E. Shirsath, M.L. Mane, S.M. Patange, S.S. Jadhav, K.M. Jadhav,
Autocombustion high-temperature synthesis, structural, and magnetic properties of
CoCrxFe2-xO4 (0 ≤ x ≤ 1.0), J. Phys. Chem. C 115 (43) (2011) 20905–20912,
https://doi.org/10.1021/jp205572m.
[27] M. El-Hilo, A.A. Dakhel, Structural and magnetic properties of Mn-doped ZnO
powders, J. Magn. Magn Mater. 323 (2011) 2202–2205, https://doi.org/10.1016/
j.jmmm.2011.03.031.
[28] M. Casas-Cabanas, M.R. Palacín, J. Rodríguez-Carvajal, Microstructural analysis
of nickel hydroxide: anisotropic size versus stacking faults, Powder Diffr. 20 (2005)
334–344, https://doi.org/10.1154/1.2137340.
[29] D. Karthickraja, S. Karthi, G.A. Kumar, D.K. Sardar, G.C. Dannangoda, K.S.
Martirosyan, E.K. Girija, Fabrication of core-shell CoFe2O4@HAp nanoparticles: a
novel magnetic platform for biomedical applications, New J. Chem. 43 (2019)
13584–13593, https://doi.org/10.1039/c9nj02510c.
[30] K. Maaz, A. Mumtaz, S.K. Hasanain, A. Ceylan, Synthesis and magnetic
properties of cobalt ferrite (CoFe2O4) nanoparticles prepared by wet chemical
route, J. Magn. Magn Mater. 308 (2007) 289–295, https://doi.org/10.1016/
j.jmmm.2006.06.003.
[31] Y. Zhang, Z. Yang, D. Yin, Y. Liu, C. Fei, R. Xiong, J. Shi, G. Yan, Composition and
magnetic properties of cobalt ferrite nano-particles prepared by the co-
precipitation method, J. Magn. Magn Mater. 322 (2010) 3470–3475, https://
doi.org/10.1016/j.jmmm.2010.06.047.
[32] C.L. Muhich, V.J. Aston, R.M. Trottier, A.W. Weimer, C.B. Musgrave, First-
Principles analysis of cation diffusion in mixed metal ferrite spinels, Chem. Mater.
28 (2016) 214–226, https://doi.org/10.1021/acs.chemmater.5b03911.
[33] S.K. Gore, S.S. Jadhav, V.V. Jadhav, S.M. Patange, M. Naushad, R.S. Mane, K.H.
Kim, The structural and magnetic properties of dual phase cobalt ferrite, Sci. Rep. 7
(1) (2017) 2524, https://doi.org/10.1038/s41598-017-02784-z.
[34] R. Sharma, P. Thakur, M. Kumar, N. Thakur, N.S. Negi, P. Sharma, V. Sharma,
Improvement in magnetic behaviour of cobalt doped magnesium zinc nano-ferrites
via co-precipitation route, J. Alloys Compd. 684 (2016) 569–581, https://doi.org/
10.1016/j.jallcom.2016.05.200.
[35] I.D. Brown, Recent developments in the methods and applications of the bond
valence model, Chem. Rev. 109 (2009) 6858–6919, https://doi.org/10.1021/
cr900053k.
[36] C. Boxall, G. Kelsall, Z. Zhang, Photoelectrophoresis of colloidal iron oxides. Part
2.—magnetite (Fe3O4), J. Chem. Soc., Faraday Trans. 2 (1998) 43527–43780,
https://doi.org/10.1039/FT9969200791.
[37] Y.H. Hou, Y.J. Zhao, Z.W. Liu, H.Y. Yu, X.C. Zhong, W.Q. Qiu, D.C. Zeng, L.S.
Wen, Structural, electronic and magnetic properties of partially inverse spinel
CoFe2O4: a first-principles study, J. Phys. D Appl. Phys. 43 (2010) 445003, https://
doi.org/10.1088/0022-3727/43/44/445003.
[38] K. Robinson, G.V. Gibbs, P.H. Ribbe, Quadratic elongation: a quantitative
measure of distortion in coordination polyhedra, Science 172 (1971) 567–570,
https://doi.org/10.1126/science.172.3983.567.
[39] P. Mishra, S. Patnaik, K. Parida, An overview of recent progress on noble metal
modified magnetic Fe3O4 for photocatalytic pollutant degradation and H2
evolution, Catal. Sci. Technol. 9 (2019) 916–941, https://doi.org/10.1039/
c8cy02462f.
[40] J.B. Silva, W. De Brito, N.D.S. Mohallem, Influence of heat treatment on cobalt
ferrite ceramic powders, Mater. Sci. Eng B-Solid. 112 (2004) 182–187, https://
doi.org/10.1016/j.mseb.2004.05.029.
[41] D. Karthickraja, S. Karthi, G.A. Kumar, D.K. Sardar, G.C. Dannangoda, K.S.
Martirosyan, E.K. Girija, Fabrication of core-shell CoFe2O4@HAp nanoparticles: a
novel magnetic platform for biomedical applications, New J. Chem. 43 (2019)
13584–13593, https://doi.org/10.1039/c9nj02510c.
[42] M.H. Habibi, H.J. Parhizkar, FTIR and UV-vis diffuse reflectance spectroscopy
studies of the wet chemical (WC) route synthesized nano-structure CoFe2O4 from
CoCl2 and FeCl3, Spectrochim. Acta Mol. Biomol. Spectrosc. 127 (2014) 102–106,
https://doi.org/10.1016/j.saa.2014.02.090.
[43] I.H. Gul, A. Maqsood, M. Naeem, M.N. Ashiq, Optical, magnetic and electrical
investigation of cobalt ferrite nanoparticles synthesized by co-precipitation route,
J. Alloys Compd. 507 (2010) 201–206, https://doi.org/10.1016/
M.C.M. Ferreira et al. Optical Materials xxx (xxxx) 113043

j.jallcom.2010.07.155.
[44] F. Wang, L.X. Song, Y. Teng, J. Xia, Z.Y. Xu, W.P. Wang, Synthesis, structure,
magnetism and photocatalysis of α-Fe2O3 nanosnowflakes, RSC Adv. 9 (2019)
35372–35383, https://doi.org/10.1039/c9ra07490b.
[45] J. Matos, S. Lanfredi, R. Montaña, M.A.L. Nobre, M.C. Fernández de Córdoba,
C.O. Ania, Photochemical reactivity of apical oxygen in KSr2Nb5O15 materials for
environmental remediation under UV irradiation, J. Colloid Interface Sci. 496
(2017) 211–221, https://doi.org/10.1016/j.jcis.2017.02.028.
[46] J. Matos, J. Arcibar-Orozco, P.S. Poon, G. Pecchi, J.R. Rangel-Mendez, Influence
of phosphorous upon the formation of DMPO-•OH and POBN-O2•− spin-trapping
adducts in carbon-supported P-promoted Fe-based photocatalysts, J. Photochem.
Photobiol., A: Chem 391 (2020) 112362, https://doi.org/10.1016/
j.jphotochem.2020.112362.

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