Z. Phys. Chem.

2019; aop

Ismat Bibi*, Sabir Hussain, Farzana Majid, Shagufta Kamal,

Sadia Ata*, Misbah Sultan, Muhammad Imran Din,
Munawar Iqbal and Arif Nazir*
Structural, Dielectric and Magnetic Studies of
Perovskite [Gd1−x Mx CrO3 (M = La, Co, Bi)]
Nanoparticles: Photocatalytic Degradation of Dyes
https://doi.org/10.1515/zpch-2018-1162
Received February 21, 2018; accepted January 18, 2019

Abstract: Nanoparticles (NPs) of Gd1−x Mx CrO3 (M = La, Co, Bi) were synthesized
by microemulsion techniques, involving simultaneous single ion substitution
philosophy. Structural, magnetic, dielectric properties, morphology, elemental
analysis and distribution size of fabricated nano-crystalline were determined.
The techniques employed for investigation are X-ray diffraction (XRD), vibrat-
ing sample magnetometer (VSM), dielectric measurement and scanning electron
microscopy (SEM), energy dispersive X-ray (EDX), photoluminescence (PL) and
atomic force microscopy (AFM), respectively. XRD pattern confirm that all the
as-synthesized NPs have orthorhombic structure and successfully substituted of
different metal ions into the regular crystal structure of GdCrO3 . The lattice param-
eters X-ray density, bulk density, porosity and grain size were calculated from
XRD pattern of Gd1−x Mx CrO3 (M = La, Co, Bi) substituted and un-substituted
GdCrO3 . The magnetic hysteresis loop of fabricated product confirmed that the
entire sample exhibits ferromagnetic behavior at room temperature. It was also
found that the fabricated NPs show excellent photocatalytic activity (PCA) against
Congo-red, about 78.24% after 55 min of incubation.

*Corresponding authors: Ismat Bibi, Department of Chemistry, The Islamia University

of Bahawalpur, Bahawalpur, Pakistan, e-mail: [email protected]; Sadia Ata, Institute
of Chemistry, University of the Punjab, Lahore, Pakistan, e-mail: [email protected];
and Arif Nazir, Department of Chemistry, The University of Lahore, Lahore, Pakistan,
e-mail: [email protected]
Sabir Hussain: Department of Chemistry, The Islamia University of Bahawalpur, Bahawalpur,
Pakistan
Farzana Majid: Department of Physics, University of the Punjab, Lahore, Pakistan
Shagufta Kamal: Department of Chemistry and Biochemistry, GC University Faisalabad,
Faisalabad, Pakistan
Misbah Sultan and Muhammad Imran Din: Institute of Chemistry, University of the Punjab,
Lahore, Pakistan
Munawar Iqbal: Department of Chemistry, The University of Lahore, Lahore, Pakistan

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2 | I. Bibi et al.

Keywords: Congo-red; dielectric; magnetic; nanoparticles; photocatalytic;

synthesis.

1 Introduction
Photocatalysis and dye removal is a multi-facetted research field. There are several
strategies like Fenton, Photo-Fenton, UV/H2 O2 photolysis (UVP) and UV/TiO2 pho-
tocatalysis (UVPC), photochemical method for degradation of persistent organic
pollutants present in liquid effluents [1–6]. Multiferroic materials have snatched
extensive attention of the researchers owing to the interesting fundamental prop-
erties, their behavior as well as potential applications for novel magnetoelectric
devices [7–12]. Metal oxide semiconductors represent a growing asset in many
industries, especially with their chemical, physical and electronic properties.
Metal oxide nanomaterials are versatile materials employed in environmental
remediation, medical technology, energy and water treatment [13–19]. One of the
attractive possibilities is mutual control of the electric and magnetic properties,
as it help out to manipulate the properties of both magnetic and electric materials
[20–23]. The rare earth orthochromites are of tremendous interest due to their opti-
cal, dielectric, multiferroic and magnetic properties which make them suitable
materials to study in the nano-regime [24–27]. It should be noted that the physical
properties of these materials such as optical, magnetic, and dielectric are poorly
understood even in the bulk phase [28–30]. Materials with ferroelectric and mag-
netic order parameters resulting in synchronized ferroelectricity and ferromag-
netism have acquired a lot of interest in mechatronic and magnetic communities
[31, 32]. One of the attractive possibilities is mutual control of the electric and mag-
netic properties, as it help out to manipulate the properties of both magnetic and
electric materials. The rare earth orthochromites are of tremendous interest due
to their optical, dielectric, multiferroic and magnetic properties which make them
suitable materials to study in the nano-regime [33].
The GdCrO3 fits to the family of rare earth orthochromites with a general
formula: RCrO3 and is reported to develop in a distorted perovskite structure
at room temperature (space group Pbnm) [34, 35]. In the orthorhombic struc-
ture of GdCrO3 , the Gd and Cr ions occupy the corner and the center positions
of the cube, respectively. The orthorhombic phase of the rare earth chromites
(GdCrO3 ) displays the magnetic and electric dipolar coupling at low temperature
and has a basic concern in magnetic and ferroelectric devices [36]. These families
of compounds have magnetic properties due to the interaction between R3+ and
Cr3+ ions leading to negative magnetization at low temperatures [37]. The nov-
elty in synthesis methods and study of the optical properties has recently grown
manifold due to interest in the single phase multiferroic oxide materials [38–41].

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 Synthesis and PCA of NPs | 3

It should be noted that the physical properties of these materials such as opti-
cal, magnetic, and dielectric are poorly understood even in the bulk phase.
GdCrO3 is a compound having no information on its optical and dielectric proper-
ties. The previous studies only discuss the structural and magnetism information
on GdCrO3 [35, 37, 42]. Therefore recently in current research effort we realized
that it is important to enhance the dielectric, magnetic and photocatalytic as well
as other physical properties of GdCrO3 by doping of other metals. Therefore in
current study, we report the Gd1−x Mx CrO3 (M = La, Bi, Co) nano crystallites pow-
der prepared by micro-emulsion method. Our major interest is study to structural,
dielectric and magnetic as well as photocatalytic behavior of the synthesized
material. The synthesized materials are strong photocatalyst for the degradation
of xenobiotic compounds.

2 Materials and methods

2.1 Synthesis of “Gd1−x Mx CrO3 (M = La, Bi, Co)” perovskite

The nanoparticles of Gd1−x Mx CrO3 (M = La, Bi, Co) were prepared by micro-
emulsion method. The stoichiometric amounts of all metal nitrates were dissolved
in de-ionized water and thoroughly stirred for 2–3 h at 50–55 °C. The entire sam-
ples were heated with continuous stirring while Cetyl-trimethyl-ammonium bro-
mide (CTAB) was used as a surfactant [43]. The resultant reaction mixtures were
further stirred for 2 h and their pH were adjusted up to 10–11 using 2M ammo-
nium hydroxide. After 4–5 h stirring the samples were kept for few hours to settle
down the precipitate. The precipitates were washed with de-ionized water until
pH decrease to 7. Finally the dried nanoparticles were grinded by using mortar and
pestle and annealed at 950 °C for 8 h in muffle furnace Vulcan A-50. Finally the
annealed powder sample of Gd1−x Mx CrO3 (M = La, Bi, Co) were characterized by
various modern and conventional techniques like SEM, EDX, XRD, PL, AFM, VSM
and dielectric measurements. As-synthesized NPs were used as photocatalyst for
degradation of 100 ppm Congo-red textile dye. This dye has been selected since it
is widely used in textile industry and is carcinogenic in nature.
The degradation was carried out under UV irradiation, while blank was run
without photo-catalyst. After certain definite time interval (3 min) the sample was
withdrawn and % degradation was determined by using UV-Visible spectrum-
photometer using following formula given below (Eq. 1)

% degradation = (C∘ ) − (Cf )/C∘ × 100 (1)

Where C° is the initial concentration of dye before degradation and Cf final

concentration of dye after degradation

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About 10 mg of prepared sample of Gd0.2 Bi0.8 CrO3 was added in a 100 ppm
solution of Congo-red. Degradation was carried out under UV-light with constant
stirring and blank was run without photo-catalyst. After certain time interval
the sample was withdrawn and centrifuged at 25,000 rpm for 5–8 min and %
degradation was monitored by UV-Visible spectrophotometer.

3 Results and discussion

Figure 1 shows the XRD patterns of all annealed samples of Gd1−x Mx CrO3
(M = La, Co, Bi) NPs. In XRD pattern of pure base GdCrO3 NPs recorded on
Philips X’ Pert PRO 3040/60 diffractometer using the Cu Kα (=1.542 Å) as radia-
tion source. The diffraction peaks are obtained between 20 and 80° 2θ at 28.2°,
34.4°, 43.2°, 47.8° and 56.7° representing the (111), (112), (211), (221) and (131)
crystal planes, respectively. All the diffraction peaks are in accordance with
orthorhombic shape of GdCrO3 nanoparticles [35].
It is clear from the diffraction pattern of the Bi, La and Co substituted GdCrO3
that the diffraction peak intensities and angle 2θ values increase as the atomic
size of substituted metal increases. With the help of Scherer’s formula (Eq. 2)
crystallite size of the samples were calculated [44, 45].

D = Kλ/βCosθ (2)

“D” represents the crystallite size for the samples, “λ” is the wave length of
X-rays which are used (1.543 Å), ” β” is the full width at half maxima ,“ θ” is the
Bragg’s angle and “K” is the constant having the value 0.9. The crystallite size

Fig. 1: XRD patterns of Gd1−x Mx CrO3 (M = La,Co,Bi) nanomaterials.

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 Synthesis and PCA of NPs | 5

of the entire sample was found in the range of 50–90 nm. The various physical
parameters like lattice constants (a, b and c), cell volume, X-ray density, bulk
density and porosity of as-synthesized Gd1−x Mx CrO3 (M = La, Co, Bi) NPs were
determined by XRD (Table 1).
The lattice constants (a, b, c) were calculated by using cell software. The lat-
tice constant “a” was decreases from 5.63 Å to 5.54 Å by the substitution of Bi,
La and Co, respectively at the place of Gd in GdCrO3 . The lattice constant “b”
was decreases from 4.92 Å to 4.73 Å and lattice constant “c” was also decreases
from 6.52 Å to 6.31 Å. While the cell volume decreases from 169.5 Å to 158.6 Å.
The cell volume of Gd1−x Mx CrO3 (M = La, Co, Bi) NPs is calculated by formula
given below:

Cell Volume = a × b × c (3)

X-ray density for the all samples was calculated using following formula:

ZM
ρX = (4)
N A V cell

Here “M” is the molecular weight, the value of “Z” is 4 for orthorhombic sys-
tem and “NA” is the Avogadro’s number. It was also noted that the X-ray density
increases from 13.30 g cm−3 to 16.49 g cm−3 . The bulk density was calculated
with the help of following formula:
m
ρm = (5)
πr2 h

Here “ρm ” is the measured bulk density; “r” is the radius of the pellet, “m” is
the mass of the pellet, and “h” is thickness of the pellet.

Tab. 1: Cell parameters (a, b and c), cell volume, and crystallite size for “La1−x GdxCr1-y FeyO3 ”
NPs.

Parameters X = 0.8 X = 0. 8 X = 0. 8 Pure

X = Co X = La X = Bi GdCrO3

Lattice constant a/A° 5.54 5.57 5.59 5.63

Lattice constant b/A° 4.73 4.78 4.84 4.92
Lattice constant c/Å 6.31 6.37 6.44 6.52
Cell Volume /Å3 158.6 162.1 163.4 169.5
Crystallite Size/nm 37.8 36.4 33.9 46.3
X-ray Density /gcm−3 16.49 15.2 14.9 13.3
Bulk Density /gcm−3 3.1 5.9 5.3 3.32
Porosity% 81 51 53 79

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The bulk density for all the samples was less than that of X-ray density. This
change shows the existence of very well pores in Nano crystallites structure. The
porosity, p was calculated by using following formula:

ρm
P=1− (6)
ρ X−ray

In the above equation, the “P” represents the porosity, “ρm ” is the bulk
density of the samples, and “ρ X−ray ” is the X-ray density of the samples.
Synthesized GdCrO3 NPs were subjected to SEM analysis to access the particle
size and morphology. Figure 2 shows SEM image of GdCrO3 nanoparticles. Scale
to measure the particle size of nanoparticles is 2.5 µm as given in the SEM image
of GdCrO3 nanoparticles. It is obvious from the SEM image that average particles
size of synthesized nanoparticles is <100 nm. Estimated particle size distribution
is from 50 nm to 90 nm. From the image it looks that particles are poly-dispersed,
and irregular in shape with variable size. Scanning Electron Microscopy is not
restricted to surface morphology only, as this technology also has the aptitude to
determine particle size of Nano-materials [46, 47].
EDX was carried out to determine the elemental composition of the fabri-
cated GdCrO3 nanoparticles. The EDX analysis (Figure 3) reveals the presence
of strong signal of Bi, Cr, Gd and O which confirm the successful fabrication of
GdxBix−1 CrO3 NPs.
More confirmation of the particle size and morphology of synthesized
Gdx Bi1−x CrO3 NPs were carried out by AFM. AFM analysis of Gdx Bi1−x CrO3
nanoparticles was carried and results are shown in Figure 4. Particle size distribu-
tion of Gdx Bi1−x CrO3 NPs are in the range of 80.73 nm as depicted by three and two

Fig. 2: Scanning Electron Microscopy of GdCrO3 nanoparticles.

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 Synthesis and PCA of NPs | 7

Fig. 3: EDX analysis of Gdx Bi1−x CrO3 NPs.

Fig. 4: Atomic force microscopy of GdCrO3 .

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dimensional representation. Grooves are not homogenous as depicted by three

dimensional image of NPs.
Results obtained from AFM analysis has been complementary to previously
discussed SEM and EDX. These results have confirmed the successful fabrication
of metal nanoparticles of Gdx Bi1−x CrO3 .
In the dielectric measurements of Gd1−x Mx CrO3 (M = La, Co, Bi) nanoparti-
cles the effect of frequency on dissipation factor and capacitance was recorded.
The pellets thickness of Gd1−x Mx CrO3 (M = La, Co, Bi) nanoparticles was
1.76 mm, 3.12 mm, 3.14 mm, respectively. The dielectric constant of Gd1−x Mx CrO3
was calculated with the help of following equation [47].

cd
ε′ = (7)
εo A
where d represent to the thickness of the pellets, c show the capacitance of the
pellets, ε∘ is the permittivity of free space and A is the flat surface of the pellets
in m2 . The Figure 5 shows the variation of dielectric constant (ϵ′) as a function of
frequency.
The dielectric constants values of Gd1−x Mx CrO3 (M = La, Co, Bi) nanopar-
ticles decrease by increasing the frequency (Table 2). At lower frequencies, the
higher value of dielectric constant is due to increased influence on the dielectric
polarization [48]. From graph it is obvious that dielectric constant decreases with
appropriate increase in frequency value. The higher values of dielectric constant
were measured at low frequencies could be recognized due to the Maxwell Wagner
type interfacial polarization mechanism that shows a main role in heterogeneous
composites.
The doping of metals (M = La, Co, Bi) in Gd1−x Mx CrO3 perovskite type NPs
modify conductivities that yields an additional polarization which is labeled as
interfacial polarization that also increases the value dielectric constant. The inter-
facial polarization responded to the external field slowly, so, it dominates in the
low frequency region while has no significant contribution in the region high
frequency [49, 50].
The dielectric loss actually measures the loss of electrical energy from the
applied electric field into the samples at different frequencies. The dielectric loss
(tanδ) was calculated using the relation given in (Eq. 8) [44].
ε′′
tanδ = (8)
ε′
Here tanδ is the loss angle, ε′′ is the imaginary part of the dielectric constant
and is an extent of the absorption of energy by the dielectric from the alternating
field ε′ is the real part of the dielectric constant.

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 Synthesis and PCA of NPs | 9

Fig. 5: (a) Variation of real part and (b) Variation of imaginary part of dielectric constant with
frequency of Gd1−x Mx CrO3 (M = La,Co,Bi) NPs.

Tab. 2: Dielectric constant, dielectric loss factor and dielectric loss of Gd1−x MxCrO3 (M = La,
Co, Bi) NPs at various frequencies.

Parameters Frequency La = 0.2 Co = 0.2 Bi = 0.2

Dielectric Constant 30 MHz 18.92 37.11 34.45

1.470 GHz 13.41 16.67 15.33
3 GHz 12.40 14.95 14.07
Dielectric Loss Factor 30 MHz 26.8 9.25 8.55
1.470 GHz 11.46 3.93 3.74
3 GHz 7.56 2.73 2.23

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PL is the spontaneous emission of light from a material following optical exci-

tation (Figure 6). The graph shows the emission of energy from GdCrO3 sample in
the form of radiation with wavelength in the range of 400–500 nm. PL is a power-
ful technique to probe discrete energy levels and to extract valuable information
about sample composition. An electron that has been excited above the conduc-
tion band of a material will eventually fall and recombine to the hole that has been
excited below the valance band after losing some energy.
The magnetic properties of Gdx M1−x CrO3 (M = Bi, La, Co) NPs were measured
using VSM Lakeshore-74071 at room temperature. The hysteresis loops measured
for Gdx M1−x CrO3 (M = Bi, La, Co) NPs are shown in the Figure 7. Magnetic hys-
teresis (M–H) loops of the synthesized samples show the ferromagnetic behavior.
At saturation point almost all of the magnetic domains are aligned so further
increase in the magnetizing force not increase in magnetic flux. The maximum
saturation magnetization (Ms∼50 emug−1 ) was observed for Gdx Co1−x CrO3 NPs

Fig. 6: Photoluminescence of GdCrO3 NPs.

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 Synthesis and PCA of NPs | 11

Fig. 7: Hysteresis loops curves for “Gd1−x Mx CrO3 (M = Bi, La, Co)” NPs at room temperature.

while lowest (Ms∼28 emug−1 ) for pure base GdCrO3 at magnetization force 10,000
Oe. By the addition of general metals Bi, La and Co content in the pure base
GdCrO3 there is increase of saturation magnetization which is due to the increas-
ing the unpaired electrons in the substituted metals [51]. The effect of substitution
of generals metals (Bi, La, Co) in GdCrO3 saturation magnetization (MS ), coercive
field (HC ) and remnant magnetization (Mr ) is given in the Table 3.
The Coercivity and Retentivity show non-linear behavior with substitution of
Bi, La and Co in GdCrO3. The results showed that substitution in GdCrO3 increase
the value of retentivity which is the magnetization left behind in a ferromag-
netic material after an external magnetic field is removed. The value of reten-
tivity is found maximum in case of Co substitution while minimum is case of Bi
substitution in GdCrO3 [52]. The coercivity which is the measure of the resistance
of a ferromagnetic material to becoming demagnetized is a good tool to classify
the ferromagnetic materials in to hard and soft magnetic materials. The smaller
coercivity in case of Gd0.2 Co0.8 CrO3 NPs proved that it is magnetically soft and can
find its best applications in electronics and storage devices. Whereas the relatively

Tab. 3: The effect of substitution of generals metals (Bi, La,Co) in GdCrO3 .

Magnetic Parameters GdCrO3 Gd0.2 Bi0.8 CrO3 Gd0.2 La0.8 CrO3 Gd0.2 Co0.8 CrO3
Coercivity (Hc)/Oe 0.765 328.3 231.13 166.455
Magnetization (Ms) (emu/g) 28.014 38.06 45.012 50.21
Retentivity (Mr) (emu/g) 0.1242 8.012 8.754 10.034

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high coercivity value of the Gd0.2 Bi0.8 CrO3 NPs made it effective for permanent
magnet formation [53].
The effect of incubation time on the degradation of Congo-red shows that the
% degradation was increased up to 78.24% as we increase the incubation time
from 0 to 55 min (Figure 8). From UV-Visible spectrum, the percent degradation
was examined through the degradation of the target dye related to reduction in
the maximum absorbance of Congo-red.
While the degradation mechanism of target dye could be illustrated as when
UV-Visible fall on the surface of nanoparticles, the photocatalytic active sites will
be created [54–61] and electron jumped from valence band to conducting band

Fig. 8: Ultra-violet visible absorption spectra of Congo-red dye recorded at different time
interval.

Fig. 9: Mechanism of photocatalysis.

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 Synthesis and PCA of NPs | 13

and making positive charge hole in the valence band whereas negative charge is
in conduction band [62].
This Positive charge hole react with the absorbed H2 O molecule and produce
very reactive OH− radical whereas electron in conduction band could react with
oxygen and converted it into O2 − radical, which finally converted into hydroxyl
radical as illustrated in Figure 9. This hydroxyl radical is responsible for the
transformation of dye molecule [63]. The synthesized material could possibly be
employed for the removal of toxic pollutants from industrial effluents [64–68].

4 Conclusions
Multiferroic substances have attracted the scientists due to the thought-
provoking fundamental properties, their behavior as well as potential applica-
tions. Gd1−x Mx CrO3 (M = La, Co, Bi) NPs were successively synthesized by micro-
emulsion method using simultaneous single ion substitution philosophy. Charac-
terization of the prepared Gd1−x Mx CrO3 (M = La, Co, Bi) NPs was completed by
various techniques as SEM, XRD, VSM and dielectric measurements. Substitution
of general metals (M = Bi, La, Co) into the regular GdCrO3 crystal structure at
the place of Gd was confirmed by XRD pattern of Gd1−x Mx CrO3 (M = La, Co, Bi)
NPs. Dielectric measurements of Gd1−x Mx CrO3 (M = La, Co, Bi) NPs shows that
substitution of general metals (M = Bi, La, Co) into the regular GdCrO3 crystal
structure at the place of Gd enhanced the ferromagnetic characteristics. It was
found that photocatalyst synthesized by micro-emulsion route is highly efficient
for the degradation of Congo-red under UV-Vis light irradiation.

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