CHAPTER-2

LITERATURE
This literature gives an overview of different research studies related to the preparation and photocatalytic
activity of nanomaterials. It explains how various synthesis methods like sol-gel, hydrothermal, and
solvothermal are used. The main focus is on how these methods affect the structure and efficiency of
materials in degrading pollutants.
2.1 Solvothermal method:
The ZnO/Ag₂CO₃ Z-scheme photocatalyst exhibited excellent performance for the degradation of
tetracycline (TC) under simulated sunlight. The optimized Z/AC-4 composite achieved 97.4% TC
degradation within 60 minutes. The band gap energies were 3.09 eV (ZnO), 2.46 eV (Ag₂CO₃), and 2.88
eV (Z/AC-4), showing that Ag₂CO₃ narrowed ZnO’s band gap and enhanced visible-light absorption.
Scavenger studies indicated that hydroxyl radicals (·OH), holes (h⁺), and superoxide radicals (·O₂⁻) were
the main reactive species, with ·OH playing the dominant role. The nano-spindle-shaped morphology
facilitated efficient charge transfer and surface activity, demonstrating the composite’s potential as a stable
and reusable photocatalyst for sustainable water purification [47]. Bimetallic M/Fe–MOFs (M = Ni, Mg,
Sn) exhibited excellent photocatalytic performance for the degradation of Rhodamine B (RhB) under
visible light. Among the samples, 10% Ni/Fe-MOF achieved over 96% RhB degradation within 2 hours.
The material had a band gap of 1.88 eV, allowing efficient visible-light absorption. Metal doping enhanced
the stability, crystallinity, and photocatalytic efficiency of MIL-88B(Fe), while the resulting crystalline
structure improved charge separation and surface reactivity, highlighting its potential as an eco-friendly
photocatalyst for dye degradation [48]. The S-scheme Bi₂MoO₆/BiOBr heterostructure exhibited
outstanding photocatalytic performance for degrading Rhodamine B (RhB), Methylene Blue (MB), and
Tetracycline (TC) under visible light. The optimized Bi₂MoO₆/BiOBr-2 composite achieved 99.6% MB,
98.1% TC, and 86.3% RhB degradation within 30 minutes. With band gaps of 2.75 eV (Bi₂MoO₆) and
2.94 eV (BiOBr), the composite demonstrated strong visible-light absorption and efficient charge transfer.
Its flower-spherical morphology enhanced surface activity and adsorption, promoting synergistic
adsorption–photocatalysis. Active species studies showed that superoxide radicals (·O₂⁻) and holes (h⁺)
were key in breaking dye chromophores and mineralizing them into CO₂ and H₂O. This highlights the
potential of S-scheme heterostructures for efficient and sustainable wastewater treatment [49].

17
2.2 Green synthesis method:
Zinc oxide (ZnO) nanoparticles were synthesized through an eco-friendly bio-waste–mediated
green synthesis approach using Garcinia Cambogia and Vigna mungo extracts as natural reducing and
stabilizing agents. The obtained ZnO nanoparticles exhibited a hexagonal wurtzite structure and
demonstrated excellent photocatalytic degradation of methylene blue (MB) under both sunlight and UV
irradiation within 50–120 minutes. The band gap energies (3.34–3.37 eV) slightly decreased compared to
pure ZnO, enhancing visible-light absorption and charge carrier dynamics. Among the samples, ZnO–
Euphorbia milii achieved 98.17% degradation under sunlight, while ZnO–Justicia spicigera reached
92.7% under UV light, both outperforming pure ZnO (73–87%). The superior performance was attributed
to the phytochemical-induced defect states, enhanced surface area, and improved charge separation,
facilitating efficient generation of reactive species. These findings emphasize the potential of bio-waste–
derived ZnO nanostructures as sustainable and efficient photocatalysts for dye-contaminated wastewater
treatment [50]. Pure and copper-doped zinc oxide (Cu–ZnO) nanoparticles were synthesized using a green
synthesis method to evaluate their photocatalytic performance in degrading hazardous organic dyes. The
synthesized materials exhibited a wurtzite crystal structure and were tested for the degradation of
methylene blue (MB), indigo carmine (IC), and rhodamine B (RhB) under UV light irradiation. The band
gap energy increased slightly from 3.10 eV (pure ZnO) to 3.23 eV (Cu–ZnO) with copper incorporation.
Despite the minor bandgap increase, Cu doping enhanced photocatalytic activity by suppressing electron–
hole recombination and improving UV light absorption. Under 75 minutes of UV exposure, 3% Cu–ZnO
achieved 91.3% degradation of MB and 92.2% of IC, while 5% Cu–ZnO reached 90.1% degradation of
RhB. The improvement in photocatalytic efficiency was attributed to enhanced charge carrier dynamics
and defect-induced active sites, highlighting the potential of Cu–ZnO nanomaterials as effective and
sustainable photocatalysts for wastewater treatment applications [51].
CuO/ZnO heterojunction nanoparticles were developed to evaluate their multifunctional
photocatalytic performance for pollutant degradation. The composite, prepared using a 1:5 molar ratio of
copper acetate to zinc acetate, formed spherical nanoparticles with a hexagonal wurtzite ZnO structure
and distinct CuO phases. Under visible light irradiation, the heterojunction exhibited outstanding
photocatalytic activity, achieving 91% degradation of methyl orange (MO), 73% of phenol, and 23.9% of
NO gas, whereas pure ZnO showed only ~40% MO and ~18.8% NO degradation. The band gap slightly
decreased from 3.2 eV (ZnO) to 3.1 eV (CuO/ZnO), enabling better light absorption. The enhanced
performance was due to the formation of a p–n junction, which improved charge separation, reduced
18
electron–hole recombination, and increased reactive species generation, demonstrating the efficiency of
CuO/ZnO heterostructures for visible-light-driven environmental purification [52]. Cobalt-doped copper
oxide (Co-CuO) nanoparticles were developed to evaluate their photocatalytic performance for dye
degradation and water-splitting applications. The nanoparticles exhibited a monoclinic crystal structure
and were tested for the degradation of methylene blue (MB) under UV–Vis light irradiation for 100
minutes. The band gap energy decreased from 2.40 eV (pure CuO) to 1.70 eV (Co–CuO), enabling
enhanced visible light absorption and charge carrier separation. The Co–CuO nanoparticles achieved 88%
degradation of MB, surpassing pure CuO (75%), due to improved electron–hole dynamics and extended
light utilization. These results highlight that transition metal doping effectively tailors the optical and
catalytic properties of CuO, making it a promising material for sustainable wastewater purification and
photocatalytic energy applications [53].
2.3 Sol-gel Method:
The Sm₂CrMnO₆ double perovskite nanoparticles showed remarkable photocatalytic activity
toward the degradation of eriochrome black T (ECBT) and malachite green (MG) dyes under visible light
irradiation. The material exhibited a narrow band gap of 1.58 eV, much lower than that of Sm₂O₃ (2.64
eV), allowing for enhanced visible-light absorption and improved photocatalytic performance. It achieved
98% degradation of ECBT within 120 minutes and maintained excellent photostability and reusability,
with only an 8% decrease in efficiency after five cycles. These results demonstrate the strong potential of
Sm₂CrMnO₆ as an efficient and durable photocatalyst for visible-light-driven wastewater treatment [54].
The ZnO/Mo₂TiC₂ MXene nanohybrids exhibited excellent photocatalytic activity for the solar-driven
degradation of tetracycline (TC) and methylene blue (MB) pollutants. The incorporation of MXene
reduced the band gap from 2.97 eV (ZnO) to 2.87 eV (ZMX-5), improving light absorption and charge
transfer efficiency. Among the prepared samples, ZMX-5 (5 wt% MXene) demonstrated the best
performance, achieving 93% degradation of tetracycline within 120 minutes with a rate constant of 24.7
× 10⁻³ min⁻¹, which is about 8.5 times higher than pure ZnO. The enhanced activity is attributed to the
formation of an effective ZnO/MXene heterojunction, facilitating efficient charge separation and reactive
species generation, highlighting its promise as a highly efficient photocatalyst for solar-assisted
wastewater treatment [55]. Transition metal-doped TiO₂ photocatalysts were developed to evaluate their
visible-light-driven degradation efficiency toward methylene blue (MB) dye. Among the prepared samples
pure TiO₂, Zn (0.01)-doped TiO₂, and Cu (0.01)-doped TiO₂—the Zn-doped TiO₂ exhibited a reduced band
gap of 2.8 eV compared to 3.0 eV for pure TiO₂, enabling enhanced light absorption and improved charge
19
separation. The Zn (0.01)-doped TiO₂ achieved a remarkable 99.64% degradation of methylene blue
within 60 minutes, outperforming undoped TiO₂ (90.4%). The flake-like morphology of the catalysts
provided a higher surface area, further boosting photocatalytic activity. These findings highlight the
superior efficiency of Zn-doped TiO₂ as a promising material for visible-light-assisted dye degradation
applications [56].
Mo-doped urea-assisted TiO₂ (Mo-U-TiO₂) nanoparticles were synthesized via a urea-assisted sol–
gel method to evaluate their efficiency in degrading azo dyes—Reactive Red 120 (RR120) and Acid Black
1 (AB1) under UV-A and natural sunlight irradiation. Mo doping reduced the band gap from 3.07 eV to
3.02 eV, enhancing visible-light absorption and charge carrier separation. The 0.2 wt% Mo-U-TiO₂ sample
achieved 99% degradation of AB1 in 120 minutes under UV-A light and over 89% degradation of both
dyes under sunlight within 180 minutes. The spherical nanoparticles exhibited excellent crystallinity and
uniform morphology. The superior photocatalytic performance is attributed to bandgap narrowing and
Mo-induced charge trapping, which minimize electron–hole recombination and enhance dye degradation
efficiency [57]. Fluorine-doped bismuth oxide (Bi₂O₃₋ₓFₓ) photocatalysts were synthesized using a sol-gel
method to assess their efficiency in degrading methylene blue (MB) and methyl orange (MO) under
visible-light irradiation. Doping with fluorine slightly reduced the band gap from 2.74 eV (pure Bi₂O₃) to
2.69 eV (Bi₂O₂.₀₆F₀.₉₄), enhancing visible-light absorption and facilitating charge separation through the
formation of localized energy states that suppress electron–hole recombination. The Bi₂O₂.₀₆F₀.₉₄ sample
achieved 52.5% MB and 63.4% MO degradation within 120 minutes, significantly outperforming pure
Bi₂O₃. The enhanced activity is attributed to F-induced oxygen vacancies, which improve light harvesting
and catalytic reactivity. The materials also maintained structural stability, confirming their durability
during photocatalytic operation [58].
2.4 Co-precipitation method:
The ZnO–TiO₂ nanocomposite demonstrated high photocatalytic efficiency for Reactive Orange
16 (RO-16) dye degradation, achieving 95.68% removal within 120 minutes under UV light. The
composite exhibited a reduced band gap of 2.94 eV compared to pure ZnO (3.12 eV) and TiO₂ (3.20 eV),
enhancing UV absorption and promoting the generation of reactive radicals for dye degradation. Its
hexagonal crystal structure and nearly spherical morphology provided a larger surface area, facilitating
efficient adsorption–photocatalysis synergy. These properties highlight the potential of ZnO–TiO₂
nanocomposites as effective photocatalysts for textile dye removal in wastewater treatment [59]. The Ce-
doped NiO nanoparticles showed remarkable photocatalytic activity toward methylene blue (MB)
20
degradation under visible light irradiation, achieving 92% degradation within 120 minutes, compared to
65% for pure NiO. The reduced band gap (~2.6 eV) enhanced visible-light absorption and charge
separation, while Ce incorporation effectively minimized electron–hole recombination and improved
charge mobility. The nanoparticles exhibited a stable body-centered tetragonal structure, further
supporting their efficiency. Overall, Ce doping significantly enhanced the photocatalytic performance and
stability of NiO, making it a promising material for visible-light-driven dye degradation [60].
2.5 Chemical precipitation method:
The iron-doped nickel oxide (Fe–NiO) nanoparticles exhibited significantly enhanced
photocatalytic efficiency for eosin yellow dye degradation under UV light irradiation, with 4% Fe–NiO
showing nearly 30% higher degradation efficiency than undoped NiO. The improvement was due to Fe
incorporation, which modified the electronic structure of NiO, promoting better charge carrier separation,
enhanced light absorption, and reduced electron–hole recombination. These effects facilitated efficient
generation of reactive oxygen species responsible for dye breakdown. The findings highlight the potential
of Fe–NiO nanoparticles as stable and efficient photocatalysts for wastewater purification and
environmental remediation [61]. The metal-doped TiO₂ photocatalysts (Ni-, Zn-, and Co-doped) exhibited
improved light absorption and photocatalytic efficiency compared to pure TiO₂ (3.2 eV band gap). Ni-
doped TiO₂ showed the best performance, achieving 95% degradation of methylene blue (MB) and 90%
degradation of neutral red (NR) within 100 minutes under UV irradiation, outperforming undoped TiO₂
(86% and 76%). The enhanced activity was attributed to band gap reduction, efficient charge separation,
and extended light utilization, demonstrating the potential of metal-doped TiO₂ nanomaterials for effective
wastewater treatment and dye degradation [62].
2.6 Wet impregnation method:
The Bi-doped TiO₂ photocatalyst exhibited a slightly reduced band gap of 3.20 eV compared to
pure TiO₂ (3.23 eV), enabling better light absorption and charge separation. It achieved 80% degradation
of methylene blue (MB) within 2 hours under UV light, outperforming pure TiO₂ (66%) and other doped
variants (43–59%). The enhanced photocatalytic activity was attributed to synergistic effects of bismuth
incorporation, which improved charge transfer efficiency and reduced recombination losses. These
findings highlight the effectiveness of Bi-doped TiO₂ nanomaterials for efficient dye degradation and
wastewater purification applications [63].

21
2.7 SILAR method:
The BiOBr/TiO₂ nanotube composite exhibited a band gap of 2.7–2.8 eV, enabling efficient
visible-light absorption and enhanced charge separation. It achieved approximately 85% degradation of
Rhodamine B (RhB) within 150 minutes under visible light irradiation, while pure TiO₂ nanotubes
degraded less than 20% under similar conditions. The superior photocatalytic activity was attributed to
the synergistic interaction between BiOBr and TiO₂, which promoted effective charge transfer and
suppressed electron–hole recombination. This demonstrates the strong potential of BiOBr/TiO₂ nanotube
arrays for sustainable and efficient wastewater treatment applications [64].
2.8 Biocompatible method:
Copper sulfide (CuS) nanoparticles exhibited a band gap of 4.16 eV and a porous, layered
morphology that promoted efficient light absorption and reactive species generation. The optimized CuS
sample (Cu:S = 1:7) achieved 89.49% degradation of Congo Red dye within 60 minutes under UV–visible
light irradiation, with the dye decomposing into intermediates and ultimately mineralizing into CO₂ and
H₂O. The nanoparticles showed a hexagonal CuS phase, demonstrating excellent photocatalytic activity
and highlighting their potential for rapid and sustainable wastewater treatment applications [65].
2.9 Supercritical antisolvent (SAS):
The Fe-doped ZnO nanoparticles exhibited a reduced band gap of 2.83 eV compared to pure ZnO
(3.22 eV), enhancing their responsiveness to visible light. While undoped ZnO achieved complete dye
degradation under UV light within 30 minutes but only 30% efficiency under visible light, the 0.75 mol%
Fe-doped ZnO sample attained 52% degradation and 36% mineralization under visible light within 180
minutes. The nanoparticles possessed a wurtzite hexagonal crystalline structure, indicating that Fe doping
effectively improves visible-light-driven photocatalytic activity, making these materials promising for the
degradation of azo dyes in wastewater treatment. [66].
2.10 Z-type hetrojunction method:
The ZnO/Diosgenin@Chitosan (ZnO/Dio@CS) Z-type heterojunction nanocomposite exhibited
excellent photocatalytic performance for Brilliant Green (BG) and Indigo Carmine (IC) degradation under
UV light. The composite achieved 88.04% IC and 86.08% BG degradation within 60 minutes, surpassing
pure ZnO. Its reduced band gap of 2.9 eV enhanced light absorption and charge separation, while the Z-
type heterojunction structure and spherical/hexagonal morphology facilitated efficient reactive species
generation. The nanocomposite also showed strong antibacterial activity against both Gram-positive and

22
Gram-negative bacteria, demonstrating its potential for multifunctional environmental remediation
applications [67].
2.11 Hydrothermal method:
The hydrothermal method is a synthesis technique used to grow crystals or nanoparticles in a
sealed vessel under high temperature and pressure conditions. It involves dissolving materials in water (or
another solvent) and heating the solution above its boiling point, allowing chemical reactions and crystal
formation to occur. This method enables the production of high-purity, uniform, and well-crystallized
materials, often at lower temperatures than traditional solid-state methods. It is widely used for preparing
metal oxides, ceramics, and nanostructured photocatalysts.
A BiFe₂O₄ heterostructure was synthesized to evaluate its photocatalytic efficiency in degrading
methyl orange (MO). The catalyst achieved 85.79% degradation of a 10 mg/L MO solution within 40
minutes under sunlight irradiation. The band gap energy ranged between 2.2-2.8 eV, enabling efficient
visible-light absorption. The nanoparticle exhibited a flower-like morphology that enhanced surface
activity, demonstrating the potential of nanoparticle based photocatalysts for environmentally sustainable
water purification systems [5]. Bi₂O₃ and Bi₂WO₆ nanoparticles demonstrated strong photocatalytic
activity for degrading 5-fluorouracil (5-FU) under solar-LED light. Total photodegradation was achieved
in 100 minutes with Bi₂O₃-3C-n, 240 minutes with Bi₂WO₆-3C-n, and 420 minutes with WO₃-3C-a. The
band gap ranged from 2.7 to 2.9 eV, allowing efficient light absorption. Their worm-like morphology
increased surface activity and provided many active sites, showing good potential for wastewater
treatment and removal of resistant organic pollutants [6].
Mn-doped Bi₂S₃ nanoflowers were synthesized to evaluate their photocatalytic efficiency for
degrading Rhodamine B under visible light. The 3% Mn-doped sample achieved nearly 97% degradation
within 60 minutes. The band gap decreased from 1.56 eV to 1.50 eV, enhancing light absorption. Mn
doping promoted efficient charge separation and reduced carrier recombination, while the nanoflower
morphology provided more active sites and facilitated faster electron transfer. These features make Mn-
doped Bi₂S₃ a promising photocatalyst for visible-light-driven pollutant degradation [14]. Ag₂O/α-Bi₂O₃
heterostructure nanocomposites exhibited excellent photocatalytic performance for the degradation of
methyl red dye under natural sunlight. The composite achieved a degradation efficiency of 93.22% within
40 minutes, significantly higher than that of the individual components. The band gaps of Ag₂O, α-Bi₂O₃,
and the composite were 1.62 eV, 2.34 eV, and 2.10 eV, respectively. Enhanced charge separation, oxygen
vacancy formation, and synergistic coupling between the components contributed to improved
23
photocatalytic activity. The rod-like morphology increased light absorption and provided a larger reactive
surface area [16]. The Ag-decorated Bi₂WO₆ composite exhibited enhanced photocatalytic performance
for the degradation of Rhodamine B (RhB) under visible light. The band gap slightly decreased from 2.7
eV (pure Bi₂WO₆) to ~2.6 eV due to the surface plasmon resonance (SPR) of Ag nanoparticles, improving
visible-light absorption. The 5 wt% Ag/Bi₂WO₆ composite achieved ~95% RhB degradation within 60
minutes, compared to 55–60% for pure Bi₂WO₆. Ag nanoparticles acted as electron traps, reducing
electron–hole recombination and enhancing photocatalytic efficiency. The material possessed a body-
centered tetragonal structure, contributing to its superior light-harvesting and photocatalytic
performance[33].
ZnS nanoparticles exhibited strong photocatalytic activity for the degradation of methylene blue and
alizarin red dyes under UV irradiation. The material achieved degradation efficiencies of 82.11% for
methylene blue and 85.51% for alizarin red within 180 minutes. The optical band gap of 3.6 eV enabled
ultraviolet light absorption and efficient generation of electron–hole pairs. The cubic zinc blende structure
provided high crystallinity and stability, enhancing overall performance. These ZnS nanoparticles show
significant potential for ultraviolet-light-driven removal of organic pollutants [2]. Zr-modified ZnO
nanoparticles demonstrated enhanced photocatalytic efficiency for the degradation of Reactive Red 120
dye under both UV-A and natural sunlight. The Zr-ZnO composite achieved nearly 100% degradation
within 120 minutes, compared to 70.7% for pure ZnO. The band gap decreased slightly from 3.11 eV to
3.05 eV, improving light absorption and charge separation. The hexagonal prism-like morphology
increased surface area and active site availability [4]. Nanocomposites gCN/ZnO, showed good
photocatalytic activity for degrading Rhodamine B dye under sunlight. The composite achieved 78%
degradation in 120 minutes, higher than pristine gCN. The band gap was reduced to 2.5 eV, improving
visible-light absorption and charge separation. Spherical ZnO on flake-like gCN increased surface area
and light capture. The strong interaction between gCN and ZnO enhanced photocatalytic efficiency,
making it promising for wastewater treatment [10].
Phosphorus doped g-C₃N₄/ZnIn₂S₄ (PCN/ZIS) showed strong photocatalytic activity for removing
antibiotics like tetracycline under visible light. The 10% PCN/ZIS degraded much more dye than pure
ZnIn₂S₄ or PCN. The band gap was reduced to 2.41 eV, improving light absorption. Phosphorus doping
and the heterojunction helped separate charges and reduce recombination. The layered structure increased
surface area and active sites, making the process fast and efficient for wastewater treatment [12]. ZnO
nanoparticles showed excellent photocatalytic activity for degrading Rhodamine B dye under UV light.
24
They achieved 95% degradation in 70 minutes. The band gap ranged from 3.26 to 3.23 eV, improving
light absorption and electron excitation. The hexagonal wurtzite structure with high crystallinity enhanced
performance, while larger particle size slightly reduced surface area at higher temperatures [17]. rGO-
ZnO and rGO-Nb₂O₅ nanocomposites showed enhanced photocatalytic activity for degrading methylene
blue under UV light. The 1% rGO-ZnO achieved 97% degradation in 90 minutes, while 1% rGO-Nb₂O₅
reached 75% in 300 minutes. The band gap of ZnO increased slightly from 3.18 eV to 3.21-3.26 eV, and
Nb₂O₅ from 2.94 eV to 3.01-3.03 eV due to rGO incorporation. rGO also increased surface active sites
and light utilization. These nanocomposites demonstrated strong potential for efficient photocatalysis[18].
Neodymium-doped ZnO (Nd-ZnO) nanoparticles exhibited high efficiency in photocatalytic
degradation of Congo Red dye under both UV and solar light. The band gap decreased from 3.26 eV (pure
ZnO) to 3.19 eV after Nd doping, enhancing light absorption and charge excitation. Under UV light, Nd-
ZnO achieved 98.5% degradation in 120 minutes, and under solar light, 91% in 240 minutes, higher than
undoped ZnO. The hexagonal rod-like morphology increased surface area, making it as highly efficient
photocatalyst [19]. Aluminium doped ZnO (Al:ZnO) nanoparticles and ZnO/Fe₃O₄/Al (MAZ)
nanocomposites showed good photocatalytic activity for degrading malathion under sunlight. Al:ZnO
(1%) degraded 80% of the dye, while MAZ reached 82% in 180 minutes. The band gap decreased to 2.91
eV (Al:ZnO) and 2.76 eV (MAZ), improving light absorption. The structures provided more surface area,
making MAZ an efficient and easily recoverable photocatalyst [23]. Copper-doped ZnO (Cu–ZnO)
nanoparticles and thin films showed better light absorption and photosensitivity. The band gap decreased
from 3.37 eV (pure ZnO) to 3.12 eV, helping them absorb more visible light. Adding Cu created defects
in the structure, which improved charge movement. The photosensitivity increased from 0.36% to 0.89%
under UV-Visible light. These Cu–ZnO films could be useful for simple optoelectronic and photoactive
applications [25]. ZnO/rGO/Au nanocomposites showed very good photocatalytic activity for degrading
methylene blue under sunlight. The band gap decreased from 3.56 eV (ZnO) to 3.37 eV (ZnO/rGO) and
3.17 eV (ZnO/rGO/Au), which helped absorb more light. The degradation efficiency improved from 87%
(ZnO) to 92% (ZnO/rGO) and 96% (ZnO/rGO/Au) in 135 minutes. The flower like structure with ZnO
rods on rGO sheets and Au nanoparticles gave more surface area for reactions [28].
ZnO nanoparticles on eucalyptus bark biochar (ZnO@EB) worked really well for cleaning real
textile wastewater. The band gap went down from 3.18 eV (ZnO) to 1.72 eV (30% ZnO@EB), which
helped it absorb more visible light. Under a 350 W lamp, it removed about 95% of blue dye in around 102
minutes after a 30-minute pre-adsorption step. The porous biochar gave more surface area, spread the ZnO
25
evenly, and exposed more active sites. Good charge separation between ZnO and biochar made the
photocatalyst very effective, and its stable structure makes it suitable for eco-friendly wastewater
treatment [30]. Copper sulphide (CuS) nanoparticles were prepared using a green method with rice starch
as a natural reducing agent. The nanoparticles had a hexagonal structure with a band gap of 4.16 eV. The
sample with Cu:S = 1:7 showed a porous, layered structure, increasing surface area and charge transfer.
Under visible light, it degraded 89.5% of Congo Red dye in 60 minutes, breaking it down into CO₂ and
H₂O. This shows that biocompatible CuS nanoparticles can be an effective and eco-friendly photocatalyst
for wastewater treatment [3]. The TiO₂ nanotubes/MoS₂ (TiO₂ NTs/MoS₂) composite exhibited remarkable
photocatalytic performance for the degradation of Rhodamine B (RhB) and Methylene Blue (MB) dyes
under visible light. The band gap decreased from 3.2 eV (pure TiO₂ NTs) to 2.1 eV (TiO₂ NTs/MoS₂),
enhancing visible light absorption and charge transfer efficiency. The catalyst achieved 76.33%
degradation of RhB in 180 minutes and complete removal of MB within 120 minutes, along with a
hydrogen evolution rate of 900.9 μmol. Its flower-like structure provided abundant active sites and
facilitated efficient light utilization, making it highly effective for environmental remediation and
photocatalytic hydrogen generation [13].
The cobalt sulfur Co-doped TiO₂ nanoparticles exhibited excellent photocatalytic performance for
the degradation of methylene blue (MB) under visible light irradiation. The doping process reduced the
band gap from 3.16 eV (pure TiO₂) to 2.65 eV, enhancing visible light absorption. The optimally doped
TiO₂ achieved ~93% degradation of MB within 120 minutes, compared to only ~10.5% for pure TiO₂. The
mixed anatase–rutile phase with a tetragonal crystal structure promoted efficient charge separation, while
Co²⁺/Co³⁺ ions created oxygen vacancies and S⁶⁺ ions stabilized Ti³⁺, further improving photocatalytic
efficiency. The synergistic effect of Co and S doping, along with the smaller crystallite size and larger
surface area, resulted in enhanced light utilization and reduced electron–hole recombination, making the
material highly effective for visible-light-driven photocatalysis [22].
The Mn-doped TiO₂ nanoparticles (MnTiO₂-NPs) demonstrated enhanced photocatalytic performance for
the degradation of methylene blue (MB) under UV light. The band gap decreased from 2.70 eV (pure
TiO₂) to 2.61 eV, improving visible light absorption and charge separation. The MnTiO₂-NPs achieved
78% MB degradation within 100 minutes, compared to 51% for pure TiO₂, due to defect sites, increased
surface area, and enhanced reactive oxygen species (ROS) generation. The nanoparticles also exhibited
superior antibacterial activity with zones of inhibition up to 21 mm. The material had an anatase crystalline
phase and nearly spherical morphology, contributing to its high photocatalytic and antibacterial
26
efficiency[29]. The La-doped TiO₂ nanocomposite showed excellent photocatalytic performance for the
removal of ammoniacal nitrogen (NH₃-N) and COD from water under visible light. The band gap
decreased from 2.98 eV (pure TiO₂) to 2.48 eV, enhancing light absorption, charge separation, and surface
reactivity. The nanocomposite achieved 70.08% NH₃-N removal and 55.11% COD removal within 120
minutes. Its spherical morphology and anatase TiO₂ phase contributed to superior photocatalytic
efficiency, stability, and reusability, making it highly effective for oil field water treatment [30].
The TiO₂–rGO nanocomposite demonstrated enhanced photocatalytic performance for the removal
of carbamazepine (CBZ) under UV and visible light. The band gap decreased from 3.40 eV (pure TiO₂)
to 2.75 eV due to rGO, which improved electronic conjugation, charge separation, and light absorption.
The composite achieved 95.32% degradation under UV light and 70.11% under visible light within 60
minutes of photocatalytic exposure. Its body-centered tetragonal structure and synergistic interaction with
rGO reduced electron–hole recombination, significantly boosting photocatalytic efficiency for
pharmaceutical contaminant removal [34]. The BaTiO₃ (BTO) nanoparticles demonstrated high
piezocatalytic efficiency for the reduction of hexavalent chromium (Cr(VI)) under mechanical energy.
Optimized BTO achieved ~94.76% Cr(VI) reduction within 1 hour of mechanical shaking at 350 rpm.
The tetragonal phase and high crystallinity enhanced piezoelectric polarization, generating more reactive
species for efficient reduction. Temperature control and precursor optimization preserved tetragonality,
maximizing performance. The nanoparticles exhibited a body-centered tetragonal structure, making them
highly effective for mechanically driven water treatment applications [35].
Copper-doped α-MnO₂ nanoparticles showed very good photocatalytic activity for degrading
methylene blue under sunlight. The 6% Cu-doped sample achieved 100% degradation in 120 minutes. The
band gap decreased from 1.58 eV (pure MnO₂) to 1.23 eV, which improved light absorption. Cu doping
helped separate charges and reduced electron hole recombination. The body-centered tetragonal structure
provided more active surface area and stability [29]. The NiFe₂O₄/CeO₂ composite demonstrated enhanced
photocatalytic performance for the degradation of methylene blue (MB) under visible light irradiation.
The band gap of the composite (~2.0–2.4 eV) was lower than that of pure NiFe₂O₄ (1.9–2.2 eV) and CeO₂
(2.9–3.2 eV), enabling improved visible light absorption. While NiFe₂O₄ alone achieved 68% degradation,
the NiFe₂O₄/CeO₂ composite (O-NFCO-10) reached 82% degradation. The type-II heterojunction at the
NiFe₂O₄/CeO₂ interface facilitated directional charge transfer, reducing electron–hole recombination.
Additionally, CeO₂ introduced oxygen vacancies that acted as reactive sites, enhancing radical generation

27
and accelerating the breakdown of MB. The composite’s spherical nanoparticle morphology further
supported efficient light absorption and photocatalytic activity [23].
The Fe₃O₄–GO, Fe₃O₄–C₃N₄, and Fe₃O₄–GO–C₃N₄ heterojunctions exhibited excellent adsorption
and photocatalytic performance for removing organic contaminants such as methylene blue (MB), methyl
orange (MO), and ketoprofen. The incorporation of GO and g-C₃N₄ increased the band gap compared to
pure Fe₃O₄ (2.07 eV) but enhanced surface area and active sites, improving adsorption and photocatalytic
efficiency. The Fe₃O₄–C₃N₄/GO–C₃N₄ composites achieved 100% MB adsorption within 1 minute, while
MO was efficiently degraded due to the synergistic effect of CN and Fe₃O₄ under light. The materials
featured sheet-like GO structures and uniformly dispersed nanoparticles, facilitating effective contaminant
removal. Overall, these heterojunctions combined adsorption and photocatalysis, making them highly
effective for rapid and efficient wastewater treatment [24]. The CdS/Ag nanocomposite exhibited
enhanced photocatalytic performance for the degradation of azo dyes such as Reactive Red 120, Direct
Blue 15, and Acid Black 1 under UV and solar light. The band gap slightly increased from 2.30 eV (CdS)
to 2.41 eV (CdS/Ag), while the Ag loading improved charge separation and reduced electron–hole
recombination, enhancing light absorption and reactive species generation. The composite achieved 93%
degradation of RR 120, 94% of DB 15, and 95% of AB 1, outperforming pure CdS (70–73% degradation).
The catalyst consisted of spherical CdS nanoparticles with hexagonal close-packed structure and Ag
nanoparticles with face-centered cubic structure, contributing to efficient photocatalytic activity and
improved dye removal under both UV and solar irradiation [26].
Cerium-substituted lanthanum ferrite nanoparticles investigated for their photocatalytic
degradation of tetracycline under visible light irradiation. The Ce-substituted samples exhibited
significantly enhanced photocatalytic activity, achieving up to 91% degradation within 120 minutes
compared to 56% for the undoped LaFeO₃. The band gap energy decreased from 2.24 eV to 1.88 eV with
increasing Ce concentration, leading to improved visible light absorption and efficient charge carrier
separation. The nanoparticles displayed an orthorhombic crystal structure. Overall, Ce-substituted LaFeO₃
demonstrated excellent potential for the removal of antibiotic pollutants from wastewater under visible
light [1]. The ZrO₂-decorated CoFe-LDH/porous MgO composite exhibited excellent photocatalytic
performance for the degradation of Indigo Carmine (IC) under UV–visible light. The band gap values
decreased from 4.03 eV to 3.14 eV with increasing ZrO₂ content, enhancing visible light absorption and
charge transfer. Among the samples, A4 showed the highest degradation efficiency of 99.8% within 12
minutes, followed by A3 (78.26%) and A2 (67.87%), while A1 showed the lowest activity (60.34%). The
28
composite also maintained over 90% efficiency even after five consecutive cycles, indicating excellent
reusability. Its flake-like structure contributed to the improved surface area and superior photocatalytic
activity [7].
The silver–nickel oxide-modified zinc oxide (Ag–NiO/ZnO) nanocomposite showed remarkable
photocatalytic efficiency for the degradation of eosin yellow (EY) dye under visible light. The band gap
was reduced from 3.16 eV (ZnO) to 2.93 eV (NiO/ZnO) and further to 2.77 eV (Ag–NiO/ZnO), enabling
better visible light absorption and enhanced charge separation. The Ag–NiO/ZnO photocatalyst achieved
about 95% degradation of EY within 60 minutes, demonstrating excellent performance. Its rod-like
structure contributed to improved light harvesting and surface reactivity. Overall, these results suggest
that Ag–NiO/ZnO is a cost-effective and scalable photocatalyst for visible-light-assisted wastewater
treatment [8]. The PW₁₂NH₄/CdS Z-type heterojunction composite demonstrated outstanding
photocatalytic performance for the degradation of tetracycline (TC) under visible light. The individual
band gaps of CdS (1.17 eV) and PW₁₂NH₄ (3.36 eV) enabled efficient charge separation and extended
light absorption. Among the tested ratios, the PW₁₂NH₄:CdS = 1:2 composite showed the best
performance, achieving ~99.7% degradation of tetracycline within 60 minutes. The catalyst’s
spherical/rod-like structure facilitated better light utilization and active site exposure, making it highly
effective for visible-light-driven photocatalytic applications [9].
The Ca-doped β-In₂S₃ photocatalyst exhibited excellent efficiency for the degradation of methyl
orange (MO) dye under visible light. The band gap decreased from 2.26 eV (pure β-In₂S₃) to 2.19 eV after
Ca doping, enhancing visible light absorption and charge separation. The doped catalyst achieved 94.97%
degradation of MO within 20 minutes, demonstrating superior photocatalytic performance. Its full-grown
flaky structure provided a larger surface area and facilitated efficient charge transfer, contributing to its
enhanced photocatalytic activity [11].
Rhodamine B dye was effectively degraded under visible light using TiO₂/graphene
nanocomposites. The material exhibited a single-phase anatase structure with a band gap of around 2.1
eV, enabling strong visible-light absorption. With 21.5% TiO₂ loading, the composite achieved a
degradation rate of 0.19 h⁻¹, showing 6–10 times higher activity than pure TiO₂. Enhanced performance
was attributed to efficient charge transfer between TiO₂ and graphene, which reduced electron–hole
recombination. Overall, the nanocomposite demonstrated excellent potential for eco-friendly dye removal
under visible-light irradiation [34]. Methylene blue (MB) dye was effectively degraded under visible light
using a g-C₃N₄/CuS composite. The material exhibited a graphitic layered structure with a band gap of
29
3.35 eV, allowing strong visible-light absorption. The composite achieved 93% degradation in 90 minutes,
with enhanced performance attributed to efficient charge separation and generation of active holes (h⁺)
and superoxide radicals (O₂⁻). Overall, the composite demonstrated excellent photocatalytic efficiency
and eco-friendly potential for dye removal [40]. Hydroxychloroquine (HCQ) was efficiently degraded
under sunlight using a TiO₂/β-Bi₂O₃ nanocomposite. The material combined TiO₂ (band gap 3.2 eV) and
β-Bi₂O₃ (band gap 2.46 eV) in a crystalline structure, enabling extended light absorption. Photocatalytic
experiments over 120 minutes showed excellent degradation efficiency, with enhanced performance
attributed to effective charge separation and the broadened absorption range. Overall, the nanocomposite
demonstrated strong potential for removing organic contaminants from water[41].
Acid Orange 7 (AO7) dye was effectively degraded using Ni-doped ZnO nanoparticles under
sunlight and UV light. The material exhibited band gap energies of 2.4 eV and 3.1 eV, which were
optimized by Ni doping to enhance light absorption. Photocatalytic tests showed 77% degradation under
sunlight and 93% under UV irradiation within 90 minutes. Improved performance was attributed to
narrowed band gap, better light absorption, and optimal catalyst dosage, while excessive doping or high
dosage reduced efficiency. The hexagonal crystal structure further supported strong photocatalytic activity
for dye removal [37]. Crystal Violet dye was efficiently degraded under visible light using MnO₂-based
nanofibrous meshes. The material exhibited band gap energies of 2.98 eV and 3.2 eV, enabling effective
light absorption. Photocatalytic experiments achieved 97% dye removal within 90 minutes, with enhanced
performance attributed to the nanofibrous crystalline structure that improved active sites and light
interaction. Overall, the MnO₂ nanofibers demonstrated strong potential for efficient dye removal and
environmental water purification [38]. Crystal Violet (CV) dye was efficiently degraded using ZnO–
Graphene Oxide (ZnO–GO) nanocomposites under UV and solar light. The material exhibited band gap
energies of 3.22–3.3 eV, allowing effective light absorption. Photocatalytic tests achieved ~95% dye
removal within 80 minutes, with enhanced performance attributed to the synergistic effect of ZnO and
graphene that improved charge separation. The wurtzite hexagonal crystal structure further supported
strong photocatalytic activity for water decontamination [39].
Ketoprofen was effectively degraded under UVA light using Co-doped ZnO and TiO₂. The Co-
doped ZnO exhibited a band gap of 3.3 eV, with 0.5% Co-ZnO achieving nearly 100% phenol degradation
in under 45 minutes and ~80% TOC removal within 1 hour, outperforming bare ZnO (~60%). Enhanced
performance was due to cobalt doping, which improved light absorption and charge separation. The
hexagonal crystal structure further supported strong photocatalytic activity for water purification
30
applications[40]. Methylene Blue (MB) and Rhodamine B (RdB) dyes were effectively degraded using
SnO nanoparticles synthesized with varying surfactant ratios. The S3 sample (1:1 Sn²⁺:TX-100) showed
the highest photocatalytic efficiency, achieving 100% MB and 91% RdB removal, with a band gap of 2.72
eV enabling strong light absorption. Complete degradation occurred in 60–90 minutes under UV light and
150 minutes under visible light. Enhanced performance was attributed to optimized morphology and band
gap tuning, which improved charge separation and photocatalytic activity[41]. Pb²⁺, Co²⁺, Cd²⁺, and Zn²⁺
ions were effectively removed from water using zeolite A (m-LTA) and zeolite Y (m-FAU) membranes on
clay supports. The m-LTA membrane achieved up to 98.96% Pb²⁺ and 92.68% Zn²⁺ removal, while m-
FAU reached 99.30% Pb²⁺ and 94.08% Zn²⁺. Enhanced performance of m-FAU was attributed to its higher
surface area (558.8 m²/g) and narrower pore channels, which improved ion rejection via size exclusion
and electrostatic interactions. Overall, both membranes demonstrated strong potential for efficient heavy
metal removal from polluted water [42].
Industrial pollutants from the leather industry were effectively degraded under visible light using
BiVO₄ nanoparticles. The material exhibited a monoclinic scheelite structure with nano-sphere and nano-
cubic morphologies and band gap energies of 2.47–2.50 eV, enabling efficient light absorption.
Photocatalytic tests showed the highest degradation efficiency of 82% at pH 08, with improved
performance attributed to enhanced crystallinity, larger surface area, reduced charge recombination, and
increased radical generation. Overall, BiVO₄ nanoparticles demonstrated strong potential for visible-light-
driven wastewater treatment [43]. Rhodamine 6G dye was effectively degraded under solar light using
CuO-based nanomaterials. Pure CuO (band gap 2.12 eV) achieved 73.51% degradation in 60 minutes,
while Ac/Ag@CuO (band gap 1.89 eV) reached 95.67% efficiency. Enhanced performance was attributed
to Ag and activated carbon co-doping, which reduced the band gap, improved visible-light absorption,
enhanced charge separation, and suppressed electron–hole recombination. Overall, the nanomaterials
demonstrated strong photocatalytic activity and potential for dye removal under solar irradiation [44].

31
2.12 Objectives of the Work
The main objective of this project is to synthesize and evaluate the photocatalytic properties of Cu-doped
SnFe₂O₄ nanocomposites prepared via the hydrothermal method. The specific objectives are as follows:
Synthesis and Characterization:
To synthesize pure and Cu-doped SnFe₂O₄ nanocomposites using the hydrothermal method and
characterize their structural, morphological, and elemental properties through XRD, SEM, and EDS
analyses.
Photocatalytic Evaluation:
To evaluate the photocatalytic degradation efficiency of Cu-doped SnFe₂O₄ nanocomposites using
Rhodamine B (RHB) dye under visible light irradiation and study the effect of Cu doping concentration
on photocatalytic activity.
Kinetic and Optimization Study:
To analyze the reaction kinetics and identify the optimal Cu doping level that achieves maximum
photocatalytic performance for potential environmental remediation applications.

32