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A Review on Nanomaterial as Photocatalysts for Degradation of Organic

Pollutants

Article in Journal of Fluorescence · July 2023

DOI: 10.1007/s10895-023-03332-x

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Journal of Fluorescence
https://doi.org/10.1007/s10895-023-03332-x

REVIEW

A Review on Nanomaterial as Photocatalysts for Degradation

of Organic Pollutants
Solomon S. Durodola1 · Olaniran K. Akeremale2 · Odunayo T. Ore1 · Ajibola A. Bayode3 ·
Hamza Badamasi4 · Johnson Adedeji Olusola5,6

Received: 11 May 2023 / Accepted: 29 June 2023

© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2023

Abstract
Eliminating hazardous organic contaminants from water is a major concern today. Nanomaterials with their textural features,
large surface area, electrical conductivity, and magnetic properties make them efficient for the removal and photocatalytic
degradation of organic pollutants. The reaction mechanisms of the photocatalytic oxidation of common organic pollutants
were critically examined. A detailed review of articles published on photocatalytic degradation of hydrocarbons, pesticides,
and dyes was presented therein. This review seeks to bridge information gaps on the reported nanomaterial as photocatalysts
for the degradation of organic pollutants under sub-headings, nanomaterials, organic pollutants, degradation of organic pol-
lutants, and mechanisms of photocatalytic activities.

Keywords Photocatalytic degradation · Organic pollutants · Nanomaterials

Introduction Kubiak et al. 2019; Ramzan et al. 2019). A report by Adeel

and his colleagues (2018) revealed that the world’s human
Water is an essential resource for life on earth; it is a known population of about 7 billion discharges approximately
fact that fresh water is an important necessity for our health. 30,000 kg/yr of natural steroid estrogen and an additional
Recent population growth and globalization have resulted in 700 kg/yr of synthetic estrogens solely from the practice of
a rapid spread of industries and, as a result, environmental birth control using pills. The introduction of these pollut-
pollution (Bayode et al. 2020, 2021). In recent times, much ants into the water bodies can be direct through the disposal
attention has been shifted to the release of toxic organic of untreated industrial wastes or indirectly through anthro-
pollutants such as synthetic dyes, pharmaceuticals, steroid pogenic activities, farm run-offs, and wastewater treatment
estrogens, pesticides, etc. into the water bodies. Synthetic plants.
dyes are among well-known occurring organic pollutants, These contaminants are detrimental to aquatic ecosystem
it has been reported that about 280,000 tons of dyes are quality and human health, impairing recreational activities
discharged in industrial effluents annually (Jin et al. 2007; and other uses of water (Wang and Yang 2016). Some of
1
Department of Chemistry, Obafemi Awolowo University,
* Solomon S. Durodola 220005 Ile‑Ife, Nigeria
solomonsun77@gmail.com 2
Department of Science and Technology Education, Bayero
Olaniran K. Akeremale University, 3011 Kano, Nigeria
okakeremale.ste@buk.edu.ng 3
Department of Chemical Sciences, Faculty of Natural
Odunayo T. Ore Sciences, Redeemer’s University, P.M.B. 230, Ede 232101,
oreodunayo@yahoo.com Nigeria
4
Ajibola A. Bayode Department of Chemistry, Federal University Dutse, Dutse,
bayodea@run.edu.ng Jigawa State, Nigeria
5
Hamza Badamasi Department of Geography and Planning Science, Ekiti State
hamza.badamasi@fud.edu.ng University, Ado Ekiti, Ekiti State, Nigeria
6
Johnson Adedeji Olusola Institute of Ecology and Environmental Studies, Obafemi
johnsonolusola06@gmail.com Awolowo University, Ile‑Ife 220005, Nigeria

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Vol.:(0123456789)
 Journal of Fluorescence

these organic pollutants are classified as persistent organic nanomaterials, and semi-conductor nanomaterials. In addi-
pollutants (POPs) because they bio-accumulate and are not tion, the application of these nanomaterials in the removal of
degradable when they enter water bodies. These organic pollut- hydrocarbons, pesticides, and dyes was elucidated. Finally,
ants can easily travel from the point of contamination to the mechanisms by which photocatalysis occurs were
a pristine area or where they have never been produced illustrated.
(Krithiga et al. 2022).
The treatment of wastewater has recently been the subject
of numerous scientific investigations. The removal of multi- Nanomaterials
component contaminants from water resources requires the
utilization of efficient water treatment techniques. The wide Nanomaterials are defined as materials with a size or
usage of biological and physicochemical treatment processes one of their dimensions that falls within the range of 1 to
in the industry is due to the simplicity of design as well 100 nm (Laurent et al. 2010; Naseem and Durrani 2021).
as the enhanced remediation capacity associated with the The unique properties of nanomaterials when compared
techniques (Crini and Lichtfouse 2019). Nevertheless, the to their bulk counterparts are significantly different, and
higher energy consumption associated with these conven- their size-dependent effects become more noticeable at the
tional water treatment technologies has been a major impedi- nanoscale level. Surprisingly, by changing the shape and
ment in the industry (Maktabifard et al. 2018). Finding a size at the nanoscale level, nanomaterials produce a dis-
single treatment method that completely covers the efficient tinct character with new features and powers (Kolahalam
removal of all varieties of organic pollutants has become et al. 2019). Nanomaterials occur in different shapes like
challenging due to the complexity and variety of organic nanorods, nanosheets, spherical, oval, cubic, cluster, flower,
chemicals used. This led to the development of alternative triangular, needle-like, branched, etc. as illustrated in Fig. 1.
treatment technologies that will ensure the removal of recal- Based on their form, size, characteristics, and constituents,
citrant organic pollutants. Some of these advanced treatment nanomaterials also exist in different forms. These include
techniques comprise UV-illuminated processes, membrane- polymeric nanomaterials, lipid-based nanomaterials, semi-
based processes, and advanced oxidation processes (Abdel- conductor nanomaterials, metal nanoparticles, and carbon-
Fatah 2018; Boulkhessaim et al. 2022; Gaur et al. 2022). The based nanomaterials.
use of non-destructive physical techniques including floccu-
lation, reverse osmosis, and adsorption on activated charcoal Metal‑based Nanomaterials
results in secondary pollution because the contaminants are
only transferred to new media, hence, there is a need for an Metals of trivalent and divalent ions are used as the build-
effective environmentally benign method for the removal of ing blocks for the creation of metal oxide nanoparticles
these pollutants. The main advantage offered by advanced (MONPs). They can be prepared using different techniques
oxidation processes is that it ensures the effective degrada- such as chemical and photochemical, due to their excellent
tion of organic pollutants via the generation of highly reac- electrical, optical, magnetic, and catalytic properties MONPs
tive hydroxyl radical, as opposed to conventional treatment are useful in many fields like photocatalysis (Khalafi et al.
processes that only ensures the physical transformation 2019), catalysis (Jalpa et al. 2019), sensors, and heavy metal
of pollutants without necessarily degrading them (Cheng removal (George et al. 2018). Metal oxide nanoparticles
et al. 2016; Krishnan et al. 2017). Among advanced oxida- (NPs) have attracted a lot of attention in many fields of sci-
tion processes, photocatalytic degradation has proven to be ence like chemistry, physics, and material sciences (Panji
a quick, cost-effective, and environmentally benign method et al. 2016). For instance, Zinc oxide has good photocatalytic
of removing persistent contaminants from water (Khan and activity because of its unique properties like large surface
Pathak 2020; Samuel et al. 2023). area, super oxidative capability, high electrochemical stabil-
Several recent studies have described the photocatalytic ity, and low toxicity enable it to have a good capacity for the
degradation of organic pollutants using different photocata- adsorption of small molecules. According to Naseem and
lysts (Mei et al. 2022; Rostami et al. 2022; Silvestri et al. Durrani (2021), ­TiO2 is the most exceptional photocatalyst,
2022; Subhiksha et al. 2022; Tang et al. 2022; Wang et al. it has low selectivity, making it ideal for degrading a variety
2022; Kanakaraju and Chandrasekaran 2023; Pattnaik et al. of pollutants like polycyclic aromatic hydrocarbons (Guo
2023). However, these studies have been singularly focused et al. 2015), chlorinated organic compounds (Ohsaka et al.
on one particular kind of photocatalyst such as metal-based 2008), dyes (Lee et al. 2008), phenols (Nguyen et al. 2016),
photocatalysts or natural minerals. The present review was Macro and micron size plastics (Nabi et al. 2021), Cyanide
designed to focus on the use of nanomaterials as photo- (Chiang et al. 2002), Nitrophenols (Augugliaro et al. 1991),
catalysts in the degradation of organic pollutants. Here, Chlorpyrifos, Cypermethrin, and Chlorothalonil (Affam and
we described metal-based nanomaterials, carbon-based Chaudhuri 2013).

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Journal of Fluorescence

Fig. 1  Different shapes of nanoparticles. (Adapted from Hamida et al. 2020)

Carbon‑based Nanomaterials mostly exhibit metallic behaviour. CNTs have unique and
beneficial characteristics that make them suitable for a vari-
Carbon-based nanomaterials have recently attracted sig- ety of electronic, biomedical, and other industrial applica-
nificant attention due to their outstanding physicochemical tions. These characteristics include distinctive optical char-
features like large surface area, excellent acid stability, and acteristics, high thermal, low cost, high surface area, high
thermal resistance that make them viable candidates for a mechanical strength, and electrical conductivity (Chavali
variety of many applications (Liu et al., 2022; Son et al., and Nikolova, 2019).
2021). Carbon-based nanomaterials are classified accord-
ing to their geometrical structure. Carbon nanostructures Semiconductor Nanomaterials
include particles that might be tube-shaped, horn-shaped,
spherical, or ellipsoidal. Nanoparticles having the shape of A wide range of various substances are used to create semi-
tubes are called carbon nanotubes; horn-shaped particles are conductor nanocrystals (NCs). They are known as II-VI, III-
nanohorns, and spheres or ellipsoids belong to the fullerene V, or IV-VI semiconductor nanocrystals, depending on the
group (Zaytseva & Neumann, 2016). Some of the shapes of periodic table groups into which these elements are formed.
carbon-based nanomaterials are shown in Fig. 2. They exhibit both metallic and non-metallic qualities. They
Carbon nanotubes (CNTs) are of two types i.e. single also have wide band gaps, modifying them demonstrates
walled carbon nanotubes (SWCNTs) and multi-walled varied properties and exhibits large band gaps. They are
carbon nanotubes (MWCNTs). They have high strength, commonly used in photocatalysis, electronic devices, drug
favorable electron affinities, and good electrical conductivity delivery, solar cells, and environmental remediation (Fang
(Scida et al., 2011, Zhao et al., 2015). The carbon allotropes et al. 2020; Sahu 2019).
known as carbon nanotubes (CNTs) are made of graphite
and are in tabular form. The outside diameter of the tubes Applications of Nanomaterials
ranges from 3 to 30 nm and had at least two layers. Electri-
cally, Single-walled carbon nanotubes can be further divided Unique properties of nanoparticles like mechanical strength,
into metallic and semiconducting SWCNTs (s-SWCNTs large surface area, optically active, electronically active, high
and m-SWCNTs), whereas multi-walled carbon nanotubes thermal conductivity, and chemically reactive make them

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 Journal of Fluorescence

Fig. 2  Different shapes of carbon based nanomaterials. (Adapted from Yuan et al. 2019)

suitable for various applications. Nanomaterials have been classified as persistent organic pollutants (POPs). The salient
used in the development of nanodevices that are found use- features of POPs include the followings.
ful in pharmaceutical and biomedical applications (Loureiro
et al. 2016; Martis et al. 2012; Nikalje 2015). Iron oxide par- 1. Persistence; POPs are not easily degradable either by
ticles such as magnetite (­ Fe3O4) or its oxidized form haema- chemical, physical, or biological degradation. They can
tite ­(Fe2O3) are the most useful for biomedical applications retain in the soil, water, and air for decades.
(Ali et al. 2016). They are also used in wastewater treatment, 2. Bioaccumulation; they build up inside the body to a
due to their high surface-to-mass ratio, natural nanoparticles point where they could be dangerous to both the envi-
(NPs) are crucial in the solid/water partitioning of pollut- ronment and human health.
ants as they can either be absorbed onto their surface, co- 3. The ability to travel vast distances; POPs can travel
precipitated during the synthesis of natural NPs, or trapped through environmental media to far locations where they
by NPs that had contaminants adsorb to their surface. (Khan have never been utilized or produced, including the Arc-
et al. 2019). They are used as sensors, biosensors, and in tic regions.
the modification of electrodes to enhance their performance 4. POPs are very hazardous and endanger both human
capability. NPs are found useful in energy storage devices, and environmental health (Alharbi et al. 2018). It has
and also applicable in the form of electrodes (Li et al. 2019), been reported that some health-related issues like
however the importance of nanomaterials in the removal reproductive defects, preterm and immune toxicity
of organic contaminants cannot be overemphasized (Veisi are associated with exposure to organochlorine pesticides
et al. 2019). (Dalvie et al. 2004; Longnecker et al. 2001; Oyekunle
et al. 2021), diseases like cancer, obesity e.t.c is found
to associate with Polychlorinated biphenyl (Penell et al.
Organic Pollutants 2014; Roos et al. 2013), also many PAHs have been
reported to possess carcinogenic and genotoxic proper-
Organic pollutants are toxic synthetic chemical compounds ties (Oyekunle et al. 2019; Rengarajan et al. 2015).
that can persist in the environment over a long period of
time. When their levels exceed the permissible limits, they
become poisonous molecular compounds that can affect Hydrocarbons
humans and cause many diseases. The main sources of these
organic compounds are industrial items such as petroleum Hydrocarbon contamination in the environment is a very
hydrocarbons, detergents, plastics, organic solvents, dyes, serious issue whether it comes from petroleum, insecti-
and insecticides. Some of these pollutants can resist degra- cides, or other hazardous organic materials. Being poi-
dation and bio-accumulate and remains for decades, they are sonous to all forms of life, petroleum hydrocarbons raise

13
Journal of Fluorescence

serious concerns about environmental pollution. Polycyclic Dyes

aromatic hydrocarbons are organic pollutants that are typi-
cally colorless, white, or light-yellow solid substances com- Dyes are compounds that give color to a surface when
posed of two or more fusions of carbon and hydrogen aro- applied through a process that modifies if only temporarily,
matic rings (Abdel-Shafy and Mansour 2016; Suman et al. the crystal structure of the colored substances (Bafana et al.
2016). The highest water solubility is seen in low molecular 2011). They are substances, both natural and artificial that
weight PAHs compounds like naphthalene, acenaphthene, add colour to the world and enhance its beauty.
and acenaphthylene while solubility declines with increas- A group of organic chemicals known as textile dyes are
ing molecular mass. They are categorized as semi-volatile frequently regarded as contaminants and are mostly released
chemicals because they have a low vapour pressure. How- into wastewater as a result of chemical textile finishing pro-
ever, as molecular weight increases, so do their boiling and cesses. According to estimates, over 10,000 different types
melting points. The International Agency for Research on of dyes and pigments are utilized in industry, and more
Cancer (IARC) has identified sixteen (16) PAHs that pose than 7 million tons of synthetic dyes are produced annually
serious risks to human health because of their propensity around the world (Ogugbue and Sawidis 2011; Robinson
to cause cancer and mutagenesis. These are Acenaphthene, et al. 2001). Azo dyes are the most used dyes and account
Benzo(k)fluoranthene, Naphthalene, Benzo(a)anthracene, for more than 60% of total dyes (Gürses et al. 2016; Shah
Chrysene, Benzo(a)pyrene, Acenaphthylene, Fluoran- 2014) and approximately 70% of all the dyes used in the
thene, Dibenzo(a,h)anthracene, Benzo(b)fluoranthene, industry are azo dyes (Lipskikh et al. 2018; Berradi et al.
Benzo(ghi)perylene, Phenanthrene, Benzo(j)fluoranthene, 2019). Azo compounds have been used in a variety of sci-
Indeno(1,2,3,d)pyrene, Anthracene, and Pyrene (European entific and industrial fields, including color waxes, oils,
Union 2005; Keith and Telliard 1979; Yun et al. 2017; gasoline, solvents, polishes, paper, varnish, food, leather,
Zhang et al. 2020). plastics, cosmetic medicine, and automobiles (Al-Khuzaie
and Al-Majidi 2020; Dixit et al. 2007; Guerra et al. 2018;
Patel and Dixit 2014).
Pesticides Additionally, they are employed as antibacterial, anti-
diabetic, and anti-tumor agents (Adu et al. 2020; Rabbani
A pesticide is any substance that is used to eradicate, et al. 2020).
deter, or restrain specific plant or animal life forms that are
regarded as pests. Most of the chemicals used in the pro-
duction of pesticides belong to the family of carbamates, Photocatalytic Degradation of Organic
organochlorides, pyrethroids, organophosphates, and other Pollutants Using Metal Oxide Nanomaterials
substances (Intisar et al. 2022). Among these classes of pes-
ticides, organochlorine is the most dangerous with deleteri- Photocatalysis is the process that takes place when a light
ous effects on human health (Rani et al. 2017). An organo- source interacts with the semiconductor components that
chlorine compound is an organic compound that has at make up the photocatalyst on its surface (Adeola et al.
least one chlorine atom covalently attached to it as the main 2023; Alegbeleye et al. 2022; Ore et al. 2023). However,
functional component. They have a wide range of appli- this process depends on in-situ photogenerated hydroxyl
cations due to their wide structural variety and divergent radicals ­(OH−), superoxide radicals ­(O2), and positively
chemical properties, OCPs are chlorinated hydrocarbons charged holes (𝘩 +) which completely degrade organic
that were extensively used in agriculture and mosquito con- contaminants. Oxidation from photogenerated holes and
trol from the 1940s to the 1960s. Examples of compounds reduction of photogenerated electrons are the two simul-
in this group include DDT, DDE, methoxychlor, Lindane, taneous processes that take place during this process
Endosulfan, Chlordane, Diclof-methyl, Dieldrin, toxaphene, (Adeola et al. 2022). Consequently, the process of remov-
mirex, Aldrin, DDD, and Benzene hexachloride. Up until ing impurities by photocatalysis is effective, ecologically
1980, the use of these organochlorine pesticides (OCPs) was benign, inexpensive, and simple (Zhang et al. 2018). Jiang
extremely successful; however, suggestions for controlled et al. (2015) synthesized an aggregate silver oxide nano-
usage of OCPs were made due to the serious health risks particle that demonstrated excellent photocatalytic perfor-
they posed, including the potential for cancer, endocrine mance in both artificial and natural light. According to
disruption, immune system disorders, reproductive issues, the result, methyl orange decomposed under near-infrared
and other chronic diseases as a result of their persistence light in 40 min and under sunlight, artificial ultraviolet, and
or strong resistance in ambient environmental conditions. visible light in 120 s. F
­ e3O4 mesoporous carbon shell was
(Augustijn-Beckers et al. 1994; Kumar et al. 2013; Syafrudin used by Angamuthu et al. (2017) to develop nanomaterial
et al. 2021). that was used to degrade the dye methylene blue, with this

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 Journal of Fluorescence

artificial nanomaterial, methylene blue dye was degraded The mechanism of the degradation of EBT and murexide
with excellent catalytic activity. In 2019, Kubiak and his is illustrated in Eqs. (1)–(4) below.
colleagues published a paper on the synthesis of extremely
crystalline photocatalysts based on T ­ iO2 and ZnO for the Fe2 O2 + hV → Fe2 O3 (e− + h+ ) (1)
oxidation of organic contaminants. The created T ­ iO2-ZnO
binary oxide systems exhibit remarkable photodegrada- h+ (VB) + H2 O → OH. (2)
tion efficiency of organic contaminants of 90%. In their
2018 study, Harun et al. (2018) examined the effec- e− (CB) + O2 → O−2 (3)
tiveness of photocatalytic degradation in the absence and
presence of a photocatalyst as well as the impact of a light
source for the decolorization of Congo red dye under solar EBT∕Murexide + h+ + O−2 + OH → Degradation products
and UV light, T ­ iO2 was the catalyst utilized. Sunlight and (4)
artificial UV light both have a 30 min degradation rate of
the dye of up to 64.72% and 66.99%, respectively. Photo-
catalytic oxidation of phenol was studied by Hayat et al. Photocatalytic Degradation of Organic
(2011), it was reported that the Photocatalytic degradation Pollutants Using Carbon‑based
efficiency of phenol was 97% using nano NiO and UV Nanostructures
laser irradiation was accomplished in a short amount of
time as compared with conventional setups like lamps. Jassal Carbon-based nanostructures could be viewed as an ideal can-
and his coworkers (2015) reported photocatalytic deg- didate for enhancing the photocatalytic effectiveness of nano-
radation of Eriochrome Black T (EBT) and Malachite MG) particles by facilitating the transferring of photo-generated
Green with degradation efficiency of 94.15% and 76.13% electrons and reducing charge recombination.
for MG and EBT respectively using nanocubes. Ullah and One report by Nguyen et al. (2018), utilized graphene
Dutta (2008) used Mn doped ZnO NPs for photodegra- oxide (GO) as a support for the deposition of ZnO NPs
dation, and their photocatalytic effectiveness was deter- through a simple hydrothermal process, in which GO pre-
mined by the degradation of aniline and MB dyes under vent ZnO particle from aggregation as well as the efficient
visible light from a tungsten lamp. It was reported that separation of photo-generated electrons and holes ­(e− and
ZnO-Mn2+ NPs can be employed as a better photocatalyst ­h+) on the surface of the ZnO. The nanocomposite was suc-
than undoped ZnO since Mn doped ZnO demonstrated cessfully used for the degradation of methyl orange (MO)
a 50% higher degradation rate than undoped ZnO. The during which more than 95% of MO was decomposed at
potential of cobalt and cobalt oxide nanoparticles as nano- optimal conditions.
catalysts for the degradation of murexide and EBT dye in In a work reported by Atchudan et al. (2017) that involves
wastewater in the presence of sunshine was investigated by the degradation of MO and MB using ­TiO2-GO nanocom-
Adekunle et al. (2020). The highest degradation efficiency posite, a maximal degradation efficiency of 84% and 100%
was reported for chemically synthesized Co-nanoparticles were obtained for MO and MB respectively by using a two-
(43.6%) toward murexide dye at 25 mg loading and 40 min step sol-gel deposition technique. Durmus et al. (2019)
exposure time, while the highest degradation efficiency for synthesized a GO/ZnO nanocomposite catalyst and was
microwave-synthesized ­Co3O4 nanoparticles (39.4%) was successfully used as a photocatalyst to degrade the basic
reported for EBT at 10 mg loading and 40 min sunlight fuchsin (BF) dye. The degradation of BF dye, a model
exposure time. Adekunle and his colleagues worked on a compound in an aqueous media, was found to be more
study comparing the photocatalytic degradation of dyes effectively photocatalyzed by the nanocomposite structure
in wastewater utilizing solar-enhanced iron oxide ­(Fe2O3) because it decreased the band gap of ZnO nanoparticles.
nanocatalysts made by chemical and microwave processes. Khataee and his co-workers in their work on photocatalytic
According to the research, microwave-produced F ­ e 2O 3 degradation of organic dyes illustrate how photogenerated
nanoparticles had the highest degradation rates for the electron-hole pairs by the synthesized nanoparticle facilitate
dyes Murexide (98%) and EBT (96%) at a 25 mg loading the degradation of organic pollutants. It was observed that
and 40 min exposure, whereas chemically produced ­Fe2O3 when ­TiO2 is irradiated with light, an electron excites out
nanoparticles had the highest degradation rates for the dye of its energy level, leaving a hole in the valence band and
Murexide (15.2%) at a 5 mg loading and 30 min sunlight electrons are promoted from the valence band to the T ­ iO2
exposure. With 15 mg of catalyst loading and 40 min of conduction band, resulting in electron-hole pairs (Khataee
exposure, the chemically produced ­Fe2O3 nanoparticles in and Kasiri 2010) as shown in Fig. 3 below.
EBT degraded at a rate of 21.4%. (Adekunle et al. 2021). Jo et al. (2017) worked on the photocatalytic degrada-
tion of oxytetracycline and Congo red using Cobalt-titanium

13
Journal of Fluorescence

Fig. 3  General mechanism of the photocatalysis on ­TiO2 nanomaterial. [Reprinted from Khataee and Kasiri 2010]

mixed metal oxides. It was discovered that the photocatalytic A list of different percentages of degradation of some
oxidative destruction of oxytetracycline and Congo red was organic pollutants by some nanomaterials as reported in
greatly improved by heterojunction formation between a low some literature is given in Table 1 below.
concentration of discrete ­Co3O4 nanoparticles and anatase
titania, which was further enhanced by the addition of trace
Graphene oxide as shown in Fig. 4.

Fig. 4  Proposed mechanism for the photocatalytic degradation of organic pollutants by C

­ o3O4/TiO2/GO nanocomposite. (Reprinted from Jo
et al. 2017)

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 Journal of Fluorescence

Table 1  Percentage degradation Organic pollutant Catalyst % degradation References

of some organic pollutants
using nanomaterials EBT Bi2WO6 NPs 74 Lai et al. (2019)
EBT KZnHCF 76.13 Jassal et al. (2015)
MG KZnHCF 94.15 Jassal et al. (2015)
EBT CO3O4 NPs 39.4 Adekunle et al. (2020)
Paracetamol TiO2-G 88 Vaiano et al. (2018)
Malathion Zn2+-doped ­TiO2 98 Nasseri et al. (2018)
EBT SnO2 NPs 94 Srivastava and Mukhopadhyay (2014)
EBT ZnFe2O4 NPs 92 Ikramullah et al. (2020)
Metronidazole BiVO4 /N-rGO 95 Appavu et al. (2018)
EBT ZnO 90 Kaur and Singhal (2015)
EBT BiFeO3 NPs 64.6 Khan et al. (2020)
Congo Red BiVO4 /N-rGO 95 Appavu et al. (2018)
EBT Fe2O3 96 Adekunle et al. (2021)
Murexide Fe2O3 98 Adekunle et al. (2021)
Chloramphenicol BiVO4 /N-rGO 93 Appavu et al. (2018)
Murexide TiO2 NPs - AC 98 Davoodi et al. (2014)
Methylene blue BiVO4 /N-rGO 98 Appavu et al. (2018)
Murexide ZnO NPs 45.1 Alkhateeb et al. (2007)
Murexide TiO2 NPs 60.1 Alkhateeb et al. (2007)
Ciprofloxacin ZnO/ZnAl2O4/rGO 90.6 Ni et al. (2018)
Murexide BiFeO3 NPs 83.4 Khan et al. (2020)
Phenol Fe-Fe3O4-GO 87 Le et al. (2018)
Phenol Fe3O4-GO 75 Le et al. (2018)
Endosulfan TiO2 99 Sivagami et al. (2016)
Chlorpyrifos TiO2 94 Sivagami et al. (2016)
Amido black dye Co/TiO2 90 Ali et al. (2018)
Azo dye CdS 95 Senasu and Nanan (2017)
Methylene blue NiO-ZnO 97 Rogozea et al. (2017)
Methylene blue AKB 94 Zhou et al. (2018)
Rhodamine B BiOI/N-doped rGO 83 Lu et al. (2018)
Remazol yellow RR dye ⍺-Fe2O3 77 Bhuiyan et al. (2020)
Acid blue 74 dye Ag-Ag2O-ZnO/GO 90 Umukoro et al. (2016)

Mechanism of Photocatalytic Activity organic pollutant species into a partially oxidized radical
cation ­(Dye+) is accomplished by injecting an electron into
A chemical reaction known as photocatalysis is initiated by the conduction band of the nanoparticle. The system-
light and takes place when the compound comes into contact dissolved oxygen and these trapped electrons combine to pro-
with photons with high enough energies to trigger free radi- duce superoxide radical anions ­(O2−), which in turn lead to
cal processes. The mechanism of organic pollutant photo- the creation of hydroxyl radicals ­(OH−). The oxidation of
oxidation can take place in two ways, direct or indirect. organic molecules is mostly caused by these ­OH− radicals
as represented by Eqs. (5) and (6) below.
(a) Direct degradation mechanism
Dye + hv → dye∗ (5)
This type of photocatalytic degradation takes place
under visible light because of the ease of absorption of Dye∗ + semiconductor ⟶ dye+ + TO−2 (6)
some visible light. This mechanism involves the excitation
The entire process can be summarized using the Fig. 5
from the ground state of the organic pollutant to the triplet
below.
excited state (organic pollutant) under visible light photons
(> 400 nm). A further transformation of the excited state
(b) Indirect dye degradation mechanism.

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Journal of Fluorescence

Fig. 5  Pictorial representation of direct organic pollutant degradation process. (Adapted from Ajmal et al. 2014)

The photocatalytic reaction starts when a photoelectron which may participate in further oxidation but also pre-
is promoted from the filled valence band of a semicon- vents electron-hole recombination, maintaining electron
ductor photocatalyst when it is exposed to radiation. The neutrality within the semiconductor molecule.
energy of the absorbed photon (hѵ) is equal to or higher
O2 + e− (CB) → O−2(ads) (9)
than the semiconductor photocatalyst’s band gap. A hole
­(hVB+) is left in the valence band because of excitation,
The hydroperoxyl radical (­ HO2−) that is formed from the
consequently leading to the generation of an electron and
superoxide ­(O2−) is protonated to form H­ 2O2, which further
hole pair ­(e−/h+) as illustrated in Eq. (7) below.
dissociates into highly reactive hydroxyl radicals ­(OH−).
TiO2 + hv(UV)→ TiO2 (e− (CB) + h+ (VB)) (7) O−2(ads) + H+ ↔ HOO.(ads) (10)
The water and the photogenerated holes in the valence
band subsequently combine to form the hydroxyl radical 2HOO.(ads) → H2 O2(ads) + O2 (11)
(Eq. 8).
.
H2 O(ads) + h+ (VB) → OH.(adS) + H+(ads) (8) Organic pollutant + OH. → CO2 + H2 O
(12)
(organic pollutant intermediates)
Adsorbed organic molecules or those that are very near
the catalyst surface are attacked non-selectively by the
hydroxyl radical that forms on the irradiation semiconduc- Organic pollutant + h+ (VB) → Oxidation products (13)
tor surface, and this causes them to mineralize to a degree
depending on their structure and stability level. Organicpollutant + e− (CB) → Reductionproducts (14)
While the photogenerated hole (­h VB + ) reacts with
Both oxidation and reduction processes occur frequently
surface-bound water or O ­ H− to create the hydroxyl radi-
on the surface of the photoexcited semiconductor photocata-
cal, the electron in the conduction (­ eCB−) is taken up by
lyst. The overall process of these reactions can be summarized
the oxygen to create an anionic superoxide radical (­ O2−),
using Fig. 6 below.

13
 Journal of Fluorescence

Fig. 6  Pictorial representation of indirect organic pollutant degradation process. (Adapted from Ajmal et al. 2014)

Conclusion photocatalytic characteristics of various materials, as well

as their interactions with certain pollutants, is therefore
The increase in organic contamination of water bodies critical for achieving optimal degradation efficiencies. It is
through anthropogenic activities is a major concern due recommended that further research should be directed into
to their bioaccumulation and adverse health effects on man the development of highly efficient photocatalytic materi-
and his environment. This paper reviewed studies address- als for the abatement of these recalcitrant organic pollut-
ing the photocatalytic degradation of organic pollutants. ants. Also, attention should be focused on improving the
It was observed that strong oxidizing agents like hydroxyl selectivity of nanomaterials for the removal of these pol-
and related radicals can break down any organic pollutant lutants so that photocatalytic technology can gain ground
into smaller degradation products that are either practi- in industrial applications.
cally innocuous or less toxic. Different organic contami-
nants like hydrocarbons, steroid estrogens, pharmaceuti-
Author Contributions Solomon S. Durodola: Conceptualization, Meth-
cals, dyes, pesticides, phenols, etc. can be photo-oxidized odology, Investigation, Writing – original draft, Writing – review &
by hydroxyl radicals. Filtration, ion exchange, coagulation/ editing. Olaniran K. Akeremale: Writing – original draft, Writing –
flocculation, aerobic degradation, anaerobic degradation, review & editing. Odunayo T. Ore: Methodology, Investigation, Writ-
ozonation, and photocatalytic processes are just a few of ing – original draft, Writing – review & editing. Ajibola A. Bayode:
Writing – original draft, Writing – review & editing. Hamza Badamasi:
the techniques that have been utilized to remove organic Writing – original draft, Writing – review & editing. Johnson Adedeji
pollutants from wastewater. As an alternative to physi- Olusola: Writing – original draft, Writing – review & editing.
cal, chemical, and biological processes, photocatalysis
employing nanomaterials showed greater potential than Funding This research received no external funding.
the aforementioned techniques. Furthermore, nanocata- Data Availability and Materials The data generated and/or analyzed
lysts quickly oxidize and are cheap, chemically stable, and will be made available upon reasonable request from the correspond-
environmental-friendly. While these photocatalysts have ing authors.
shown relatively high degradation of the studied organic
pollutants, it appeared that the efficiency of the process is Declarations
largely driven by the choice of photocatalysts. The choice Ethical Approval Not Applicable.
of photocatalyst equally depends on the target pollutant.
There is significant variation in the ability of different Competing Interest The authors declare that they have no competing
photocatalysts to interact with specific pollutants and interests.
initiate essential chemical processes. Understanding the

13
Journal of Fluorescence

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