Journal of Environmental Management 270 (2020) 110906

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Journal of Environmental Management

journal homepage: http://www.elsevier.com/locate/jenvman

Review

Present applications of titanium dioxide for the photocatalytic removal of

pollutants from water: A review
Kannappan Panchamoorthy Gopinath a, *, Nagarajan Vikas Madhav a, Abhishek Krishnan a,
Rajagopal Malolan a, Goutham Rangarajan b
a
Department of Chemical Engineering, SSN College of Engineering, Kalavakkam, Chennai, 603110, Tamil Nadu, India
b
Department of Chemical Engineering & Applied Chemistry, University of Toronto, 200 College Street, Ontario, M5S 3E5, Canada

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

Keywords: The evolution of modern technology and industrial processes has been accompanied by an increase in the uti­
Photocatalysis lization of chemicals to derive new products. Water bodies are frequently contaminated by the presence of
Immobilization conventional pollutants such as dyes and heavy metals, as well as microorganisms that are responsible for various
Nanostructures
diseases. A sharp rise has also been observed in the presence of new compounds heretofore excluded from the
Emerging pollutants
Organic pollutants
design and evaluation of wastewater treatment processes, categorized as “emerging pollutants”. While some are
TiO2 harmless, certain emerging pollutants possess the ability to cause debilitating effects on a wide spectrum of living
organisms. Photocatalytic degradation has emerged as an increasingly popular solution to the problem of water
pollution due to its effectiveness and versatility. The primary objective of this study is to thoroughly scrutinize
recent applications of titanium dioxide and its modified forms as photocatalytic materials in the removal and
control of several classes of water pollutants as reported in literature. Different structural modifications are used
to enhance the performance of the photocatalyst such as doping and formation of composites. The principles of
these modifications have been scrutinized and evaluated in this review in order to present their advantages and
drawbacks. The mechanisms involved in the removal of different pollutants through photocatalysis performed by
TiO2 have been highlighted. The factors affecting the mechanism of photocatalysis and those affecting the
performance of different TiO2-based photocatalysts have also been thoroughly discussed, thereby presenting a
comprehensive view of all aspects involved in the application of TiO2 to remediate and control water pollution.

1. Introduction
Water resources are some of the most valuable and crucial natural
resources on Earth, while simultaneously facing the greatest demand.
This has led to the scarcity of clean and safe water fit for consumption
due to so much of it being utilized elsewhere (Mekonnen and Hoekstra,
2016). The primary agents that cause water pollution have traditionally
been contaminants found in industrial effluents, such as dyes from the
textile and cosmetic industries, as well as heavy metal ions, found in
wastewater from paint industries, automobile manufacturing and elec­
trical industries.
Dyes are substances that are used to impart colours to other sub­
stances that lack those specific colours, usually for design purposes or to
improve the attractiveness of the product. The primary negative impact
of dyes on wastewater is the presence of colour. Heavy metals are metals
that have a density greater than 5 g/cm3, such as cadmium (Cd), lead
(Pb), chromium (Cr), zinc (Zn) and mercury (Hg). Industries in which
electroplating and surface treatment are conducted generate large
quantities of heavy metal-containing wastewater.
Extensive investigations and studies on the major causes of water
pollution have led to the designation of certain contaminants as
“emerging pollutants” (EPs), the monitoring of which has only become
possible due to recent advancements in detection technologies and
standards (Gasperi et al., 2014). The emerging pollutants have been
segregated into various classes depending on the purpose they serve and
their origin, in order to streamline the analysis of their presence and
methods of their removal. They are categorized as follows:
(i) Persistent organic pollutants (POPs)
(ii) Pharmaceuticals and personal care products (PPCPs)
(iii) Endocrine disrupting chemicals (EDCs)
(iv) Agricultural chemicals (pesticides, herbicides)

* Corresponding author. Associate Professor Department of Chemical Engineering SSN College of Engineering, Kalavakkam Chennai, 603110, India.
E-mail address: gopinathkp@ssn.edu.in (K.P. Gopinath).

https://doi.org/10.1016/j.jenvman.2020.110906
Received 22 March 2020; Received in revised form 26 April 2020; Accepted 1 June 2020
Available online 10 June 2020
0301-4797/© 2020 Elsevier Ltd. All rights reserved.
K.P. Gopinath et al.
Organic pollutants in wastewater largely consist of organic com­
pounds such as polychlorinated benzenes and hexachlorobenzene that
are used in power transformers and the paint industry are classified as
persistent organic pollutants, meaning that they are difficult to degrade
and remove (Bao et al., 2012). Ingestion by aquatic organisms like fish
and by animals on land leads to large scale biomagnification since they
do not degrade. It is apparent that their presence in water leads to an
extremely negative impact on health of both humans and animals.
Exposure to a synergistic mixture of pharmaceuticals may also lead
to overdoses and endocrine disruption (Jones et al., 2004). Endocrine
disrupting chemicals are a class of emerging water pollutants that
interfere with the human body’s endocrine system, a framework of
glands functioning as a set of feedback loops, through which important
hormones are circulated throughout the body for the purposes of regu­
lation of various organs. EDCs interfere with the endocrine system
through a variety of mechanisms. Some of these mechanisms are the
demonstrable abilities of some chemicals to mimic the molecules of
hormones in the receptor areas of the human body, leading to them
being perceived as hormones by the human body (Ribeiro et al., 2017).
This is applicable to receptors of estrogen, androgen and aryl hydro­
carbons. They are also capable of interacting with binding proteins and
can alter hormone metabolism (Yang et al., 2006).
Wastewater released by pharmaceutical industries is also a possible
health risk if contamination of drinking water occurs, since pharma­
ceutical compounds are highly soluble in water (Kümmerer, 2008). Due
to unobserved and the lack of regulation, PPCPs have become near
ubiquitous in aquatic environments (Bu et al., 2013). Prolonged con­
sumption of antibiotic components may lead to the unintentional
development of immunity to their effects (Webb et al., 2003) due to
intake being greater than the accepted daily intake (ADI) (Malchi et al.,
2015).
Microorganisms such as bacteria and viruses that are found in un­
treated household sewage water that contains fecal matter and other
biodegradable molecules are able to thrive in the water due to the
availability of food and a medium for growth. This leads to both the
causation and spread of a variety of diseases. The most common bacteria
found in water is Escherichia coli, which is transferred to water from the
excreta of farm animals and humans. It is responsible for diarrhea and
renal failure, with some of its strains also linked to colitis and homolytic
ureic syndrome (Chart, 2000). Salmonella causes diseases like typhoid
fever and salmonellosis (Fowler and Gala �n, 2018). Vibrio cholera is the
pathogen that causes cholera by the production of the cholera toxin
(Rivera-Ch� avez and Mekalanos, 2019). Some bacterial pathogens also
have the ability to grow in water, such as Pseudomonas aeruginosa, which
results in diarrhea and Shanghai fever (Chuang et al., 2014) and
Legionella, which is the primary agent in the transmission of Legion­
naire’s disease (Rajasurya and Surani, 2019).
Titanium dioxide (TiO2) is documented to be an important photo­
catalyst, since it has been seen as active under the ultra violet spectrum.
For a material to be considered as a useful and efficient photocatalyst, it
should be able to undergo a change in its oxidation state without also
undergoing decomposition. It is inexpensive compared to other mate­
rials used for water treatment, and can be created easily in a laboratory
as well (Gaya and Abdullah, 2008; Han et al., 2009; Hu et al., 2010).
TiO2 undergoes a change in its oxidation state without also undergoing
decomposition, an important characteristic of a good photo catalyst
(Kavita Kabra et al., 2004; Meng et al., 2010). It has high efficiency of
degradation even in the presence of weak light, and displays fast re­
sponses (Malato et al., 2002). This means that it serves as an efficient
alternative to chemical oxidation for complete mineralisation, which
consumes energy and involves the formation of a large number of un­
desirable intermediates (Oller et al., 2011). The highly specific surface
area means that the rate of photocatalysis is relatively unaffected by the
occupation of some of those sites by other molecules like those of water
(Z. Q. Wang et al., 2017).
The utilization of titanium dioxide in the form of nanostructures is an
2
Journal of Environmental Management 270 (2020) 110906
increasingly popular option in the field of photocatalysis due to the
significantly increased surface area, faster rates, non-toxic nature,
biocompatibility and ease of preparation (Guan et al., 2016). Further­
more, they possess dramatically different properties in comparison to
the macro-scale material, particularly in the optical, magnetic and
electrical aspects, with further room for modification by varying the
method and conditions of synthesis. Besides possessing exceptional
catalytic characteristics, TiO2 nanoparticles are effective when used as
antimicrobial agents against strains such as E. Coli, showing the capacity
to kill bacterial cells in the presence of light without harming parent
tissues, making their potential application in the field of medicine
possible (Tsuang et al., 2008).
A major advantage of TiO2 that makes it highly preferable for usage
in treatment of water over other semiconductors like CdS and ZnO is that
it does not produce toxic products upon decomposition like the others do
(Malato et al., 2009). It is also superior to chlorination in the same re­
gard. The easily modifiable nature of the TiO2 surface is also a major
benefit, and its morphology can be changed to include nanotubes (Zhang
et al., 2006), which have greater mass transfer rates and adsorption of
non-biodegradable organic compounds, and mesoporous surfaces (Liu
et al., 2009; Seo and Park, 2009), which can facilitate ion transfer within
particles. When used as a sphere with almost no dimensionality, the rate
of photocatalytic degradation of organic components is very high (Liu
et al., 2011). These have high surface area, increased mass transfer rates
(Liu et al., 2010), a highly crystalline structure (Hexing Hexing Li et al.,
2007) and a large number of active sites (Zheng et al., 2010). Degussa
P25, which consists of 25% rutile and 75% anatase, is the most widely
used form of TiO2, due to the inhibition of electron-hole recombination
(García-Lo �pez et al., 2019). Other common forms of TiO2 used include
nanotubes which have intricate pathways allowing for the transfer of
radiation and enhanced ionic diffusion (Bauer et al., 2011) and nano­
sheets, which have powerful adhesive features (Yang et al., 2008). The
rate of the light-induced reaction occurring on the surface is also
affected by the acid-base equilibrium in the system, since TiO2 is
amphoteric in nature (Prihod’ko and Soboleva, 2013).
Its adsorption capacity can be improved by increasing the accessi­
bility of active sites on its surface, as well as defects in the bulk (Wen
et al., 2015), along with the usage of co-catalytic systems (Tu et al.,
2013; Yu et al., 2014). TiO2 forms junctions when combined with carbon
nanotubes (De Angelis et al., 2014; Hamadanian et al., 2014), graphitic
carbon (Wang et al., 2010) and carbon black (Cong et al., 2011). The
uptake of radiation from the incident light can also be improved by
reducing the extent of absorption of the radiation by other components
in the system (Prihod’ko and Soboleva, 2013).
TiO2 also has several restrictions when used as a photocatalytic
method of water treatment. It absorbs less than 5% of the actual visible
and ultraviolet radiation falling on its surface (Yin et al., 2003). Its
adsorption capabilities, particularly when dealing with organic pollut­
ants, are fairly limited (Dong et al., 2015a). When used in the form of
nanoparticles, they tend to agglomerate and become larger particles,
causing a reduction in the surface area and active sites, and also exhibit
very high scattering, both of which contribute to a reduction in the ef­
ficiency (Gao et al., 2011; Mallakpour and Nikkhoo, 2014). Recovery of
the residues of treatment and particles of TiO2 when used in the form of
a slurry is also extremely difficult.
A major challenge posed by the use of TiO2 lies in its band gap. In
order to overcome the problem of the band gap of TiO2, it is not un­
common to use TiO2 nanostructures doped with other substances in
order to improve the catalytic ability. This occurs primarily due to in­
crease in adsorption and decrease in charge carrier recombination (Xu
et al., 2002). The application of doped TiO2 catalysts has been studied in
detail in the past, having been shown to be a cost-effective means of the
removal of contaminants from wastewater (Khairy and Zakaria, 2014).
Furthermore, the incorporation of dopants such as platinum (Zhou et al.,
2018) has enabled the use of TiO2 even under visible light conditions
due to generation of new energy levels and an improved and stable
K.P. Gopinath et al. Journal of Environmental Management 270 (2020) 110906

nanocrystalline structure, leading to the use of TiO2 in everyday appli­
cations. Other materials typically used as dopants include both metals
and non-metals such as iron, copper carbon, nitrogen, platinum and
sulphur among others. The functioning of doped TiO2 nanoparticles can
be attributed to the generation of hydroxyl radicals (OH�), which
contribute significantly to the degradation of molecules (Cavalcante
et al., 2016). The various modifications with which it has been used are
discussed in Table 1.
This review aims to present an objective and comprehensive sum­
mary of the recent advancements in the application of TiO2 in water
remediation. Reviews have been conducted in recent literature
exploring the viability of TiO2 in the removal of personal care products
(Awfa et al., 2018) and microbes (Uyguner Demirel et al., 2018). Re­
views have also placed special emphasis on doped photocatalysts
(Bhanvase et al., 2017) and on the mechanism of the reaction involved
(Dong et al., 2018; Kusiak-Nejman and Morawski, 2019). However, to
the best knowledge of the authors, there has been no review in recent
literature that has covered the breadth of topics as carried out in this
review. The remediation of more than five different pollutant classes
using TiO2 has been explored while the mechanism involved in each
case has also been highlighted. Structural modifications have been also
been thoroughly evaluated for their advantages and negatives.
2. Literature review
The purpose of this review is to perform an assessment of the various
applications of titanium dioxide and its photocatalytic properties for
water treatment. The different types of pollutants that can be reme­
diated by the usage of TiO2, their negative effects on the health of
humans and animals, the mechanisms by which TiO2 is capable of per­
forming photodegradation on the various pollutants, the favourable
properties that it possesses, its limitations, and the several modifications
and improvements made to it in order to improve its efficiency and
performance have been analyzed and evaluated. Scientific journals and
books pertaining to the fields of water treatment, photocatalysis and
titanium dioxide and its properties and modifications were thoroughly
evaluated in order to select findings relevant to the content of this re­
view. To do the same, Google Scholar, Elsevier and Springer Link were
utilized. Search terms included but were not limited to “Conventional
methods of wastewater treatment”, “Titanium dioxide properties”,
“Advanced oxidation processes”, “Titanium dioxide nanoparticles and
nanocomposites”, “Photocatalysis”, “Titanium dioxide immobilization”
and “Titanium dioxide-based composites”. The abstracts and contents of
various scientific findings received scrutiny for the purposes of the se­
lection of data important to this review.
3. Mechanism of action of TiO2
Since TiO2 is a semiconductor, the energy band gap between the
valence band and the conduction band is quite small. When light in the
visible or the ultraviolet region of the spectrum (typically UV-A, which
has a wavelength range of 315–400 nm (Xin et al., 2004)) falls on the
semiconductor surface, electrons in the valence band gain energy and
become excited, and thus move to the conduction band. Electrons may
flow to or from the adsorbate, allowing for the formation of both posi­
tively and negatively charged species on the surface (Martinez and
Hammer, 2011), with the actual photonic efficiency observed to be very
low for photocatalysis (less than 1%) (Mendive et al., 2011). For TiO2,
the band gap has a range of 3–3.2 eV, while the wavelength of maximum
absorption (λmax) is around 400 nm. The excitation of electrons in the
valence band of TiO2 and their subsequent transfer to the conduction
band has been illustrated in Fig. 1. When irradiated with light of this
wavelength, the surface of TiO2 gets heated up and may reach temper­
atures as high as 30,000 � C. The reaction that occurs is typically an

Table 1
Methods of modification of TiO2 in order to rectify various shortcomings.
Modification performed Examples of materials used for Reasons for modification Description and remarks References
construction

Doping Graphite, graphene oxide, Band gap between valence and
semiconducting metal oxides conduction band is difficult to
(ZnO), metals (Cu, Zr) overcome by UV and visible light
Composites Carbon nanotubes. metallic Combination of favourable properties
oxides, graphene oxides for photocatalysis of all constituents
Complexes Porphyirin-TiO2 Absorption of ultraviolet and visible
light
Immobilization Glass beads and spheres Immobilization instead of suspension
means that recovery of TiO2 particles
after degradation is unnecessary
Photosensitization Dyes, titanium complexes Improving photocatalytic efficiency by
increasing the rate
Nanoporosity TiO2 Improvement of photocatalytic activity
and adsorption
Nanomaterials TiO2 Minimizes dimensionality and
quantum effect
Nanorods Anatase/rutile/titanate rods Increases specific area and
mesoporosity
Photoelectrocatalysis TiO2 as nanorods or nanowires Allows for light usage, oxidation and
charge separation to be utilized
simultaneously
Nanosheets TiO2, graphene High specific surface area, large
number of active sites/facets
Nanotube arrays TiO2 Capable of incorporation of CO2 into
hydrocarbons; significant degradation
of dyes
Photocatalytic photonic TiO2 Visible light absorption and high
crystals performance UV are possible
Micro and nano spheres TiO2 Zero dimensionality; high surface area;
exhibits high degradation of organics
and dyes
Addition of dopant causes formation of an Zaleska, (2008)
energy band in between the two, leading
to reduction in the band gap
─ Woan et al., (2009)
─ Chang et al., (2009)
TiO2 particles are fixed onto supports (Cunha et al., 2018;
instead of being suspended. Disinfection Daneshvar et al., 2005a,
rates are slightly lower 2005b)
Improves generation of electrons and (Gołąbiewska et al., 2018;
holes Macyk et al., 2010)
Highly ordered, high purity Zhang et al., (2007)
High surface-to-volume ratio, specific (Bavykin et al., 2006;
surface area, increased delocalization of Evtushenko et al., 2011;
opposite charges Grabowska et al., 2018)
Greater BET surface area, dye adsorption (Hafez, 2009; J. Li et al.,
is stronger 2007)
Fast recombination is prevented and (Garcia-Segura and Brillas,
oxidation is done directly by the holes 2017; Yang et al., 2013)
Increased separation and delayed (Guo et al., 2012; Sun et al.,
recombination of holes 2016)
Absorption spectrum of nanotube arrays Zhou et al., (2015)
is extremely wide
Slow photon energy region overlaps with (Athanasekou et al., 2018;
spectral region; reflection losses are Curti et al., 2015)
minimal
Prepared using titanium (Liu et al., 2011; Nakata and
tetraisopropoxide or titanium Fujishima, 2012)
tetrabutoxide in the presence of a polymer

3
K.P. Gopinath et al.
oxidation reaction that results in the decomposition of the pollutant, by
making use of the dissolved oxygen present in water.
TiO2 þ hυðEnergy ​ from ​ the ​ lightÞ→e ðelectronÞ þ hþ ðholeÞ (1)
e─ þ O2 (dissolved oxygen) → O2�─ (superoxide radical) (2)
þ
h þ H2O → H þ OH þ �
(3)
The hydroxyl radical formed from this reaction is responsible for the
decomposition of contaminants in water, which it achieves by acting as
an oxidizing agent. Extra steps must be taken in order to preserve the
electro-neutrality of the particles, by making sure that the reduction of
oxygen and the oxidation of the pollutants occur simultaneously to
prevent suppression of the recombination process by oxygen (Boroski
et al., 2009).
Recent studies have revealed that the superoxide radicals are capable
of sometimes superseding the hydroxyl radicals for favourability in the
mechanism for a reaction involving photocatalytic degradation (Yao
et al., 2017). They may undergo protonation to form the hydroxyperoxyl
radical, which has the ability to scavenge unwanted radical products,
thereby delaying the recombination of the holes and electrons (Chong
et al., 2010).
O2�─ þ HO� → HO2� (4)
The overall pathway by which heterogeneous photocatalysis in the
presence of TiO2 is performed consists of five steps:
(i) Mass transfer of the molecules that later undergo degradation to
the surface of the photocatalyst (Chong et al., 2010)
(ii) Adsorption of the molecules onto the active sites of TiO2, and
photo-excitation of the electrons in the valence band (Wang et al.,
2015)
(iii) Photocatalytic degradation of the adsorbed molecules
(iv) Desorption of the products of degradation
(v) Mass transfer of these products away from the surface of TiO2
Fig. 1. Comparison of the energy levels and band gaps in pure TiO2 and doped TiO2.
4
Journal of Environmental Management 270 (2020) 110906
The mechanism described is wholly compliant and representative of
that followed by advanced oxidation processes (AOPs), one of the many
classes of water treatment techniques developed as a replacement for
conventional wastewater treatment techniques, such as chemical pre­
cipitation and biological treatment (Andreozzi et al., 1999). AOPs
consist of the degradation and decomposition of the pollutants by the
utilization of hydroxyl radicals (�OH) and other reactive oxygen species
(Prasse et al., 2015), which are produced in situ. They are capable of
degrading molecules that are immune to attack by traditional treatment
methods (Prieto-Rodríguez et al., 2013). The general lack of specificity
of the radicals produced generally leads to the occurrence of scavenging,
a process by which undesirable molecules are removed by a free radical
(Keen et al., 2014). From analysis of the corresponding values of the
Gibb’s free energies for the above mechanism, the overall process is
found to be thermodynamically favourable and spontaneous (Kudo and
Miseki, 2009).
There are 5 major types of products obtained after photocatalytic
degradation, and the method of photocatalysis should be chosen such
that an optimal method that takes into account environmental effects
and ease of recovery can be designed (Malato et al., 2013).
(i) Products of dehalogenation (known to be a slow process) (Pri­
hod’ko and Soboleva, 2013) and hydroxylation
(ii) Products of oxidation of the alkali chain
(iii) Products of isomerization and cyclation (where the atoms
themselves are preserved)
(iv) Products from the opening of an aromatic ring
(v) Decarboxylation products
The rate of photocatalysis, while ideally expected to follow a first
order rate expression, exhibits a deviation from it due to it involving
absorption and occurring on a solid surface. One of the possible rate
expressions is given by the Langmuir-Hinshelwood mechanism:
K.P. Gopinath et al.
dC ksKC
RateðrÞ ¼ ¼ (5)
dt KC þ 1
where k is the rate constant, s is the limiting amount for adsorption on
the surface, K is the adsorption equilibrium constant and C is the con­
centration of the substrate in the bulk at equilibrium (Ohtani, 2008). The
various factors affecting the photocatalytic activity of TiO2 have been
discussed in Table 2.
4. Removal of heavy metals
Metal ions present in water can be reduced to their ground state by
the electrons produced through photo-excitation of TiO2, provided that
the reduction potentials are favourable.
Mnþ þ ne →M (6)
Reductive removal of metallic ions can also be enhanced by an in­
direct method, which involves the addition of electron donors that can
be sacrificed, such as methanol or formaldehyde.
R─CH2OH þ �OH → R─CH�─OH þ H2O (7)
M nþ
þ R─CH ─OH → M
� (n 1)þ
þ R─CHO (8)
It is also possible for metallic ions to be oxidized even further to
higher oxidation states by the presence of hydroxyl radicals or holes, if
the oxidation state that they are currently occupying is not the highest
possible one (Litter, 2015).
Mnþ Hydroxyl ​ radical=holes Mnþ1 (9)
������������!
Heavy metals can be widely described as those with high atomic
weight and density much higher than that of water. They have found
widespread use in various industries due to their comparatively lower
reactivities and strength (Tchounwou et al., 2013). However, toxic
heavy metals such as lead accumulate rapidly in environmental struc­
tures and in crops and can often cannot be degraded by biological means
(Zhang et al., 2011). Heavy metals have been reported extensively to be
highly toxic to various organs in the human body, with the consequences
as severe as mutations and cancer (Shaheen et al., 2016). It is important
to understand that heavy metals are, in fact, crucial to the functioning of
human bodies when present in the right components. Heavy metals have
also been shown to affect plants in a severe manner, with studies
reporting a lack of nutrient uptake and poor productivity when grown
on soil containing heavy metals (Khan et al., 2015). TiO2 has been re­
ported as a time and cost efficient means of removing heavy metals, with
initial studies suggesting the reduction of heavy metals to lower oxida­
tive states followed by their deposition on the catalyst (Kyung et al.,
Table 2
Factors affecting the mechanism of photocatalysis by TiO2.
Name of the factor Description of the effect
pH Acidity or basicity of the medium affects the photo-induced reaction
occurring on the surface of TiO2
TiOH þ Hþ ⇔ TiOHþ 2 (acidic)
TiOH þ OH─ ⇔ TiO─ þ H2O (basic)
Initial concentration Degradation rate increases with increase in concentration; very high
of pollutant concentration will cause reduction in rate due to absorption by dye
molecules and saturates TiO2 surface
TiO2 loading Reaction rate initially increases with increase in loading, then
decreases; Optimum loading and availability of active sites must be
maintained; Depends on reactor dimensions
Light intensity Rate increases linearly at low intensities (Rate of decolourization is
enhanced); proportional to square root of intensity at moderate values
(half order); Zero order at high intensities, recombination competes
with separation
Size and structure Number of photons striking TiO2 increases with the increase in
available surface area; Degussa P25 is highly effective
5
Journal of Environmental Management 270 (2020) 110906
2005).
TiO2 has been successfully utilized for the photocatalytic reduction
of Ni2þ, Cd2þ, Pb2þ and Cu2þ in a reaction that followed first order
kinetics. Heavy metal removal improved with reducing pH, implying an
ability to function in acidic conditions. Studies have also shown that
adsorption was the mechanism involved in the removal of heavy metals,
aided by the large surface area generated by the nanoparticles (Mahdavi
et al., 2013). The TiO2 nanoparticles also exhibited potential for reuse
and a capacity to work at room temperature conditions, with the
adsorption capacity fitting existing isotherms such as the Langmuir
isotherm, making nano-TiO2 an encouraging option for the removal of
heavy metal ions from wastewater (Poursani et al., 2016). TiO2 has also
proven to be efficient in the removal of arsenic from industrial waste­
water working as a photocatalytic adsorbent. TiO2 showed the ability to
be used in successive cycles and the ability to retain its functionality
after regeneration. In the process, other heavy metals ions present in the
industrial wastewater sample such as Cu2þ, Cd2þ and Pb2þ also
exhibited decrease in concentrations, proving that simultaneous
removal of several heavy metal ions was possible with no sludge gen­
eration, making the process well-equipped in the economic, technical
and environmental aspects (Luo et al., 2010). Titanium nanotubes ar­
rays, modified with coupling agent KH-570, have proven to be highly
effective in the degradation of heavy metal ions such as Pb2þ, Cu2þ and
Cr6þ present in water. The arrangement of the array led to increased
surface area and photocatalytic efficiency while the addition of the
coupling agent improved the interaction between titania and the ions.
However, the modified catalyst required UV for efficient functioning
and it was reported that the performance was a direct function of the
turbidity of the waste water (Yan et al., 2017). Despite the drawbacks,
this catalyst requires further evaluation due to its benefits.
TiO2 has a long and extensive track record in the removal of mer­
cury, Hg2þ to Hg0, from wastewater, both as a photocatalyst (Skubal
and Meshkov, 2002) and as an auxiliary factor (Zhang et al., 2004). The
photocatalytic process has been found by studies to be optimal in a pH
range of 3–7, with sol-gel method proving highly effective in synthe­
sizing particles with appreciable surface area. The catalyst showed
increasing efficiency when the pH was increased in the range and
showed appreciable kinetics (Dou and Chen, 2011). TiO2 nanotubes
were discovered to be extremely effective in the removal of Cu2þ ions
from water, accompanied by hydrogen production. Nanotubes possess
significantly higher surface area than conventional nanoparticles owing
to their shape and structure, a fact that makes possible high catalytic
activity. The amount of hydrogen produced was found to be a function of
the amount of Cu2þ present in water, with an initial amount of 10 mol%
of Cu2þ in TiO2 found to be the most optimal (Xu et al., 2011). Removal
of chromium Cr6þ ions to Cr3þ has been shown to be possible through
Optimum condition References
Positively charged in acidic media; holes (Fatehizadeh et al., 2014; Poulios and
dominant; pH < 6.8 (preferable for Tsachpinis, 1999)
heavy metals)
Negatively charged in basic media;
hydroxyl radicals dominant (pH > 6.8)
─ (Chong et al., 2009; Sakthivel et al.,
2003)
400–500 mg/L for azo dyes; de- (Dolat et al., 2015; Gonçalves et al.,
excitation observed at high 1999; So et al., 2002; Umar and
concentrations of 2000 mg/L Abdul Aziz, 2013)
─ (Herrmann, 1999; Reutergådh and
Iangphasuk, 1997; Sauer et al., 2002)
─ (Gao and Liu, 2005; Muneer et al.,
2005)
K.P. Gopinath et al.
the use of doped TiO2 catalysts. Over 99% removal efficiency was ob­
tained when doped with iron and exposed to visible light. There is su­
perior electron transfer between the doped TiO2 and the heavy metal ion
in comparison to pristine TiO2, another factor contributing towards the
enhanced performance (Xu et al., 2014). The removal of Cr3þ ions was
implemented by doping TiO2 grown on graphene oxide with manga­
nese. The reaction is initiated with the movement of electrons from Cr6þ
to the catalyst to yield Cr3þ, followed by further electron movement to
yield Cr0 atoms (Chen et al., 2016). Co-doping of TiO2 with silver and
manganese has yielded excellent results in the removal of Cr6þ and
Cu3þ ions from water through a thermodynamically spontaneous
adsorption mechanism. The co-doped catalyst showed the capacity to
reduce even trace amounts of the heavy metal ions, thereby presenting
itself as a highly promising option for practical applications (Gullipilli
and Rupakula, 2018). Doping with gadolinium has also returned good
results in the removal of Cr6þ ions but the results were not as promising
as those obtained from iron and silver/manganese doped TiO2 catalysts
(Eddy et al., 2018). Removal of Cr6þ from wastewater was also ach­
ieved through the creation of a composite of TiO2 with EDTA on a
carbon sheet-basis which displayed excellent photoreduction capabil­
ities. The complex possesses high coordination, with the carbon sheet
serving as a support in which the TiO2 nanoparticles and the EDTA
molecules are dispersed (Luo et al., 2018).
The removal of Pb (II) ions by TiO2 was found to improve signifi­
cantly on the addition of MnO2, despite a decrease in the surface area.
Attractive interactions were observed between the ions and dopant,
resulting in greater amounts of the ion getting adsorbed by the catalyst
(Kobayashi et al., 2017). Removal of heavy metals found in nuclear
wastes such as cesium (Csþ) and strontium (Sr2þ) has also been carried
out by doping TiO2 nanotubes with chromium ions. The charge
imparted to the nanotubes greatly improves the removal ability, along
with the enhanced surface area (Youkui Zhang et al., (2017a, 2017b)).
Arsenic, a common groundwater contaminant, has been found by
studies to be effectively reduced by TiO2 doped with iron. The intro­
duction of iron ions made possible the adsorption and catalytic activity
using visible light by reducing the band gap. 1 wt% of iron was found to
produce optimal results at a pH of 7, indicating its viability as a pro­
spective arsenic removing agent (Garza-Ar� evalo et al., 2016).
Nanocomposites have also found applications in the removal of
heavy metals from water. One method suggested to remove lead from
wastewater is by using (CD-PCL-TiO2) bio-nano-composites made by
two step process of sol gel synthesis of the TiO2 particles and polymer
solution blending. This method has a considerable advantage as it does
not introduce any type of secondary pollutant into the treated water
(Seema et al., 2018).
Polythiophenes are polymerized thiophenes that are sulphur het­
erocyclics. When coupled with to make a composite, they show high
selectively towards heavy metal ions. This is caused by the fabrication of
a self-doped TiO2 (O ) on PThþ occurs in PTh/TiO2 composite. How­
ever the doping is unstable in non -acidic solutions. Heavy metal ions
like zinc, copper and lead have been absorbed in varying quantities,
based on the amount of nano-catalyst present, due to the synergetic
effect between PTh and TiO2. An impressive selective adsorption prop­
erty of the composite was recorded, where by Zn2þ> Pb2þ≫ Cu2þ was
absorbed in ascending order, by which the absorption of copper could be
suppressed (Chen et al., 2018). This can hence be used in a multistage
process in the future, where by zinc and lead are removed by this
composite and copper by another specialized composite, there-by
reducing the load.
The photoelectrocatalytic removal of Cr6þ was reported to be nearly
three times quicker than conventional photocatalysis by TiO2. The uti­
lization of nano-spherical structures further increased the area of reac­
tion and resulted in further enhancement (Zhao et al., 2017). Cr6þ was
also removed by the incorporation of Ag3PO4 in TiO2 nanotube arrays
and the setup was found to be equally effective in the removal of organic
dyes (Q. Z. Wang et al., 2017).
6
Journal of Environmental Management 270 (2020) 110906
Mesoporous hollow titaniananospheres were combined with 3-ami­
nopropyl triethoxysilane, and the resulting composite displayed photo­
catalytic degradation efficiencies of Cu2þ, Cd2þ and Pb2þ that are 12.7,
17.5 and 1.8 times respectively of those displayed by naked hollow
titania nanospheres (Hang et al., 2017). Reduced graphene oxide (rGO)
and TiO2 nanospheres were integrated and used to remove Agþ ions
from water, with the rGO causing enhanced charge carrier recombina­
tion. The maximum adsorption capacity was 34.8 mg/g (Abbas and
Al-Ghaban, 2019). Graphene-like TiO2@C composite is also used to
remove Pb2þ from water, with an adsorption capacity of 331.7 mg/g
(Gan et al., 2019). Some other specific applications of TiO2 in the
removal of heavy metals have been mentioned in Table 3.
5. Removal of dyes
When dyes present in water undergo photocatalytic degradation,
there are two possible mechanisms by which their photodegradation can
be explained. The first is the indirect mechanism, wherein the dye un­
dergoes excitation due to the energy provided to it by the visible light,
which leads to it entering its triplet excited state, and it is then further
converted into a semi-oxidized radical through the injection of electrons
into the conduction band of titanium dioxide (Ajmal et al., 2014).
Dye þ hυ→Dye � ðintermediateÞ (10)
Dye� þTiO2 →Dyeþ þTiO2 (11)
The second pathway by which dyes undergo photodegradation is the
direct mechanism, in which the dye molecules interact with the hy­
droxyl radicals produced, as well as with the electrons and holes formed
due to excitation in the conduction band, which lead to reduction and
oxidation of the dyes respectively (Konstantinou and Albanis, 2004).
The indirect mechanism is found to predominate over the direct
mechanism, and the extent of degradation is also discovered to be more
pronounced and much faster (Zhang et al., 1998).
The release of coloured and toxic dyestuffs by industries into water
bodies has witnessed a gradually increasing trend in the recent past,
with adverse effects being felt not only by aquatic organisms but also by
humans in an indirect manner. These dyes are often not bio-degradable
and accumulate in the bodies of organisms (Sakthivel et al., 2003). The
removal of dyes from water can be considered as an extension of
removal of heavy metals from water, due to their combined presence in
the effluents of many industries (Chen et al., 2002). Due to the
impracticality of removing only one of them at a time, it becomes
necessary to use the right catalysts that can bring about their removal
simultaneously in a manner as effective and inexpensive as possible
(Gola et al., 2018). Azo dyes have been shown to be carcinogenic in
nature and complicated to degrade (Chung, 2016). The accumulation of
dyestuffs in natural resources such as soil and water, leading to dramatic
changes in their characteristics, poses another critical challenge, with
studies showing dyes to be directly responsible for the killing of nutri­
tional microbes and in the degradation of water bodies (Savin and
Butnaru, 2008).
Typically, methods such as flocculation, adsorption filtration and
dialysis have been utilized to remove dyes from water. However, these
methods have often failed to display consistency and reliability, with
any structural degradation and removal of colour proving to be
incomplete. The release of incompletely-degraded wastewater into other
resources leads to further pollution of groundwater and the water table
(Raman and Kanmani, 2016). One suggested solution has been the
application of TiO2 nanostructures owing to its well-known positives
such as excellent catalytic ability and high surface area.
Titanium dioxide has been reported to be a highly effective
degrading agent when used on an immobilized support, with the catalyst
showing efficient removal characteristics of three azo dyes: C.I Acid
Orange 10, 12 and 8, denoted by AO10, AO12 and AO8. Total removal of
colour was noted, with AO10 exhibiting the most favourable reaction
K.P. Gopinath et al. Journal of Environmental Management 270 (2020) 110906

Table 3 Table 3 (continued )

Applications of TiO2 in the removal of heavy metals. Dopant Heavy metal Remarks References
Dopant Heavy metal Remarks References targeted
targeted
found to be appreciable,
– Chromium The nanocrystals Chen et al., the catalyst also showed
(Cr6þ) exhibited superior (2017) the ability to be reused
bonding characteristics consistently, especially
due to the presence of in equimolar
polyethylene glycol concentrations of TiO2
during the synthesis. The and graphene oxide.
kinetics was found to be β-cyclodextrin Copper The addition of Triki et al.,
highly favourable for (Cu2þ) β-cyclodextrin slowed (2017)
photocatalysis. down the precipitation of
– Chromium The reaction was Islam et al., the complex Cu(NH4)2þ,
(Cr6þ) significantly quickened (2019) leading to more efficient
by the addition of formic removal of the heavy
acid. This can be metal from water.
attributed to its function – Cobalt The adsorption ability Sharaf El-Deen
as a hole scavenger. (Co2þ) was found to be vastly et al., (2016)
Ytterbium Chromium Besides displaying Zhang et al., Nickel superior to conventional
(Cr6þ) tremendous removal (2016) (Ni2þ) catalysts due to the
characteristics with increased surface area of
respect to Cr6þ, the the nanotubes. A catalyst
doped catalyst also loading of 0.1 g was
showed efficient removal found to produce the best
of the dye methyl orange results, with pH 5 being
due to the synergic reported to produce the
interactions of electron – best results. Greater
hole pairs in the affinity for cobalt than
structure. nickel was observed.
Zero valentiron Arsenic Catalytic activity was L�
opez-Mu~ noz
(ZVI) (As3þ and superior when low pH et al., (2017)
As5þ) conditions were kinetics and energy requirements. There was nearly a 95% removal of
implemented alongside total organic content in the dyes over 6 h, further highlighting the
the incorporation of ZVI.
effectiveness of TiO2 in removing the three industrial dyes. The func­
– Arsenic The presence of Fausey et al.,
(As3þ) graphene oxide (2019) tioning of the catalyst can be attributed to the conversion of the double
promoted the bond between two nitrogen atoms in an azo group to an NHþ 4 ion
development of hydroxyl (Khataee et al., 2009). TiO2 hosted by a framework shell comprising of
radicals, leading to the the zeolite ZIF-8 has been reported to exhibit appreciable photocatalytic
oxidation of As3þ to the
removable As5þ form.
activity for the dye rhodamine blue. Besides the superior efficiency of
Poly(acrylic acid- Lead (Pb2þ) The nanoparticles Sanchez-Sala TiO2 nanoparticles supported by a zeolite framework in comparison to
co-maleic acid) showed high adsorption et al., (2018) pristine TiO2 nanoparticles, greater reusability was also reported, a fact
[PAMCA] capacity owing to the that can be attributed to the enlarged pore size of the zeolite framework
large surface area
(Chandra et al., 2016). Common dopants associated with the use of TiO2
generated by synthesis to
sol-gel method. as a photo-catalyst have been discussed in Table 4.
Embedded in Lead (Pb2þ) Over 99% removal of Idris et al., The dye methylene blue has also been successfully degraded by the
polyvinyl ions was achieved before (2016) utilization of TiO2 nanoparticles, with complete degradation being
alcohol – 3 h, with optimal achieved within a few hours. A drastic improvement in performances
alginate beads performance obtained at
a pH of 7. The catalyst
was noted when TiO2 was in the micro- and nano-scales. The effec­
also showed remarkable tiveness of the photocatalyst increased corresponding to an increase in
reuse properties. the mass of TiO2 catalyst utilized. Similarly, an increase in the pH also
– Lead (Pb2þ) The monolith was Sharma et al., resulted in an increase in the rate of the reaction (Dariani et al., 2016).
Cadmium produced by nanocasting (2017)
Highly crystalline TiO2 particles were synthesized using solvothermal
(Cd2þ) the nanoparticles. This
way, the problem of methods and supported by egg shells to decompose methylene blue and
water miscibility of rhodamine R6 dyes to notable effect. The utilization of solvothermal
nanopowders is method of synthesis and the presence of egg shell support appeared to
mitigated. The large have improved the effectiveness of the catalyst to the increased surface
surface area and
adsorption capacities
area characteristics caused by dispersion and synergic effects. Optimal
improved the performance was obtained when the support and catalyst were taken in
photocatalytic equal amounts, with the fact the support used in the process can be
degradation of the ions derived from natural sources acting as an additional positive to make it a
by the monolith.
highly promising option in the future for photocatalysis (Singh et al.,
Graphene oxide Zinc (Zn2þ) Reaction was carried out Kumordzi et al.,
in the presence of solar (2016) 2017).
radiations, with the TiO2 nanotubes have displayed remarkable efficiency in removing
presence of graphene the commercial dye Orange II. Preparation by hydrothermal method
oxide improving utilizing the solvent NaOH yielded the best results for the degradation of
performance in the
conditions.
the dye, with thermodynamic studies revealing that the degradation
ZnO – alginate Copper While the catalytic Kanakaraju followed physical adsorption mechanism. The catalytic process showed
beads (Cu2þ) activity and removal was et al., (2017) an increase in rate in response to increasing temperatures (Zulfiqar
et al., 2018). TiO2 nanoparticles have also been reported to degrade

7
K.P. Gopinath et al.
Table 4
Applications of TiO2 in removal of organic dyes from water.
Dopant Dye targeted Remarks
Boron (B) Acid yellow 1 100% removal was obtained
within 2 h by the addition of
boron. The reaction was found
to proceed twice as quicker in
comparison to the use of
pristine TiO2.
Gold (Au) Methyl Non-uniform doping was found
orange to be superior to uniform
doping due to the generation of
interfaces between pure and
doped material.
– Rhodamine B Superior performance was
Congo red obtained when solar radiation
Methylene was used instead of artificial
blue UV light. The low toxicity of
the treated water also
highlights the biocompatible
nature of the catalyst.
Magnesium Congo red The introduction of Mg dopant
(Mg) nearly doubled the
performance of standard TiO2
P25. This can be attributed to
the reduced band gap as a
consequence of doping,
enabling visible light
irradiation.
Gold (Au) Methylene The doped catalyst was found
blue to be highly stable and efficient
Auramine O in the removal of dyes. The
Basic red 5 catalyst was shown to
Basic blue 7 withstand successive oxidation
and reduction due to its unique
structure and composition.
Significant reuse potential was
also observed.
Iron (Fe3þ) Acid orange 7 The doped catalyst showed
excellent degradation
capacities under UV, visible
and solar light. No notable
decrease in efficiency was
noted after 6 cycles of use.
Cobalt (Co) Amido black The removal process was found
to be spontaneous due to the
negative values of free energy
obtained. Up to 90%
degradation was achieved after
doping with cobalt, due to the
increased surface area and
improved interaction between
the catalyst and pollutant.
Iron (Fe3þ) Eriochrome While doping significantly
Platinum black-T improved performance when
(Pt4þ) compared to pure TiO2,
platinum was found to produce
superior results to iron. The
improved surface area led to
greater absorption rates while
greater synergic effects
resulted in enhanced drug
degradation.
Carbon (C) Violet-3B The rate of degradation of dyes
Nitrogen was found to be inversely
(N) proportional to the initial
concentration of dyes. The
result of co-doping was much
higher specific surface area
and consequently improved
adsorption. Over 95% colour
removal was achieved.
– Crystal violet The synthesis conditions were
found to strongly influence the
photocatalytic efficiency.
Samples with lower
crystallinity were reported to
Journal of Environmental Management 270 (2020) 110906
Table 4 (continued )
Dopant Dye targeted Remarks References
References
have inferior degradation
Bessegato efficiency due to the short
et al., (2015) lifespan of generated electron-
hole pairs.
methyl orange and Congo red dyes in the presence of solar radiations
Zhang et al., which contain nearly 5% UV. The degradation was found to strongly
(2017a,
depend on the concentration of TiO2 used, with a concentration of 500
2017b)
mg/L proving optimal for the removal of Congo red and 1500 mg/L for
methyl orange. Total colour removal was observed in both cases, making
Bharati et al., industry-scale application possible (Ljubas et al., 2015).
(2017) TiO2 has shown remarkable performance in the degradation of
rhodamine B dye when doped by platinum, nickel and a combination of
both. The generation of a matrix with a large surface area resulted in
greatly enhanced catalytic ability, while its ferromagnetic nature also
made reuse possible. It was even reported that the stability of the
Bhagwat et al.,
catalyst improved in subsequent cycles, making doped TiO2 a viable
(2017)
solution for future dye removal (Pol et al., 2016). Doping using man­
ganese also made possible the degradation of the dyes methylene blue
and methylene orange under visible conditions. The catalytic activity
under visible conditions can be attributed to the creation of excited in­
termediate states. However, the incorporation of zirconia and cobalt
Ren et al., affected the activity of the catalyst to reduce the two dyes in the negative
(2017) manner (Gnanasekaran et al., 2016). The addition of dopants such as Cr,
Fe, Co, Ni and Cu to TiO2 resulted in significantly increased surface areas
and enhanced degradation rates of methylene blue and methyl orange.
The catalytic activity varied based on the dopant used, with Cu returning
the best results due to relatively lower energy requirements and slowed
charge carrier recombination (Kerkez-Kuyumcu et al., 2015). Co-doping
by iron and nitrogen was found to result in an enhancement in the
Han et al.,
(2018)
photocatalytic degradation of the Reactive Red dye 198 (RR dye 198) in
a reaction that exhibited first-order characteristics. The creation of su­
peroxide species is viewed as the reason behind the enhanced activity of
the catalyst (Kaur et al., 2016).
Doping using non-metals such as nitrogen and sulphur has also
Ali et al.,
(2018) shown to be possible in improving the photocatalytic efficiency of TiO2
and in making it functional in the visible range. In this case, the
improvement can be attributed to the creation of N2p and S2p levels
which effectively reduces the bandgap. A composite of TiO2 and gra­
phene was utilized as a base for the simultaneous incorporation of S and
N. Superoxide radicals were generated and contributed to the removal of
the dyes Congo red and methylene blue, making it different from other
Pal et al., doped catalysts which generate hydroxyl radicals (Brindha and Siva­
(2016)
kumar, 2017). Doping with sulphur led to a remarkable increase in the
photocatalytic efficiency against the dye malachite green. The
improvement can be attributed to a change in the spatial orientation of
the TiO2 lattice and a reduction in the band gap (McManamon et al.,
2015).
TiO2 nanorods, when doped with carbon, have shown exceptional
effectiveness in the degradation of dyes such as methylene blue and
Putri et al., rhodamine B. The unique structure of the material generated greatly
(2019) contributes to the increased photocatalytic efficiency. However, the
requirement of temperature conditions approaching 450 � C does make
further studies necessary in order to implement the technology on a
wider scale (Shao et al., 2017). Methyl orange was removed with a high
degree of efficiency by TiO2 nanosheets doped with recycled ytterbium.
The recycling of the dopant makes this process highly cost-efficient and
a feasible choice for future applications. Furthermore, the removal of
Amin and
Alazba, methyl orange is accompanied by the catalytic reduction of Cr6þ ions,
(2017) making the process multi-functional (Zhang et al., 2016). Brilliant green,
a dye which has found use as a common antiseptic and anti-bacterial
fluid, has been found to be degraded by TiO2 doped by strontium with
the charge carrier recombination halted, leading to increased efficiency
8
K.P. Gopinath et al.
(Sood et al., 2015).
The most common and prominent application of TiO2 nano­
composites lies in the removal of dyes in water, with extensive studies
carried out in this domain. MgO/TiO2 is known to be used in photo
catalysis. The photo catalytic methanation of carbon dioxide through
reduction (Li et al., 2014) and production of bio diesel (Dahl et al., 2014)
are some of the other industrial applications of the MgO/TiO2 com­
posite. Transition metals can also be used to increase the photo-catalytic
behavior of TiO2. Fe–TiO2 composite manufactured sol-gel method at
room temperature using titanium tetraisopropoxide (TTiP) and iron (III)
chloride have been used in the degradation of methylene blue dye under
visible light. The composite seems to work at a pH of 10 for the degra­
dation of methylene blue (Anwar and Mulyadi, 2015).
Polymer groups form good films on to which TiO2 can be immobi­
lized onto. The bond formed in this photo-catalyst is a Ti–O–C chemical
bond that is formed through the mechanism of dehydration reaction
between TiO2 and a hydrophilic polymer like polyvinyl alcohol during
the heat treatment process of the immobilized catalyst. High degrada­
tion of methyl orange under UV light has been recorded and has an
enhanced reusability (Lei et al., 2012).
TiO2/CuO composite nano-fibers made by electro-spinning has been
studied for its photo catalytic abilities. The composite had enhanced
mesoporosity and a large specific surface area that permitted efficient
reactant adsorption and mass transfer and absorbance of various
wavelengths of light acid. Orange II, an azo dye was degraded with this
composite. ZnS/TiO2 nano-composite is a very potent photocatalyst, and
this can be attributed to quantum size effects existed in the nano-scale
TiO2 particles or unique physicochemical properties of the porous ma­
terials. It degrades Acid Blue 113, a commonly used industrial diazo dye,
up to 99.0% with minimal use of the catalyst (37 mg) under ultra violet
light (Talebi et al., 2017). It is also used in the degradation of
parathion-methyl and polyoxometalates (Xiaodan et al., 2006).
TiO2–SiO2 nanoporous composite has been made with high anatase
content in order to enhance surface properties for catalytic action. The
catalyst is used often in the degradation of methylene blue, with one
study using rice husk as a template for the composite (Hui et al., 2015).
The nanocomposite of Cu–TiO2–SiO2 prepared by sol-gel method,
has also been tested for its photo-degradation. The enhanced adsorption
of organic compounds has been attributed to the presence of SiO2, while
the addition of copper causes a reduction in the band gap. 95% degra­
dation of Rhodamine B dye present in wastewater has been recorded
using this composite (Li et al., 2012). F/W co-doped TiO2–SiO2 com­
posite aerogels have been developed in recent times that show
photo-degradation activity under visible spectrum. The fluorine content
enhanced the pore capacity of the material. The composite with a F/W
ratio of 0.1 showed the maximum efficiency for the photo-catalysed
degradation of the Rhodamine B (Liu et al., 2019). Immobilized
PDMS-SiO2-chitosan@TiO2 composites on pumice (pumice-PSCT) was
used for the degradation on methylene blue in the visible light region
(Shao et al., 2019).
NaYF4:(Gd, Si)/TiO2 phosphor composites made by a two-step pro­
cess (solution combustion and sol-gel method) have also been used in
the removal of organic dyes from wastewater. The NaYF4:(Gd, 1% Si)
phosphor with TiO2 has an enhanced absorption ability due to the bend
of the phosphor/TiO2 energy band interface under ultraviolet and
visible spectrum An example of a near infrared spectrum photo-catalyst
is the related NaYF4: Yb, Tm@TiO2. These are core shell structured
nanoparticles synthesized by a two-step wet-chemical route. The energy
transfer route between NaYF4:Yb,Tm and TiO2 strengthens the photo-
catalytic activity of the composite (Tang et al., 2013). Nano-crystalline
films of TiO2/palygorskite have also been employed in the treatment
of water. The composite is based on palygorskite, a magnesium
aluminium phyllosilicate (Mg,Al)2Si4O10(OH)⋅4(H2O) that is found in
clay.
TiO2–SnO2 composites that are meso-porous and nano-crystalline in
nature have also been used in photo-degradation of wastewater due to
9
Journal of Environmental Management 270 (2020) 110906
their large surface area (Alagarasi et al., 2019). SnO2/TiO2 nano­
structures have also been used in the degradation of methylene green.
The combined effect of reduced recombination rate, improved surface
area and superior crystallinity have been found to be responsible for its
high efficiency. The composite is also known for its reusability, and has
also been shown to be able to control microbiological growth of gram
positive and gram negative bacteria under solar radiation (Magdalane
et al., 2019). CdS/CdTiO3–TiO2 composites have been made using mi­
crowave hydrothermal process. The composite has a characteristic
litchi-like structures. It was noted that the conditions of the
microwave-assisted hydrothermal synthesis changed the properties of
the composite. The composite is more effective at basic conditions for
the degradation of crystal violet, showing the synergistic effect of the
components of the composite (Li et al., 2016).
A composite need not always have to be made of different elements.
TiO2 composite consisting of anatase interacting with a Ti3þ containing
rutile phase is an example of a purely titanium based composite. The
composite made at 600 � C showed the highest rate of de-colouration of
methyl orange, which has been explained by electronic transfer between
the anatase and rutile phases of the set up. However, analysis of this
composite revealed that this composite shows no photo catalytic activity
without a co-catalyst such as copper in some reactions. Another method
used to improve the photo catalytic ability of this composite is to enforce
platinum as nanoparticles in the composite through photo-deposition
(Hamdy et al., 2014). Another composite used in treatment of waste­
water is the TiO2–montmorillonite composite. Montmorillonite used as
clay is a cost effective, non-toxic, high surface area compound with a
high swelling ability. Decolourisation of different dyes such as crystal
violet, methylene blue, rhodamine, methyl orange and Congo red under
ultraviolet light was seen with varied degradation results (arranged in
descending order of degradation) (Djellabi et al., 2015). Methylene blue
has also been degraded by this composite.
BiVO4/TiO2–NaY zeolite composite prepared by hydrothermal syn­
thesis has been used to degrade methylene blue under ultra violet ra­
diations. It is the ability of zeolite to adsorb methylene blue dye that
makes this composite a strong photo-catalyst. The composite exhibited
higher visible light photo-catalytic performance. The highest obtained
photo catalytic efficiency for Acid red 10 dye degradation was 99.91%
(Rahimi et al., 2019). Ag2O/TiO2 composites on nano-graphene plate­
lets has been studied with respect to their degradation of methylene blue
under UV and visible light irradiation. The presence of oxidizing agents
such as hydrogen peroxide and per-sulphate has a positive effect on the
photo degradation of the dye. This could be due to the formation of
hydroxyl free radical or the fact that H2O2 acts as an electron acceptor.
However, this composite is sensitive to anions present in wastewater
such as carbonate, nitrate, hydrogen phosphate, chloride, and sulphate
(Saleh et al., 2019).
Another composite derived based on environmental conservation
aspects is the fly ash/TiO2 composite. The composite had a specific
surface area nearly ten times more than fly ash, making it a very efficient
catalyst. Simultaneous removal of copper, methyl orange and sodium
dodecyl benzene sulfonate with 90% efficiency under ultraviolet light
achieved (Visa et al., 2015). Mesoporous TiO2-PVA nano-composites
have been used to selectively remove methylene blue from methylene
blue-methyl orange mixtures (Jaseela et al., 2019). The composite
nanofibers of polyvinyl alcohol/poly(N,N-dimethylaminopropyl acryl­
amide) hydrogel and TiO2 is another example of an organic based
composite. It is prepared by electrospinning. TiO2 was immobilized in
the electrospunfibers for an easy recovery of TiO2 after the waste
treatment. The repulsion of protonated amine groups in the polymer
chains that are charged, due to the swelling up of hydrogel nanofibers
when they are brought in contact with acidic conditions, is seen. High
efficiency of photo-catalytic decomposition of dye was obtained by the
fast swelling of hydrogel in the acidic conditions (Yun et al., 2010).
Composites can also be made from biomolecules. Enzyme-photo bi-
functional synergistic catalysis in water treatment has been recorded.
K.P. Gopinath et al.
Polydopamine (chloroperoxidase tethered) CPO/HRP-TiO2 nano-
composite is an example of an enzyme-based TiO2 composite. It is
made by in-situ polymerization along with ultrasound bombardment
size reduction technique for nano-composite fabrication. Aniline blue,
crystal violet and 2,4-dichlorophenol were degraded by this composite.
The mechanism proposed for the disappearance was a direct enzymatic
attack on the chromophore of the dye, thereby decolorizing it. A major
concern when enzymes are used is their sensitivity. The unique feature
of the composite is the enhanced thermal stability, its passivity to
organic molecules like N, N-dimethylformamide and pH (Cheng et al.,
2018). Multi walled carbon nanotube increase the adsorptive power of
TiO2 when the two are combined and used as a composite photo catalyst
as (MWCNT/TiO2). This makes it more efficient during the degradation
of organic molecules such as methyl orange. MWCNT also plays the role
of a dispersing agent that ensures that TiO2 agglomerating is prevented
and ensuring that more surface area is exposed for catalysis to occur.
This pair is used in the degradation of methyl orange (Saleh and Gupta,
2012).
Textile wastewater can also be treated using TiO2/Activated carbon
composites. The composite can be used in batch or continuous opera­
tions. Acridene, Indigo carmine, Methyl blue, Rhodamine B, various
concentrations of Methyl orange, and acid orange II have been degraded
using this photo catalyst. TiO2/CAC composite has also been recorded
degrading the azo dye Sunset Yellow. The catalyst is found to be reusable
(Rajamanickam and Shanthi, 2014). Silver embedded C–TiO2 compos­
ites, made through specialized nanofabricated sol gel methods, also have
enhanced properties. The photo-catalytic degradation of methyl orange
dye in wastewater was observed (Hassan et al., 2018). Graphene oxi­
de–TiO2 composites have been studied for their role in water treatment
as filtration membranes, being used as sheets wherein filtration occurs
due to fuzzy channels formed during synthesis of the composite. They
are very effective in removal of common water pollutants of dye origin
such as methyl orange and rhodamine B. They were also observed to
capture additional amount of dye molecules (Xu et al., 2013).
GO-TiO2 nano-composites with varying composition of GO have
been used for the degradation of acid navy blue dye. It was noted that
the greater the presence of GO, the more is the removal of the dye from
effluent (Ahmed et al., 2019). Reduced graphene oxide also has been
used along with TiO2 as a photo degrading composite. A study used car
bumper waste as a source of carbon, thereby up-cycling waste into a
novel and high performance carbon based photo catalyst. It has been
characterized by the photo-catalytic degradation of methylene blue dye.
The technology can be improved in the future by converting various
sources of plastic into useable carbon that can be used for photo catalytic
purposes(Mohamed and Alsanea, 2018). Hybrid rGO-TiO2/Co3O4
nanocomposite was prepared by co-precipitation and was used in the
removal of methylene blue and crystal violet dyes from wastewater. The
addition of rGO is seen to be effective by narrowing the TiO2/Co3O4
band gap and facilitating the occurrence of the reaction under visible
light. The component of rGO is also responsible for inhibiting
electron-hole recombination, hence promoting the degradation of the
dye. This composite therefore displays a possibility for implementation
in the removal of pollutants of organic origin from colouring, petroleum
and leather industries (Ranjith et al., 2019).
The g-C3N4/TiO2nanocomposite has also been seen to degrade
Rhodamine B dye under visible light. The highest amount of degradation
was seen when the composite was used in the shape of nanotubes
composite when compared to other shapes and structures made from the
composite (Monga and Basu, 2019). Graphitic carbon nitride-titanium
dioxide-graphene aerogel (g–C3N4–TiO2-GA) are used in the removal
of Rhodamine B dye from waste water. Assembled by a hydrothermal
approach, it shows nearly complete degradation of the dye under visible
spectrum of light (J. J.Zhang et al., 2018a, 2018b). The composite
g-C3N4/TiO2/PAA/PTFE ultra filtration membrane shows excellent hy­
drophilicity, anti-fouling and water flux. The degradation of methylene
blue has been recorded. Different self-cleaning mechanisms under UV
10
Journal of Environmental Management 270 (2020) 110906
and visible light irradiations have been observed in the immobilized
composite (Chi et al., 2019). C.I. Direct Red 23 degradation has been
recorded under UV light by TiO2 supported on glass beads. The degra­
dation was seen to be more profound under acidic conditions and the
optimum addition of hydrogen peroxide into the wastewater treatment
process helped in the photo-catalytic degradation of the dye, which has
been explained by the formation of hydroxyl group free radicals in the
wastewater (Daneshvar et al., 2005a). This has also been used in the
batch recirculated packed bed degradation of phenols (Jadi et al., 2016).
Impregnation of TiO2 on to borosilicate glass spheres has been employed
in the degradation of methylene blue dye at 400 � C(Cunha et al., 2018).
Degradation of methylene blue was also performed using a com­
posite of TiO2/g-C3N4/Fe3O4 with a specific surface area of 66.2 m2/g.
The composite was made from nanosheets of TiO2/g-C3N4 with Fe3O4
particles being dispersed through them. The highest photocatalytic ac­
tivity of the composite was exhibited when weight fraction of Fe3O4 was
5 wt%, with 96% removal (Abbasi et al., 2019). Another g–C3N4–TiO2
composite was used to remove methyl orange, with a rate constant of
0.189 min─1 (Gu et al., 2017). Another composite of TiO2 (MNTC
nanosheets) is formed from nanorods co-doped with Mo/N on carbon
nanofibers, and displayed a high degradation capability of 79.8% to­
wards methylene blue (Qiu et al., 2019). Graphene-like TiO2@C nano­
sheets were developed to degrade methylene blue, exhibiting adsorption
of 444.8 mg/g (Gan et al., 2019). TiO2 nanosheets are also used as a
basis for a composite with Cu-biphenylamine (TNS/Cu(BA)) which de­
grades 99–99.6% of methyl orange and rhodamine B at 120 and 160 min
respectively (Khan et al., 2018), and with Ag, achieving 100% photo­
catalytic efficiency during degradation of Congo red in 20 min (Nair and
Jagadeesh Babu, 2017).
Quantum dots of SnO2 were anchored on TiO2 nanospheres, and the
resultant composite degraded 100 mL of 10 mg/L methylene orange
completely in just 15 min in the presence of UV–visible light (Du et al.,
2016). Nanorods with three-dimensional hyperstructures are used to
make nanospheres of Pd/TiO2 used for degradation of methyl orange in
the presence of visible light (H. Wang et al., 2019). A combination of
Fe3O4 and TiO2nanospheres was implemented to degrade Congo red,
with an absorption rate of 100% when ultrasound waves of 30W power
were used to intensify absorption (Ghaforyan et al., 2017). Oleic acid
has also been combined with TiO2nanospheres and used to degrade
rhodamine B in the presence of visible light (Cao et al., 2018).
Alternatively, water containing methylene blue has been efficiently
treated by photoelectrocatalysis. Doping TiO2 using fluorine made
possible visible light operation and enhanced the creation of electron
hole pairs, thereby resulting in enhanced performance when compared
to conventional photocatalysts (Liu et al., 2017). Metanil yellow and
remazol red B dyes were also shown to be removed from water samples
by photoelectrocatalysis across a range of concentrations and pH values
(Nurdin et al., 2018). Hydrogen production was observed as a byproduct
of rhodamine B removal by Pd doped TiO2nanorods via photo­
electrocatalysis in the presence of solar light. The ability of Pd atoms to
retain charges in the rod structure was noted as a key aspect of the
structure and its enhanced performance (Yilmaz et al., 2017).
Many studies have shown that the degradation ability of the catalyst
can be enhanced by using TiO2 as a photonic crystal. Studies on samples
of titania inverse opals supported the above statement due to their
effective degradation of Phenols, Methylene blue and Rhodamine under
the UV spectrum(Likodimos, 2018). Photonic crystals coated with
Nanoparticles of gold have been seen to degrade 2,4- dichlorophenol
using xenon short-arc lamp as a light-emitting source for the visible
spectrum (Lu et al., 2012). Inverse TiO2 opal photonic crystal coupled
TiO2/poly(3- hexylthiophene) (bilayer TiO2/P3HT) has been seen to
degrade methylene blue under the visible spectrum (Liao et al., 2010).
The photonic crystal of TiO2/SiO2 has been seen to degrade acetalde­
hyde (Y. X. Wang et al., 2019). Similar catalysts have been made and the
degradation of Rhodamine dye was observed under monochromatic 365
nm irradiation (Likodimos, 2018). An nc-TiO2/SnO2 inverse opal
K.P. Gopinath et al.
composite membrane when used as a photocatalyst, shows the ability to
degrade methyl orange under UV radiation. Cu2O NCs/TiO2 has been
seen to degrade Rhodamine B and Bisphenol A under UV–visible light
(Geng et al., 2015). A catalyst of inverse TiO2/Pt opals Schottky struc­
tures on the Ti substrate effectively degrades phenols (Chen et al., 2010).
The degradation of hepatotoxin, microcystin-LR in water by N–F codo­
ped TiO2 under the Visual spectrum is another example of visible
light-activated (VLA) catalysis. Methylene blue dye has been used as a
model dye in testing the degradation power of dye-sensitized anatase
TiO2 inverse opal films (Likodimos, 2018). A novel Photonic crystal
structural-induced Cu3SnS4/Ti3þ-TiO2 p-n coaxial heterojunction
array has shown its photocatalytic ability to produce hydrogen and
degradative Methyl orange efficiently (Li et al., 2017).
6. Removal of pharmaceuticals and personal care organic
compounds
The hydroxyl radical produced by photo-excitation of TiO2 is capable
of oxidizing almost all electron-rich organic molecules in water non-
selectively.
�
OH þ Organic compound → Intermediates → CO2 þ H2 (12)
The same result is also obtained from the interactions of the electron
holes with the organic molecules (Umar and Abdul Aziz, 2013).
For example, when it reacts with hydrocarbons, the following reac­
tion takes place:
R–H þ HO� → R� þ H2O (13)
Oxidation of organic pollutants may proceed in two ways: aliphatic
oxidation, in which hydrogen atoms are removed from the molecule by
the hydroxyl radicals, which cause the formation of new radicals, and
aromatic oxidation, where the aromatic molecule is oxidized by mo­
lecular oxygen and superoxide radicals in the presence of UV light
(Augugliaro et al., 2012). The latter may occur by one of three ways:
attachment of the hydroxyl radical to the aromatic ring, abstraction of a
hydrogen atom from the molecule or substitution of radicals in the ring
(Dougna et al., 2015). It is also necessary to ensure that degradation of
organic pollutants is performed extensively until the Total Organic
Carbon (TOC) of the water is minimal. This is due to the generation of
toxic organic intermediates upon the degradation of the initial pollutant
(Ani et al., 2018).
Aromatic oxidation predominantly transpires during the removal of
the various classes of pharmaceutical pollutants from water, nearly all of
which have an aromatic ring as a base structure. Pharmaceutical com­
pounds that can be oxidized by TiO2-produced hydroxyl radicals include
analgesics such as dicolfenac (Achilleos et al., 2010) and sulphame­
thoxazole(Carbonaro et al., 2013), antibiotics such as amoxicillin
(Dimitrakopoulou et al., 2012) and moxifloxacin (Van Doorslaer et al.,
2012) and antiepileptics such as carbamazepine (Dai et al., 2012).
Conventional wastewater treatment methods have proven inade­
quate at removing persistent organic substances from the water,
necessitating a more efficient method for their removal (Ratola et al.,
2012). Similarly, they have also shown to be sub-optimal for the removal
of drugs from wastewater emerging from medical sources (De la Cruz
et al., 2013). Consequently, the organic substances, found in day-to-day
routine in the form of cosmetic and personal care products and drugs,
accumulate in the water bodies surrounding industries, making them
sources of intense pollution (Carbonaro et al., 2013). These organic
pollutants have consequently been named persistent organic pollutants
(POPs) due to the difficulty in degrading them and their ability to resist
various treatment methods. It is not uncommon to observe POPs present
even in wastewater samples that have been treated by conventional
methods (Dong et al., 2015b). The presence of pharmaceuticals in
wastewater poses a greater danger to aquatic organisms and the sur­
rounding environment than humans but extensive research has still been
11
Journal of Environmental Management 270 (2020) 110906
carried out to analyse the potential negative effects on the health of
humans (Jones et al., 2005). It is critical to acknowledge the problems
created by pharmaceutical and other organic waste to the functioning of
aquatic organisms. The presence of organics in water has been shown to
be toxic to these organisms, interfering with the functioning of their
organs, while also proving tough to degrade. As a consequence, they
accumulate in organisms and are carried across the food chain (Ebele
et al., 2017). Parabens and phenoxyethanol, commonly used in cos­
metics due to their antibacterial nature, have received widespread
attention due to their ill-effects on humans. Phenoxyethanol deposited
from everyday use has perilous effects on the flora and fauna (Brausch
and Rand, 2011) while parabens have been studied to strongly influence
hormonal activity in humans (Jagne et al., 2016). These organic com­
pounds are present in concentrations too low for conventional methods
to remove them, demanding the application of novel photocatalysts for
the removal of pharmaceuticals and personal care products (PPCPs).
Degussa P25, a nanocrystalline structure comprising of a mixture of
rutile and anatase TiO2, was successfully used in the removal of 4 highly
common pharmaceuticals from water: diclofenac, ibuprofen, sulpha­
methoxazole and acetaminophen. Light emitting diodes (LEDs) were
used as a source of radiation and were found to be more effective when
the light supplied was of lower wavelength. Microcystin – LR, a known
toxin present in water, was also degraded by a similar photocatalytic
reaction (Eskandarian et al., 2016). When irradiated using UV light,
Degussa P25 TiO2 nanoparticles supported on single-walled carbon
nanotubes (SWCNTs) were found to be effective in the degradation of
certain organic compounds including but not limited to diclofenac,
iopamidol, triclosan and sulphamethoxazole. However, the utilization of
solar irradiation, the effectiveness of the novel photocatalyst dropped
significantly. Furthermore, the removal of the supported TiO2 was
shown to be made possible by simple operations such as centrifugation,
making it a promising candidate for the removal of organics from
wastewater (Murgolo et al., 2015). TiO2 has also been reported as a
potent removing agent against aspirin, reaching a high degree of effec­
tiveness even when irradiated by solar light. The photocatalytic degra­
dation yielded organic acids, of which acetic acid was found in the
largest concentrations (Mukherjee et al., 2016). TiO2 P25 has shown
remarkable efficiency in the removal of the pain relieving drug acet­
aminophen, also known as paracetamol. An optimal pH of 9.0 was
shown to produce the best results in the photocatalytic degradation of
the drug, while the catalyst showed the ability to be used as a slurry or
on an immobilized support to produce effective results (Jallouli et al.,
2017). The drugs diclofenac and ibuprofen were also degraded using a
layer of TiO2 nanoparticles grown on a membrane made of a hydrophilic
polymer such as polyethersulfone and polyvinylidene fluoride.
Furthermore, excellent reuse characteristics were observed from the
layer and the membrane, with no significant loss in performance re­
ported for several cycles (Fischer et al., 2015). TiO2 has also shown the
capacity to reduce the antibiotic chlorhexidinedigluconate when used as
a suspension or when supported by calcium alginate beads. The presence
of a support greatly improves the reuse ability of the catalyst but carries
the caveat of inferior performance. Furthermore, the supported catalyst
also reduced other common pharmaceutical wastes such as ibuprofen,
carbamazepine and atenolol, making possible its large-scale application
(Sarkar et al., 2015).
The effectiveness of TiO2 photocatalyst has been shown to improve
considerably upon the process of doping. Doping with nitrogen
enhanced the photocatalytic degradation of the drug spiromycin in the
presence of visible light. A high degree of total organic content (TOC)
removal was reported after doping, a fact that can be attributed to the
narrowed band gap (Vaiano et al., 2015). In another study, co-doping
TiO2 nanoparticles using nitrogen and sulphur resulted in exceptional
degradation characteristics of commonly found drugs ibuprofen and
naproxen. This can be attributed to the synergic interactions between
the two dopants and the base TiO2, resulting in greater adsorption area
for the pharmaceuticals to occupy. Furthermore, the catalyst also
K.P. Gopinath et al.
showed strong reuse properties and exhibited no major loss in perfor­
mance after six cycles. When a similar doping process was carried out on
TiO2 nanosheets, the enhancement in performance was not as impres­
sive as that obtained from nanoparticles due to the comparatively lesser
area generated. However, the performance of the doped nanosheets and
nanoparticles were found to be superior to their pristine counterparts
(Eslami et al., 2016). Platinum doping resulted in a notable increase in
the degradation efficiency of the drugs ifosafamide and cyclophospha­
mide when compared to pure TiO2 nanoparticles. The degradation of
both compounds released phosphate ions, PO34 , improving the photo­
catalytic efficiency of TiO2 (Ofiarska et al., 2016). TiO2 co-doped with
bismuth and boron was utilized in the removal of ifosafamide, with an
optimal Bi:B ratio of 3:1 being reported. Furthermore, a constant ratio of
the drug and TiO2 returned optimal photocatalytic results under stim­
ulated light conditions. Besides ifosafamide, other drugs such as cyclo­
phosphamide, imatinib and 5-fluorouracil were also efficiently
decomposed by TiO2(Fiszka Borzyszkowska et al., 2016).
Studies have shown the reduction of the compounds phenoxyethanol
and propyl-paraben, used in cosmetics, to be assisted by doping TiO2
nanostructures with iron. While both pure and doped TiO2 exhibited
efficient reduction characteristics, doping enhanced the production of
electron and hole pairs, leading to superior performance. However,
doping resulted in a decrease in surface area due to the covering of
pores, a factor that is offset by other properties (Bonfrate et al., 2017).
Doping with noble metals such Ag, Au, Pt and Pd has also been shown to
result in excellent removal properties of a mixture of parabens from
water. The process was shown to shown require minimal amounts of
ozone to function, with a loading of 0.5 wt% Ag proving to be the most
effective in terms of catalytic properties. While the requirement of UV
and ozone increased the energy requirements for the process, it was
shown that the cost decreased over time, making TiO2 doped with noble
metals a feasible long-term solution for the removal of parabens from
water (Joa ~o F. Gomes et al., 2017a, 2017b). Doping amorphous TiO2
with carbon resulted in high values of surface area and pore volume,
making it an excellent option for photocatalysis. This doped catalyst was
utilized in the removal of 4-chlorophenol in the presence of visible light
and showed excellent results. There was a marked decrease in the
recombination of charge carriers, leading to improved performance of
the doped catalyst (Shao et al., 2015). 4-chlorophenol has also been
effectively degraded by TiO2 nanoparticles doped with hydrated
ammonium iron sulphate, (NH4)2Fe(SO4)2.6H2O, in the presence of
solar radiations and light from LED. The activity was found to improve
by a factor of eight when compared to pristine TiO2 nanoparticles, with
over 99% chlorophenol degraded to a less toxic compound. The doped
catalyst was also found to be stable over several cycles and showed
appreciable reuse characteristics (Villaluz et al., 2019).
TiO2–Fe2O3 nanocomposites have been used in for their anti-
bacterial effects. Iron based composites can also be made to show dual
effect of being a photo-Fenton and a photo-catalyst. Fuller’s earth (FE)
and Foundry sand (FS) are incorporated in the making of the composite
in order to attain the in-situ dual effect. The degradation of phenazone, a
common analgesic drug, was recorded by the composite. The composite
beads were very durable and were recycled multiple times (Talwar et al.,
2019). Pilot plant studies have also been conducted on the degradability
of pentoxifylline by the composite. The time for degradation was noted
to be significantly low (Bansal and Verma, 2018a). Magnetic MIL-101
(Fe)/TiO2 composite prepared by solvothermal process has been used in
the photo-catalytic degradation of tetracycline under solar light. The
degradation by this composite is highly efficient and cost effective in
nature (He et al., 2019).
Another carbon based composite reported in literature is the mag­
netic carbon nanotube-TiO2 composite. The photo-degradation of car­
bamazepine and sulfamethoxazole under solar irradiation has been
carried out using the composite. The fast kinetics and high photo-
degradation activity toward micro-pollutants increase the chances of
future usage (Awfa et al., 2019). The composite TiO2/WO3 has been
12
Journal of Environmental Management 270 (2020) 110906
used for the degradation of antibiotics in combination with Pulsed
discharge plasma. 4% by weight of WO3 doping content presented the
optimal photo catalytic performance. The composite has been used to
degrade Chloramphenicol. TiO2/WO3 composites have good reusability
as well as stability. The proposed mechanism is that the joint effect of
PDP along with the titanium composite degrades the drug yielding
phenolic ring molecules by a series of free radical reactions (Guo et al.,
2019a).
Pentoxifylline can be removed from waste water by treating it with
Fe–Ag–TiO2 composite under solar radiation. The composite has can be
reused multiple times and the time for treatment was significantly
reduced due to the modified in-situ dual effect of the composite (Bansal
and Verma, 2018b). The drug can also be removed by Fe–TiO2cataylst
(Bansal and Verma, 2018a). The degradation of phenazone by Fe–TiO2
composite has also been explored in studies (Talwar et al., 2019). Pulsed
discharge plasma coupled with reduced graphene oxide/TiO2 nano­
composites have been used in the removal of flumequine from waste­
water. rGO/TiO2 could further improve the removal efficiency in PDP
system (Guo et al., 2019b). It has also been recorded degrading Sulfa­
methoxazole, Erythromycin and Clarithromycin (X. Y. Wang et al.,
2019). Another carbon based composite used in removal of anti-biotics
is the TiO2/Graphene oxide composite. It has been recorded removing
ciprofloxacin (Khan et al., 2019). CdTe/TiO2heterostructure photo­
catalysts have been used in removal of tetracycline hydrochloride. The
efficiency of the process can be improved using the Z scheme approach
(Gong et al., 2018). Sulphur TiO2 catalysts were immobilized on circular
aluminium plates using polysiloxane. Sulphur was incorporated into the
photo-catalyst of TiO2 through the lattices of TiO2 as sulphur cations. It
is used in the degradation of 2, 4 dichlorophenol under direct irradiation
of a metal halide lamp. In a surprising twist, the degradation of the
compound in the attached form was slower than the suspended catalyst.
However, the attached catalyst was more dependable for long term use
and was satisfactory reusability (Gar Alalm et al., 2018). A novel
TiO2–ZnO/clay used in the form of photonic crystals has been used in
the degradation of Antipyrine and acetaminophen.(Tobajas et al., 2017).
Photoelectrocatalysis has also been shown to be a promising method
of removing drugs from water, with acetaminophen in particular being
the focus of studies. Optimal removal was noted at a pH of 3 but the
production of byproducts acts as a deterrent (Borr� as-Ferrís et al., 2019).
Coating of TiO2 nano-arrays using N, S made possible the removal of
diclofenac with a promising degree of effectiveness. A removal effi­
ciency of around 70% was noted at pH 5 and the reaction was found to
be strongly influenced by the ions present in the wastewater (Cui et al.,
2018). Doping TiO2 nano-arrays with Cu also resulted in comparable
removal of diclofenac. The effect was found to be strongly dependent on
the relative amounts of Cu2O and CuO added as dopant material (Hua
et al., 2016). Similarly, the drug 5-fluorouracil was also reduced to
non-toxic levels in wastewater by TiO2 photoelectrocatalysis (Mazierski
et al., 2019). Removal of paracetamol by Au doped TiO2 was shown to be
repeatable and efficient over multiple cycles by using electrodes of
optimal specifications. Total removal of the pollutant was observed in
less than 30 min (Hern� andez et al., 2018). Sulphamethoxazole was also
removed in a similar vein, with a strong increase in reaction rate noted
with decreasing pH and increasing potential (Su et al., 2016).
Hydrothermal synthesis was used to prepare nanospheres of TiO2,
Fe3O4 and carbon-nanofibers which degraded ibuprofen, attaining
photocatalytic efficiencies of 80–100% in 8–125 min (Yilmaz et al.,
2020). The TNS/Cu(BA) composite covered earlier degraded 53% of
TCP in 180 min (Khan et al., 2018). The MNTC composite mentioned
earlier is also highly effective against bisphenol-A and sulfamethoxazole
(Qiu et al., 2019). Other examples of removal of pharmaceuticals and
personal care products using TiO2 have been shown in Table 5.
7. Removal of pesticides
The primary reason for the removal of pesticide residues from water
K.P. Gopinath et al. Journal of Environmental Management 270 (2020) 110906

Table 5
Application of TiO2 photocatalysts in the removal of drugs from water.
Dopant Drug targeted Intended use of drug Remarks References

– Amoxicillin Antibiotic Maximum removal of the two drugs was achieved at 7.6 pH. Degradation Chinnaiyan et al., (2018)
Metformin Diabetic drug was primarily carried out by the formation of hydroxyl radicals.
– Cephalexin Antibiotic Optimum pH was found to be 7 for the degradation of the drug. The Fazilati et al., (2018)
removal of cephalexin was reported to be achieved to a greater extent
under UV irradiation when compared to amoxicillin.
– Clarithyromicin Antibiotic Degradation was found to be maximum at a pH of 5 for a dosage of 0.5g of (Meriç; Ozkal,
€ 2018)
antibiotic per litre of TiO2 solution.
– Sulfamethoxazole Antibiotic The synergy present between the two drugs slowed down the degradation Cai and Hu, (2017)
Trimethoprim Antibiotic process. Aniline was generated as a product during the degradation of
sulfamethoxazole and was found to be non-toxic.
– Venlafaxine Antidepressant Activity was found to be optimal at a pH of 10, with a maximum Lambropoulou et al., (2017)
degradation efficiency of 96% being achieved. A drastic decrease in
toxicity was also noted.
– Cefazolin Antibiotic An optimal pH of 5 yielded the best degradation results. Degradation was Shokri et al., (2016)
shown to be possible with both immobilized and suspended TiO2
photocatalyst. TiO2 suspensions were found to be better than immobilized
catalysts for degradation and there was no major decrease in efficiency
after 10 cycles.
Sertraline Antidepressant The effectiveness was found to be inversely proportional to the initial Rejek and
concentration of the antibiotic. While both suspended and immobilized Grzechulska-Damszel,
catalysts were shown to be feasible, fixed catalysts returned the superior (2018)
results.
– Buspirone Anti-anxiety drug TiO2 photocatalytic degradation yielded products similar to those formed Ruokolainen et al., (2016)
Promazine Antipsychotic by metabolism. Control of the reaction was also shown to be possible by
varying UV supply.
Boron (B) Metoprolol To prevent strokes, heart attacks Doping with boron significantly enhanced the photocatalytic Cavalcante et al., (2015)
and kidney disorders (beta blocker performance of TiO2. 5 wt% doping yielded the best results of about 70%
drug) drug removal. The enhanced performance can be attributed to increased
surface area and formation of Ti3þ.
– Gemfibrozil Lipid regulating agent The degradation rate constant was found to be maximum at a pH of 5. Alvarez-Corena et al.,
Around 95% drug removal was achieved. (2016)
Nitrogen Carbamazepine Anticonvulsant The rate of degradation was found to be directly proportional to the Horovitz et al., (2016)
(N) Analgesic temperature. The porous structure of the catalyst significantly improved
the efficiency of degradation.
– Metamizol Analgesic The removal of the drug was achieved through oxidation and followed Ambalavanar and Habekost,
two different rate patterns. The rate was found to increase until reaching a (2018)
constant value.
Platinum Tetracycline Antibiotic Doping resulted in a change in the internal electric field of the catalyst. Lyu et al., (2019)
(Pt) This change resulted in increased hole transfer and consequently
increased catalytic activity. Performance was improved further by
creating a structure where amorphous TiO2 was filled in the pores of Pt-
doped TiO2.

is their extremely high toxicity. This can be achieved by mineralisation, improper endocrine functioning (Blair et al., 2015). Furthermore, the
a process by which all of the inorganic components of the organic potential of pesticides as a carcinogen has also received extensive
pesticide are released through degradation. TiO2 is capable of per­ attention (Alavanja and Bonner, 2012). Similar to dyes and pharma­
forming photocatalytic degradation on pesticides. ceuticals, conventional wastewater treatment methods cannot
completely remove the pesticides present, leading to the risk of accu­
(14) mulation of toxic substances in different organisms across the environ­
Photo excitation ​ of ​ TiO2
Organic ​ pesticides Intermediates
Adsorption
��������������������! ment (Vanraes et al., 2017). However, TiO2 has shown a high degree of
performance in the degradation of pesticides, both in pristine and doped
Intermediates → CO2 þ SO4 2 þ SO4 3 þ SO3 (15) forms.
Chlorpyrifos, a phosphate-based pesticide, has been reported to be
The radicals produced from the above reaction later react with dis­
degraded through photocatalysis using TiO2 nanoparticles. Nearly 80%
solved oxygen and produce organic peroxyl radicals (ROO�) which are
of the pesticide was degraded within a day and the catalyst was shown to
instrumental in ensuring complete mineralisation of the pesticide (Vela
be effective in the presence or absence of bacteria. However, the pres­
et al., 2017).
ence of bacteria did result in a slight decrease in the pesticide degra­
The utilization of pesticides in agriculture has become mandatory in
dation. The catalytic process required UV radiation, with visible light
order to meet the ever-growing food demands resulting from a dramatic
proving an inadequate energy source for the reaction (Farner Budarz
increase in the global population. While pesticides thoroughly effective
et al., 2019). The pesticides profenofos and quinalphos were reduced by
in improving the production and preventing agricultural losses, they are
a similar mechanism by TiO2 nanoparticles under UV radiation. The
accompanied by several drawbacks from an environmental perspective
catalyst showed encouraging potential for reuse over multiple cycles
(Liu et al., 2012). Similar to dyes, pharmaceuticals and personal care
without any significant loss in activity. The performance was shown to
products, pesticides are often fatal to aquatic organisms due to their
be affected by factors including but not limited to the concentration of
extremely high biological toxicity. Other effects, while not lethal,
TiO2, time of radiation and pH of the system (Amalraj et al., 2016). TiO2
include a sharp decrease in the speed and activity of aquatic organisms
has also been reported to be efficient in the treatment of a stream con­
(Shuman-Goodier and Propper, 2016). Furthermore, they are often
taining a combination of 4 different pesticides: diuron, alachlor, iso­
non-biodegradable leading to accumulation in successive organisms.
proturon and atrazine. While the catalyst was shown to be effective in
Pesticides can be responsible for both acute and chronic health effects,
treating both pure and normal water, the presence of other pollutants in
reaching extents as severe as the disruption of the immune system and

13
K.P. Gopinath et al.
normal water resulted in a noticeable decrease in the efficiency of TiO2.
This can be attributed to the inhibition of formation of radicals which
quicken the catalytic reaction (Cruz et al., 2017). TiO2 nanowires have
been proven to be exceptionally effective in the degradation of atrazine,
owing to their large surface area and pore volume. Further factors such
as the low-cost nature of the synthesis and potential ability to be reused
over several cycles make nanowires a tantalizing prospect for future
removal of pesticides from water (Zhang et al., 2015).
Imidacloprid has been reported to be effectively degraded by TiO2
nanoparticles in a cylindrical reactor. The structure of the reactor, with
coaxial cylinders, enabled greater contact between the catalyst and the
polluted water, thereby improving the catalytic performance. Further­
more, the reactor also displayed the potential to be used in both batch
and continuous modes, further highlighting its versatility and efficiency
(Ahmari et al., 2018). TiO2 P25 has also been widely viewed as a pho­
tocatalytic removal agent of pesticides. In a study, six commonly found
pesticides and insecticides malathion, fenotrothion, quinalphos, vin­
clozoline, dimethoate and fenarimol were removed using TiO2 P25
under solar light. Another commercially available TiO2 form, Kronosvlp
7000, was studied but was found to be less effective than P25 due to
inferior area and pore volume characteristics (Vela et al., 2018). TiO2
P25 has also exhibited a high degree of effectiveness in the removal of
diazinon from water, with an optimal pH of 6 providing over 99%
degradation of the pesticide. The reaction was mainly found to be a
function of the amount of UV supplied to the catalyst and reaction
duration. Furthermore, concentration of TiO2 and aeration have also
been shown to positively influence the catalysis (Kalantary et al., 2015).
Structural modification of TiO2 nanotubes has been shown to consid­
erably enhance the removal efficiency of the pesticide simazine. The
method proposed to modify the structure of the nanotubes was by
varying the time of anodization, with an optimal anodization time of 10
min was producing the best results (Suhaimy et al., 2018).
Iron-doped TiO2 exhibited remarkable performance characteristics
in the degradation of the pesticide diazinon, with an optimal degrada­
tion effectiveness of nearly 85%. The introduction of iron significantly
made the reaction faster under both UV and ultrasonic radiations, with
the latter proving more conducive to degradation when used separately.
However, maximum efficiency was obtained when both were used
together alongside Fe-doped TiO2 (Tabasideh et al., 2017). Doping with
cerium has been reported to yield excellent results in the removal of the
commonly found pesticide metolachlor. The separation of the dopant
and TiO2 was found to be straightforward due to the magnetic properties
of cerium. The incorporation of cerium dopant increased the porosity
and reduced the charge carrier recombination, thereby improving the
efficiency markedly (Mermana et al., 2017). Cerium has also found
similar use in the removal of another highly common pesticide, glyph­
osate. Optimal loading of cerium was found to be 0.45% by weight.
Additionally, manganese and lanthanum have also been explored as
potential dopants for the removal of glyphosate. Of the three, manga­
nese had the best performance characteristics, followed by cerium and
then lanthanum. All three had an optimal loading of 0.45%, with con­
centrations exceeding the optimal value resulting in a sharp decrease in
the efficiency (Umar et al., 2016).
Cerium has also found application as a dopant in the photocatalytic
removal of the pesticide dicamba under visible light. Ce loading of 1 wt
% was found to produce the best results and yielded complete degra­
dation in 2 h. The performance was also found to be optimal in basic
conditions, yielding non-toxic byproducts which can be removed from
water by simple and well-understood means. The aggregation of Ce also
ensured an increase in the surface area and pore volume, with these
factors directly increasing the catalytic efficiency of Ce doped TiO2 in
comparison to the pristine catalyst (Maddila et al., 2016). Doping with
boron yielded in superior degradation properties of the pesticides
diuron, o-phenylphenol, 2-methyl-4-chlorophenoxyacetic acid and ter­
buthylazine in comparison to the non-doped catalyst. The stability and
reuse potential of the catalyst was also found to improve dramatically
14
Journal of Environmental Management 270 (2020) 110906
upon doping with boron. The presence of boron atoms in the interstices
of the TiO2 lattice can be viewed as the reason for the enhanced func­
tioning and stability of the doped catalyst. While photocatalysis was
found to be highly efficient when used separately, removal was found to
be faster when photocatalysis was used alongside ozonation of the
pesticides (Quin~ ones et al., 2014). Doping using other non-metals such
as carbon, nitrogen and fluorine has also resulted in an enhancement in
degradation ability of TiO2. This can widely be attributed to the pre­
vention in the recombination of electron and hole pairs in the presence
on visible light. The insecticides thiamethoxam and imidacloprid
experienced total degradation by the doped photocatalysts at different
wavelengths. Additionally, the catalyst was found to stable and capable
of running for multiple cycles without losing its efficiency, making it a
highly promising option for industrial use (Joseph and Thiripur­
anthagan, 2018).
The technique of TiO2 photoelectrocatalysis has also been success­
fully employed in the removal of the herbicide atrazine from aqueous
samples. Near complete removal of the pollutant was achieved within
30 min of reaction, with first order kinetics noted (Komtchou et al.,
2016). Atrazine was also removed from groundwater by using TiO2-g­
raphite photoelectrocatalysts and was found to produce reduction
effectiveness as high as 99.7% (Turan et al., 2019), marginally higher
than the previously reported study.
8. Removal of hormones and other endocrine disrupting
compounds (EDCs) from water
The removal of endocrine disrupting compounds (EDCs) from water
is a significant problem in water treatment. EDCs are compounds that
have been proven to interfere with the functioning of the endocrine
system, resulting in compromised reproductive, neurological and im­
mune systems. In younger populations, the effects include incomplete
physical and mental development (Burkhardt-Holm, 2010). Exposure to
endocrine disruptors mainly occurs through food and water while it is
also possible for EDCs to enter through dust and other particulates
present in air. The movement of EDCs from the mother to the fetus is also
a stark possibility (Monneret, 2017). EDCs enter the aquatic environ­
ment mainly as a result of human activities, ranging from wastewater
treatment plants to the discarding of chemicals by industries and
households. The vast majority of wastewater plants cannot completely
degrade EDCs and as a consequence, they are released into the aquatic
environment. Furthermore, living organisms also act as a source of EDCs
(Tijani et al., 2013). Besides affecting humans, the presence of EDCs has
also been shown to be harmful to marine organisms. High concentra­
tions of estrogen in water have resulted in decreased reproductive ca­
pacities and feminization of fish (Tetreault et al., 2011). EDCs include
heavy metals, DDT, bisphenolA, hormones and certain drugs. Phtha­
lates, among the most common EDCs found in factories, have been re­
ported to be carcinogenic in males (Villeneuve et al., 2010) and
bisphenol A has been shown to be potentially correlated to male sexual
dysfunction (Li et al., 2009). Furthermore, hormones possess the ability
to affect organisms even when present in trace concentrations (Tabata
et al., 2001). The inability of conventional treatment methods to remove
EDCs along with the increased emphasis on cleaner methods of water
purification have led to the emerge of TiO2 as a viable solution for the
removal of EDCs (Tong et al., 2012).
Thin TiO2 films have demonstrated appreciable ability to degrade
steroidal hormones in an aqueous medium. Estradiol, progesterone and
levonorgestrel were degraded by an immobilized layer on TiO2 when
irradiated by artificial light. Progesterone was removed with the highest
effectiveness in comparison to other hormones, with the addition of
hydrogen peroxide further enhancing the degradation of all three hor­
mones (AlAani et al., 2017). The effective removal of EDCs using dop­
ants has been shown in Table 6. Removal of estrogens and
estrogen-imitators such as bisphenol A has also been shown to be
possible with TiO2. The application of inexpensive UV-LED was found to
K.P. Gopinath et al. Journal of Environmental Management 270 (2020) 110906

be viable for the total removal of the biological activities of estrone,
estriol, 17β-estradiol, ethinylestradiol and bisphenol A. Enhanced elec­
trostatic interaction between the target compounds and TiO2 was ach­
ieved at lower pH ranges (Arlos et al., 2016). Removal of estrone, the
female hormone found in least concentrations, was also shown to be
possible by using P25 TiO2. Hydroxylated compounds of estrone were
generated as by-products during the degradation process and were
shown to be removed by further photocatalysis (Sornalingam et al.,
2018). Titania photocatalyst was found to be effective in the removal of
17α-estradiol from water, and displayed commendable energy efficiency
in the process (Zatloukalova � et al., 2017). In comparison to other es­
trogenic hormones, estriol and estrone have been found to be compar­
atively harder to degrade. High concentrations of P25 TiO2 have proven
to be efficient in the removal of estriol from aqueous media. Higher
concentrations resulted in greater absorption of light, thereby resulting
in superior performance (Ramírez-S� anchez et al., 2017).
The hormone testosterone is the primary male hormone and is
responsible for the development of male reproductive faculties. Testos­
terone was completely degraded by TiO2 and resulted in the formation
of valuable by-products comparable to those produced by natural
metabolism (Ruokolainen et al., 2016). The enhanced functioning of
TiO2 can be attributed to the fact that catalytic activity occurs in two
manners, through transfer of electrons and or by formation of hydroxyl
radicals. Doping of TiO2 by silver enabled the removal of the hormone
dexamethasone from water. Further performance enhancement was
achieved by the addition of hydrogen peroxide, with both UV and visible
light acting as viable sources of energy (Pazoki et al., 2016).
The removal of 17-ethynyl estradiol, 4-nonylphenol and bisphenol A
was achieved by a series of thin layers of TiO2 and was found to be
effective in both plug flow and batch reactor setups. Bisphenol A was
found to be the most challenging to degrade, requiring longer durations
when compared to 17-ethynyl estradiol which offered the least resis­
tance to degradation. The estrogenic nature of the products formed by
degradation was found to be significantly lesser when compared to the
original EDCs, implying the process to be safe and repeatable (Solcova
et al., 2016). Decabromodiphenyl ether is an emerging pollutant finding
use as a flame retardant. The major challenges posed by this pollutant lie
in its resistance to degradation and capability to accumulate in organ­
isms. The removal of decabromodiphenyl ether was made possible by
the utilization of TiO2 photocatalysts in conjunction with phytor­
emediation techniques through wetland plants. The conjunctive system
was found to be highly effective in the removal of the EDC, with the

Table 6
Applications of TiO2 in the removal of endocrine disrupting compounds (EDCs) from water.
Dopant Compound targeted Intended use of Remarks References
compound

Gold (Au) Triclopyr Herbicide The presence of ozone was found to greatly enhance the removal Maddila et al.,
process, with 100% removal reported in 2 h. It was also possible to (2015)
recover the catalyst and use it in successive cycles while retaining the
performance.
Gold (Au) 2,4-dichlorophenoxyacetic acid Herbicide The TiO2 base material chosen to create the nanobelts were found to Chenchana et al.,
have a profound influence on the quality. The incorporation of Au (2019)
nanoparticles further improved the efficiency of photocatalysis, to
produce a non-toxic water product.
Gold (Au) Phenol Intermediaries in The shape of the dopant molecules determined the nature of the T�
oth et al., (2019)
synthesis intermediate products formed.
Palladium 2,4-Dichlorophenoxyacetic acid Herbicide The junction between the dopant and base material was specifically Merenda et al.,
(Pd) Methylene blue Dye modified by varying the concentrations used. Unattached distribution (2019)
of the dopant molecules led to optimum results.
Nitrogen (N) Thiamethoxam Insecticide Photocatalysis and photoelectrocatalysis were both found to occur in Maulidiyah et al.,
Iron (Fe) the degradation of the pesticide. Functioning under visible and UV light (2017)
was shown to be possible in both processes.
Zirconium 4 – nitrophenol Insecticide Exceptional reuse ability was observed in the co-doped nanoparticles. Naraginti et al.,
(Zr) Methylene blue Dye The size and distribution of the dopants led to an increase in the (2015)
Silver (Ag) Methyl orange Dye efficiency of the catalyst with an increase in dopant concentration.
Magnesium Paracetamol Analgesic An increase in the zeta potential accompanied the decrease in band gap da Silva et al.,
(Mg) Diclofenac sodium Anti-inflammatory energy after doping. Introducing supports such as silica enhanced the (2016)
Rhodamine B drug degradation process further.
Dye
Palladium MethylparabenEthylparaben Cosmetics Rate was found to be directly proportional to the number of carbon Gomes et al.,
(Pd) PropylparabenButylparabenBenzylparaben atoms present in the paraben compound. The results obtained showed (2017)
Platinum Ag and Pd to be well suited for the function of dopant, owing to the
(Pt) ability to influence the reaction even at low concentrations.
Silver (Ag)
Gold (Au)
Tungsten Sulphamethoxazole Antibiotic An increase in the concentration of the doped catalyst was Ioannidou et al.,
accompanied by a transition from first order to zero order reaction (2017)
mechanism. The presence of pollutants slows down the degradation
process in wastewater samples. An increase in the anatase content was
also noted after doping.
Silver (Ag) Sulphamethoxazole Antibiotic For UV-C, Ag showed the best performance in the degradation of the Zanella et al.,
Copper drug while co-doping also exhibited promising results. Au proved to be (2018)
(Cu) the most effective in presence of stimulated solar radiation. No major
Gold (Au) decrease in performance was noted over three cycles.
Nitrogen (N) 4-chlorophenoxyacetic acid Herbicide The introduction of hydroxyl groups into the catalyst resulted in the Abdelhaleem and
formation of hydrogen bonds which in turn led to better catalytic Chu, (2017)
activity. The rate of degradation was found to increase after reuse.
– Malathion Pesticides The presence of an electron acceptor such as Na2S2O8 significantly Vela et al., (2018)
Fenotrothion improved the degradation of the pesticides. TiO2 P25 was found to be
Quinalphos more suitable for the photocatalytic degradation of the pesticides than
Vinclozoline Kronosvlp 7000. Malathion was found to be the fastest to degrade while
Dimethoate Fenarimol offered the most resistance.
Fenarimol

15
K.P. Gopinath et al.
product reported to be non-toxic. Both rice and reed were found to be
excellent plants in phytoremediation, with TiO2 photocatalysis
increasing the uptake of the compound by the plants (Chow et al., 2017).
Studies have also shown the utilization of TiO2-based composites in
the removal of EDCs from aqueous media. The primary advantage pre­
sented by this approach lies in the amalgamation of properties of the
parent molecules used to make the composite. Cardanol based pro­
phyin/TiO2 composites have been used to remove 4-nitrophenol from
wastewater. They are advantageous as cardanols are extracted from
cashew nut shells, a waste product in the cashew industry, and hence
have an environmentally green approach and source. However it must
be made with extensive care as cardanols are highly toxic as such. Hence
they are combined with metals such as zinc, iron and cobalt before
impregnating them on the TiO2 catalyst (Vasapollo et al., 2011).
Recirculation type reactor designs can be incorporated with immo­
bilized catalyst. In one study a low cost and environmentally-friendly
TiO2-coated clay beads catalyst was used. The solid supporting was
proved by the clay matrix. The reactor was very economical to run due
to its low energy requirement. The immobilized catalyst has been
employed in the degradation of the water persistent pesticide Mono­
crotophos, a highly potent chemical compound, in a fixed bed reactor
(Sraw et al., 2018).
The removal of phenol by nanotube arrays impregnated with C3N4
via electrophotocatalysis was reported to yield performances nearly four
times better than pure TiO2photoelectrocatalysis due to the change in
band gaps (Wang et al., 2018). A three dimensional hydrogel
nano-structure created by the incorporation of graphene in TiO2 was
found to be exceptionally competent in the removal of bisphenol A even
in low concentrations by photoelectrocatalysis. The performance is
boosted in particular by the high electrical conductivity of graphene.
Outstanding regeneration properties were observed and the catalyst was
found to be effective even after 10 cycles. The incorporation of
adsorption alongside photoelectrocatalysis resulted in superior perfor­
mance in comparison to standalone methods (Zhang et al., 2018a,
2018b). Propyl paraben has been degraded in studies by using TiO2
nanotubes doped with WO3. The tendency of the photoelectrocatalyst to
remain functional despite repeated use is a major benefit and removal of
99% was noted in a span of 30 min at pH 3 (Martins et al., 2017).
9. Removal of microbes
TiO2 has also exhibited a significant amount of anti-microbial ac­
tivity (Matsunaga et al., 1985), and can be used as a disinfecting ma­
terial in water. Production of malondialdehyde by the bacteria E. coli by
a process called lipid peroxidation, which occurs when the cell mem­
brane suffers damage, is used as an index to measure the extent of
bactericidal activity of TiO2 when in an illuminated condition. After 30
min of illumination, an exponential increase in the production was
observed, and the kinetics determined from this indicated rapid cell
death, as well as a significant reduction in cell respiratory capabilities.
From this result, it was concluded that the presence of illuminated TiO2
causes irreparable damage to the cell membranes of the bacterial cells,
and the effect was more pronounced when higher dosages of TiO2 are
used. The occurrence of lipid peroxidation requires the presence of
radicals, and the process is self-propagated due to the formation of a
peroxy radical intermediate. MDA itself undergoes oxidative photo­
catalytic degradation, allowing for easy access to the cells themselves
(Maness et al., 1999). This property is also used for the killing of cancer
cells (Cai et al., 1991).
The effectiveness of bactericidal techniques are determined by their
effective disinfection time (EDT), which is the time taken for total
inactivation of bacteria in the absence of illumination, without the po­
tential for regrowth. For TiO2, no re-growth occurs in the following 60 h
in the dark, with the decline in the concentration of bacteria continuing
in the dark (Karunakaran, 2013).
The anti-microbial effects of photocatalysis have also been
16
Journal of Environmental Management 270 (2020) 110906
extensively explored elsewhere (Huang et al., 2008). Decreasing particle
size was found to cause an increase in the bactericidal capabilities, with
nano-TiO2 particles being the most effective (Prasad et al., 2011).
Immobilization of TiO2 removes the need for recovery and regeneration
of the catalyst, but is also linked to a decrease in photocatalytic effi­
ciency when compared to regular suspensions (Malato et al., 2013).
Increased permeability of ions into the cell membranes has also been
suggested as a possible mode of disinfection (Nasser et al., 2006). Toxins
released from dying bacterial cells are also degraded effectively by TiO2
(Kayano Sunada et al., 1998; Srinivasan and Somasundaram, 2003).
A variety of harmful microorganisms, such as Escherichia coli, pose a
threat to different water bodies around the globe. Typically, these mi­
crobes produce toxic compounds once they enter the human system, to
which they are carried by water used for different applications (Egli
et al., 2002). The life span of these organisms is governed by a plethora
of factors such as the external temperature, turbidity of water, pH of
water and the presence of other organisms (Laxma Reddy et al., 2017).
While sunlight has proven to be an effective means of killing many or­
ganisms, it is difficult to implement this idea on an industrial scale.
Other ideas include treatment with elements such as chlorine but the
generation of toxic compounds renders these methods impractical
(Mahmood et al., 2012). Microbes play a crucial role in transferring
illnesses to humans by using water as a medium of transportation. These
diseases range from simple colds to severe manifestations such as
cholera, caused by Vibrio cholerae, and typhoid, caused by Salmonella
typhi (Ashbolt, 2004). Furthermore, these pathogenic organisms also
affect aquatic organisms in a severe manner, resulting in the rapid
depletion of fish population in select locations around the globe (Leung
and Bates, 2013). In this light, it is crucial to develop and study pho­
tocatalysts which can catalyze the degradation of microorganisms an
energy-efficient and environmental-friendly manner.
TiO2 nanoparticles, applied in the form of a thin film, have proven to
be highly effective in the photocatalytic removal of E. coli from water.
The cells were inactivated in a rapid and efficient manner owing to the
expansion of the cell membrane when adsorbed by TiO2 and exposed to
light. Loss of the protoplasm has been mooted as a possible effect of the
membrane expansion alongside distortion of the cell, with the rapid
degradation of the acids also contributing to the expansion of the
membrane (Joost et al., 2015). TiO2 nanotubes have also found similar
anti-microbial applications in water purification, with E. coli and
Staphylococcus aureusthe target organisms. Both organisms were
degraded by more than 97% when exposed to 24 h of UV radiation in the
presence of the photocatalyst. On the other hand, TiO2 P25 nano­
particles did not exhibit similar anti-microbial nature when maintained
under the same conditions. This indicates that the bactericidal nature of
nanotubes is down to its shape, structure and the ability to generate a
large amount of hydroxyl radicals (Podporska-Carroll et al., 2015).
However, TiO2 P25 has been shown to be highly effective against mi­
crobes in the right conditions. Salmonella typhimurium and Listeria
monocytogenes were both degraded by the photocatalyst under UV
light. However, the latter was found to be more resistant to degradation
in comparison to the former. The mechanism followed was broadly
similar to other cases wherein the cell wall and membrane were
damaged leading to the spillage of inside contents. The concentration of
TiO2 nanoparticles greatly influenced the catalytic reaction, with a
concentration of 1 g/L yielding the best results (Long et al., 2014).
Doping with nitrogen has been proven to result in enhanced inactivation
of the bacterial species Escherichia coli, Pseudomonas aeruginosaandBa­
cillus cereus. Doping was carried out by using different nitrogen con­
taining compounds such as urea, ammonia and triethyl amine. Doping
with urea produced the best results in terms of rate of bacterial inacti­
vation and degree of completion. However, for B. cereus, only triethyl
amine doped TiO2 achieved total removal. As a consequence, it was
determined that the nature of the species was a major influence behind
the inactivation of bacterial species alongside the doping material
(Makropoulou et al., 2018). TiO2 nanopowder doped with nitrogen has
K.P. Gopinath et al. Journal of Environmental Management 270 (2020) 110906

also been explored as an anti-bacterial option in studies. The bandgap of
TiO2 was reduced by the introduction of the dopant, making photo­
catalysis quicker and possible with visible light. Introduction of fluorine
was also explored and a similar result was observed in terms of band gap.
However, while the nitrogen atoms were found in the interstices, fluo­
rine atoms were found on the surface. In both cases, the E. coli inacti­
vation efficiency was found to be superior to that of pure TiO2. The
synergy exhibited between TiO2 and the dopant was found to be a reason
behind the enhanced performance (Milosevic et al., 2017).
Studies have shown iron-, manganese- and magnesium-doped TiO2
as a highly efficient means of removing the influenza virus H1N1 from
water. The catalysis was shown to be possible in the presence of even a
weak source of visible light, with over 99% removal efficiency observed
in the span of 30 min. Furthermore, removal using UV light was also
possible but is not viewed as a feasible option due to the fact the reaction
can be carried out using visible light (Choi and Cho, 2018). Similarly,
TiO2 nanofibres doped with copper displayed excellent f2 virus and
E. coli removing properties. Simultaneous removal of both microor­
ganisms was shown to be possible under visible light and the reaction
was shown to be largely independent of the pH. The removal of the virus
was directly reliant on the concentration of the catalyst and the intensity
of light while having an inverse relationship with the virus quantity.
However, it was noted that the removal of the virus was higher when it
was present singularly than when present alongside the bacteria. This
can be attributed to competition for spaces during adsorption (Zheng
et al., 2018). TiO2 doped with copper and silver showed remarkable
efficiency in inactivating the virus bacteriophage MS2 and bacteria E.
coli. The novel nanowire benefitted from the strong anti-microbial
properties of silver particles and the performance was found to be su­
perior to those of pristine TiO2 or TiO2 doped with only copper or silver.
This can be put down to the mutually beneficent interactions between
copper, silver and TiO2. The water obtained after purification was
determined to meet the standards set for drinking water and declared
safe to consume, thereby indicating the potential of this novel photo­
catalyst for applications of larger dimensions (Rao et al., 2016). Simi­
larly, doping with manganese and cobalt has resulted in the yielded in
the enhanced inactivation of the virus coliphage MS2 when compared to
TiO2 P25. The introduction of dopants made possible the degradation of
viruses under visible light due to narrowing of the band gap. Co-doping
was found to produce the best results due to the favourable interactions
between the dopants, with over 99% of the virus concentration reduced
within 20 min. The reaction was also shown to be possible under arti­
ficial light but solar radiations returned the best results in terms of mi­
crobial inactivation (Venieri et al., 2015). Other examples of the
removal of microbial species using doped TiO2 are seen in Table 7.
10. Industrial applications and perspectives
Photocatalysis using titanium dioxide is an extensively researched
field with very great future potential, as evidenced by the large number
of materials and experiments conducted on industrial wastewater that
have been covered in this review. The TiO2-based materials that have
been synthesized have varying advantages, such as high reusability or
efficient degradation. Despite this, the actual applications of TiO2 for
industrial-scale applications in wastewater treatment are far and few in
between. This is likely due to the fact that TiO2 is a very expensive
material, and preparation of nanostructures and composites based on it
is also difficult, as well as the high energy requirements involved in
supplying visible and ultraviolet light.
From our review of various forms of TiO2, nanostructures proved to
be the most efficient modification of TiO2 for the purposes of photo­
catalysis. This is attributed to their increased surface area and enhanced
surface chemistry. Nanostructures are known to mineralise organic
compounds more effectively at more easily attainable mild operating
conditions. They are also more cost effective (once synthesized), and are
therefore preferable for large-scale and industrial applications.
11. Conclusion
Utilization of water on a large scale in households and various in­
dustries has resulted in widespread contamination of existing water
bodies and resources. The various common water pollutants have been

Table 7
Applications of TiO2 nanostructures in the removal of microbes from water.
Type of TiO2 Dopant Organism Remarks References
nanostructure targeted

Rutile TiO2 – Escherichia coli TiO2 was modified by hydrothermal means to make the utilization of solar radiation Song et al., (2016)
nanoparticles possible. Hydrogen peroxide was used as a solvent to carry out the modification and
to generate hydroxyl radicals.
Nanotubes Silver (Ag) E. coli The functionality of the catalyst was shown to improve significantly by incorporating Mangayayam et al.,
FeOx. The catalyst also exhibited highly promising reuse properties and could be (2017)
separated from the degraded bacteria easily.
Nanoparticles Silver (Ag) E. coli A core and shell structure was developed, leading to greater adsorptive surface area (Sreeja and Shetty, 2017)
and reusability. The degradation activity increased with an increase in the amount of
catalyst used and was inversely related to the concentration of cells.
Nanotubes Selenium E. coli Selenium nanoparticles drastically increased the surface density of the nanotubes, Bilek et al., (2019)
nanoparticles resulting in much higher catalytic performance.
Nanotubes ZnO S. aureus The structure of the catalyst and the Zn ions released by the dopant resulted in the Yao et al., (2018)
enhanced activity of the catalyst.
Nanotubes Silver (Ag) S. aureus The removal of S. aureus was accompanied by the removal of dyes such as methylene Viet et al., (2018)
blue and methylene orange from water. More than 99% of the bacteria was removed
in an hour.
Nanofibres Copper (Cu) Bacteriophage f2 The antimicrobial action was carried out in the presence of humic acid, commonly Cheng et al., (2019)
found in agriculture. The concentration of humic acid was found to be inversely
related to the overall efficiency of the catalyst. Humic acid also have a detrimental
effect on the reuse potential of the catalyst.
Nanoparticles – Bacteriophage The effectiveness was found to reduce in the presence of quartz, due to the possible Syngouna and
MS2 covering offered by quartz to the virus. The nanoparticles were shown to be effective Chrysikopoulos, (2017)
both in the presence and the absence of ambient light.
P25 nanoparticles – Cryptosporidium TiO2 was used in the form of slurry and was found to be highly efficient in the Abeledo-Lameiro et al.,
removal of the protozoan species. Furthermore, separation of the catalyst through (2016)
sedimentation was achieved.
Nanopowder Zinc (Zn) Candida albicans A removal efficiency of 95% is noted after 30 min. The synergy between Zn and Y Wang et al., (2014)
Yttrium (Y) S. aureus dopants leads to the increased production of hydroxide radicals which leads to more
efficient cell wall decomposition.

17
K.P. Gopinath et al.
enumerated, and the negative effects that they have on the human body
and on aquatic life when ingested have been briefly described. The
various physical and chemical features of TiO2 that make it highly
suitable as an AOP for the treatment of water have been analyzed, such
as its low cost, and high stability to chemical reactions and corrosion. Its
major limitations, which include the low efficiency of uptake of incident
radiation, and the difficulty of removal of TiO2 particles have also been
reviewed. The various mechanisms employed for photocatalytic degra­
dation employed by TiO2 have also been thoroughly reviewed. The
preparation of various modified forms of TiO2 by doping, immobiliza­
tion, and by the formation of composites and different types of nano­
structures have also been extensively studied, and specific applications
of these modified forms in the removal of several conventional and
emerging contaminants from water have been reviewed. The various
shortcomings of the developed modifications also received scrutiny, and
the best possible options available for water treatment after their
application in the design of photocatalysts were highlighted and their
salient features elucidated, with titanium dioxide photocatalysis as such
being a highly efficient water treatment method. The large volume of
existing literature and ongoing research indicates that this field of
research is a highly promising one, and further progress is inevitable.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
This research did not receive any specific grant from funding
agencies in the public, commercial or not-for-profit sectors.
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