Chemical Physics Letters 792 (2022) 139384

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Chemical Physics Letters

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

Optical, structural and photocatalytic properties of rare earth element Gd3+

doped MgO nanocrystals
R. Vijaya Shanthi a, b, R. Kayalvizhi c, M. John Abel d, Neyvasagam K.b, *
a
Department of Physics, Parvathy’s Arts and Science College, Dindigul 624002, India
b
Department of Physics, The Madura College, Madurai 625011, India
c
Department of Physics , E.M.G Yadava Women’s College, Madurai 6250014, India
d
Department of Physics, University College of Engineering, Bharathidasan Institute of Technology Campus, Anna University, Tiruchirappalli-24, Tamil Nadu, India

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

Keywords: In this work, a cost-effective and ecologically friendly way was chosen for the preparation of magnesium oxide
Co-precipitation (MgO) and gadolinium doped MgO (Gd3+-doped MgO) nanoparticles. The Gd3+ ions caused a shift in the
Photocatalyst acceptor level, which is proved by the obtained band gap values of the samples which is found to be reduced for
Gd-doped MgO
Gd3+-doped MgO rather than pure MgO. Three bands related to F + and F oxygen deficiency defects may be seen
Nanoparticles
UV irradiation
in the photoluminescence spectra of produced nanomaterials. Crystallinity, particle size, and surface area, of
these synthetic photocatalyst were all measured. The photo activity of Gd3+-doped MgO with different weight
percent (1, 3, and 5) of Gd3+ has been studied in Methyl Orange (MO) and Methylene Blue (MB) degradation.
The photocatalytic behavior of magnesium oxide nanoparticles and rare earth element Gd3+-doped magnesium
oxide was studied, and the photocatalytic rate was enhanced by doping of gadolinium under UV radiation was
observed. The impact of operational variables like pH and PZC was evaluated. When the efficiency of all pro­
duced nanoparticles was compared, it was discovered that the 5 wt% Gd-doped MgO nano powder performed
better rather than the rest of the materials.

1. Introduction
Researchers have been inspired in recent centuries by the remarkable
characteristics of nanomaterials to create simpler and less expensive
ways for producing nanostructures of technologically significant mate­
rials. Owing of their potential uses in catalysts, solid electrolytes, color
display, solar energy converters, flat panel displays, optical amplifiers,
photodiodes, host material in solid-state lasers, electroluminescent de­
vices, and solar cells, metal oxide nanomaterials have gotten a lot of
interest [1–5]. Organic dyes that are used in the textile and dye in­
dustries have an impact on both humans and aquatic ecosystems. In the
realm of environmental restoration, the extraction of organic pollutants
from the outflow of industrialized waste water has gotten a lot of
consideration. The biodegradation rate is poor for the carbon content of
organic dyes, so that it is hazardous to the environment. To eliminate
organic contaminants, variety of methods has been used, including
adsorption, filtering, flotation, and chemical oxidation. Nevertheless,
the majority of the methods listed above need an expensive treatment
procedure and also creates dangerous by-products. As a result of these
facts, in the area of environmental cleanup, the photocatalysis has ac­
quired a lot of interest which using low-cost light sources or everlasting
sunlight to degrade organic contaminants without producing hazardous
residues [6,7].
Researchers are interested in developing efficient and cost-effective
photocatalysts for the catalytic photodegradation method. Photo­
degradation using synthetic catalysts is a heterogeneous process in
which the light-absorbing photocatalyst is in solid phase and an organic
pollutant is in a gaseous or liquid phase [8]. For photodegradation of
organic dyes semiconductor metal oxides have been extensively
researched as synthetic photocatalysts. CuO, ZnO, TiO2, WO3, Fe2O3,
and other metal oxides were utilized as active photocatalyst nano­
materials for the decomposition of organic pollutants [9 –14]. For its
distinctive mechanical, chemical, electrical, and optical characteristics,
MgO is a well-examined photocatalyst and the major reasons for the
acceptance of MgO materials have been recognized as their low cost and
biocompatibility. The interdisciplinary uses of MgO, such as transparent
ceramics, paint, superconductor goods, refractory, pollution absorbent,
and plasma display panel were investigated based on its photocatalytic

* Corresponding author.
E-mail address: srineyvas@yahoo.co.in (K. Neyvasagam).

https://doi.org/10.1016/j.cplett.2022.139384
Received 25 October 2021; Received in revised form 10 January 2022; Accepted 16 January 2022
Available online 28 January 2022
0009-2614/© 2022 Elsevier B.V. All rights reserved.
R. Vijaya Shanthi et al.
Fig. 1. (a, c) XRD patterns of MgO and Gd doped MgO nanoparticles, (b) Variation in lattice constant (a) with respect to Gd3+ content.
characteristics [15 –18]. Particularly, photodegradation investigations
of a variety of dyes, notably methyl orange, methylene blue, congo red,
by Dobrucka; Aziz and Karim; and Karthik et al. respectively have been
performed out successfully utilizing MgO NPs as a photocatalytic ma­
terial [19 –21]. Conversely, the photocatalytic use of MgO nanoparticles
is severely restricted due to its large band gap. Furthermore, only a low
quantity of active free radicals was produced due to its high rate of
electron–hole (e–h) pair recombination results in less photocatalytic
effectiveness. To overcome this issue, many researchers employing
doping of other metal ions into the host material having wide band gap.
Specifically, an auxiliary band structure is created below the conduction
band of host material while doping of additional metal ions into its
crystal lattice, which aids in the harvesting of greater electromagnetic
spectrum. Furthermore, oxygen vacancies are also produces in the
crystal framework due to metal ion doping, which improves the catalytic
activity of that material.
Rare earth metal ions doping have lately gained a lot of interest in the
realm of photocatalysis. The inclusion of rare earth metal ions reducing
electron-hole pair coupling and also enhances photocatalytic perfor­
mance. The partially filled 4f orbital structure of rare earth metals is
advantageous for trapping electrons, which improves catalytic activity
by reduces charge carrier recombination. To increase the degrading ef­
ficiency of TiO2, and ZnO many rare earth elements such as Erbium,
lanthanum, gadolinium, and samarium have been adopted as dopant.
For example, Sm-doped ZnO, La-doped TiO2, Er- doped ZnO, Gd-doped
TiO2, are reported in literatures, in which the authors studied the pho­
tocatalytic activities among various dyes and established the synergistic
effects of RE metal ions [22 –25]. Among the RE metal ions, Gd (gado­
linium) with partially-filled f orbitals has a largely favorable influence
on electrical, magnetic and luminescent characteristics when employed
as a dopant [26 –28]. According to Yayapao et al, the rate constant for
Gd doped ZnO was around 2.72 times greater than pure ZnO under UV
radiation in methylene blue degradation [29].
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Chemical Physics Letters 792 (2022) 139384
Efficiency of MgO nanoparticles as a photocatalysts is critically
influenced by their surface characteristics, such as surface shape,
porosity, and surface area. The technique of synthesis, such as sol–gel,
hydrothermal, sonochemical, [30 –31] etc., has a significant impact on
the surface characteristics and shape of MgO nanoparticles. Since they
require complex technology, intense temperature, and various chem­
icals as surfactants or templates, most synthesis techniques are not
applicable to commercial scale. Meanwhile, the wet chemical precipi­
tation technique for MgO nanoparticle synthesis has numerous benefits,
including a one-step procedure, technological simplicity, cheap cost and
large scale production. In connection, with the above-mentioned facts
the goal of current study is to improve the photocatalytic properties of
MgO nanoparticles by utilizing suitable rare earth metal ion Gd (gado­
linium) to restrict the recombination of electron – hole and also
increasing the light absorption capacity MgO nanoparticles. The syn­
thesized photocatalyst is examined with various characterization tech­
niques and are discussed in the following sections.
2. Materials
The reagents and chemicals used in this study comprised magnesium
chloride hexahydrate [MgCl2⋅6H2O], gadolinium chloride hexahydrate
[GdCl3⋅6H2O], ethanol (C2H5OH), methyl orange [C14H14N3NaO3S],
and methylene blue [C16H18ClN3S], which were bought from Sigma
Aldrich AR grade with 99.9% and employed without purification.
2.1. Method of preparation
Utilizing magnesium chloride as an Mg2+ ion source and sodium
hydroxide as an OH‾ source the magnesium oxide nanoparticles were
made. 0.1 M magnesium chloride was diluted in 200 ml distilled water
using the standard laboratory method. With constant stirring, a 30 ml of
4 M sodium hydroxide solution was dropped into the produced
R. Vijaya Shanthi et al.
magnesium chloride solution. Within a few minutes, in the reaction
beaker a white precipitate of magnesium hydroxide was revealed. For
the next 6 h, the stirring persisted. The white precipitate was then pu­
rified and rinsed with ethanol and distilled water multiple times before
being cured at 80 ◦ C for 12 h. Employing an agate crusher, the dry
powder was milled into a very tiny powder. Magnesium chloride was
used to make magnesium oxide nanoparticles. Finally, calcination at
700 ◦ C for 3 h yielded the fine powder of MgO. By adopting gadolinium
chloride as a Gd3+ ion source and subtracting the suitable quantity of
magnesium chloride salt, and the experimental method was performed
step by step as same as mentioned above for the production of Gd doped
MgO nanoparticles. Further the synthesized materials are labeled as MG,
GMG1, GMG3, and GMG5 for pure MgO, 1 wt%: MgO, 3 wt%: MgO, and
5 wt%: MgO, respectively in the rest of the manuscript.
2.2. Photocatalytic experimental setup
The photo-catalytic tests were conducted out at room temperature in
a spherical glass reactor with a UV light source of Philips 125 W lamp
with a wavelength of 365 nm. The irradiation was done in the air at­
mosphere within the reactor setup with direct concentrating of light
onto the reaction mixture, and all of the tests were done using double
distilled water. 0.1 g of photocatalyst is distributed in 100 ml of 35 mg/L
MO and MB solution separately in a usual experiment. Throughout the
experiment, the reaction solution was continuously agitated using a
magnetic stirrer. The reaction mixture was agitated for 60 min preceding
irradiation to achieve adsorption/desorption stability. At predetermined
time intervals, aliquots were taken from the solutions and promptly
centrifuged and screened to eliminate the catalyst particles before being
submitted to spectrophotometric measurement to quantify the residual
dye content. To determine the MO and MB degradation effectiveness,
the following formula was applied:
( )
c percentage which is observed from the calculated values Fig. 1b. These
η = 1− × 100(%) (1)
c0
3. Results and discussion
3.1. XRD characterization
In the scan range of 2θ from 20 to 80◦ , Fig. 1a displays the XRD
spectra of MG, GMG1, GMG3, and GMG5 nanoparticles with different
percentages of Gd3+ ions. The obtained patterns are well matched with
standard JCPDS card No. 87–0651, which verifies a cubic phase and the
Fm-3 m space group [32]. The influence of Gd3+ contents ranging from 1
to 5 wt% on the lattice parameters of MgO was studied. There is no
change in the phase configuration of the MgO nanoparticles while
doping which is revealed in the XRD patterns of doped samples. It’s also
worth noting that there is no peak for gadolinium oxide (Gd2O3) was
identified in the diffraction spectra, indicating that doping happened
within the MgO unit cell. When the concentration of Gd3+ was raised,
the peaks did not alter in intensity, but they did get broader when
compared to pure MgO. It’s possible that the high concentration of Gd3+
doping ions is suppressing crystal formation. The below given
Debye–Scherer equation (Eq. (2)) was used to determine the average
crystallite sizes (D) for all samples:
Kλ
D= (2)
βcosθ
Where λ is the wavelength of incident X-ray, β is the peak width at
half maximum, and θ is the Bragg diffraction angle, and K is the Scherer
constant (K = 0.9). Using above equation, the average crystallite size
was determined to be 43, 37, 32, and 27 nm, respectively for MG, GMG1,
GMG3, and GMG5 samples. Applying the equation following, the values
of the lattice constant (a) of MgO and Gd3+ doped MgO nanoparticles are
calculated (Eq. (3)).
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Chemical Physics Letters 792 (2022) 139384
Table 1
Calculated lattice constant and grain size of MgO and Gd doped MgO
nanoparticles.
Samples Peak position (2θ) Lattice constant a (Å) Grain size (nm)
MgO 42.84 4.2015 43
1 wt% Gd: MgO 42.54 4.2234 37
3 wt% Gd: MgO 42.25 4.2441 32
5 wt% Gd: MgO 42.06 4.2659 27
Fig. 2. FT-IR spectra of MgO and Gd doped MgO nanoparticles.
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
a=d h2 + k2 + l2 (3)
The lattice constant (a) value of pure MgO 4.2015 Å and is slightly
increases to around 4.2659 Å in accordance to the increase of Gd3+
findings support the presence of Gd3+ dopant into the MgO crystal lat­
tice, as revealed in Table 1. The discrepancies in ionic radii of the Mg2+
(0.72 Å) and Gd3+ (0.94 Å) ions are responsible for these occurrences
[33,34]. Due to the lattice instability and accompanying stresses of the
MgO unit cell during the doping treatment, the Gd3+ seems to easily
integrate into the MgO crystal framework. As the concentration of Gd3+
in the MgO lattice increased, the peak at the (2 0 0) plane shifted to the
lesser value of 2θ, as seen in Fig. 1c. These findings revealed that Gd3+
ions replaced Mg2+ in the MgO lattice, causing alterations in the lattice
constant (a) because Mg2+ has a lower ionic radius than Gd3+. Varia­
tions in bond length and bond angles between atoms produced varia­
tions in the lattice strain and planes, as seen by these computed values of
lattice constant and crystallite size. The d-space value increases as ten­
sile stress increases, causing peaks to move to lower 2θ values [35].
Rare-earth ion doping has been shown to inhibit the formation of MgO
crystals in general. However, doping MgO with Gd3+ions causes a
reduction in crystal size, which is due to the production of Gd–O–Mg,
which inhibits crystal development [37]. Based on the obtained crys­
tallite size, all of the synthesized materials are nanometer in scale, and
the XRD investigation revealed that all of the synthesized particles have
a high degree of crystallinity and homogeneity.
3.2. FT-IR characterization
In analyzing chemical bonding and functional groups in materials, as
well as identifying the material’s compositional components, FT-IR is
one of the most important methods. Fig. 2 shows the FT-IR spectra of
MG, GMG1, GMG3, and GMG5 nanomaterials. All of the synthesized
nanomaterials showed a broad and strong absorption peak at 3424 cm− 1
that was attributed to O–H stretching vibration of the hydroxyl group.
During observations, the absorption peak corresponds to the H–O–H
bending vibration of absorbed H2O molecules is located at 1573 cm− 1
R. Vijaya Shanthi et al. Chemical Physics Letters 792 (2022) 139384

Fig. 3. (a) UV-DRS absorbance spectrum of MgO and Gd doped MgO nanoparticles, (b) Tauc’s plot of MgO and Gd doped MgO nanoparticles.

[36,37]. The peak ascribed to metal–oxygen bonds at 564 cm− 1 which is

linked with the stretching vibration of Mg–O, indicating that MgO has
formed [38]. The FTIR spectrum revealed no additional absorption
bands, indicating that the produced NPs are nearly pure and free of
considerable impurities. Because of the enhanced lattice disruption
caused by the earlier doping of Gd3+ into Mg-O, the metal oxide peak for
doped samples has a broad range of absorption nature around the low
wavenumber region. Due to the alteration in bond length caused by the
substitution of Gd3+ ions instead of Mg2+ ions, the metal oxide ab­
sorption peak shifts towards higher wave number side with more Gd
doping. The FT-IR measurements substantiated the sample’s XRD
results.

3.3. Diffuse reflectance spectroscopic studies

The photocatalytic properties of produced nanomaterials are studied

using optical characterization. DRS measurement was performed with
the goal of estimating the energy band gap of the produced nano­
materials, and the findings were evaluated. Fig. 3(a, b) shows the optical
absorption patterns and Tauc’s plots of MG, GMG1, GMG3, and GMG5
nanopowders. The absorption edge migrated toward the longer wave­
lengths area with increased Gd3+ dopant content, as shown in the ab­
sorption curves, suggesting that the band gap is narrowing. Tauc’s plot
curves were constructed to correctly estimate the band gaps of the
synthesized samples. The direct band gap was determined using the
equation below,
αhν = A(hν − Eg )1/2 (4)
Where α is the absorption coefficient, hν is the photon energy, and Eg
is the optical band gap. Extrapolating the linear portion of the graph
drawn between (αhν)2 and hν yielded the Eg values. The calculated band
gap values are 3.81, 3.67, 3.54, and 3.43 eV respectively for MG, GMG1,
GMG3, and GMG5 nanopowders. That this, band gap narrowing is de­
picts by Tauc’s plot also. The sp-d transfer interaction between the band
electrons of the parent Mg atoms and localized electrons in the f orbitals
of the dopant Gd atoms might justify these decrease in band gap with
rising Gd3+ dopant content. In the produced materials, structural flaws
and contaminant atoms also attributed to this band gap suppression
[39]. As a consequence of the optical band gap study, the light ab­
sorption range of the produced nanopowders was increased by Gd3+
dopant, making them ideal for light harvesting applications including
photocatalytic activity.
Fig. 4. PL spectra of MgO and Gd doped MgO nanoparticles.
3.4. Photoluminescence spectroscopy
Fig. 4 shows the photoluminescence (PL) spectra of MG, GMG1,
GMG3, and GMG5 nanopowders at room temperature using 370 nm
light excitation. The presence of singly ionized oxygen voids, which are
the major contributors of hydroxyl radical production necessary for the
photo photodegradation mechanism, is confirmed by the peak centered
at 426 nm [40]. The emission of visible light, such as blue and green
fluorescence, is caused by deep-level emissions (DLE). Oxygen va­
cancies, magnesium vacancies, oxygen interstitials, magnesium in­
terstitials, and oxygen anti-sites are all deep level defects in MgO [41].
The blue emissions at 487 nm in all samples are may be correspond to
electron transition from interstitial defects to oxygen vacancies [42].The
rise in blue emission amplitude shows that raising Gd3+ dosage in the
MgO crystal lattice raises the deep donor level of Mg interstitial. The
emission peaks at 541 nm were attributed to the radiative switchover of
an electron from the deep donor level of Zn interstitial to an acceptor
level induced by the singly ionized charged state of the deficiency in
MgO [43]. The upsurge in intensity indicates that the Gd3+ ions in the
MgO lattice produce more oxygen vacancies. Gd3+ ions are successfully
integrated into the MgO lattice, as evidenced by the increased blue and
green emissions of Gd3+ doped samples. In contrast, due of the rise in
non-radiative traps caused by structural disturbance, the predominant
violet emission peak intensity of doped MgO nanoparticles is gradually

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R. Vijaya Shanthi et al. Chemical Physics Letters 792 (2022) 139384

Fig. 5. SEM micrographs of (a) Pure MgO, (b) 1 wt% Gd: MgO, (c) 3 wt% Gd: MgO, (d) 5 wt% Gd: MgO nanoparticles.

Fig. 6. EDAX spectra of (a) Pure MgO, (b) 1 wt% Gd: MgO, (c) 3 wt% Gd: MgO, (d) 5 wt% Gd: MgO nanoparticles.

5
R. Vijaya Shanthi et al. Chemical Physics Letters 792 (2022) 139384

Fig. 7. N2 adsorption/desorption plot of (a) Pure MgO, (b) 1 wt% Gd: MgO, (c) 3 wt% Gd: MgO, (d) 5 wt% Gd: MgO nanoparticles.

reduced with increasing Gd3+ concentration as compared to pure MgO

[44].

3.5. Morphological studies

Fig. 5(a-d) shows SEM images of MG, GMG1, GMG3, and GMG5
nanopowders at 1 μm range. Within the nanoscale domain, the synthe­
sized nanomaterial is made up of randomly scattered larger spherical
particles. During synthesis, nanoparticle agglomeration and the forma­
tion of non-uniform crystalline grains were observed. The catalyst par­
ticle size and shape did not differ significantly among the nanoparticle
studied, although the degree of agglomeration increased somewhat as
the Gd3+ concentration rose. The agglomeration of nanoparticle
increased the cluster formations, which might lead to spongier surface of
the material. The SEM images of the prepared nanopowder reveal the
slightly rough surface with porous nature of the particles. This porous
nature paved a way for more active sites to adsorb dye molecules. In
reality, high surface area to volume ratio of nanoparticles has a high
surface energy, which causes agglomeration of the nanoparticles, which Fig. 8. Pore size distribution of MgO and Gd doped MgO nanoparticles.
is typical in nanopowders. EDAX spectra were used to determine the
chemical compositions of produced MG, GMG1, GMG3, and GMG5
nanopowders, as displayed in Fig. 6(a-d). In Gd doped MgO nano­
powders, these spectra revealed the existence of Mg, O, and Gd, but the
spectrum of undoped MgO nanopowder revealed just oxygen and
magnesium ions. The EDAX data indicates that Gd3+ was effectively
Table 2
adopted as a dopant in the MgO crystal lattice.
The comparative measures on BET measurements of the materials.
Material BET analysis
3.6. Brunauer emmett and teller (BET) characterization
Pore volume (cm3g− 1) Pore size (nm) Surface area (m2g− 1)
In general, a nano catalyst’s surface area is one of the most signifi­ MgO 0.1217 21 78.3
cant factors that influence its efficiency and activity in a reaction. The 1 wt% Gd: MgO 0.1571 24 91.7
BET technique, which is founded on the theoretical concept of a 3 wt% Gd: MgO 0.1894 30 142.2
5 wt% Gd: MgO 0.2268 33 194.4
monolayer creation in the physical adsorption of gas molecules, is

6
R. Vijaya Shanthi et al.
Fig. 9. UV absorbance spectrum of MO dye with catalyst (a) Pure MgO, (b) 1 wt% Gd: MgO, (c) 3 wt% Gd: MgO, (d) 5 wt% Gd: MgO nanoparticles at
normal condition.
regarded the most practical approach for measuring surface area [45].
The nitrogen adsorption–desorption isotherms of all MG, GMG1, GMG3,
and GMG5 nanopowders are respectively shown in Fig. 7 (a-d). Ac­
cording to the IUPAC classification, pure and Gd3+-doped MgO nano­
particles possess type IV adsorption–desorption isotherms. The H3
hysteresis loops were also identified, according to the IUPAC classifi­
cation. Fig. 8 reveals the pore size distribution of MG, GMG1, GMG3,
and GMG5 nanopowders comparatively. Table 2 lists all surface pa­
rameters of MG, GMG1, GMG3, and GMG5 nanopowders, including
average pore size, surface area, and pore volume, and compare them to
the equivalent values of pure MgO nanopowder. The amount of adsor­
bed gas grew as the quantity of Gd3+ ions rose, and the hysteresis loops
got wider throughout a range of relative pressures. The increased surface
area with higher ion concentration is acknowledged with these findings
[46]. This finding shows that even at small dosage of Gd3+ ions, the
doping operation increases the surface area of MgO nanopowder. The
average pore diameters for MG, GMG1, GMG3, and GMG5 nanopowders
were determined using the BJH technique. All of the samples had
average pore diameters of less than 50 nm and greater than 2 nm,
indicating that they are all mesoporous in nature. These findings
demonstrate that the lower particle size is responsible for the higher
surface area of Gd3+-doped MgO nanoparticles, as verified by SEM and
XRD studies.
4. Photocatalytic studies
Figs. 9 & 10 (a-d) compares the degradation UV spectrum of MO and
MB dyes using MG, GMG1, GMG3, and GMG5 nanopowders respectively
with irradiation durations of 160 min. A heterogeneous process in which
light-absorbing photo-catalyst is a solid material and an organic
pollutant contains in the liquid or gaseous phase is defined as catalytic
photo deterioration. Stimulation of electrons from the valence band (VB)
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Chemical Physics Letters 792 (2022) 139384
to the conduction band (CB) of the photo-catalyst which generates the
holes in the VB, referred to as holes in valance band, are two common
mechanisms of photo deterioration. The holes in the valence band and
independently roaming electron in the CB can either reunite and the
received light energy is discharge as heat radiation, or subsequently
interact to generate reactive agents such as hydroxyl radical (OH•) and
superoxide ion (O2• − ). The organic molecules are oxidizing in an un­
selective manner by these reactive species. The deterioration reached a
maximum magnitude as the Gd3+ concentration rose. The degradation
effectiveness of GMG5 was 81% and 83%, for MO and MB dye respec­
tively which was greater than that of pure MgO catalyst when the same
quantity of catalyst was loaded and the reaction duration was the same
and is calculated from the plot between C/C0 and reaction time as shown
in Fig. 11 (a, b). This is supported by the fact that the primary peak of
MO and MB dye fell to its lowest level after 160 min, indicating that the
GMG5 nano-catalyst attained the maximum efficiency. This might be
because the band gap narrowing in Gd3+-doped ZnO increases the ab­
sorption of light photons, the DRS studies reveals this. 5 wt% Gd3+-
doped MgO has a larger surface area than MgO, which might contribute
to greater efficiency. The activity of MgO nanopowder is clearly
enhanced by a modest number of Gd3+ ions (1 wt%), which might be
attributed to a segregation of photo-generated electrons and hole by
trapping level created in the material. In PL studies the electron trapping
is evident by the suppression in fluorescence intensity for the doped
samples. The Gd3+ ions existing on the MgO surface must interact with
the electrons supplied to the oxygen molecules to create oxidative agents
such as the superoxide radical ion (O2• − ), as explained by the reaction
process below:
Synthesized nano catalyst + hν → h+ (vb) + e− (cb) (5)
Gd3+ + e− → Gd2+ (6)
R. Vijaya Shanthi et al. Chemical Physics Letters 792 (2022) 139384

Fig. 10. UV absorbance spectrum of MB dye with catalyst (a) Pure MgO, (b) 1 wt% Gd: MgO, (c) 3 wt% Gd: MgO, (d) 5 wt% Gd: MgO nanoparticles at
normal condition.

Fig. 11. (a) Plot between C/C0 and time for MO dye with different catalyst, (b) Plot between C/C0 and time for MB dye with different catalyst,
Gd2+ + O2 → O2• −
+ Gd3+ (7)

O2 + e− → O2• −
(super oxide anions) (8)
O2• −
+ MO & MB → H2O + Mineralized intermediates + CO2 (16)
O2 •−
+ H2O → HO2 + OH • •
(9)
Adsorption of H2O or OH at valence band holes on the surface of
−

2HO2• → H2O2 + O2• (10) Gd3+-doped MgO might create active •OH species. Because of the
instable Gd2+ ions, electron-hole recombination is quicker which may
e− + O2 → OH− + OH• (11) quickly transfer electrons form Gd ions to oxygen molecules. This is
e− + H2O2 → OH− + OH• (12) because the partly filled f-orbital in Gd3+ in doped MgO nanopowders,
traps conduction band electrons and prevents valence band hole re-
h+ + OH− → OH• (13) coupling. However, the unstable electrons of Gd2+ state, which has
readily triggers an electron release, resulting in O2• − and ultimately
+
h + H2O → H + OH + •
(14)
•OH radicals.
•
OH + MO & MB → H2O + Mineralized intermediates + CO2 (15)

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R. Vijaya Shanthi et al. Chemical Physics Letters 792 (2022) 139384

Fig. 12. (a) Point of zero charge measurements of MgO and Gd doped MgO catalyst, (b) Percentage of degradation of MO and MB dye with catalyst 5 wt%Gd: MgO at
different pH.

4.1. Determination of PZC value of the produced catalyst material
The pH levels at which the surface charge of the elements equal zero
under specified circumstances are known as points of zero charge (PZC).
This does not imply that no charge at pH of PZC on the surface, but
rather that it means equally distributed negative and positive charges on
the surface of the material. PZC readings might aid in the optimal
choosing of a solution’s pH value for the treatment of dye degradation.
For metal oxide catalysts, a solution pH above PZC values would be
optimal for treating cation-contaminated effluents, whereas a solution
pH below PZC values would be better for capturing anions. This is due to
the fact that the catalyst’s surface charge is positive below PZC and
negative at pH above the PZC. Here the salt titration method is applied
for analyzing the PZC of the MG, GMG1, GMG3, and GMG5 nano­
powders. To determine the PZC a graph is plotted between initial pH
value (pHi) and the difference in pH after the addition of nanoparticles
(ΔpH). According to the Fig. 12a, the estimated PZC of the pure MgO
nanopowder is pH 11.11, which is close agree with the previous reports
[47 –49]. It is noted from the graph that the PZC of the doped material
get reduces on the increase of Gd3+ concentration and it is pH 10.09 for
GMG5 material. Here we examine the photocatalytic performance of the
prepared photocatalyst by degrading both cationic (MB) and anionic
(MO) dyes. So it is essential to note both the highest surface positive pH
value as well the highest surface negative pH value and it is found to be

Fig. 13. UV absorbance spectrum with catalyst 5 wt% Gd: MgO of (a) MO dye at pH 4 (b) MB dye at pH 12, (c) Plot between C/C0 and time for MO dye with different
catalyst, (d) Plot between C/C0 and time for MB dye with different catalyst.

9
R. Vijaya Shanthi et al.
Fig. 14. Radical scavenging experiment for (a) MO dye and (b) MB dye with 5 wt% Gd: MgO.
pH 4 and pH 12 respectively. This was proved experimentally with
GMG5 catalyst and is discussed in the forthcoming section.
4.2. Effect of solution pH on degradation process
Fig. 12b shows the impact of the reaction solution pH on photo­
catalytic degradation effectiveness of MO and MB dye with GMG5
catalyst as a function of time. At pH 4, the maximum efficiency was
achieved for MO dye. Furthermore, the rate constant was at its highest at
pH4. The photocatalytic decomposition of MO is lesser at other pH
values. This may be explained by the fact that MO molecules have a
negative charge while the surface of GMG5 is positively charged below
PZC that is below pH 10.09 in this study. Through the coulombic in­
teractions between the GMG5 catalysts particle and the dye molecule at
pH 4, methyl orange anions are readily adsorbed onto the catalyst
Fig. 15. Comparative rate constant plots of (a) MO dye and (b) MB dye. (c, d) Error bar chart of rate constant for MO and MB dye.
10
Chemical Physics Letters 792 (2022) 139384
surface. The highest positive charged surface of the GMG5 catalysts is
obtained at pH 4 as per the PZC plot so that the degradation of MO dye is
extreme at this pH 4. On the other side the maximal degradation was
achieved for MB dye is at pH 12. This is somewhat because of at pH 12
the surface charge of the GMG5 catalysts highly negative as proved from
PZC plot. Due to this high negative charge of the GMG5 catalysts and the
cationic nature of MB dye, the maximum coulombic interactions was
exhibits and leads to this maximal degradation at pH 12. The UV spec­
trum for the degradation of MO and MB dye with GMG5 catalysts at their
respective pH values are illustrated in Fig. 13 (a, b) and their corre­
sponding plots between relative concentration differences as a function
of reaction time is depicts in Fig. 13 (c, d).
R. Vijaya Shanthi et al. Chemical Physics Letters 792 (2022) 139384

Table 3 MgO and Gd3+-doped MgO nanostructures. High surface area and
Comparison table on photocatalytic activities of MgO and Gd doped MgO porous structure of 5 wt% Gd3+-doped MgO nanopowder is proven by
nanoparticles. BET findings. Thus these high optical absorption capability, high surface
Dye Samples Rate constant (R2) Degradation area and porous structure of 5 wt% Gd3+-doped MgO nanopowder
(k) (s− 1) value % resulted in efficient photocatalytic degradation of MO and MB dye. The
MgO 4.27 × 10-3 0.93852 52.54 PZC of the MgO and Gd3+-doped nanoparticles was estimated and with
Methyl 1 wt% Gd: MgO 5.31 × 10-3 0.94071 57.37 those results the impact of solution pH was well studied. Based on this
Orange 3 wt% Gd: MgO 8.07 × 10-3 0.98921 71.87 work our findings should make it possible to consider Gd3+-doped MgO
5 wt% Gd: MgO 11.26 × 10-3 0.98933 81.66
as a potential option for photocatalysts and other light harvesting
5 wt% Gd: MgO 14.01 × 10-3 0.99381 88.56
at pH 4 application.
MgO 4.04 × 10-3 0.9638 49.97
Methylene 1 wt% Gd: MgO 4.51 × 10-3 0.94875 51.70 Declaration of Competing Interest
Blue 3 wt% Gd: MgO 7.31 × 10-3 0.98992 67.94
5 wt% Gd: MgO 11.17 × 10-3 0.98884 83.38
5 wt% Gd: MgO 15.53 × 10-3 0.96449 92.46
The authors declare that they have no known competing financial
at pH 12 interests or personal relationships that could have appeared to influence
the work reported in this paper.

4.3. Active species scavenging experiment References

The radical scavenging experiment was carried out to identify the
majority active species involved in the photodegradation process
[Fig. 14 (a, b)]. For this experiment, 10 mmol of isopropyl alcohol (IPA)
was utilized as •OH scavenger and para-benzoquinone (PBQ) for O2• − .
The photocatalytic test was done with GMG5 catalysts and maintaining
the respective pH says 4 for MO and 12 for MB dye. Interestingly, for the
MB dye the degradation was readily affected in the presence of PBQ.
This is because the surface charge of the catalysts were highly negative
at pH 12 according to the previous findings, hence the electron readily
creates the O2• − here which plays a crucial role in MB degradation. On
the other side addition of IPA were vastly influence the MO degradation
and this is because at pH 4 the surface charge is highly positive so that
•OH radicals created by h+ playing a vital role in MO degradation. These
results were well matched with the previous photocatalytic experiments.
4.4. Kinetics studies
The observations strongly demonstrate that the produced Gd3+ has
higher photocatalytic activity in degrading both MO and MB dyes when
compared to pure ZnO. The related kinetics graphs reported for photo­
catalytic degradation pattern of dye molecules are well reflect the first-
order Langmuir-Hinshelwood model. The plots of ln C0/C as a function
of irradiation duration for MO and MB dyes are shown in Fig. 15 (a, b).
The equation for calculating the rate constant k is:
( )
c
ln = kt (17)
c0
Table 3 shows the rate constant and regression coefficient (R2) values
for the synthesized MG, GMG1, GMG3, and GMG5 nanopowders. The
high regression coefficient values suggest that the photo degradation of
MO and MB dyes by the developed photo catalysts as a function of
irradiation duration is well-linear. The error bar chart for the linear fit
curve was shown in Fig. 15 (c, d).
5. Conclusion
In this report, we looked at a simple method for making MgO
nanoparticles via wet chemical preparation. The MgO and Gd3+-doped
MgO nanoparticles’ XRD spectra revealed polycrystalline and cubic
structures, correspondingly. The production of MgO nanoparticles as
well as the inclusion of the doping element gadolinium was shown by
FTIR studies. The inclusion of gadolinium enhanced the shape of the
aggregated sphere-like MgO nanostructure, according to SEM exami­
nation. DRS was used to quantify the optical band gap of MgO and Gd3+-
doped nanoparticles, which decreased from 3.81 eV to 3.43 eV for 5 wt%
Gd3+-doped MgO nanopowder. The decomposition of MO and MB dye
was used to examine the photocatalytic potential of the hierarchical
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