Literature review

Titanium, particularly in the form of titanium dioxide (TiO2), has emerged as a

promising catalyst for the degradation of organic pollutants. Its unique properties,
such as high photocatalytic activity, chemical stability, and non-toxicity, make it an
attractive choice for environmental remediation applications. Nowadays, owing to the
high rate of global economic development, and rapid progress of industrialization and
urbanization, a series of environmental problems have inevitably occurred. Among
them, the water body has been severely polluted due to the industrial wastewater
discharged at will and the intervention of human activities. Numerous industries such
as pharmaceuticals, textiles, printing with dyeing, and pesticides all discharge large
amounts of wastewater into our ecosystems. Pollutants generally include organic
pollutants (dyes, pesticides, antibiotics, fertilizers, and pharmaceutical ingredients),
inorganic pollutants, and nutrients. However, organic pollutants are the leading cause
of environmental pollution because they can stay in our living environment.
Therefore, efficient purification of organic pollutants in water has attracted
continuous global attention. Among the photocatalytic materials, TiO2, ZnO, CdS,
MnO2, g−C3N4, and other semiconductor photocatalysts have been widely studied
and applied. TiO2 has been recognized as one of the idealized photocatalytic materials
due to its good oxidation performance, excellent photochemical stability, low
production cost, non-toxicity, and harmlessness. However, their further development
has lagged for a long time, mainly because of the formidable chemical synthesis of
high-quality TiO2-based photocatalyst. The significant growth in research activities
on TiO2 based heterojunction photocatalysts in recent years has been mainly attributed
to the advances in synthesis techniques and the development of new semiconductor
photocatalysts. Titanium dioxide (TiO2) and zinc oxide (ZnO) are both photocatalysts
that can degrade organic pollutants when exposed to ultraviolet light. Iron oxide
(Fe2O3) can be used in heterogeneous Fenton processes to generate hydroxyl radicals,
which can also degrade organic pollutants. Copper oxide (CuO) and manganese oxide
(MnO2) are versatile catalysts that can be used in various oxidation reactions,
including the degradation of organic pollutants. But we are going to use titanium
dioxide (TiO2) for the organic pollutant degradation(Water). Titanium dioxide as
photocatalyst has attracted the attention of scientists. According to (Wang,2022)
Titanium dioxide is widely used in the degradation of various organic pollutants in the
environment because of its advantages of low cost,non-toxicity, high efficiency and
high stability. However, the photocatalytic performance of (TiO2) is limited due to its
small visible light absorption range and high recombination rate of photogenerated
electrons and holes.
Mechanism and Efficiency
Doping modification is a technique that introduces different impurity elements into
the TiO2 lattice. It has several advantages for enhancing the photocatalytic
performance of TiO2 (Cao et al. 2021). First, it can promote the Doping modification
is a technique that introduces different impurity elements formation of the anatase
phase, which has higher activity than the rutile phase (Anitha & Khadar 2020).
Second, it can reduce the grain size and increase the specific surface area and light
absorption capacity of TiO2 (Zhang et al. 2020). Third, it can adjust the band gap
and conduction band (CB) position of TiO2, thus extending its visible light response
range and photo-generated carrier separation efficiency (Yao et al. 2023). Fourth, it
can increase the number of surface hydroxyl groups and oxygen vacancies of TiO2,
thus improving its adsorption capacity and redox ability for organic pollutants
(Ansari et al. 2016; Liu et al. 2016). The doping elements can be classified into two
types: metal elements and non-metal elements. Metal element doping can create new
energy levels within the band gap of TiO2, enabling it to absorb visible light. For
instance, TiO2 doped with metal elements, such as iron, cobalt, nickel, and copper,
can exhibit different colors and degrade organic pollutants more effectively
(Basavarajappa et al. 2020). Non-metal element doping can alter the electron affinity
and ionic radius of TiO2, affecting its charge transfer and recombination process. For
example, TiO2 doped with non-metal elements, such as nitrogen, sulfur, and carbon,
can increase the electron density of the CB and suppress the hole recombination, thus
enhancing its photocatalytic activity (Sedrati et al. 2014; Zhang et al.
2021a, 2021b, 2021c). Bagwasi et al. (2013) conducted research on the
photocatalytic degradation mechanism of 2,4-dichlorophenol (2,4-DCP) using 10%
bismuth-modified nitrogen-doped TiO2 (Bi/N-TiO2) under visible light irradiation.
The proposed degradation mechanism is illustrated in Figure 1. The research revealed
that substitutional nitrogen in the nitrogen-doped TiO2 (N-TiO2) creates a new state
just above the valence band (VB) of TiO2, resulting in a narrower band gap that
enables visible light absorption. During visible light irradiation, four possible
transition routes are proposed for the degradation of 2,4-DCP: excited electrons from
the nitrogen impurity band are transferred to the CB of TiO2 and possibly further
transferred into the CB of Bi20TiO32 particles through a heterojunction formed
between N-TiO2 and Bi20TiO32. Electrons formed from the nitrogen impurity band are
captured by oxygen molecules, leading to the generation of superoxide radicals (
). Superoxide radicals react with electrons and protons, forming hydrogen peroxide
(H2O2), and hydrogen peroxide reacts with superoxide radicals, resulting in the
formation of hydroxyl radicals (OH•), hydroxide ions (OH−), and molecular oxygen
(O2) through a series of reactions. The visible light absorption by Bi/N-TiO2 and the
effective charge carrier separation facilitated by bismuth species play a significant
role in enhancing the photocatalytic activity of Bi/N-TiO2 for the degradation of 2,4-
DCP. Bayan et al. (2020) conducted a study and found that co-doping TiO2 with zinc
and fluorine ions induces the formation of oxygen vacancies on the catalyst surface.
The presence of these vacancies enhances the generation of hydroxyl radicals (OH−)
on the nanoparticle surface, which play a crucial role in the photocatalytic process.
Additionally, zinc doping influences the formation of active species. Zinc ions (Zn 2+)
can trap electrons or holes, disrupting their stable configuration. Trapped electrons
can react with oxygen molecules to produce superoxide radicals ( ), while trapped
holes can react with hydroxyl anions to form hydroxyl radicals (OH−). In the
photocatalytic process, the model pollutant used is the organic azo-dye methylene
blue (MB). The cationic functional groups of MB molecules initially adsorb onto the
catalyst nanoparticle surface. Subsequently, the radical decomposition of MB takes
place, leading to the opening of the central aromatic ring and the formation of
intermediate degradation products. Finally, the photocatalytic decomposition
culminates in the production of inorganic molecules such as CO2, , ,
and . These reactions occur under both UV and visible light irradiation.
Figure 1
The Applications in Water Pollution
Wastewater treatment plants can remove a large majority of the pollution. However,
several trace organic compounds or refractory compounds cannot be degraded by the
conventional treatment. These pollutants mostly result from domestic and industrial
use of pharmaceutical preparations, printing and hygiene products, and pesticides. In
recent years, photocatalytic technology has broadened its application in the treatment
of organic wastewater. Under the conditions of sufficient O and light, TiO2 uses the
photogenerated electrons and holes to degrade almost all organic pollutants in water
and convert them into CO2, H2O, and other inorganic substances. (Saif et al,2022)
prepared lanthanide (Nd3+, Sm3+, Eu3+, Gd3+, Dy3+, and Er3+)-doped TiO2 using
the sol-gel method and evaluated their photocatalytic activity in the treatment of
actual sewage. In the actual sewage treatment plant application, the mineralization
efficiency of Gd3+-TiO2 and Eu3+ TiO2 on chemical oxygen demand (COD)
reached 67% and 50%, respectively, after 6 h of light. (Lima et al,2020) used
Ag/TiO2 photocatalytic material to degrade the hormones which would exist in the
sewage treatment plant. The results showed that the degradation rate of the hormone
by Ag/TiO2 reached 95% after 3.5 h. In addition to organic pollutants, photocatalytic
technology can achieve better treatment of inorganic substances in water. (Peng et
al,2019) prepared TiO2-CuO/HSC composites. Degradation rates of ammonia
nitrogen in water reached 61% and 100% when experiments were operated under
ordinary light and ultraviolet light, respectively.
Dyeing wastewater discharged from printing and dyeing factories contains a large
number of dye molecules. These dye molecules usually contain a mine groups,
aromatic rings, azo groups, etc. Therefore, the chromaticity of dye wastewater is
difficult to meet standards for discharge. Traditional biological and physical treatment
methods for removing organic pollutants, which include precipitation, adsorption,
flocculation, reverse osmosis, and ultrafiltration, are inefficient and unsuitable for
industrial applications. So, people choose photocatalytic degradation as an alternative
technology to solve the pollutants. TiO2 can not only effectively remove the color of
wastewater, but also decomposes the pollutants into small molecules such as CO2 and
H2O. (Xu et al,2023) successfully prepared Ag/TiO2 layered structure and reported
the degradation rate of the dye under the sunlight reached 99%, while the degradation
rate of pure TiO2 was 43%.(Ji et al, 2021) used C/TiO2 microsphere to degrade the
rhoda mine B. The results showed the degradation rate of rhoda mine B reached 96%
within 140 min, and the degradation rate still maintained above 80% after the material
was used for three times. (Fu et al, 2020) use graphene oxide/TiO2 (GO/TiO2)
composites to degrade the dyes and reported the degradation rate of the dyes reached
96% within 2.5 h.
Tannery wastewater is also a major problem in industrial wastewater because of
the containing of large amounts of poorly biodegradable organic chemicals. The
general biological treatment method can make the effluent reach the standard, but it
still needs multiple treatments to remove most of the COD, color and some organic
recalcitrant compounds. So, the photocatalytic treatment using TiO2 become a new
method to treat tannery wastewater. (He et al,2019) used Mn-doped TiO2 material to
degrade the tannery wastewater. The degradation rate of organic pollutants under
sunlight was nearly 90%. (Bordes et al, 2015) deposited the fine-structured
photocatalytic TiO2 coatings on austenitic stainless steel coupons by atmospheric
plasma spraying (APS) and the total organic carbon (TOC) removal reached 49%,
while the decolorization rate reached 75%. Therefore, they reported that the decreased
TOC and color removal of the resulting effluent evidenced the effectiveness of the
developed coatings for photocatalytic treatment of industrial tannery wastewater.
The large-scale use of pesticides such as herbicides and insecticides have a
significant impact on aquatic environment. The harmful effects of these compounds
are due to their toxicity and high mobility and persistence in aqueous media. In fact,
only a small part of the applied pesticides can protect agricultural products, while
most pesticides are lost to the environment through volatilization, hydrolysis,
photolysis, or degradation by microbial action. The characteristics of pesticide
wastewater lead to ineffective treatment by physical and biological methods, so
photocatalytic oxidation is used to treat this type of wastewater, for example
organophosphorus pesticides can be mineralized and decomposed by TiO2 and
converted into non-toxic CO2, H2O, and PO4−. (Abdennouri et al,2019) prepared a
nano-TiO2 supported on pillared clay and found that the material can efficiently
degrade 2,4-dichlorophenoxyacetic acid, 2,4-dichlorophenoxypropionic acid, and
other pesticides in the environment. Both of the degradation reached about 80%.
As an important component of energy, petroleum plays a decisive role in the
sustained and rapid development of the national economy. Due to river convergence
and marine accidents, a large amount of low-density and water-insoluble oil flows
into the ocean every year, causing marine oil pollution and threating to marine life.
Traditional processing is performed by mechanical methods, and biological processes
are often used as auxiliary processing steps, followed by advanced processes such as
adsorption, membrane filtration, and reverse osmosis. However, due to the presence
of high concentrations of toxic aromatic and aliphatic hydrocarbons in addition to the
presence of phenols and refractory compounds, the biological processes cannot meet
the standard of reuse. Studies have shown that TiO2 photocatalysts can float on the
water surface and are efficient in the degradation of toxic and recalcitrant pollutants.
(Shivaraju et al, 2019) prepared N-doped TiO2. They reported the degradation rate of
oil and grease and other organic pollutants in wastewater can reach about 90%.
The pollution of pharmaceuticals in industrial wastewater is serious problem.
Traditional wastewater treatment removes most of the pollutants through
sedimentation, filtration, adsorption, or biological processes, however, bio-toxic and
non-degradable organics usually remain in the water at concentrations above the ppb
discharge or reuse limit. Using TiO2 for photocatalytic reaction would be a good
method to solve this problem. (Solís-Casados et al, 2020) used Sn-doped TiO2 to treat
diclofenac, paracetamol, and ibuprofen under visible light. The results showed the
maximum removal rate of diclofenac was 25%, the maximum removal rate of
paracetamol was 25%, and the removal rate of ibuprofen was 18%. All of the three
drugs were effectively reduced. Malakootian et al. [237] used Fe3+ doped
TiO2 materials to degrade pharmaceutical wastewater and antibiotic-added synthetic
solutions. The results showed that the degradation rates of antibiotics can reach 70%
and 97%, respectively. Besides all used the TiO2 to degrade the pharmaceutical
wastewater and obtained satisfied result.