Inorganic Chemistry Communications 170 (2024) 113170

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Inorganic Chemistry Communications

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Short communication

Zn0.5Ni0.5MnxFe2-xO4 magnetically separable nano ferrite: A highly efficient

photocatalyst for environmental remediation
Santosh Arade a , Pramod Agale a , Sagar Balgude b, Sunil Patange c , Dattatray Hingane d ,
Paresh More a,*
a
Department of Chemistry, K. E. T’s, V. G. Vaze College, Mulund (E), Maharashtra, India
b
Department of Chemistry, Abasaheb Garware College, Pune, Maharashtra, India
c
Department of Physics, Shrikrishna Mahavidyalaya, Osmanabad, Maharashtra, India
d
Department of Chemistry, Mahatma Phule Mahavidyalaya, Pimpri, Pune, Maharashtra, India

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

Keywords: The escalating pollution from industries poses a severe threat to water resources, necessitating efficient photo­
Zn0.5Ni0.5MnxFe2-xO4 catalysts for environmental remediation. In this study, we introduce a novel Zn0.5Ni0.5MnxFe2-xO4 nano ferrite,
Photodegradation synthesized via sol–gel auto-combustion method. The phase purity of Zn0.5Ni0.5MnxFe2-xO4 nano ferrites was
Nano ferrite
confirmed from X-ray diffraction (XRD) and Fourier Transform Infrared (FTIR) Spectroscopy. The microstruc­
RO dye
Rietveld refinement
tural investigation of nano ferrites was investigated using Field Emission Scanning Electron Microscopy (FESEM)
TEM and Transmission Electron Microscopy (TEM). The catalyst’s magnetic properties allow easy separation,
addressing the challenge of catalyst retrieval in photocatalysis. Incorporating Zn, Ni, and Mn at tetrahedral and
octahedral sites enhances crystallinity, crucial for catalytic efficiency. This mixed metal oxide catalyst demon­
strates superior photocatalytic activity, with Zn0.5Ni0.5MnFeO4 exhibiting a remarkable 97% degradation of
Reactive Orange (RO) dye under sunlight. Notably, the photocatalyst displays stability and reusability over
multiple cycles. The study provides valuable insights into the potential of Zn0.5Ni0.5MnxFe2-xO4 ferrite as a
magnetically separable, efficient photocatalyst for environmental remediation.

1. Introduction smell, posing risks such as elevated biochemical oxygen demand (BOD)
and potential carcinogenic effects [5–8]. Further, the dying process
Rapid industrialization and urbanization have degraded natural precipitates highly coloured effluents in water resources, which is
water resources to such an extent that there is not only scarcity in aesthetically unpleasant and severely damage the marine ecosystem [9].
availability of drinking and potable water but also several risks to These hazardous pollutants must be removed or treated before being
human and animal health. Dye contaminants obtained from the textile, released to avoid water pollution. Polluted water can be treated using
printing and many other industries play a vital role in damaging the many processes like, chemical, physical, and biological. However
environment. During fabric dying in the textile industry, up to 15 % of chemical processes have an edge over other two as the process is very
the dye remains unbind to fabrics and ends up in textile wastewater fast but the release of toxic intermediate during degradation limits the
effluents. Further a large amount of dye is released into the wastewater usefulness of process. Physical processes involve the techniques such as
stream during washing of fabric. These industries generate tons of ef­ filtration, adsorption, and transfer of pollutants from one stage to
fluents every day and at times they are discharged into the water bodies another. Limitation of these process is, it may generate more harmful
without treatment [1–4]. Azo dyes, including Methylene Blue (MB) and secondary pollutants. Biological processes are commercially unfit for the
Reactive Orange (RO), are widely used in industries, particularly tex­ highly loaded and dangerous contaminants and thus the methods are
tiles, contributing significantly to wastewater pollution. Effluents from inefficient and inapplicable [10–14]. These limitations can be overcome
these industries contain high concentrations of these dyes, adversely by using mixed metal oxides i.e. ferrites as the photocatalyst. In pho­
impacting aquatic ecosystems. The discharged chemicals increase tocatalysis the biggest challenge is separation of catalyst from the re­
chemical oxygen demand (COD), toxicity, and alter watercolor and action mixture. The key benefit of using ferrite as a catalyst is that it can

* Corresponding author.
E-mail address: paresh.m34@gmail.com (P. More).

https://doi.org/10.1016/j.inoche.2024.113170
Received 1 May 2024; Received in revised form 7 September 2024; Accepted 12 September 2024
Available online 14 September 2024
1387-7003/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
S. Arade et al. Inorganic Chemistry Communications 170 (2024) 113170

be effortlessly separated from the reaction mixture with the help of an

external magnet [15,16]. Further, ferrite is highly versatile catalyst with
good selectivity and surface area. Recently, zinc ferrite has attracted a
lot of attention from researchers due to its excellent photocatalytic ac­
tivity. Hossein et al reported photodegradation of crystal violet dye
using ZnFe2O4 catalyst in 30 min in the presence of sunlight [17].
Photocatalytic degradation MB dye by NiFe2O4 nanoparticles under ­
visible irradiation was studied by Alamier et al and reported 98.5 %
degradation in 70 min [18].
Inspired with the photocatalytic activities of Zn and Ni ferrite and
with the assumption that synergistic effect of Zn and Ni together at the
tetrahedral site will enhance catalytic properties of mixed metal oxide.
We herein report synthesis and application of mixed metal oxide
Zn0.5Ni0.5MnxFe2-xO4 ferrite in the photodegradation of RO as the model
dye contaminants. The synergistic effect of Zn, Ni, Mn, and Fe increases
the crystallinity and morphology of as synthesized Zn0.5Ni0.5MnxFe2-xO4
ferrite, which will be responsible for its catalytic application in photo­
degradation of RO dye. To the best of our knowledge this is the first
report in which photodegradation of RO dye over Zn0.5Ni0.5MnxFe2-xO4
nano ferrite were studied using sunlight. Evidently, this study offers
guidance for the removal of contaminants under sunlight irradiation.

Fig. 1. Rietveld Refined Pattern of Zn0.5Ni0.5MnxFe2-xO4 nano ferrite samples

2. Experimental
(x = 0.0, 0.25, 0.50, 0.75, and 1.0).

2.1. Materials
of Zn0.5Ni0.5MnxFe2-xO4 (B1, B2, B3, B4 and B5), nano ferrites were
Metal salts such as Zn (NO3)2 ⋅6H2O, Ni (NO3)2⋅6H2O, Mn determined on (Shimadzu model UV-2700) spectrophotometer. The
(NO3)2⋅6H2O, Fe (NO3)3⋅9H2O, and the reagents such as ammonia and photodegradation of RO dye was studied on a UV–Visible spectropho­
glycine were the starting materials used for the synthesis of the catalyst. tometer (Shimadzu model 1800). X-ray Photo-electron Spectroscopy
All chemicals used in the synthesis were of analytical grade with a purity (XPS) was performed using a K-ALPHA+spectrometer (Thermo Scien­
greater than 99 % and were used as received without further purifica­ tific Instruments, UK).
tion. The chemicals were procured from Loba Chemicals India. Photo­
degradation was carried out using RO as a model dye. 2.4. Photocatalytic degradation of reactive orange dye

2.2. Synthesis of Zn0.5Ni0.5MnxFe2-xO4 (where, x = 0.0, 0.25, 0.50, The photocatalytic activity of as-synthesized Zn0.5Ni0.5MnxFe2-xO4
0.75, and 1.0) nano ferrites nano ferrites was investigated using RO dye as a model contaminant.
The experiments were conducted in a 250 mL Pyrex reactor, with a
Zn0.5Ni0.5MnxFe2-xO4 nano ferrite were synthesized using sol–gel cooling system employed to maintain a constant solution temperature.
auto-combustion method. According to the chemical formula Photodegradation trials were carried out with a 100-ppm dye concen­
Zn0.5Ni0.5MnxFe2-xO4 (where, x = 0.0, 0.25, 0.50, 0.75, and 1.0) ferrites, tration under sunlight exposure for 2 h. In each trial, 100 mL of 100 ppm
each salt was weighed individually and dissolved in 25 mL of distilled RO dye solution was prepared, to which 0.2 g of the catalyst was added.
water. All the four solutions were mixed under stirring till all the salts The solution was then stirred in the dark to establish adsorp­
are dissolved. To this mixture of salt solution 40 mL of glycine was tion–desorption equilibrium. After 30 min, the solution was exposed to
added, followed by altering pH of the solution in the range of 8–9 using sunlight and samples were periodically withdrawn to assess the residual
liquid NH3, which results in the formation of sol. The sol was concen­ RO dye levels using a UV–visible spectrophotometer.
trated on the hot plate at 90◦ C. The heating results in conversion of sol The formula for calculating the percentage of dye residual is typically
to more viscous homogeneous gel, which on further heating form expressed as [19]:
product. When the required amount of glycine gets consumed, the gel
C0 − Ct
ignites, the reaction stops, and auto combustion completed within a % Dye Residual = X 100 (1)
C0
minute. As a result of which a chocolate- brown powder was formed as
the product. The obtained powder was then sintered in the furnace at where Ct is the concentration of the dye at time t and C0 is the initial
800◦ C for 5 hrs. it was cooled to room temperature and characterized concentration of the dye.
using various spectral techniques. The samples were labelled as B1 (x =
0.0), B2 (x = 0.25), B3 (x = 0.50), B4 (x = 0.75) and B5 (x = 1.0). 3. Results and discussion

2.3. Characterization The XRD pattern of Zn0.5Ni0.5MnxFe2-xO4 nano ferrites with the
concentration (x = 0.0 to 1.0) were used to investigate the structure and
The room temperature powder XRD data were recorded on Philips the impurities present in the given system. The peaks as depicted in the
(Xpert) X-ray diffractometer using Cu kα radiation (λ = 1.5418 Å) in the Fig. 1, are the characteristic peaks of Zn0.5Ni0.5MnxFe2-xO4 nano ferrites.
2θ range from 10◦ to 90◦. FTIR spectra of Zn0.5Ni0.5MnxFe2-xO4 nano The reflections from (111), (220), (311), (222), (400), (422), (511),
ferrites were recorded using KBr pellets on 3000 Hyperion Microscope (440), (531), (442), (620), (533), (622), (444), (711) and (642) planes
with vertex 80 FTIR spectrometer. The surface morphology of were attributed to the XRD peaks at 2θ = 18.21◦, 30.15◦, 35.48◦, 37.11◦,
Zn0.5Ni0.5MnxFe2-xO4 nano ferrites were characterized on a JEOL JSM- 43.13◦, 53.59◦, 57.08◦, 62.65◦, 65.97◦, 67.01◦, 71.13◦, 74.24◦, 75.22◦,
7600F FEG-SEM. Magnetic measurements at room temperature were 79.22◦, 82.27◦ and 86.98◦ respectively. Absence of any impurity peak in
carried out using a vibrating sample magnetometer (VSM) on a Quan­ Zn0.5Ni0.5MnxFe2-xO4 nano ferrites suggest that the catalyst is highly
tum Design USA make SQUID system (Model MPMS XL). The band gap crystalline and very pure. The results obtained on the X-ray diffraction of

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S. Arade et al. Inorganic Chemistry Communications 170 (2024) 113170

Table 1
Summary of the Rietveld refinement factors like expected factor (Rexp), weighted profile factor (Rwp), goodness-of-fit (χ2), Average Grain Size(D), lattice parameter
(a), and X- ray density (Dx), Lattice Strain (ε), Surface area and % Crystallinity.
compound Rexp Rwp χ2 D (nm) (±2nm) a (Å) x-ray density LatticeStrain ε Surface area % Crystallinity %Porosity Bulk density db (g/cm3)
(dx) (10-3) (m2/g)

x = 0.00 7.12 9.10 1.87 48.54 8.4252 5.4854 1.843 22.53 91.13 28.14 3.942
x = 0.25 6.81 8.61 1.61 55.74 8.4317 5.3227 1.885 20.22 88.14 25.17 3.983
x = 0.50 7.43 9.40 1.88 50.97 8.4921 5.2291 1.501 22.51 87.12 23.03 4.025
x = 0.75 7.79 9.74 1.95 59.64 8.5879 5.2122 0.729 19.30 85.16 20.88 4.124
x = 1.00 7.61 9.61 1.71 63.84 8.5917 5.1895 2.355 18.11 84.13 19.39 4.183

Zn0.5Ni0.5MnxFe2-xO4 and the Rietveld refinement are summarized in catalyst (B5) has less surface area as compared to the remaining catalyst
Table 1. The results are in accordance with the previously reported of the series. However, the performance of the catalyst depends not only
literature values [20]. Various R-factors such as expected factor (Rexp), upon surface area but also it depends upon various other parameters
profile factor (Rwp) and goodness-of-fit (χ2), obtained from the Rietveld such as active sites and distribution of cations at the tetrahedral and
refinement suggest that the refinement is good. The goodness of-fit (χ2) octahedral sites [26].
falls in the range between1.61 and 1.95, these values are excellent for Surface area, Percentage crystallinity, Percentage porosity and Bulk
the estimation [21]. The profile fitting is good if χ2 is lower, hence the density of Zn0.5Ni0.5MnxFe2-xO4 nano ferrites was determined using Eqs.
refinement was carried out till we get minimum χ2 function [22]. The (2)–(5) respectively [29] and are listed in Table 1.
average crystalline size of Zn0.5Ni0.5MnxFe2-xO4 ferrites was determined
6000
from the reflection of the (311) plane of the spinel structure using the Surface area = (2)
D × dx
Debye-Scherrer formula as discussed elsewhere [23]. The average
crystallite sizes of the synthesized materials were found to be in the where D is grain size and dx is x- ray density.
48.54–63.84 nm range. The lattice parameters obtained from XRD The surface area is impacted by the degree to which grain boundaries
analysis ranged between 8.4252 and 8.5917 Å, aligning well with are broken down. It is clear from the Table 1 that with the increase in the
Vegard’s law [24,25]. This phenomenon indicates a linear increase in grain boundary surface area decreases for Zn0.5Ni0.5MnxFe2-xO4 nano
lattice parameter as Mn substitution increases. This increase is attrib­ ferrites, similar trend was reported by Aadil et al [29].
uted to the replacement of smaller Fe3+ ions (0.76 Å) with larger Mn2+
ions (0.82 Å) within the spinel ferrite lattice. Consequently, the intro­ ACP
Perecentage Crystallity = (3)
duction of Mn2+ ions result in unit cell expansion while maintaining AAP
cubic symmetry. Furthermore, there is an observed decreasing trend in This content ACP and AAP denote area under the crystalline peak and
X- ray density (dx) values with increasing Mn concentration, which can all diffraction peaks.
be attributed to the expansion of the nanoparticles lattice parameter ( )
[25,26]. db
Perecentage Porosity = 1 − × 100 (4)
Stability of Zn0.5Ni0.5MnxFe2-xO4 (x = 0.0 to 1.0) catalysts was dx
confirmed through Williamson Hall plot. Strain in all the samples were
measured by plotting a graph of βcos θ versus 4sin θ which are straight where db is bulk density and can be determined using the following
lines (Fig SI 1). The slope of the lines gave angle strain which can be equation.
obtained by extrapolation of lines to the Y axis. All the values of the m
Bulk density = (5)
strain are listed in the Table 1, very low values of the strain indicates that π r2 t
the catalyst is highly stable [27,28]. Further surface area of Crystallinity and porosity are in direct variation with each other,
Zn0.5Ni0.5MnxFe2-xO4 (x = 0.0 to 1.0) catalysts was determined using Eq. with the decrease in crystallinity porosity decreases (Table 1). Similar
(2) and are listed in Table 1. It is clear from Table 1 that the optimised

Fig. 2. FTIR spectra a) 400–4000 cm-1b) 400–800 cm− 1

range of Zn0.5Ni0.5MnxFe2-xO4 nano ferrite samples (x = 0.0, 0.25, 0.50, 0.75, and 1.0).

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S. Arade et al. Inorganic Chemistry Communications 170 (2024) 113170

Fig. 3. FESEM images of Zn0.5Ni0.5MnxFe2-xO4 nano ferrite (a-b), (c-d), (e-f), (g-h), and (i-j) along with corresponding particle size information (k-o) for (x = 0.0,
0.25, 0.50, 0.75, and 1.0).

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S. Arade et al. Inorganic Chemistry Communications 170 (2024) 113170

Fig. 4. (a-b) TEM images, (c) HRTEM and (d) SEAD pattern of Zn0.5Ni0.5MnFeO4 (x = 1.0) nano ferrite.

trend in crystallinity and porosity was reported by Aadil et al [29]. With of secondary spherical-shaped nanoparticles (Fig. 3a-b). These nano­
the decrease in porosity the bulk density increases [29], similar trend of particles have an average size falling within the range of 130 nm. The
porosity and bulk density was observed in Zn0.5Ni0.5MnxFe2-xO4 nano clustering phenomenon in the undoped sample can be attributed to the
ferrite (Table 1). secondary growth of these nanoparticles. Upon introducing Mn2+
The band positions of the Zn0.5Ni0.5MnxFe2-xO4 nano ferrites were doping into Zn0.5Ni0.5MnxFe2-xO4 (samples B2-B5), we notice that the
investigated by FTIR spectroscopy. From Fig. 2a, it is shown that Mn2+ same morphology was retained, but there was a noticeable increase in
doped in Zn0.5Ni0.5MnxFe2-xO4 exhibits an Infrared (IR) spectrum with the particle size. This increase in particle size was clear in the FESEM
two bands in the 400–600 cm− 1 range [30]. In the IR spectrum of all images of samples B2-B5. To provide a quantitative representation of
spinel’s, two characteristic broad metal–oxygen bands can be seen. The this size variation, we have included the average particle size histogram
highest frequency band (ν1), usually observed in the 560–590 cm− 1 for Zn0.5Ni0.5MnxFe2-xO4 ferrites in Fig. 3k-o. It is worth noting that as
range, corresponds to the intrinsic stretching vibrations of metal ions at the Mn2+ content increases, there is a corresponding increase in the
the tetrahedral site (Mtet-O), while the lowest frequency band (ν2), average particle size. This observation underscores the impact of Mn
typically seen in the 460–390 cm− 1 range, is assigned to octahedral- doping on the particle size of Zn0.5Ni0.5MnxFe2-xO4 ferrites and reaffirms
metal stretching (Moct-O). It is also important to note that with the in­ the retention of the clustered morphology throughout the doping
crease in Mn2+ content in the Zn0.5Ni0.5MnxFe2-xO4 system, these bands process.
broaden. This broadening may be attributed to shifts in the Fe3+- O2− In this analysis, TEM images B5 (x = 1.0) are featured in Fig. 4a-b,
complex at the tetrahedral and octahedral sites being replaced by the which closely align with the findings observed in FESEM images.
Mn2+–O2− complex [30]. Additionally, weak bands at 1385 cm− 1, 1580 Furthermore, the HRTEM image in Fig. 4c reveals distinct lattice fringes
cm− 1, and 1610 cm− 1 correspond to nitrate ions, bending H-O-H vi­ with a spacing of 0.28 nm, corresponding to the (220) lattice plane of
brations, and carboxyl groups, respectively [23]. A broad peak located Zn0.5Ni0.5MnFeO4 nano ferrite. This HRTEM image provides a clear
at 3350 cm− 1 is attributed to absorbed water molecules, indicating the insight into the crystal structure at a nanoscale level. To affirm the
presence of surface-adsorbed moisture [31]. crystalline nature of the Zn0.5Ni0.5MnFeO4 ferrite sample, Fig. 4d shows
The morphology of Zn0.5Ni0.5MnxFe2-xO4 nano ferrites was examined its Selected Area Electron Diffraction (SAED) pattern. Notably, the
through field emission scanning electron microscopy. Fig. 3 displays presence of a bright arc within the diffraction circle in the SAED pattern
FESEM images comparing undoped and Mn doped Zn0.5Ni0.5MnxFe2-xO4 strongly suggests the formation of clusters that exhibit highly preferred
ferrites. In the case of the undoped sample (B1), we observe an aggre­ orientations. Additionally, the SAED pattern reveals the presence of
gated cluster-like morphology, which has developed due to the presence various lattice planes, which align well with the XRD results, further

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S. Arade et al. Inorganic Chemistry Communications 170 (2024) 113170

Fig. 5. (a-d) EDS elemental mapping of Zn, Ni, O, Fe, Mn of Zn0.5Ni0.5MnFeO4 nano ferrite and (f) EDS spectrum of a Zn0.5Ni0.5MnFeO4 (x = 1.0) nano ferrite.

reinforcing the crystalline nature of the sample. the relative concentrations of these elements in the material. Fig. 6b
The TEM images in Fig. 5 provide valuable insights into the delves into the high-resolution spectra of the Zn 2p region. In this
elemental composition of Zn0.5Ni0.5MnFeO4 ferrite. Notably, the Energy spectrum, we pinpoint the specific binding energies of Zn2+, registering
Dispersive X-ray Spectroscopy (EDS) elemental mapping analysis con­ at 1020.8 eV for Zn 2p3/2 and 1043.9 eV for Zn 2p1/2. This unequivocally
ducted on this ferrite (Fig. 5a-e) reveals a uniform distribution of establishes the oxidation state of Zn as 2 + within the Zn0.5Ni0.5MnFeO4
nanoparticles within clusters, indicating a well-dispersed composition of nano ferrite [32]. Fig. 6c depicts the high-resolution spectra of the Ni 2p
Zn, Ni, O, Fe, and Mn throughout the material. Furthermore, Fig. 5f region. Analogous to Zn and Mn, the characteristic peaks of Ni2+
presents the EDS spectrum for Zn0.5Ni0.5MnFeO4 ferrite, and it is note­ materialize with precision at binding energies of 854.0 eV and 872.2 eV,
worthy that no impurity peaks are evident in the spectrum. This absence corresponding distinctly to Ni 2p3/2 and Ni 2p1/2 [33]. The high-
of impurities serves as compelling evidence, affirming the high purity of resolution spectra of the Mn 2p region are shown in Fig. 6d. Here, the
the Zn0.5Ni0.5MnFeO4 ferrite material. characteristic peaks of Mn2+ manifest at binding energies of 640.5 eV
The X-ray photoelectron spectroscopy (XPS) analysis of and 652.2 eV, aligning precisely with the anticipated Mn 2p3/2 and Mn
Zn0.5Ni0.5MnFeO4 nano ferrite, B5 is comprehensively detailed in 2p1/2 peaks, thereby confirming the oxidation state of manganese in the
Fig. 6a-f. Fig. 6a, represents a survey scan that offers a holistic ferrite [34]. In Fig. 6e, the high-resolution spectra of the Fe 2p region are
perspective on the elemental composition within the ferrite. It discerns showcased, with characteristic peaks of Fe 2p3/2 and Fe 2p1/2 emerging
the presence of key elements, including Zn, Ni, Mn, Fe, and O, via robustly at 710.2 eV and 724.1 eV binding energies [32]. These peaks
distinct characteristic peaks. This survey scan is pivotal in quantifying firmly establish the oxidation states of iron within the Zn0.5Ni0.5MnFeO4

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S. Arade et al. Inorganic Chemistry Communications 170 (2024) 113170

Fig. 6. (a) Survey scan of XPS, (b) Zn 2p core level XPS spectra, (c) Ni 2p core level XPS spectra, (d) Mn 2p core level XPS spectra, (e) Fe 2p core level XPS spectra,
and (f) O 1 s core level XPS spectra of the Zn0.5Ni0.5MnFeO4 (x = 1.0) nano ferrite.

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S. Arade et al. Inorganic Chemistry Communications 170 (2024) 113170

Fig. 7. Magnetic hysteresis loops of Zn0.5Ni0.5MnxFe2-xO4 (x = 0.0 to 1.0)

Fig. 8. UV–Visible spectra of Zn0.5Ni0.5MnxFe2-xO4 (x = 0.0 to 1.0) nano ferrite.
nano ferrite.

tetrahedral (A) and octahedral (B) sites [30]. Notably, Mn2+ ions exhibit
Table 2 a preference for tetrahedral (A) sites over Fe3+ ions, whereas Fe3+ ions
Magnetic parameters (Saturation Magnetization Ms, Remanence Mr, Coercivity show a stronger preference for octahedral (B) sites. Zn2+ ions prefer­
Hc, Magnetic Moment nB, Anisotropy constant K) at room temperature of entially occupy tetrahedral (A) sites, while Ni2+ ions favor octahedral
Zn0.5Ni0.5MnxFe2-xO4 system as function of Mn content (x). (B) sites. The introduction of Mn2+ ions at the expense of Fe3+ ions at
Samples Ms Mr Hc Mr/Ms nB(μB) K(erg/g) octahedral (B) sites decreases the A-B sublattice interaction experienced
(emu/g) (emu/g) (Oe) by Fe3+ ions [30]. Consequently, the concentration of Fe3+ ions at
x = 0.00 101.988 9.834 40.264 0.09642 4.3411 0.4112 tetrahedral (A) sites diminishes, further reducing the A-B sublattice
x = 0.25 94.292 8.299 32.653 0.08801 4.0097 0.3607 contact at octahedral (B) sites. Moreover, an increase in Fe3+ ion con­
x = 0.50 87.854 4.808 19.832 0.05473 3.7324 0.2351 centration at octahedral (B) sites enhances B-B interactions, leading to
x = 0.75 85.279 4.413 14.382 0.05175 3.6195 0.1757 spin canting and subsequent reduction in B sublattice magnetization
x = 1.00 50.288 2.183 13.236 0.04341 2.1324 0.2742
[39]. Although Mn2+ and Fe3+ ions possess identical magnetic moments
(5 μB), spin canting occurs at tetrahedral (A) sites due to modest ex­
change interaction between the two ions. The rise in manganese (Mn)
Table 3 concentration within the ferrite leads to a reduction in the magnetic
Cation distribution using Bertaut Method and mean ionic radius (rA and rB) of moment of the A sublattice, consequently resulting in an overall
the Zn0.5Ni0.5MnxFe2-xO4 ferrite.
decrease. Additionally, elevated Mn2+ ion concentrations drive Fe3+
Compound (x) A-site B-site rA(Å) rB (Å) ions from tetrahedral to octahedral sites, augmenting the concentration
0.00 Zn0.08Fe0.92 Zn0.42Ni0.5Fe1.09 0.676 0.697 of Fe3+ ions at octahedral sites. Furthermore, cations at octahedral sites
0.25 Zn0.1Mn0.25Fe0.65 Zn0.4Ni0.5Fe1.1 0.672 0.697 play a crucial role in photo Fenton-like catalysis [40]. Therefore,
0.50 Zn0.12Mn0.4Fe0.48 Zn0.38Ni0.5Mn0.1 Fe1.02 0.670 0.695 Zn0.5Ni0.5MnxFe2-xO4 nano ferrites exhibit potential for excellent photo
0.75 Zn0.15Mn0.6Fe0.25 Zn0.35Ni0.5Mn0.15 Fe1.00 0.669 0.693
1.00 Zn0.15Mn0.85Fe0.0 Zn0.35Ni0.5Mn0.15 Fe1.00 0.664 0.693
degradation of RO dye.
The UV–Visible absorption spectra of Zn0.5Ni0.5MnxFe2-xO4 nano
ferrite samples with varying manganese (Mn) content, B1 to B5 (x = 0.0
ferrite. Lastly, Fig. 6f elucidates the high-resolution spectra of the O 1 s to 1.0) were investigated. Fig. 8 depicts UV–Visible absorption spectra of
region. The deconvolution of these peaks into three distinct components, Zn0.5Ni0.5MnxFe2-xO4 nano ferrite. In the pristine state, B1 (x = 0.0), the
characterized by binding energies at 529.18 eV, 529.31 eV, and 530.97 absorption edge is observed at a lower wavelength, indicating the
eV, is undertaken. These distinct components correspond to oxygen bandgap energy. As the manganese content increases, denoted by the
binding within the ferrite, corroborating prior findings in line with transition from B1 to B5, a noticeable red shift in the UV–Visible ab­
established reports [35]. sorption spectra is observed, indicating a shift towards higher wave­
The hysteresis loops recorded for Zn0.5Ni0.5MnxFe2-xO4 nano ferrites lengths. The absorption edge for B1 (X=0.0) is located at approximately
are depicted in Fig. 7, illustrating a gradual decrease in their magnetic 595 nm, corresponding to an estimated bandgap of 2.08 eV. As the
properties. Table 2 summarizes the magnetic parameters derived from manganese content increases in subsequent samples, the absorption
these hysteresis loops. The magnetization of ferrites is known to be edge gradually shifts to higher wavelengths. This shift is indicative of an
influenced by the composition and arrangement of ions at tetrahedral increased bandgap in the nano ferrite samples, as seen in the trend from
and octahedral (Table 3). Utilizing the Bertaut method [36], the site B1 to B5. Furthermore, the bandgap values are observed to decrease
occupancy in Zn0.5Ni0.5MnxFe2-xO4 ferrites was determined. An from B1 (2.08 eV) to B5 (1.93 eV), reflecting the impact of manganese
observed trend indicates a decrease in saturation magnetization (Ms), incorporation on the electronic structure of Zn0.5Ni0.5MnxFe2-xO4 nano
remanent magnetization (Mr), and coercivity (Hc) with increasing ferrite. The bandgap widening suggests changes in the electronic
concentrations of manganese [37]. This decrease is attributed to non- configuration and optical properties of the nano-ferrite as manganese
zero Yafet-Kittel (Y-K) angles, indicating triangular-type spin configu­ concentration increases. These findings hold significance for under­
rations on B sites that reduce A-B interactions [38]. In the spinel system standing the optical properties of nano-ferrite materials and can guide
comprising Zn-Mn-Ni ferrites, Fe3+ and Mn2+ ions occupy both their potential applications, especially in areas where tailored bandgap

8
S. Arade et al. Inorganic Chemistry Communications 170 (2024) 113170

Fig. 9. (a) Spectral changes during the degradation of RO dye in the presence of Zn0.5Ni0.5MnFeO4 (B5); (b) a plot of the change in absorbance vs. irradiation time in
the presence of the different Zn0.5Ni0.5MnxFe2-xO4 photocatalysts; (c) plot of Degradation (%) of RO dye in presence of photocatalysts; (d) Recyclability of the
Zn0.5Ni0.5MnFeO4 photocatalyst.

and absorption characteristics are crucial. displayed the highest photocatalytic activity for RO dye degradation,
The study investigated the photocatalytic performance of with about 97 % RO degradation achieved in 75 min. The degradation
Zn0.5Ni0.5MnxFe2-xO4 nano ferrites synthesized for the purpose. This rate of RO dye followed the trend: B5 > B4 > B3 > B2 > B1. This trend
investigation focused on their ability to degrade RO dye as a model indicates that degradation efficiency increases with an increase in the
pollutant when exposed to sunlight at room temperature. In Fig. 9 (a), Mn2+ content, suggesting that Zn0.5Ni0.5MnFeO4 ferrite is particularly
the spectral changes during the degradation of RO dye with effective for RO dye photodegradation. Furthermore, the experimental
Zn0.5Ni0.5MnFeO4 ferrite were monitored over time. Initially, a charac­ data for Zn0.5Ni0.5MnxFe2-xO4 nano ferrites (B1-B5) were used to
teristic peak of RO dye was observed at 418 nm, and as sunlight expo­ determine reaction kinetics. The rate constants for B1, B2, B3, B4, and
sure continued, the absorbance of RO dye at this peak gradually B5 ferrites were found to be 0.097, 0.104, 0.109, 0.110, and 0.115
decreased. After 75 min of degradation, the characteristic peak dis­ min− 1, respectively. This indicates that sample B5 exhibits high photo­
appeared completely, indicating the complete photodegradation of RO. catalytic activity, following a pseudo-first-order kinetics pattern.
Fig. 9(b) displays the absorbance of RO dye in the presence of various The stability and reusability of the B5 photocatalyst were assessed
Zn0.5Ni0.5MnxFe2-xO4 ferrites at different time intervals under sunlight under sunlight irradiation, and the results are presented in Fig. 9d. The
irradiation. In contrast, a control experiment was conducted without photocatalyst demonstrated exceptional performance, remaining effec­
any catalyst. Without a catalyst, RO dye degradation was minimal under tive throughout the course of four cycles. This indicates that the catalyst
sunlight, whereas the presence of a catalyst led to observable RO dye is robust and can be employed repeatedly for various photocatalytic
degradation. Interestingly, among the ferrite samples, B1 exhibited applications. The promising stability of Zn0.5Ni0.5MnFeO4 suggests its
lower catalytic activity for the photodegradation of RO dye compared to potential utility in future photocatalytic activities beyond reactive or­
the other samples under sunlight irradiation. Approximately 86 % of RO ange degradation. Its ability to maintain catalytic efficiency over mul­
was degraded after 90 min of irradiation for sample B1, while all other tiple cycles highlights its suitability for broader environmental
samples (B2-B5) exhibited more than 92 % RO degradation in the same remediation and wastewater treatment applications.
time frame (Fig. 9c). Among all the ferrite samples, Zn0.5Ni0.5MnFeO4 The investigation of catalyst loading, pH, and degradation time on

9
S. Arade et al. Inorganic Chemistry Communications 170 (2024) 113170

Fig. 10. (a) Percentage Degradation versus Catalyst Loading, (b) Percentage Degradation versus pH of Dye Solution, and (c) Degradation Time versus Catalyst
Loading on the Zn0.5Ni0.5MnFeO4 Photocatalyst.

the efficiency of Zn0.5Ni0.5MnFeO4 photocatalyst for dye degradation photocatalyst’s light harvesting capability. Furthermore, pH emerged as
applications revealed intriguing insights. Initially, varying the weight a crucial parameter influencing dye degradation efficiency (Fig. 10b). A
percentage of the catalyst from 0.05 g to 0.2 g demonstrated a notable pH of 6.8 was identified as facilitating maximum degradation of the RO
impact on the degradation of the RO dye (Fig. 10a). Remarkably, the dye, emphasizing the importance of pH regulation in optimizing pho­
optimal catalyst loading of 0.1 g resulted in the complete disappearance tocatalytic processes. Lastly, the investigation into degradation time
of the dye within a remarkably short span of 75 min. Beyond this optimal (Fig. 10c) reaffirmed the rapid degradation capability of the
point, an increase in catalyst loading led to a decline in the degradation Zn0.5Ni0.5MnFeO4 photocatalyst, particularly evident at the optimal
rate, attributable to the shielding effect compromising the catalyst loading of 0.1 g, where complete dye degradation occurred

Table 4
Comparison of photocatalytic dye degradation with some other nano catalyst.
Sr. No. Photocatalyst Catalyst wt. Dye Dye Conc. % Removal Time (min) Synthesis Method Ref.
(ppm)

1 Cu0.9Mn0.05Ag0.05O 5 mg Methylene Blue 5 ppm 83.9 150 Co-precipitation [40]

2 Ni-doped copper oxide 5 mg Allura red 10 ppm 91.4 48 Wet chemical route [41]
3 CeZn.CuO 10 mg Methylene Blue 5 ppm 81.64 100 Co-precipitation [42]
4 ZnO@GO 10 mg Rhodamine-B 5 ppm 83.6 90 ultrasonication [43]
5 MnFe2O4 20 mg Direct Red81 dye 35 ppm 56.50 120 hydrothermalroute [44]
6 Zn0.3Ni0.7Fe2O4 0.1 g Methylene Blue 30 ppm 96.90 120 Co-precipitation method [45]
7 NiFe2O4 40 mg Malachite Green 20 ppm 82.8 150 Simple solution combustion [46]
8 CuFe2O4 40 mg Malachite Green 20 ppm 94.5 150 Simple solution combustion [46]
9 ZnFe2O4 40 mg Malachite Green 20 ppm 65.3 150 Simple solution combustion [46]
10 1-xCoxFeCrO4 0.2 g MB dye 10 ppm 96 % 85 Sol-gel auto-combustion [47]
11 Zn0.5Ni0.5MnFeO4 0.2 g Reactive Orange 100 ppm 97 75 Sol-gel auto-combustion This study

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S. Arade et al. Inorganic Chemistry Communications 170 (2024) 113170

emission peak intensity generally indicates greater recombination of

electron-hole pairs, while a lower intensity suggests reduced recombi­
nation and enhanced participation of photoexcited charge carriers in
subsequent photoreactions [48]. In the case of B1, a higher intensity of
the PL emission peaks at 501 nm and 748 nm is observed, indicating a
higher rate of electron-hole recombination. Conversely, the B5 sample
exhibits a significantly lower PL intensity at the same wavelengths,
suggesting a more efficient separation of photogenerated electron-hole
pairs. This reduced recombination in the B5 sample points to its po­
tential for improved photocatalytic activity due to the extended lifespan
of the charge carriers. Overall, the comparison between B1 and B5
clearly demonstrates that the B5 nano ferrite has a more effective in­
hibition of electron-hole recombination, which could enhance its utility
in various photocatalytic applications [49].
The photocatalytic degradation mechanism of RO dye by
Zn0.5Ni0.5MnFeO4 under sunlight irradiation was investigated using
common scavengers to identify the reactive species involved in the
process. As shown in Fig. 12a, the addition of isopropyl alcohol (IPA)
and ethylenediaminetetraacetic acid (EDTA) significantly hindered the
degradation process, indicating that holes (h+) and hydroxyl radicals
( OH) play an active role in photocatalysis. Conversely, the degradation
•

Fig. 11. PL spectra of Zn0.5Ni0.5MnFe2O4 (B1) and Zn0.5Ni0.5MnFeO4 (B5) process remained largely unaffected by the addition of benzoquinone
nano ferrites. (BQ) and silver nitrate (AgNO3), suggesting that superoxide radicals
(O2− ) and electrons (e− ) contribute only minimally to dye degradation.
•

within 75 min. In summary, our study highlights the intricate interplay Fig. 12b illustrates the proposed photocatalytic mechanism of
between catalyst loading, pH, and degradation time in maximizing the Zn0.5Ni0.5MnFeO4 under sunlight irradiation. The photocatalytic
efficiency of the Zn0.5Ni0.5MnFeO4 photocatalyst for dye degradation mechanism of Zn0.5Ni0.5MnFeO4 is influenced by the positions of its
applications. These findings provide valuable insights for the develop­ conduction band (CB) and valence band (VB) edges, which can be esti­
ment and optimization of photocatalytic processes aimed at environ­ mated using Eqs. (6) and (7) respectively [50].
mental remediation and wastewater treatment.
ECB = χ − Ee − 0.5Eg (6)
After conducting the reusability study, we further examined the
structural and morphological properties of our samples using XRD, EVB = ECB + Eg (7)
FESEM, and EDS techniques (see Supporting Information, Figs. SI 2, 3).
The analysis of these figures reveals no significant changes, confirming Here, ECB and EVB represent the potentials at the conduction band and
the stability of our Zn0.5Ni0.5MnFeO4 photocatalyst for dye degradation. valence band edges, respectively; Ee is the free electron energy
Additionally, recent studies on various photocatalyst materials available (approximately 4.5 eV) in the hydrogen spectrum; Eg is the semi­
in the literature are summarized in Table 4. From this comparison, it can conductor band gap energy; and χ is the absolute electronegativity of the
be concluded that the Zn0.5Ni0.5MnFeO4 photocatalyst synthesized via a semiconductor. For Zn0.5Ni0.5MnFeO4, the calculated χ is 5.80 eV,
facile sol–gel auto-combustion method demonstrates competitive pho­ yielding band edge potentials of 2.27 eV for the VB and 0.34 eV for the
tocatalytic activity compared to other photocatalysts [41–47,23]. CB. Upon sunlight irradiation, Zn0.5Ni0.5MnFeO4 becomes activated,
Fig. 11 illustrates the PL spectra of the Zn0.5Ni0.5MnFe2O4 (B1) and generating electron-hole pairs within its structure. The holes in the VB
Zn0.5Ni0.5MnFeO4 (B5) nano ferrites, where the behavior of photo­ react with water molecules to produce OH radicals, while the electrons
•

generated electron-hole pairs was investigated. In photoluminescence in the CB reduce O2 to form O2− radicals. These reactive species,
•

(PL) spectroscopy, the intensity of the emission peaks provides insights particularly hydroxyl and superoxide radicals, play a critical role in the
into the recombination rate of these charge carriers. A higher PL degradation of RO dye molecules, leading to their breakdown into

b)
a)

Fig. 12. (a) The influence of the different scavenger on the photodegradation efficiency of RO using Zn0.5Ni0.5MnFeO4 (b) Possible mechanism for the photocatalytic
degradation RO dye using Zn0.5Ni0.5MnFeO4.

11
S. Arade et al. Inorganic Chemistry Communications 170 (2024) 113170

harmless byproducts like CO2 and H2O [51]. Appendix A. Supplementary data

Zn0.5Ni0.5MnFeO4 + hυ → e-cb + h+vb (8) Supplementary data to this article can be found online at https://doi.
h+vb + H2O →h+vb + (H + OH ) → OH + H
+ • • +
(9) org/10.1016/j.inoche.2024.113170.

e-cb + O2 →O2- (10) References

•

-•
O2 + (OH + H ) → HO2 + OH
+ –
(11)
• •

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