Ceramics International xxx (xxxx) xxx

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Visible light activated Mg, Co co-doped hematite for effective removal of

reactive red 35 from textile wastewater
Ankit Kumar a, 1, Stuti Kartikey Trivedi a, 1, Lakshita Phor b, Jaideep Malik c, Samir Bhargava d,
Vishakha Kaushik a, Parveen Kumar a, Surjeet Chahal a, *
a
Materials & Nano Engineering Research Laboratory, Dept. of Physics, School of Physical Sciences, DIT University, Dehradun, 248009, India
b
Dept. of Physics, Deenbandhu Chhotu Ram University of Science and Technology, Murthal, 131039, Haryana, India
c
Department of Chemistry, National Tsing Hua University, Hsinchu, 30013, Taiwan
d
Faculty of Pharmacy, School of Pharmaceutical & Populations Health Informatics, DIT University, Dehradun, 248009, India

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

Handling Editor: Dr P. Vincenzini The exceptional hike in industrialization has led to water pollution mainly due to the organic wastes from textile,
printing and leather industries. Photocatalysis has emerged as one of the best methods to decompose organic
Keywords: waste from wastewater. In this regard, Mg and Co co-doped, Mg0.5Co0.5FeO3 nanoparticles have been synthesized
Hematite using a modified hydrothermal method followed by annealing at different temperatures (300, 400, 500 and
Hydrothermal
600◦ C). The structural properties were investigated with the help of XRD and FTIR. FE-SEM depicted that the
Photocatalysis
synthesized particles have a spherical morphology and the average particle size lies in the nano region (8-20 nm).
Reactive red dye
Wastewater remediation The photocatalytic activity of the synthesized catalysts was tested under visible light for the degradation of 20
ppm reactive red 35 (RR-35) dye. Thethe enhanced photocatalytic efficiency of F400 can be attributed to its
optimum band positions which was confirmed using scavenger tests for the presence of various active species.
Further, a combination of sonocatalysis, H2O2, and photocatalysis was employed and this synergistic approach
resulted in an impressive enhancement in the degradation efficiency of F400 catalyst.

1. Introduction noted that RR35 is not compatible with silk, wool, and polyester fabrics.
These dyes are particularly well-suited for achieving vibrant colors in
Water pollution presents a substantial hazard to both aquatic and white and color-resistant printing, as well as for tinting white back­
human life, and its escalation over the past decade has garnered global grounds in printing applications. Additionally, RR-35 demonstrates a
attention from the research community. The primary source of the water reasonable degree of photostability when exposed to sunlight [1].
pollution is the organic waste from pharmaceutical, textile, printing and Wastewater can be treated by various physical and chemical methods
various other industries, that has been directlydisembogued into natural like photocatalysis, coagulation, reverse osmosis, flocculation, chlori­
water sources without any further treatment. Wastewater from the nation, and filtration [2–7]. However, photocatalysis is considered as
textile industry contains contaminants such as dyes, chemicals, heavy one of the most promising, efficient and eco-friendly method. It can be
metals and solids, which can adversely affect ecosystems if discharged categorized into homogeneous and heterogeneous processes based on
untreated. Dyes are particularly challenging due to their persistence and the nature of the photocatalyst. Homogeneous photocatalysis includes
resistance to treatment, and if released untreated, the textile wastewater metal complexes like Cr, Cu, Fe, etc., as a catalyst where hydroxyl
can harm aquatic as well as human life and contaminate, drinking water radicals generated by higher oxidation state of these metal ion com­
sources. These pollutants include organic dyes like methylene blue, acid plexes increase the rate of degradation process [8–10]. However, het­
fuchsin, rose bengal, reactive red-35 (RR-35), rhodamine-B, phenol red, erogeneous photocatalysis includes many reactions to degrade the
p-Nitrophenol, etc. Out of these dyes, RR-35 has not been explored much pollutant dyes, where, on light irradiation, catalysts form photo­
which stands as a monoazo commercial dye, primarily employed in the generated e− − h+ pairs which further react with water and oxygen (O2)
dyeing of cotton, viscose, flex, and jute materials. However, it should be to form •OH and •O−2 radicals, respectively, that serves as active species

* Corresponding author.
E-mail address: [email protected] (S. Chahal).
1
Equal contribution.

https://doi.org/10.1016/j.ceramint.2023.09.095
Received 26 July 2023; Received in revised form 7 September 2023; Accepted 11 September 2023
Available online 12 September 2023
0272-8842/© 2023 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Ankit Kumar et al., Ceramics International, https://doi.org/10.1016/j.ceramint.2023.09.095
A. Kumar et al. Ceramics International xxx (xxxx) xxx

for photocatalytic degradation [11].

The metal oxides like TiO2, ZnO, MnO2, SnO2, MgO, Fe2O3, RuO2 and
CeO2 have been widely used as photocatalysts for various applications
[12–19]. But the photocatalytic efficiencies of most of these catalysts are
limited to the UV region, which is present in a limited portion in the
natural sunlight. Therefore, the scientific community is seeking for
photocatalysts that can efficiently utilize visible region of the sunlight.
In low band gap materials, iron oxide-based materials are one of the
promising photocatalysts in the visible region owing to their excellent
optical and physical properties [20–24]. Iron oxides exhibit many
crystalline phases such as akagenite (β-Fe2O3), hematite (α-Fe2O3),
magnetite (Fe3O4) and maghemite (γ-Fe2O3). Among these oxides, the
photocatalytic activity of α-Fe2O3 remains comparatively on the higher
side. Although there is still scope for improvement in its efficiency as
doping of foreign metal ions in α-Fe2O3 matrix may enhance its effi­
ciency towards wastewater treatment via photocatalysis [25]. Asif et al.
reported Co doped Fe2O3 nanospheres synthesized via a facile sol­
vothermal method [26]. The synthesized samples were then subjected to
the activation of peroxymonosulfate (PMS) for p-hydroxybenzoic acid
(p-HBA) degradation. Here, the 3% Co doped samples exhibited the
highest efficiency for PMS activation. In another article, Hmamouchi
et al. reported that pure and Co doped α-Fe2O3 were synthesized and Fig. 1. XRD pattern of synthesized samples annealed at 300, 400, 500
and 600 ◦ C.
showed reduction in the band gap with Co doping [27]. Here, pristine
and Co doped α-Fe2O3 catalysts were used for the degradation of the
methylene blue dye in visible light. However, doping of Co significantly centrifuged and washed with distilled water and ethanol. The pre­
increased the degradation efficiency as compared to pure α-Fe2O3. cipitates were then dried overnight in the oven at 100 ◦ C. In the final
Highest degradation efficiency came out to be 91.8% after 120 min of step the obtained powdered samples were annealed in a muffle furnace
light irradiation. Similarly, Mg-doping has also enhanced the photo­ at 300 ◦ C, 400 ◦ C, 500 ◦ C and 600 ◦ C, and hereafter, the synthesized
catalytic efficiency significantly for the degradation of various pollut­ samples were named as F300, F400, F500, and F600, respectively, for
ants. A study showed that Mg doped titanium dioxide with varying further discussion.
magnesium concentration was synthesized using the sol-gel method
[28]. It has been observed from the analysis that the dopant has a higher 2.3. Characterizations
surface area in comparison to pure TiO2. The degradation efficacy of the
synthesized catalysts towards methyl orange (MO) dye under visible Various crystalline properties of Mg0.5Co0.5FeO3 were analyzed by
light has been found to be highest in Mg doped TiO2. Almost complete XRD Rigaku Ultima IV (λ = 1.5418 Å) with Cu-Kα source in the range
degradation of MO dye was observed after 230 min of irradiation. 20◦ - 70◦ . The average particle size and their morphology were
Further, Etacheri et al. showed that Mg-doping in ZnO nanomaterials confirmed using Carl Zeiss (ultra plus55) scanning electron microscope
enhanced the photocatalytic activity of 0.10-MgZnO due to its superior (SEM). Different functional groups were also detected and analyzed by
textural properties and wide band gap [29]. Therefore, magnesium and Shimadzu -IRAffinity-1S Fourier transform Infra-red spectroscopy
cobalt doping in α-Fe2O3 can be helpful in waste water treatment with (FTIR). Optical properties of the catalyst were studied by UV–Vis spec­
increased photocatalytic activity in the presence of visible light [30]. In troscopy (UV–Vis. 3600 plus) coupled with diffuse reflectance spec­
this manuscript, Mg and Co co-doped α-Fe2O3 has been synthesized troscopy (DRS). Photocatalytic experiments were monitored using
using a modified hydrothermal method and annealed at various tem­ Shimazdu-1800 UV–Vis spectrophotometer.
peratures. The synthesized samples have been tested for structural,
morphological and optical properties to explore their impact on the 2.4. Photocatalytic activity
photocatalytic efficiency towards the degradation of RR-35 under visible
light. A solution containing 20 ppm of reactive red-35 (RR-35) dye was
prepared in distilled water. To achieve adsorption-desorption equilib­
2. Experimental section rium, the dye solution was mixed with a 1 mg/mL quantity of catalyst
and stirred in darkness for 30 min. Subsequently, the suspension was
2.1. Chemicals exposed to visible light using a 300 W OSRAM halogen lamp placed
inside a black-coated chamber. To assess the reaction kinetics and
Magnesium chloride hexahydrate (Merck, 98%), cobalt (II) nitrate photocatalytic efficiency of the synthesized catalysts, samples were
hexahydrate (SRL, 99%), ferric nitrate nonahydrate (SRL, 98%), urea extracted from the suspension at regular intervals of 20 min. For the
(Sigma Aldrich, 99–100.5%), ethanol (Merck), sodium oxalate (SRL, investigation of sonocatalysis, the F400 sample was subjected to ultra­
99.9%), isopropyl alcohol (SRL, 99.5%), benzoquinone (Sigma-Aldrich, sonic treatment in an ultrasonic bath, both in the presence and absence
98%), H2O2 (SDFCL, 30%). of visible light. Additionally, in certain experiments, 1 mL of H2O2 was
added to the suspension to seek further enhancement in the degradation
2.2. Synthesis efficiency of the catalyst. Sodium oxalate (1 mM), isopropyl alcohol (0.1
mL), and benzoquinone (1 mM) were individually introduced as scav­
Mg and Co co-doped α-Fe2O3 was synthesized by a modified- engers to the suspension. These scavengers were used to study the
hydrothermal method using Fe(NO3)3.9H2O (7 mM), Co(NO3)2 (1.75 presence of active species during the photocatalytic reaction.
mM), MgCl2 (1.75 mM) and urea (180 mM) with distilled water (500
mL) and ethanol (50 mL) as solvent. The solution was then subjected to
vigorous stirring for 15 min to get a homogenous solution. It was then
placed for heating in an oven at 90 ◦ C for 6 h. The solution was then

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Table 1
Derived parameters from XRD pattern and FE-SEM images.
Sample a (= b) c (104) Crystallite Size (D) (nm) Surface Area Dislocation Density (1018) Strain=(c0− c)/
Stress (GPa) = Average Particle
Name (110) (Å) (Å) = Kλ/βcosθ (m2/g) (m) = 1/D2 c
0
⸹(c0− c)/c
0 Size (nm)

F300 5.027 13.194 6.44 178.40 0.0241 0.0418 9.46 8.34

F400 5.032 13.221 13.97 82.32 0.0051 0.0398 9.00 8.55
F500 5.024 13.207 19.43 59.22 0.0026 0.0408 9.23 11.94
F600 5.027 13.203 29.26 39.32 0.0011 0.0411 9.31 19.38

planes, respectively. The XRD pattern has been used to calculate the
Table 2
crystallite size, stress, strain, and dislocation density. The FWHM
Various peaks identified in FTIR spectra.
showed that crystalline properties are increasing with an increase in
F300 (in cm- F400 (in cm- F500 (in cm- F600 (in cm- Functional temperature which corroborates well with increased crystallite size.
1 1 1 1
) ) ) ) group
Ideal lattice parameters for α- Fe2O3 are 5.04 Å for a (110) and 13.77 Å
3400 3400 3400 3400 O–H stretching for c (104). The ionic radii of Mg2+ (0.66 Å) is almost similar to the ionic
1637 1744 1740 1738 N–H vibrations
radii of Fe3+ (0.65 Å) but lower than that of Co2+ (0.75 Å), which
1366 1366 1365 1365 O–H vibrations
1347 1346 1346 1346 N–O bending
suggests that there should be an increase in lattice parameter with an
533 518 517 512 Fe–O stretching increase in the concentration of dopant [32,33]. However, the presence
417 420 424 433 Fe–O stretching of intrinsic lattice defects can result in a decrease in the lattice param­
eter. The surface area was calculated using the formula: Scal = 6/(Dρ),
where ρ is the theoretical density of Fe2O3 (5.225 g/cm3) and found to
3. Results and discussion
be decreasing with increased calcination temperature [30,34,35]. The
lattice defects in the form of stress and strain have been calculated and
3.1. XRD analysis
presented in Table 1.

The XRD pattern of Mg0.5Co0.5FeO3 at different annealing tempera­

3.2. Morphological analysis and growth mechanism
tures of 300, 400, 500 and 600 ◦ C is shown in Fig. 1. Different planes like
(012), (104). (110), (113), (024), (016), (018), (214) and (300) have
FE-SEM images of synthesized samples annealed at 300, 400, 500
been identified, which corresponds to the rhombohedral structure of
and 600 ◦ C are shown in Fig. 2. The spherical morphology of the par­
hematite that matches well with JCPDS file number (84–0311) [31].
ticles has been identified. Average particle size has also been calculated
Lattice parameters a and c have been calculated from (110) and (104)
for different samples and found to be 8.34, 8.55, 11.94 and 19.38 nm for

Fig. 2. FE-SEM images of synthesized F300, F400, F500 and F600 samples.

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Fig. 3. The particle size distribution of F300, F400, F500, and F600 samples.

NH3 + H2 O→NH + + OH − (2)

CO2 + H2 O → CO−2 + 2H + (3)

Fe3+ + OH − + CO−2 →FeCO3 OH (4)

FeCO3 OH → FeOOH + CO2 (5)

FeOOH → α − Fe2 O3 (6)

3.3. FTIR analysis

The FTIR spectra of Mg0.5Co0.5FeO3 with different annealing tem­

peratures of 300, 400, 500 and 600 ◦ C are shown in Fig. 4. Different
peaks along with their functional groups are identified here The pres­
ence of characteristic peaks at 417 cm− 1 and 533 cm− 1 confirms the
successful synthesis of α-phase Fe2O3 as they represents metal oxygen
(Fe–O) vibrations in rhombohedral structure of hematite [36]. The
bands present at 1347 cm− 1 and 1637 belong to N–O and N–H bending
vibrations respectively represent the traces of some unreacted pre­
Fig. 4. FTIR spectra of synthesized samples annealed at 300, 400, 500
cursors. Stretching vibrations at 3400 and 1366 cm− 1 signify the pres­
and 600 ◦ C.
ence of O–H groups.

F300, F400, F500 and F600, respectively, which is in good agreement

with the crystallite size calculated from the XRD patterns. The particle 3.4. UV-DRS analysis
size distribution for different samples has been shown by the bar dia­
gram in Fig. 3. During the hydrothermal process, initially, urea hydro­ UV-DRS analysis was conducted to assess the band gap of the syn­
lyzed into NH3, and CO2 as shown in equation (1). Further, equations (2) thesized samples as shown in Fig. 5. Fig. 6 illustrates the Tauc plot for
and (3) showed that these bi-products were then hydrolyzed into NH+ 4
different samples of Mg0.5Co0.5FeO3 annealed at temperatures of 300,
and CO2−3 ions, respectively. Fe
3+
ions then reacted with newly gener­ 400, 500, and 600 ◦ C. The band gap energy (Eg) has been determined by
ated OH− and CO2− 3 to form FeCO3OH nuclei, described by eq. (4).
extrapolating the linear portion of the curve. Eg is found to increase with
FeCO3OH then decomposes into FeOOH and CO2 in eq. (5). On temperature up to 400 ◦ C and then decrease with further increase in
annealing, FeOOH at various temperatures for 3 h, α-Fe2O3 phase has temperature. This behavior can be attributed to the presence of vacancy
been obtained, as presented in eq. (6). For doped samples, stoichio­ defects in the material. Conduction band minima and valence band
metric ratio of Mg and Co-precursors have been added to the solution at maxima were calculated using the following equation [37,38]:
the initial stage. (see Table 2) EVB = χ − Ee + 0.5 Eg (7)
H2 NCONH2 + H2 O → 2NH3 + CO2 (1)
ECB = EVB − Eg (8)

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A. Kumar et al. Ceramics International xxx (xxxx) xxx

Fig. 5. UV-DRS spectra of synthesized samples annealed at 300 ◦ C, 400 ◦ C, 500 ◦ C and 600 ◦ C.

Fig. 6. Tauc plot of synthesized samples annealed at 300 ◦ C, 400 ◦ C, 500 ◦ C and 600 ◦ C.

where Ee = free electron energy (4.5 eV) and χ = absolute electroneg­ to remove such contaminants in the presence of visible light using the
ativity (5.87 eV). synthesized catalysts. Fig. 7 (a) shows that with irradiation time, the
relative concentration of dye decreases and is minimal while using the
F400 catalyst. The % degradation has been calculated using equation (9)
3.5. Photocatalytic activity
and is maximum (84.9%) for F400 among all the synthesized catalysts,
which is excellent as compared to available literature [1]. In Fig. 7 (c),
RR-35 dye is a water contaminant, a volatile organic compound, and
the analysis of –ln(C/C0) versus time plot indicated that the degradation
is used in the printing and textile industries. The contaminants from
reaction follows the first-order kinetics (represented by equation (10))
these industries are hazardous for human as well as aquatic life.
as the values of correlation coefficient (R2) lie in the range 0.95–1 [39].
Therefore, photocatalytic degradation of RR-35 dye has been carried out

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A. Kumar et al. Ceramics International xxx (xxxx) xxx

Fig. 7. The results of the degradation of RR-35 dye under visible light illumination using synthesized catalysts: (a) the plot of C/C0 versus irradiation time, (b)
percentage degradation with time, (c) the linear fitting of –ln(C/C0) with irradiation time, and (d) the corresponding values of K and R2.

Table 3
Parameters calculated from UV–Vis. spectroscopy and photocatalytic analysis for synthesized catalysts F300, F400, F500 and F600.
E E E K (min− 1×10-3) t (min.) t (min.) E (kWhm− 3 order− 1 ×104)
Sample Name Degradation (%) g (eV) VB (eV) CB (eV) 1/2 90 EO

F300 62.4 2.04 2.39 0.35 8.28 83.7 278.1 5.46

F400 84.9 2.11 2.43 0.32 15.95 43.4 144.4 1.46
F500 40.3 2.09 2.42 0.33 4.21 164.6 547.0 20.35
F600 34.8 2.08 2.41 0.33 3.53 196.3 652.4 29.27

Table 4
The photocatalytic parameters calculated using various modes of catalysis for RR-35 degradation using F400 catalyst.
K (min− 1×10-3) t (min) t (min) E (kWhm− 3 order− 1 ×104)
Mode of catalysis Degradation (%) 1/2 90 EO

Photocatalysis 84.9 15.95 43.4 144.4 1.47

Sonocatalysis 8.4 0.62 1112.5 3696.6 808.44
Sonophotocatalysis 94.4 24.0 28.9 95.9 0.64
Sonophotocatalysis + H2O2 98.4 32.8 21.1 70.2 0.33

The highest reaction’s rate constant (K) was observed for F400, as calculated using equations (11) and (12), respectively [40]. Further,
determined from the slope of the linear fit. All the parameters calculated EEO, the electrical energy consumption for achieving 90% degradation of
have been shown in Table 3. Using the rate constant, t1/2 and t90 were the pollutant in 1 m3 of water has been calculated using equation (13)
which has been effectively reduced for the F400 catalyst [40] (see
Table 4).
C0 − C
% degradation = × 100 (9)
C0
( )
C
− ln = Kt (10)
C0

ln(2)
t1/2 = (11)
K

ln(10)
t90 = (12)
K

P × t90 × 1000
EEO = (13)
V × 60 × log (C0 /C)
Fig. 8. The schematic of the reaction mechanism for the degradation of RR-35
using synthesized catalysts in the presence of visible light. Where P-power, V-voume of the suspension, C0-initial dye concentration

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A. Kumar et al. Ceramics International xxx (xxxx) xxx

Fig. 9. (a) Degradation (%) in the presence of scavengers and (b) reusability of F400 for 5 successive runs.

Fig. 10. Different parameters for the degradation of RR-35 dye for various catalytic processes using F400 catalyst (a) C/C0 versus irradiation time, (b) percentage
degradation with time, (c) linear fitting of –ln(C/C0) with irradiation time and (d) values of K and R2 for each sample.

and C- at any time t, t90-time taken to degrade the pollutant by 90% of its used to capture h+, •O−2 , and •OH, respectively. The results, illustrated in
initial concentration, t1/2-time taken to degrade the dye by 50% of its Fig. 9(a), reveal that the highest degradation efficiency occurs in the
initial concentration. presence of BQ as ECB lies lower compared to the O2/•O2− potential
(− 0.046 eV). This indicates that the contribution of •O2− radicals in the
3.5.1. Mechanism degradation of RR-35 dye is minimal under these conditions. On the
Fig. 8 shows the plausible reaction mechanism when the dye solution other hand, in the presence of IPA, the % degradation is lower, as the EVB
containing the synthesized catalysts is subjected to visible light treat­ of Mg0.5Co0.5FeO3 lies just below the H2O/•OH potential (2.4 eV),
ment. The e− are transferred from VB to CB of Mg0.5Co0.5FeO3 leaving resulting in the maximum contribution of •OH radicals in the degrada­
the holes (h+) behind. The photogenerated e− and h+ are responsible for tion of the dye. Sodium oxalate also reduced the degradation effectively
the dye degradation, as the e− interact with O2 to generate •O−2 and h+ as it captured h+ which is responsible for the formation of •OH.
with H2O to give •OH. These radicals disintegrate the organic dye into Conclusively, •OH radicals are present as the main active species for the
H2O and CO2 along with dye by-products. But as the O2/•O−2 potential degradation of RR-35 dye as H2O/•OH potential lies in between the EVB
(− 0.046 eV) does not fall in between ECB and EVB, while the H2O/•OH and ECB of F400. The reusability of F400 was estimated by using the
potential (2.4 eV) does. Therefore, the main active species responsible sample again and again after washing and drying. The sample showed
for photocatalysis can be •OH. Further experiments have been con­ excellent efficiency up to 5 runs with a mere drop of ~5% efficiency as
ducted to prove this proposed mechanism of RR-35 degradation. shown in Fig. 9(b).
The experiments were conducted to further improve the efficiency of
3.5.2. Scavenger test the F400 catalyst as depicted in Fig. 10(a–d). The photocatalysis was
On light irradiation various radicals or ions have been generated that combined with sonocatalysis and the addition of H2O2 to the dye solu­
played a vital role in the degradation of the dye. Therefore, to investi­ tion. As expected, the catalytic efficiency of F400 was low in sonoca­
gate the kind of active species majorly involved in the degradation talysis alone as the energy is not sufficient for the production of excitons.
process, scavenger tests were performed. The scavengers, sodium oxa­ Although, in the case of sonophotocatalysis the degradation efficiency
late (Na2C2O4), benzoquinone (BQ), and isopropyl alcohol (IPA) are has been increased to 94.4% due to the production of a larger number of

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A. Kumar et al. Ceramics International xxx (xxxx) xxx

hydroxyl radicals [41]. The addition of H2O2 with sono-photocatalysis [9] J.M. Rosa, A.M.F. Fileti, E.B. Tambourgi, J.C.C. Santana, Dyeing of cotton with
reactive dyestuffs: the continuous reuse of textile wastewater effluent treated by
further enhanced the degradation efficiency by 4% due to an increase
Ultraviolet/Hydrogen peroxide homogeneous photocatalysis, J. Clean. Prod. 90
in the number of •OH radicals. Conclusively, the results showed that the (2015) 60–65, https://doi.org/10.1016/j.jclepro.2014.11.043.
synthesized F400 catalysts can be efficiently used to degrade the volatile [10] F. Moccia, L. Rigamonti, A. Messori, V. Zanotti, r. Mazzoni, Bringing homogeneous
organic compounds present in the wastewater released from various iron catalysts on the heterogeneous side: solutions for immobilization, Molecules
26 (2021) 2728, https://doi.org/10.3390/molecules26092728.
industries. [11] A. Trenczek-Zajac, M. Synowiec, K. Zakrzewska, K. Zazakowny, K. Kowalski,
A. Dziedzic, M. Radecka, Scavenger-supported photocatalytic evidence of an
extended type I electronic structure of the TiO2@Fe2O3 interface, ACS Appl. Mater.
4. Conclusion
Interfaces 14 (33) (2022), https://doi.org/10.1021/acsami.2c06404,
38255–38269.
Novel Mg0.5Co0.5FeO3 photocatalysts were synthesized using a [12] N. Rani, S. Chahal, S. Mahadevan, P. Kumar, R. Shukla, S.K. Singh, Hierarchical
modified hydrothermal method followed by annealing at various tem­ magnesium oxide anchored cerium oxide nanocomposites for improvement in
magnetic properties and photocatalytic performance, Nanotechnology 31 (2020)
peratures, resulting in the successful formation of the α-Fe2O3 phase. X- 37, https://doi.org/10.1088/1361-6528/ab96e8.
ray diffraction (XRD) analysis confirmed the increased crystallinity of [13] Y. Li, Y. Peng, L. Hu, J. Zheng, D. Prabhakaran, S. Wu, T.J. Puchtler, M. Li,
the samples with higher annealing temperatures. The synthesized cat­ K. Wong, R.A. Taylor, S.C.E. Tsang, Photocatalytic water splitting by N-TiO2 on
MgO (111) with exceptional quantum efficiencies at elevated temperatures, Nat.
alysts were then employed in the photocatalytic degradation of RR-35 Commun. 10 (2019) 4421, https://doi.org/10.1038/s41467-019-12385-1.
dye under visible light. The highest degradation efficiency of 84.9% [14] G. Zhu, W. Zhu, Y. Lou, J. Ma, W. Yao, R. Zong, Y. Zhu, Encapsulate α-MnO2
was observed for the F400 catalyst on 2 h of light irradiation, attributed nanofiber within graphene layer to tune surface electronic structure for efficient
ozone decomposition, Nat. Commun. 12 (2021) 4152, https://doi.org/10.1038/
to its favorable band positions for the generation of •OH radicals, which s41467-021-24424-x.
has paramount importance in the degradation process. To investigate [15] S. Devi, Suman, S. Chahal, S. Singh, P. Kumar, S. Kumar, V. Kumar, Novel magnetic
the degradation mechanism of RR-35, scavenger tests utilizing BQ, IPA Fe2O3/CNT nanocomposites: application towards the treatment of dye wastewater,
Ceram. Int. 49 (2023) 20071–20079, https://doi.org/10.1016/j.
and sodium oxalate were conducted that supported the proposed ceramint.2023.03.130.
degradation mechanism. To enhance the degradation efficiency further, [16] H. Kumari, Sonia, S. Chahal, Suman, P. Kumar, A. Kumar, R. Parmar,
a combination of sonocatalysis, H2O2, and photocatalysis was employed Photocatalytic degradation of RB dye via cerium substituted SnO2 photocatalysts,
Mater. Sci. Eng. B 296 (2023), 116654, https://doi.org/10.1016/j.
and this synergistic approach resulted in an impressive degradation ef­
mseb.2023.116654.
ficiency of 98.4%. These findings highlight the potential of the F400 [17] A. Singh, V. Kaushik, S. Chahal, A. Goswami, S. Nain, Efficient degradation of
catalyst for the degradation of volatile organic contaminants and its methylene blue dye and antibacterial performance of shape controlled RuO2
suitability for wastewater remediation applications. nanocomposites, ChemistrySelect 6 (2021) 10038–10050, https://doi.org/
10.1002/slct.202102546.
[18] S. Chahal, L. Phor, A. Kumar, S. Kumar, S. Kumar, R. Kumar, P. Kumar,
Photocatalytic Degradation of Organic Dye by CeO2/CNT/GO Hybrid
Declaration of competing interest Nanocomposites under UV-Light for Wastewater Treatment, Environmental
Science and Pollution Research, 2023, https://doi.org/10.1007/s11356-023-
The authors declare that they have no known competing financial 26184-1.
[19] C.A. Jaramillo-Páez, J.A. Navío, M.C. Hidalgo, M. Macías, ZnO and Pt-ZnO
interests or personal relationships that could have appeared to influence
photocatalysts: characterization and photocatalytic activity assessing by means of
the work reported in this paper. three substrates, Catal. Today 313 (2018) 12–19, https://doi.org/10.1016/j.
cattod.2017.12.009.
[20] Suman, V. Sharma, S. Devi, S. Chahal, J.P. Singh, K.H. Chae, A. Kumar, K. Asokan,
Acknowledgments P. Kumar, Phase transformation in Fe2O3 nanoparticles: Electrical properties with
local electronic structure, Physica B 620 (2021), 413275, https://doi.org/10.1016/
Surjeet Chahal would like to acknowledge the DIT University, Deh­ j.physb.2021.413275.
[21] L. Phor, S. Chahal, V. Kumar, Self-cooling by ferrofluid in magnetic field, SN
radun for the seed money grant (DITU/R&D/2022/017/Physics).
Applied 388 Sciences 1 (12), 1-9. https://doi.org/10.1007/s42452-019-1738-z.
[22] L. Phor, V. Kumar, Self-cooling device based on thermomagnetic efect of
References MnxZn1− xFe2O4 (x = 0.3, 0.4, 0.5, 0.6, 0.7)/ferrofluid, J. Mater. Sci. Mater.
Electron. 30 (2019) 9322–9333, https://doi.org/10.1007/s10854-019-01262-8.
[23] S. Devi Suman, V. Sharma, S. Chahal, P. Goel, S. Singh, A. Kumar, P. Kumar, Phase
[1] P. Bansal, D. Sud, Photocatalytic degradation of commercial dye, CI Reactive Red
transformation and structural evolution in iron oxide nanostructures, Mater. Sci.
35 in aqueous suspension: degradation pathway and identification of intermediates
Eng., B 272 (2021), 115329, https://doi.org/10.1016/j.mseb.2021.115329.
by LC/MS, J. Mol. Catal. Chem. 374–375 (2013) 66–72, https://doi.org/10.1016/j.
[24] S. Kang, J. Jang, R.C. Pawar, S. Ahn, C.S. Lee, Low temperature fabrication of
molcata.2013.03.018.
Fe2O3 nanorod film coated with ultra-thin g-C3N4 for a direct z-scheme exerting
[2] N. Bahadur, N. Bhargava, Novel pilot scale photocatalytic treatment of textile &
photocatalytic activities, RSC Adv. 8 (2018), 33600, https://doi.org/10.1039/
dyeing industry wastewater to achieve process water quality and enabling zero
C8RA04499F.
liquid discharge, J. Water Proc. Eng. 32 (2019), 100934, https://doi.org/10.1016/
[25] S. Chahal Suman, S. Singh, P. Goel, A. Kumar, O. Singh, P. Kumar, Understanding
j.jwpe.2019.100934.
the role of Ni ions on the photocatalytic activity and dielectric properties of
[3] M.S.S. Abujazar, S.U. Karaağaç, S.S.A. Amr, M.Y.D. Alazaiza, M.J.K. Bashir, Recent
hematite nanostructures: an experimental and DFT approach, J. Phys. Chem. Solid.
advancement in the application of hybrid coagulants in coagulation-flocculation of
156 (2021), 110118, https://doi.org/10.1016/j.jpcs.2021.110118.
wastewater: a review, J. Clean. Prod. 345 (2022), 131133, https://doi.org/
[26] A.H. Asif, N. Rafique, R.A.K. Hirani, H. Wu, L. Shi, H. Sun, Heterogeneous
10.1016/j.jclepro.2022.131133.
activation of peroxymonosulfate by Co-doped Fe2O3 nanospheres for degradation
[4] L. Zhang, X. Liu, M. Zhang, T. Wang, H. Tang, Y. Jia, The effect of pH/PAC on the
of p-hydroxybenzoic acid, J. Colloid Interface Sci. 604 (2021) 390–401, https://
coagulation of anionic surfactant wastewater generated in the cosmetic production,
doi.org/10.1016/j.jcis.2021.06.161.
J. Environ. Chem. Eng. 11 (2023), 109312, https://doi.org/10.1016/j.
[27] S. Hmamouchi, A. Yacoubi, B. Chafik, E. Idrissi, Using egg ovalbumin to synthesize
jece.2023.109312.
pure α-Fe2O3 and cobalt doped α-Fe2O3: structural, morphological, optical and
[5] J. Wang, H. Liu, Y. Gao, Q. Yue, B. Gao, B. Liu, K. Guo, X. Xu, Pilot-scale advanced
photocatalytic properties, Heliyon 8 (2022), E08953, https://doi.org/10.1016/j.
treatment of actual high-salt textile wastewater by a UV/O3 pressurization process:
heliyon.2022.e08953.
evaluation of removal kinetics and reverse osmosis desalination process, Sci. Total
[28] B. Avasarala, S. Tirukkovalluri, S. Bojja, Magnesium doped titania for
Environ. 857 (2023), 159725, https://doi.org/10.1016/j.scitotenv.2022.159725.
photocatalytic degradation of dyes in visible light, Environ. Anal. Toxicol. 6
[6] A. Nielsen, L. Garcia, K. Silva, L. Sabogal-Paz, M. Hincapié, L. Montoya, L. Galeano,
(2016), 1000358, https://doi.org/10.4172/2161-0525.1000358.
A.G. Balzategui, F. Reygadas, C. Herrera, S. Golden, J. Byrne, P.F. Ibáñez,
[29] V. Etacheri, R. Roshan, V. Kumar, Mg-doped ZnO nanoparticles for efficient
Chlorination for low-cost household water disinfection – a critical review and
sunlight-driven photocatalysis, ACS Appl. Mater. Interfaces 4 (5) (2012), https://
status in three Latin American countries, Int. J. Hyg Environ. Health 244 (2022),
doi.org/10.1021/am300359h, 2717–2725.
114004, https://doi.org/10.1016/j.ijheh.2022.114004.
[30] S. Chahal, L. Phor, S. Singh, A. Singh, J. Malik, P. Goel, A. Kumar, Ankita,
[7] A. Cescon, J. Jiang, Filtration process and alternative filter media material in water
P. Kumar, An efficient and unique method for the growth of spindle shaped Mg-
treatment, Filtr. Proces. Alternative Filter Media Mater. Water Treatment, Water 12
doped cerium oxide composed of nanorods for photodegradation of p-Nitrophenol,
(2020) 3377, https://doi.org/10.3390/w12123377.
Ceram. Int. 48 (2022) 28961–28968, https://doi.org/10.1016/j.
[8] T.S. Jamil, H. Roland, H. Michael, R. Jens-Uwe, Homogeneous photocatalytic
ceramint.2022.04.145.
processes for degradation of some endocrine disturbing chemicals under UV
irradiation, J. Water Proc. Eng. 18 (2017) 159–168, https://doi.org/10.1016/j.
jwpe.2017.04.005.

8
A. Kumar et al. Ceramics International xxx (xxxx) xxx

[31] B.L.S. Zhong, J.S. Hu, H.P. Liang, A.M. Cao, W.G. Song, L.J. Wan, Self-assembled [37] B. Choudhury, A. Choudhury, Lattice distortion and corresponding changes in
3D flowerlike iron oxide nanostructures and their application in water treatment, optical properties of CeO2 nanoparticles on Nd doping, Curr. Appl. Phys. 13 (2013)
Adv. Mater. 18 (2006) 2426–2431, https://doi.org/10.1002/adma.200600504. 217, https://doi.org/10.1016/j.cap.2012.07.014.
[32] L. Phor, S. Chahal, V. Kumar, Zn2+ substituted superparamagnetic MgFe2O4 spinel- [38] N.S. Arul, D. Mangalaraj, R. Ramachandran, A.N. Grace, J.I. Hana, Fabrication of
ferrites: investigations on structural and spin-interactions, J. Adv. Ceram. 9 (2020) CeO2/Fe2O3 composite nanospindles for enhanced visible light driven
576–587, https://doi.org/10.1007/s40145-020-0396-3. photocatalyst and supercapacitor electrode, J. Mater. Chem. A 3 (2015)
[33] L. Wu, W. Wang, S. Zhang, D. Mo, X. Li, Fabrication and characterization of Co- 15248–15258, https://doi.org/10.1039/C5TA02630J.
doped Fe2O3 spindles for the enhanced photo-fenton catalytic degradation of [39] J. Iqbal, X. Liu, H. Zhu, C. Pan, Y. Zhang, D. Yu, R. Yu, Trapping of Ce electrons in
tetracycline, ACS Omega 6 (49) (2021), https://doi.org/10.1021/ band gap and room temperature ferromagnetism of Ce4+ doped ZnO nanowires,
acsomega.1c04950, 33717–33727. J. Appl. Phys. 106 (2009) 1–7, https://doi.org/10.1063/1.3245325.
[34] Y. Zhang, R. Si, C. Liao, C. Yan, Facile alcohothermal synthesis, size-dependent [40] N.N. Mahamuni, Y.G. Adewuyi, Advanced oxidation processes (AOPs) involving
ultraviolet absorption, and enhanced CO conversion activity of ceria nanocrystals, ultrasound for waste water treatment: a review with emphasis on cost estimation,
J. Phys. Chem. B 107 (2003) 10159–10167, https://doi.org/10.1021/jp034981o. Ultrason. Sonochem. 17 (2010) 990–1003, https://doi.org/10.1016/j.
[35] L. Lu, J. Pan, D. Zhu, Quality requirements of iron ore for iron production, Iron ultsonch.2009.09.005.
Ore: Mineralogy, ProcessinMineral., Proces. Environ. Sustain.g and Environmental [41] G. Tezcanli-Guyer, N.H. Ince, Degradation and toxicity reduction of textile dyestuff
Sustainability (2015) 475–504, https://doi.org/10.1016/B978-1-78242-156- by ultrasound, Ultrason. Sonochem. 10 (2003) 235–240, https://doi.org/10.1016/
6.00016-2. S1350-4177(03)00089-0.
[36] S. Chahal Suman, A. Kumar, P. Kumar, Zn doped α-Fe2O3: an efficient material for
UV driven photocatalysis and electrical conductivity, Crystals 10 (2020) 273,
https://doi.org/10.3390/cryst10040273.