As industrialization
progresses, there is a large release of hazardous
pollutants into the environment. These pollutants, which contain nitro
compounds and organic dyes, are extremely dangerous due to their toxic
and carcinogenic nature. An efficient, environmentally benign, and
economical catalyst to degrade environmental pollutants or convert
them into useful products has been of sustained interest in recent
years. In this context, we report a simple and inexpensive combustion
fabrication of NiCrFeO
4
using different fuels such as glycine,
polyvinyl alcohol (PVA), and urea, showing tremendous catalytic and
photocatalytic functionalities. Rietveld refinement and X-ray diffraction
studies confirmed the formation of single-phase ferrites, with crystallite
sizes ranging from 3.9 to 43.31 nm. The values of optical band gap,
obtained from the diffused reflectance spectroscopy technique, lie
in the visible region range (1.50–1.60 eV), and hence, all
the synthesized ferrites can act as good photocatalysts in the presence
of visible light. All the NCF nanocatalysts were utilized for the
reduction of nitroarenes and photocatalytic degradation of various
cationic (RhB and MB) and anionic (MO) dyes and their mixture. NCFP
displayed excellent activity for the reduction and oxidation reactions
owing to its large surface area and low optical band gap. Furthermore,
the photo-oxidative degradation by NCFP was also enhanced due to its
low recombination of charge carriers as confirmed by the photoluminescence
(PL) spectroscopy. NCFP efficiently reduces nitrobenzene to aminobenzene
with 95% yield using sodium borohydride as the reducing agent in methanol
medium at RT in 10 min. The results of photocatalytic activity have
shown that the degradation efficiency of NCFP follows the order RhB
> MB > MO in their unitary solution. Furthermore, in the case
of the
mixture of dyes, NCFP showed enhanced photocatalytic degradation for
cationic dyes (RhB and MB) compared to that of anionic dye (MO). From
the performance point of view, this catalyst can be useful in industrial
application because of its high stability, greater catalytic efficiency,
and cost-effectiveness.
In the present paper, nanocrystalline samples of NiCrFeO4 were synthesized by the combustion method using different
fuels
such as glycine, urea, and poly(vinyl alcohol) and subjected to heat
treatment at different temperatures of 600, 700, 800, and 1000 °C
for 6 h. The formation of phases with highly crystalline structures
was confirmed by XRD and Rietveld refinement analysis. The optical
band gap of NiCrFeO4 ferrites lies in the visible range,
making them suitable photocatalysts. BET analysis reveals that the
surface area of the phase synthesized using PVA is much higher than
that synthesized using other fuels at each sintering temperature.
In addition, there is a significant decrease in the surface area with
sintering temperature for the catalysts prepared using the fuels PVA
and urea, while it almost remains constant in the case of glycine.
Magnetic studies demonstrate the dependence of saturation magnetization
on the nature of the fuel and on the sintering temperature; moreover,
the coercivity and squareness ratio confirm the single domain nature
of all the synthesized phases. We have also performed photocatalytic
degradation of the highly toxic Rhodamine B (RhB) dye by employing
all the prepared phases as photocatalysts using the mild oxidant H2O2. It is observed that the photocatalyst prepared
using PVA as the fuel exhibited the best photocatalytic activity at
all sintering temperatures. All the three photocatalysts prepared
using different fuels showed a decrease in the photocatalytic activity
with increasing sintering temperature. From the chemical kinetic point
of view, the degradation of RhB by all the photocatalysts was found
to follow pseudo-first-order kinetics.
The present study reports the synthesis of nanocrystalline LaFe 0.5 Cr 0.5 O 3 via a solvent-free combustion method using glycine, poly(vinyl alcohol), and urea as fuels, with superior photocatalytic activity. Rietveld refinement and powder X-ray diffraction data of nanomaterials demonstrate the existence of an orthorhombic phase that corresponds to the Pbnm space group. The crystallite size of nanoperovskite samples lies in the range of 20.9−36.4 nm. The Brunauer−Emmett−Teller (BET) surface area of the LaFe 0.5 Cr 0.5 O 3 fabricated using urea is found to be higher than that of the samples prepared using other fuels. The magnetic measurements of all samples done using a SQUID magnetometer showed a dominant antiferromagnetic character along with some weak ferromagnetic interactions. The optical band gap of all nanosamples lies in the visible range (2−2.6 eV), making them suitable photocatalysts in visible light. Their use as a photocatalyst for the degradation of the rhodamine B dye (model pollutant) is studied, and it has been observed that the catalyst fabricated using urea shows excellent degradation efficiency for rhodamine B, i.e., 99% in 60 min, with high reusability up to five runs. Additionally, the degradation of other organic dyes such as methylene blue, methyl orange, and a mixture of these dyes (rhodamine B + methylene blue + methyl orange) is also investigated with the most active photocatalyst, i.e., LFCO-U, to check its versatility.
This paper presents
the rare earth doping effect on the structural,
optical, and magnetic properties of bilayered Ruddlesden–Popper
oxides Sr
2
La
0.5
R
0.5
FeMnO
7
(R = La, Nd, Sm, Gd, Dy). Moreover, we are reporting for the first
time a new rare earth-doped bilayered perovskite oxide series for
the highly toxic methylene blue dye degradation in wastewater under
visible light. Structural analysis of the PXRD data using the Rietveld
refinements confirms the formation of the phases in tetragonal symmetry
with the
I
4/
mmm
space group. The
unit cell lattice parameters (
a
&
c
) and the cell volume (
V
) decrease monotonically
from La- to Dy-doped samples owing to the decrease in the lanthanide
ionic radii. The X-ray photoelectron spectroscopy analysis indicates
the existence of the Mn ions in the mixed valence state. The DRS study
shows that the energy band gap value decreases on moving from La to
Gd substitution; however, it further increases for the Dy-doped sample.
The magnetic measurements reveal that all the phases exhibit dominant
anti-ferromagnetic interactions with Neel temperature (
T
N
) observed at 150, 147, 138, 113, and 117 K for La-,
Nd-, Sm-, Gd-, and Dy-substituted phases, respectively. However, the
presence of an unsaturated hysteresis loop observed in the isothermal
magnetic field (
H
) vs magnetization (
M
) plot also indicates the existence of weak ferromagnetic interactions.
The investigation of the photocatalytic activity of the synthesized
samples was done by carrying out photo-oxidative degradation of methylene
blue (MB) dye pollutants. The results show that the photodegradation
enhances by doping with heavier rare earth ions with the exception
of the Dy-doped sample. The Gd-doped catalyst shows the maximum degradation
efficiency of 99.03% in 50 min under visible light irradiation. The
scavenging experiments confirmed that the
·
OH was the
main/dominant oxidizing agent involved in the degradation of the MB
dye.
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