Chemosphere 268 (2021) 128873

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Review

Role of nanocatalyst in the treatment of organochlorine compounds -

A review
Mohamed A. El-Sheikh a, b, Tony Hadibarata c, *, Adhi Yuniarto d,
Palanivel Sathishkumar e, **, Eslam M. Abdel-Salam a, Abdulrahman A. Alatar a
a
Botany & Microbiology Department, College of Science, King Saud University, P.O. Box. 2455, Riyadh, 11451, Saudi Arabia
b
Botany Department, Faculty of Science, Damanhour University, Damanhour, 22516, Egypt
c
Department of Environmental Engineering, Faculty of Engineering and Science, Curtin University Malaysia, CDT 250, 98009, Miri, Malaysia
d
Department of Environmental Engineering, Faculty of Civil, Planning, and Geo-Engineering, Institut Teknologi Sepuluh Nopember, Surabaya, 60111,
Indonesia
e
Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry, South China Normal University, Guangzhou, 510006,
PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Role of nanocatalyst in the organo-

chlorine compounds (OCs) treatment
is reviewed.

Nanophotocatalyst mediated treat-
ment is a best approach to manage
the OCs.

Multiple factors influencing on the
nanophotocatalyst for OCs treatment.

Further research is needed on in situ
photodecontamination of
nanophotocatalyst.

a r t i c l e i n f o a b s t r a c t

Article history: Since a few centuries ago, organochlorine compounds (OCs) become one of the threatened contaminants
Received 16 July 2020 in the world. Due to the lipophilic and hydrophobic properties, OCs always discover in fat or lipid layers
Received in revised form through bioaccumulation and biomagnification. The OCs are able to retain in soil, sediment and water for
20 October 2020
long time as it is volatile, OCs will evaporate from soil and condense in water easily and frequently, which
Accepted 31 October 2020
pollute the shelter of aquatic life and it affects the function of organs and damage system in human body.
Available online 4 November 2020
Photocatalysis that employs the usage of semiconductor nanophotocatalyst and solar energy can be the
Handling Editor: Derek Muir possible alternative for current conventional water remediation technologies. With the benefits of uti-
lizing renewable energy, no production of harmful by-products and easy operation, degradation of
Keywords: organic pollutants in rural water bodies can be established. Besides, nanophotocatalyst that is synthe-
Nanophotocatalyst sized with nanotechnology outnumbered conventional catalyst with larger surface area to volume ratio,
Organochlorine compounds thus higher photocatalytic activity is observed. In contrast, disadvantages particularly no residual effect
Photocatalysis in water distribution network, requirement of post-treatment and easily affected by various factors
Photodecontamination
accompanied with photocatalysis method cannot be ignored. These various factors constrained the
Pollutant remediation
photocatalytic efficiency via nanocatalysts which causes the full capacity of solar photocatalysis has yet
Semiconductor

* Corresponding author.
** Corresponding author.
E-mail addresses: hadibarata@curtin.edu.my (T. Hadibarata),
salemsathishkumar@gmail.com (P. Sathishkumar).

https://doi.org/10.1016/j.chemosphere.2020.128873
0045-6535/© 2020 Elsevier Ltd. All rights reserved.
M.A. El-Sheikh, T. Hadibarata, A. Yuniarto et al. Chemosphere 268 (2021) 128873

to be put into practice. Therefore, further modifications and research are still required in nano-
photocatalysts’ synthesis to overcome limitations such as large band gaps and photodecontamination.
© 2020 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1. Characteristics of OCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2. Source of OCs pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3. Negative impact of OCs on ecosystem and human . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.4. Current and emerging remediation technologies for OCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.5. Photocatalysis in remediating OCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.6. Mechanism of heterogenous photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.7. Factors affecting photocatalysis mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.8. Photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.9. Reaction temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.10. pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.11. Light intensity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.12. Concentration and type of pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.13. Dissolved oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.14. Addition of oxidant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.15. Advantages and disadvantages of photocatalysis via nanocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.16. Surface modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.17. Doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.18. Addition of oxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.19. Composite system with carbonaceous nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.20. Coupling with other technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Credit author statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

1. Introduction problem being a concerned issue worldwide (Skrbi


c and
Marinkovi c, 2019; Joseph et al., 2020). Persistent organic pollut-
Clean and affordable water supply is one of the global envi- ants (POPs) referred to wide scope of organic compounds which
ronmental challenges in current rapid urbanization and industri- able to withstand chemical, biological or photolytic degradation
alization era (Ibrahim et al., 2016; Meena et al., 2018; Zahari et al., (Rani et al., 2017; Ateia et al., 2020; Hu et al., 2021). The structure,
2018; Anandan et al., 2020). Water insecurity issues calls for source and possible treatment of the well-known OCs are pre-
attention since contamination of natural water resources exacer- sented in Table 1. In general, OCs are originated from nature (eg.
bated by anthropogenic activities (Ibrahim et al., 2016; Jasni et al., volcanic eruptions) or human activities (eg. agricultural use,
2017a; Sathishkumar et al., 2020; Lincy et al., 2020). Wide range manufacturing industries, etc.) (Engvild 1986; Wang et al., 2018;
of contaminants in water bodies include organic pollutants, path- Ohura et al., 2019; Joseph et al., 2020; Potapowicz et al., 2020).
ogens, heavy metals and radioactive pollutants threatens aquatic During industrialization process, the production of OCs was exag-
ecosystems as well as human being (Sathishkumar et al., 2012, gerated and uncontrolled. One of the Asia countries, China manu-
2014; Hamsawahini et al., 2015, 2016; Azhari et al., 2016; Ibrahim factured about 260 million kilogrammes of pesticides in year 1994,
et al., 2016; Jasni et al., 2017b; Liang et al., 2020; Mata et al., overall production of HCH and DDT between year 1950e1983 is
2020; Elias et al., 2020). Even worse, pathogenic microorganisms about 4.9 billion kilogrammes and 0.4 billion kilogrammes,
contaminated in water supply leads to different kind of waterborne respectively (Li et al., 1999, 2001). At that moment, majority of
diseases, malnutrition, reduced immunity, damage to physical and people do not realise that the drawbacks of OCs on human health
cognitive growth (Pandey et al., 2014). Therefore, safe source of and environment as they lack of professional knowledge and
water has to be guaranteed to maintain healthy lifestyle and sani- awareness.
tation (Guerrant et al., 2013). Next, characteristics of OCs are semi-volatile and able to travel
Due to the rapid urbanization and industrialization, most of the over long period of time in the environmental compartments,
countries are exposed to organochlorine compounds (OCs) such as including water and atmosphere (Potapowicz et al., 2020). OCs
polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p- accumulates in animals as well as human bodies through bio-
dioxins (PCDDs), hexachlorobenzene (HCB), dibenzofurans accumulation and biomagnification (Kim and Kang, 2019; Buah-
(PCDFs), dichlorodiphenyltrichloroethane (DDTs), hexa- Kwofie et al., 2018). Due to the characteristics of OCs, they had
chlorocyclohexane isomers (HCHs) and chlordane compounds been spread around the world and effect on both humans and
(CHLs) for different kind of applications (Taiwo, 2019; Hu et al., environment (Tholkappian and Rajendran, 2011; Sathishkumar
2021). This scenario has been increasing dramatically and this et al., 2009). In addition, the long term exposure of these

2
M.A. El-Sheikh, T. Hadibarata, A. Yuniarto et al. Chemosphere 268 (2021) 128873

Table 1
The structure, source and possible treatment of the well-known organochlorine compounds.

Organo Chlorine Source Possible treatment References

Electrical equipment; oil used in motors and hydrolic system; Aerobic degradation; Catalytic (Sowers and May 2013; Tang
fluorescence light ballast membranes;Persulfate oxidation et al., 2015; Vlotman et al., 2019)

Polychlorinated biphenyls (PCBs)

PCDDS are the by-products of industrial and combustion Aerobic co-composting; thermal (Lundin et al., 2013; Huang et al.,
processes; coolants and dielectric fluids in electrical equipment. degradation 2019)

Polychlorinated dibenzo-p-
dioxins (PCDDs)
Fungicide Photocatalytic; thermal (Yin et al., 2013; Pan et al., 2020)
degradation

Hexachlorobenzene (HCB)
Waste inceneration; pulp and paper bleaching Biodegradation; solid phase (Shelepchikov et al., 2019; Thanh
extraction et al., 2019)

Polychlorinated dibenzofurans
(PCDFs)
Insecticide Bioaugmentation; (Gao et al., 2015; Song et al.,
mechanochemical 2019)

Dichlorodiphenyltrichloroethane
(DDTs)
Insecticide Biochar; chemical oxidation (Silvani et al., 2019; Wacławek
et al., 2019)

Hexachlorocyclohexane isomers
(HCHs)
Insecticide Biodegradation; (Yamada et al., 2008; Cuozzo
photodegradation et al., 2012)

Chlordane compounds (CHLs)

contaminants will bring cancers, weaken the function of organs or
body system while the aquatic life and wildlife are endangered as
they cannot adapt the environment changes suddenly. Some
studies had been done on the concentration of OCs in developing
countries and recorded in Table 2. There are several conventional
water treatment technologies capable to remove/degrade envi-
ronmental pollutants including OCs. However, these conventional
technologies have some limitations, such as production of toxic by-
products, cost-ineffective, high electricity consumption and diffi-
cult operation (Pichel et al., 2019). Thus, new technologies that
capable in remediating water pollution efficiently after taken fac-
tors like costs, energy usage and environmental impact into ac-
count should be developed to overcome the shortcomings of
conventional methods. In this regard, nanoremediation that utilizes
various nanoparticles and nanocomposites may be a probable so-
lution for water pollution (Sarkar et al., 2017). Nanotechnology that
manipulates materials and structures at the nanoscale level
(1e100 nm) is a potential technology in remediating water con-
taminants (Baruah et al., 2015). With nanotechnology, matter can
be controlled at the nanoscale and materials with specific charac-
teristics and capacities can be produced. Nanomaterials that are
small in size and high in surface area to volume ratio can be
employed in detection of high-sensitive contaminants (Alshahrani
et al., 2018; Panahi et al., 2018). Application of nanotechnology in
environmental context encompasses of catalysis, pollutants sensing
3
and detection, pollution prevention and remediation (Ra ileanu
et al., 2013; Panahi et al., 2018; Zahari et al., 2018). In this review,
photocatalysis mechanisms that utilize nanophotocatalysts in
eliminating contaminants and pathogenic microorganisms in water
are discussed.
1.1. Characteristics of OCs
In comparison with OCs and other chemical compounds, OCs are
more halogenated and chlorinated which are hard to decay so they
have long life to exist in environment. This is because of the high
strength of carbon-chlorine bond cannot overcome by the hydro-
lysis process and chlorine substitution. OCs in atmosphere and
water can spread over a large scale of regions through wind and
rainfall easily due to the semi-volatile properties itself (Chu et al.,
2006; Ashraf, 2017). Especially, PCBs, dioxins (PCDDs) and DDT in
OCs are discovered in fat cells of humans and animals body which
have characteristics that tend to dissolve in lipids are known as
lipophilic as well as it able to hide in fats for many years. Other than
lipophilic, OCs are hydrophobic also hence it always presents in
solid phase which separates from soil, water and body cells and
prone to deposit in fatty tissue of organism’s body. The residual of
OCs which run off from earth surfaces are penetrated underground
water cause the aquatic life highly exposed to the contaminants and
accumulate in their bodies through bioaccumulation process (Jones
M.A. El-Sheikh, T. Hadibarata, A. Yuniarto et al.
Table 2
Concentration of OCs in some countries.
Country Location
Iran Zayandehrud River
China Yangtze river
India Gangga river
Australia Brisbane River
Turkey Euphrates River
Pakistan Indus River
Italy Tiber River
Thailand Mae Klong River
Vietnam Coastal area
Malaysia Selangor
and de Voogt, 1999). For further explanation, mobility of OCs which
does not adsorb by medium are free to move in water or atmo-
sphere and its lipophilic properties which allows the OCs adsorb on
living things easily and lead to bioaccumulation process (Chu et al.,
2006; Ashraf, 2017). Except form bioaccumulation, bio-
magnification process contributing in concentration of OCs also.
There is some difference between bioaccumulation and bio-
magnification process. Bioaccumulation is the accumulation of OCs
occurs in same species by taking OCs directly from environment
which increase with time, whereas biomagnification is the accu-
mulation of OCs across food chain or food web which increase with
tropic level. The parameters that affect the process of bio-
accumulation are fat contents of species, rate of growth, age, di-
etary habits while process of biomagnification affect by the trophic
level, size, rate of metabolic and fat content (Ren et al., 2017;
Romero-Romero et al., 2017). Apart from the process above, the
remaining OCs in water might volatilize into air and condense in air
again then its mobiles over long distance and re-deposit on an
object again (Ashraf, 2017). The reason that the OCs would disperse
in a wide area is because of its semi-volatile properties and lead
previous scenario occurs repeatably. However, some researchers
found that OCs with low concentration of chlorine can break down
by using plant enzymes. OCs with low concentration of chlorine are
easier to retransform or degrade by the enzymes present in roots of
plant (Phragmite saustralis) through enzymatic reaction (Chu et al.,
2006). Additionally, other major factors that affect the distribution
of OCs are atmospheric circulation. Wind control the travel distance
of OCs in air and surface air temperature which fluctuate with
seasons contributed in the concentration of OCs in atmosphere.
These temperature fluctuation and wind movement are influence
on the volatility of OCs. The volatilization of OCs could increase in
air during the surface air temperature increased. The concentration
of OCs increase as the volatility of OCs increase resulting in humans
has high chance contact with OCs. In addition, global warming or
climate change contributed in the presence of OCs in both water
and atmosphere. Second emission of OCs enhanced by the global
warming (Ma et al., 2004; Wang et al., 2016). Global warming
which known as global average temperature increase cause the
glaciers melts and sea level rise. These results are associated with
the second emission of OCs increase. For example, OCs exist in
ground and ocean re-emitted to atmosphere as temperature rise,
glaciers melting which increase the sea level enhance the exposure
of OCs to freshwater ecosystems and the occurrence of droughts or
flooding increase the re-emission rate of OCs (Wang et al., 2016).
1.2. Source of OCs pollutants
Generally, OCs can be discovered in environmental compart-
ments, including water, air, food and soil. The OCs in aquatic
ecosystem are majorly sourced from industrials’ direct discharge,
wastewater, run off from land surfaces, accumulation in
4
Chemosphere 268 (2021) 128873
Concentration References
0.1e51.5 ng/g dw Varnosfaderany et al. (2020)
0.1e92.97 ng/L Jin et al. (2019)
0.053e10.4 mg/L Sah et al. (2020)
ND-83.9 ng/g Duodu et al. (2017)
ND-0.032 mg/kg ww Varol and Sünbül (2017)
0.81e61.9 ng/g ww Robinson et al. (2016)
0.07e74.75 ng/L Montuori et al. (2016)
4.12e215.09 mg/g dw Poolpak et al. (2008)
0.196e3730 ng/g dw Tham et al. (2019)
1.3e4493 ng/L Elfikrie et al. (2020)
atmosphere, abiotic and biotic movement, pharmaceutical or food
chain transfer (Wenning and Martello, 2014). On the other hand,
the OCs discover on land are from usage of pesticides or herbicides
sprays in agriculture field, furnaces in household area and trans-
portation in landfills (Ashraf, 2017). The concentration of OCs in
some countries is summarized in Table 2. Since World War II, the
usage of pesticides has been increased because of the development
of social-economic growth rapidly, development in agriculture field
and to control diseases (Wong et al., 2005). Therefore, high con-
centrations of OCs in pesticides are highly stored in food which has
high content of fat and protein since past decades (Tieyu et al.,
2005). A study was done near Singapore coastal area and
polluted with OCs. The content of OCs near Singapore’s coastal area
are high because the domestic and international activities. Do-
mestic activities indicate the shipping activities, industrial activities
and land development activities while international activities
referred to the usage of pesticides over neighbouring country
(Obbard et al., 2007).
1.3. Negative impact of OCs on ecosystem and human
The presence of OCs brings huge impacts on humans, wildlife
and aquatic life. The effect of POPs on humans and environment
depend on the exposure level. The higher the POPs exposure level,
humans and biodiversity have high potential to have serious
impact. For instance, the usage of pesticides in agriculture field is
remained in soil and it will permeate into underground through
precipitation. As mentioned previously, lipophilic and hydrophobic
properties cause the residue of OCs survive for long time and able to
adsorb on body of living things or sediment as it degrades very
slow. Adsorption and biomagnification of OCs in food web will
bring a big impact on the top level of consumer in food chain or
food web (Jones and de Voogt, 1999). The content of OCs in aquatic
life increase with the level of trophic transfer thus the content of
OCs is the highest in the last level of trophic transfer. As we know,
human beings regularly used to consume aquatic life such as edible
fishes, crabs and shrimps are exposed to the highest content of OCs
which will affect function of humans’ organs.
Once humans exposed to large amount of OCs, nervous, im-
mune, endocrine and reproductive system are all affected and
cannot function as normal. Humans have high potential to have
cancer, weaken immune system, disruption of nervous system and
damage on function of sex steroid and thyroid, these conditions will
bring cardiovascular diseases, heart attack and high blood pressure
(Carpenter, 2011). As shown in Table 3, various research groups
have been confirmed the occurrence of OCs in the mother’s breast
milk which may be affect the infant growth. Humans preferred
breast milk to feed infant as it contains high nutrition and without
any artificial additive. Unfortunately, breast milk which contains
OCs will ingest by infant through breastfeeding because the con-
taminants will bioaccumulate in the fatty tissue in breast milk
M.A. El-Sheikh, T. Hadibarata, A. Yuniarto et al. Chemosphere 268 (2021) 128873

(Nickerson, 2006). According to a study in Hong Kong, thirty-seven
of female dispose tissue were collected and analysed, main
composition is 2.79 ng/g fat of DDTs, 0.72 ng/g fat of HCHs and
0.19 ng/g fat of PCBs (Poon et al., 2005). The contaminants are very
tiny and invisible by our naked eyes. Thus, partial of OCs will
transfer and accumulate in infant’s body which might affect the
organ function and growing process. The lethality of OCs is far away
from what we know. A critical scenario happened in year 1958,
production of flour and sugar polluted with parathion which is one
of the compositions in pesticides cause people in Kerala death
(Gupta, 2004).
Furthermore, OCs implicated living style of wildlife in wetland.
In year 1960e1962, the Tule Lake National Wildlife Refuge in Cali-
fornia loss approximately 1100 birds of 10 species and the food
chain of marsh ecosystems affected due to the DDT remaining in
water (Keith, 1966). The foetus of animal is affected which cause the
hatching rate decrease, mortality rate and wasting syndrome in-
crease as OCs affect hormones production resulting in teratogenic
and the reproductive organ and nervous system was also affected
(Martyniuk et al., 2020; Yin et al., 2020). Other than that, the her-
ring gulls in Lake Ontario who exposed to OCs have size reduction,
livers enlargement, porphyria, stockpile of peritoneal fluid in body,
mucoserous exudates in subcutaneous tissues and pericardial fluid
(Gilbertson and Fox, 1977; Fry, 1995). With the appearance of OCs
include DDE, PCBs, dioxins and PCDFs in Great Lakes, the habitat
and mating behaviour of aquatic birds are threatened. OCs are not
only the main factors affecting marine life, but also reduce the
number of marine life. Climate change force the marine life to
mitigate the current situation otherwise they will be facing
extinction problem. If the species under threatened category
exposed to OCs, the toxicity and effect of OCs will be amplified and
cause the number of species reduced (Fry, 1995; Wang et al., 2016).
1.4. Current and emerging remediation technologies for OCs
Several conventional and emerging water disinfection methods
are portrayed in Table 4 along with their working principles, ad-
vantages and disadvantages. Indeed, chemical treatment methods
that are widely applied in disinfection of water notably chlorina-
tion, ozonation, chloramination and treatment with chlorine di-
oxide showed high efficiency in safeguarding public health against
pathogenic microorganisms. Besides, recontamination in the dis-
tribution system of water can be prevented with residual effect of
chemical treatment technologies (EPA, 2011). However, water with
unfavourable odour and taste, difficult operation and high main-
tenance capital are often resulted from chemical treatment of water
resources (WHO, 2017a). Most importantly, disinfection by-
products (DBPs) formation during the reaction between disinfec-
tants and organic matter are harmful to human being (Baruah et al.,
2015). Physical treatment methods in particular filtration, ultravi-
olet (UV) lamps and pasteurisation do not generate hazardous by-
products like chemical methods. In addition, further benefits such
as easy operation, no requirement of chemicals and absence of
odour and taste issues made implementation of physical treatment
successful. But, physical treatment is not energy-efficient,
replacement and proper disposal of materials are often required
during cleaning process (Pichel et al., 2019). Hence, these limita-
tions leads to further research and establishment of alternative
technologies that addresses several issues such as energy efficiency,
formation of DBPs, dependence on chemical access, environmental
friendliness and sustainability (Pichel et al., 2019). Several
advanced water treatment methods with minimal application in
medium or large scale comprises of solar pasteurisation, solar
disinfection (SODIS), photocatalysis, cavitation and electrochemical
disinfection (Pichel et al., 2019).
1.5. Photocatalysis in remediating OCs
The combination of photochemistry and catalysis, photo-
catalysis is a method where chemical reaction is driven concur-
rently with light and catalysts (Saravanan et al., 2017). There are
two categories of photocatalysis process namely homogenous
photocatalytic processes (utilize metal complexes like copper,
chromium and iron as catalysts) and heterogenous photocatalytic
processes (utilize semiconducting nanophotocatalysts like zinc
oxide (ZnO), titanium dioxide (TiO2), tungsten oxide (WO3) and
zinc stannate (Zn2SnO4)) (Baruah et al., 2015; Saadon et al., 2016;
Saravanan et al., 2017). Heterogenous photocatalysis that employs
nanostructures of metal oxide semiconductors to degrade various
organic pollutants in water is discussed in this review. Additionally,
heterogenous photocatalysis, a potential advanced oxidation pro-
cesses (AOPs) outnumbered several remediation techniques with
traits such as high efficiency, easy operation, non-toxic, energy-
efficient, eco-friendly, complete mineralization of organic pollut-
ants, no issues on waste disposal and low cost (Saravanan et al.,
2017; Zhu and Zhou, 2019; Parul et al., 2020; Vagia and Petsas,
2020). Photocatalysts play an important role in photocatalysis,
therefore the selection of a good semiconductor photocatalyst is
vital (Zhu and Zhou, 2019). Properties of an excellent semi-
conductor photocatalyst include inert biologically and chemically,
stable against photo erosion, photoactive, inexpensive, non-toxic
and capable of utilizing visible and UV part of the electromag-
netic spectrum (Baruah et al., 2015; Saravanan et al., 2017). In this
regard, nanophotocatalysts that have large surface to volume ratios

Table 3
Comparison of OCs in human breast milk in some countries.

Country Year Population Biphenyls Dichlorodiphenyltrichloroethane Chlordane compounds Hexachlorocyclohexane isomers Hexachlorobenzene
(PCBs) (DDTs) (CHLs) (HCHs) (HCB)

Japan 1998 49 200 290 85 210 14

India 2000 8 30 420 0.9 650 1.0
Iran 2017 30 2345 2617 570
China 2000 54 33 3550 1.6 5.2 1.7
Cambodia 2000 49 25 1500 1.6 5.2 1.7
Philippines 2000 10 72 190 15 4.7 e
Vietnam 2000 48 76 2200 4.5 36 3.2
e2001
Malaysia 2003 17 80 1600 23 230 11
Taiwan 2013 68 9.81 0.539
e2016

Reported Concentration level: ng/g lipid wt.

Ref.: Chen et al. (2018); Konishi et al. (2001); Kunisue et al. (2002); Kunisue et al. (2004); Minh et al. (2004); Shahmoradi et al. (2019); Sudaryanto et al. (2005); Wong et al.
(2002).

5
M.A. El-Sheikh, T. Hadibarata, A. Yuniarto et al. Chemosphere 268 (2021) 128873

Table 4
Current and emerging remediation technologies for water pollution.

Remediation Principles Advantages Disadvantages References

technologies

Conventional water remediation technologies

Chlorination Add chlorine or chlorine by-products
into water where formation of
hypochlorous acid (HOCl) and
hypochlorite ion (OCl) eliminate
pathogens
Chloramination Reaction between ammonia and
chlorine to form monochloramine
(NH2Cl) to disinfect water
Chlorine dioxide Reaction between chlorine or an acid
(ClO2) with sodium chlorine to treat water
Ozonation Produce ozone (O3) with input of dry
oxygen or air though a high voltage
electrodes system to treat water
Ultraviolet (UV) lamps Prevent microorganisms from growth - Effective in cysts, viruses and spores
and replication by passing water though inactivation
UV light
Pasteurisation Boil water to the boiling point for a
minute until bubbles are formed
Filtration Remove microorganisms physically
from water by passing through porous - Minimizes water turbidity and
bed or thin film
Emerging water remediation technologies
Solar pasteurisation Destroy pathogens by heating water
with energy from the Sun
Solar disinfection Utilize bactericidal effect of solar
(SODIS) radiation to treat water
Photocatalysis Inactivate microorganisms with
advance oxidation technology
- Effective in inactivating bacteria and - Form disinfection by-products (DBPs). - Pichel et al.
virus. - Residual protection with excess Ineffective against cysts and eggs of protozoa (2019);WHO,
chlorine in water against and helminths. - Unfavourable taste and odour. (2017a);EPA
recontamination. - Less effective in turbid and organic-rich (2011)
waters. - Affected by pH value. - Hazardous and
corrosive chorine gas. - Requires maintenance
and trained operators. - Depend on chemical
access
- Form less disinfection by-products - Disinfectants manufactured on-site. - Less (EPA, 2011)
(DBPs). - Residual protection in water disinfection efficiency than other methods. - (Pichel et al.,
against recontamination. - Less Requires maintenance and trained operators. - 2019)
unfavourable taste and odour issues. Depend on chemical access.
- Less dependence on pH value - Expensive Pichel et al.
- Residual protection in water against - On-site manufacture of disinfectant (2019);
recontamination - Requires maintenance and trained operators WHO
- Form disinfection by-products (DBPs) (2017a);
- Unfavourable taste and odour EPA (2011)
- Effective in bacteria, viruses and - Disinfectants manufactured on-site EPA (2011)
protozoa inactivation - No residual protection in water against Pichel et al.
- Do not depend on chemical access recontamination (2019)
- Requires less contact time and low - Expensive
concentration - Requires maintenance and trained operators
- Form disinfection by-products (DBPs)
- Requires high energy input
- Requires replacement of UV lamps EPA (2011)
- Not energy efficient Pichel et al.
- No unfavourable taste and odour - Mercury in lamps are toxic (2019)
issues - Proper disposal is needed for residual lamps
- No formation of hazardous by- - Decreased efficiency with the presence of
products poor water transmittance, chemical fouling and
- Do not depend on chemical access formation of biological film
- Requires maintenance and trained operators
- Expensive
- Simple operation - Consume a lot of fuel Pichel et al.
- Do not depend on chemical access - Not sustainable economically and (2019)
environmentally (WHO,
2017b)
- Do not depend on chemical access - Depend on pore size of filter Pichel et al.
- Regular cleaning of filter is needed (2019)
microorganisms content - RO cannot be used for microorganisms (WHO,
- High water quality output with removal 2017b)
reverse osmosis (RO) mechanism - RO mechanism is expensive, not energy (Dvorak and
efficient and requires chemical input for Skipton,
membrane cleaning 2014)
- Inexpensive - Depend on climatic conditions Pichel et al.
- Easy to use - Long period of time needed (2019)
- Do not depend on electricity - No residual protection in water against Ray and Jain
- No formation of hazardous by- recontamination (2014)
products
- Do not depend on chemical access
- Inexpensive - Depend on climatic conditions Pichel et al.
- Easy to use - Long period of time needed (2019)
- Do not depend on electricity - No residual protection in water against
- No formation of hazardous by- recontamination
products - Pre-treatment is needed for water with high
- Do not depend on chemical access turbidity
- Potential inactivation against viruses,
protozoa and bacteria
- Minimal changes in odour and taste
- High bactericidal effect - Depend on chemical access Pichel et al.
- Depend on climatic conditions (2019)
- Requires replacement of UV lamps
- Not energy efficient
- Mercury in lamps are toxic
- Proper disposal is needed for residual lamps
- Decreased efficiency with the presence of
poor water transmittance, chemical fouling and
formation of biological film
- Requires maintenance and trained operators
- Expensive

6
M.A. El-Sheikh, T. Hadibarata, A. Yuniarto et al.
Table 4 (continued )
Remediation Principles
technologies
Cavitation Causes cellular damage by forming and - No formation of hazardous by-
collapsing microbubbles within a liquid products
Electrochemical Inactivate microorganisms by passing
disinfection an electric current though water with
electrodes
possess higher capability in adsorbing target molecules (Baruah
et al., 2015). Besides, photocatalysis that employs usage of sun-
light or near-UV light as irradiation source made water treatment in
remote locations probable (Baruah et al., 2015; Saravanan et al.,
2017).
1.6. Mechanism of heterogenous photocatalysis
The principal mechanism of heterogenous photocatalysis is
illustrated in Fig. 1. First, photocatalysis depends on the light energy
and catalyst, where semiconductor catalyst is used to detect the
light irradiation. When equivalent or higher light energy (pho-
tons,hv) compared to the band gap energy of semiconductor fall on
the semiconductor’s surface, electron-hole pairs are produced.
Consequently, electrons (e-) in the valence band gain energy and
move to the conduction band. Thus, holes (hþ) are created in the
valence band of the semiconductor (Saravanan et al., 2017; Nguyen
et al., 2020).
Holes (hþ) created in the valence band undergo oxidation pro-
cess as portrayed in Fig. 2. These positively-charged holes oxidises
water (H2O) molecules on the photocatalyst’s surface to form hy-
droxyl radicals that are responsible for pollutants degradation.
Hydroxyl radicals that have effective oxidizing power react with
organic pollutants present in water to generate intermediate radi-
cals. These intermediate radicals finally decomposes to carbon di-
oxide (CO2) and water after experienced several radical chain
reactions in the presence of oxygen (O2) molecules (Saravanan
Fig. 1. Schematic diagram of semiconductor photocatalytic mechanism.
Chemosphere 268 (2021) 128873
Advantages Disadvantages References
- Post-treatment of catalyst particles in treated
water is needed
- Expensive Pichel et al.
- Continuous energy supply is needed (2019)
- Do not depend on chemical access Dular et al.
(2016)
- Do not depend on chemical access - Continuous energy supply is needed Pichel et al.
- Electrodes have limited lifetime (2019)
- Calcareous deposits on electrodes will reduce
the efficiency
et al., 2017; Nguyen et al., 2020).
Reduction process in the conduction band is carried out by
electrons (e-) as illustrated in Fig. 3. Dissolved oxygen (O2) species
in the air are reduced by electrons to generate superoxide anions.
Subsequently, superoxide anions form hydrogen peroxide (H2O2)
after attach to intermediate radicals created in oxidation process.
Finally, water molecules will be formed as end-product of reduction
mechanism (Saravanan et al., 2017).
However, the concentration of organic matter affects the num-
ber of holes produced in the valence band. The number of holes can
be elevated with higher concentration of organic matter, thus
minimizes the recombination of electrons in the valence band. In
short, efficiency of photocatalysis can be enhanced with higher
concentration of organic matter (Khan et al., 2015).
1.7. Factors affecting photocatalysis mechanism
The efficiency of photocatalysis in degrading pollutants is
affected by several parameters in particular characteristics and
concentration of catalyst, reaction temperature, pH, light intensity,
pollutant’s properties and concentration, amount of dissolved ox-
ygen as well as oxidants.
1.8. Photocatalysts
Due to the surface of photocatalysts are often the redox reaction
sites in photocatalytic activity, surface properties of catalysts
7
M.A. El-Sheikh, T. Hadibarata, A. Yuniarto et al. Chemosphere 268 (2021) 128873

Fig. 2. Schematic diagram of oxidation mechanism.

Fig. 3. Schematic diagram of reduction mechanism.

influences the catalyst’s efficiency (Khan et al., 2015). To illustrate, through the reactor. Hence, photodegradation of pollutants is
ZnO with the spherical shape proved to have higher efficiency over ineffective due to aggregation of catalyst particles (R
aileanu et al.,
ZnO with spindle and rod shape due to larger surface area 2013).
(Saravanan et al., 2013). Besides, higher efficiency in photocatalysis
is recorded with catalyst that has large surface area to size ratio. The
1.9. Reaction temperature
reason behind is the number of active sites and the transfer rates of
interfacial charge carrier are increased with the elevation in surface
Photocatalysis depends on reaction temperature as photo-
area to volume ratio of catalyst (Cernuto et al., 2011). Moreover,
catalytic activity can be enhanced in optimum reaction tempera-
concentration of catalyst also influences the pollutants degradation
ture. The range of optimum reaction temperature differs in various
efficiency of photocatalysis. Available total surface is for contami-
materials used in photocatalysis as the activation energy of each
nants adsorption is enhanced with the effect of elevated amount of
material is dissimilar. In general, photocatalysis can be operated at
catalyst. Nevertheless, the catalyst concentration has to be kept
room temperature because heat energy is not needed for photonic
optimum in the photocatalytic reactor as excess catalyst increases
activation in photocatalysis mechanism. However, the degradation
the water suspension opacity and minimizes light irradiation
rate is reduced by higher temperature than the optimum reaction
8
M.A. El-Sheikh, T. Hadibarata, A. Yuniarto et al.
temperature ranges because recombination of electron-hole pairs
and desorption of adsorbed reactant species are caused. Therefore,
reaction temperature in the photocatalytic reactor has to be kept in
the optimum range (Saravanan et al., 2017).
1.10. pH
pH is one of the vital factors that affects the photocatalytic
degradation of pollutants. The hydrophobicity, size of its com-
pounds, net charge of pollutants, concentration of produced hy-
droxyl radicals and charging of photocatalyst’ surface are
determined by the pH value in the reactor (Raileanu et al., 2013). In
general, pH value influences the electrostatic interactions between
pollutants and charged particles that affects the rate of adsorption
in the surface of photocatalyst (Saravanan et al., 2017). Hence, op-
timum pH should be established for the specific photocatalyst,
target pollutant and pollution matrix to achieve maximum effi-
ciency in degrading pollutants (Raileanu et al., 2013).
1.11. Light intensity
Dependence on light intensity is significant in photocatalysis
mechanism as the formation of electron-hole pairs are determined
by the light intensity as well as wavelength. Sufficient photon en-
ergy is needed to overcome the band gap energy in the surface of
photocatalysts. Production of hydroxyl radicals is enhanced with
elevated light intensity, thus increased pollutant removal is
observed (Raileanu et al., 2013). Conversely, excessive light irradi-
ation favors recombination of electron-hole pairs which further
decrease rate of reaction (Saravanan et al., 2017).
1.12. Concentration and type of pollutants
The preliminary concentration of pollutants has inverse rela-
tionship with the rate constant of the reaction where increase of
concentration of pollutants reduces the rate constant of degrada-
tion. Photocatalysis degrade pollutants on the surface, therefore
when catalytic sites are preoccupied with high preliminary con-
centration of pollutants, further increase in the pollutants’ con-
centration will not impact the concentration of catalysts. Hence, the
rate constant in the first order is minimized. Besides that, the
concentration of adsorbed intermediates increases when the pre-
liminary concentration of pollutants is higher. Therefore, overall
rate of degradation is affected by concentration of pollutants
(Raileanu et al., 2013). Apart from that, the nature and properties of
pollutants influences the degradability of photolysis. The degra-
dation rate is suppressed with increased number of nitro group in
the pollutant molecules. Faster degradation is observed in mole-
cules with electron-donating substituents such as hydroxyl group
compared to electron-consuming substituents particularly the
nitro group. Additionally, photocatalysis can also be enhanced with
methyl group of toluene compounds. In short, the structural
properties and position of substituents of pollutants affects the
photocatalytic reactivity (R aileanu et al., 2013).
1.13. Dissolved oxygen
Dissolved oxygen that accepts electrons in the conduction band
can prevent the recombination of electron-hole pairs. Besides, ox-
ygen is also the source needed to generate carbon dioxide and other
reactive oxygen species. This stabilizes the intermediate radicals
and aid in the photocatalytic activity. Similarly, dissolved oxygen
content must be kept optimally as excess oxygen may inhibit
adsorption of pollutants on active sites due to hydroxylation of the
9
Chemosphere 268 (2021) 128873
ileanu et al., 2013).
catalyst surface (Ra
1.14. Addition of oxidant
For photocatalysis that has low oxygen levels, addition of
external oxidants like hydrogen peroxide (H2O2), potassium
bromate (KBrO3) and ammonium persulfate ((NH4)2S2O8) into the
semiconductor suspension can elevate the degradation efficiency of
pollutants. Recombination of electron-hole pairs can be obstructed
with more electron acceptors in photocatalysis. Furthermore, in-
crease of hydroxyl radicals and oxidizing species in the photo-
catalytic activity can enhance the degradation efficiency of
intermediate molecules. Nonetheless, this oxidant addition has to
be adequate or else excess oxidants may resulted in decreasing of
reaction rate in the reactor (R
aileanu et al., 2013).
1.15. Advantages and disadvantages of photocatalysis via
nanocatalysts
The advantages and limitations of photocatalysis via nano-
catalysts are listed in Tables 4 and 5 in comparison to conventional
methods of water treatment. As shown in Table 5, the disadvan-
tages of photocatalysis involve the usage of UV irradiation to boost
the degradation efficiency of pollutants. However, these disad-
vantages can be eliminated if solar energy is used for photocatalysis
process.
Photolysis that makes use of solar energy for energy generation,
water purification and environmental safeguarding is favored.
However, several photocatalysts particularly ZnO and TiO2 are
proven to be inactive under visible light with insufficient photon
energy to overcome their large band gaps. Therefore modifications
had to be applied on the photocatalysts as well as photocatalysis
process to overcome these limitations as well as utilize the full
potential of solar photocatalysis (Saravanan et al., 2017). Methods
that able to improve the photocatalysis technology include surface
modification, doping, addition of oxidants, composite system with
carbonaceous nanomaterials and coupled with other technologies
as shown in Table 6.
1.16. Surface modification
Surface of photocatalyst can be improved with pre-treatments
like sulfation, halogenation and reduction with hydrogen. Sulfa-
tion of catalyst resulted in elevation of adsorption ability and sur-
face acidity, hence increases the adsorption coverage of substrates.
Besides, photocatalyst can also be sensitized by semiconductors or
coated with metals with the effect of escalating the transport of
electrons to dissolved oxygen (Cassaignon et al., 2013).
1.17. Doping
Doping of photocatalyst can be done with both metal and non-
metal nanoparticles. Both doping methods capable in preventing
the recombination of electron-hole pairs and enhancing the ab-
sorption of visible light (Nguyen et al., 2020). Metal doping able to
generate new acceptor level under the preliminary conduction
band as well as new donor level above the preliminary valence
band. In consequence, the band gap energy of semiconductor for
photon energy to overcome is reduced (Chen et al., 2010). On the
other hand, doping with non-metals have benefits of increased
production rate of hydroxyl radicals, preventing agglomeration of
particles and impeding phase transformation (Khan et al., 2014). In
short, doping of photocatalyst improved the efficiency of
photolysis.
M.A. El-Sheikh, T. Hadibarata, A. Yuniarto et al. Chemosphere 268 (2021) 128873

Table 5
Benefits and limitations of photocatalysis via nanocatalysts.

Advantages of photocatalysis via nanocatalysts Constraints of photocatalysis via nanocatalysts

Increased surface area to volume ratio that attained higher reactivity on the
surface of photocatalyst (Baruah et al., 2015).
Antimicrobial nanomaterials can treat water and minimize fouling at the
same time (Baruah et al., 2015).
Probable alternative for conventional treatment methods that have high
energy consumption as photocatalysis utilizes renewable solar energy to
function (Saravanan et al., 2017).
Do not form harmful by-products such as DBPs (Saravanan et al., 2017; Pichel
et al., 2019).
Capable in degrading various harmful molecules (Saravanan et al., 2017).
Required lower chemical input in comparison with conventional methods
(Saravanan et al., 2017).
Reaction time is moderate and only room temperature is needed (Saravanan
et al., 2017).
No residual treatment of water in the distribution network (Baruah et al., 2015).
Post-recovery is required for catalyst particles in treated water to recycle the catalysts
and prevent leaching of new pollutants (Pichel et al., 2019).
Penetration of photon energy reduced when fixation of catalyst into an inert substrate
occurred. The pollutants degradation efficiency is then minimized (Pichel et al., 2019).
Quantum yield (Ratio of reaction rate to rate of absorption of radiation) is reduced with
rapid recombination process of electron-hole pairs (Zhu and Zhou, 2019).
Several significant factors that resulted in low remediation rate of pollutants (Zhu and
Zhou, 2019).

Table 6
Variety of nanocatalyst treatment for organochlorine compounds.

Treatment Pollutant References

Nano-photocatalysts based on nanocarbon Dichoro-diphenyltrichloroethane (DDT), Aldrin (C12H8Cl6), lindane (C6H6Cl6) and Khaydarov et al. (2013)
etitanium polychlorinated biphenyls (PCBs)
TiO2 photocatalyst Dichloromethane (CH2Cl2), chloroform (CHCl3) and carbon tetrachloride (CCl4) Hsiao et al. (1983)
TiO2 photocatalyst with solar light Diuron (C9H10Cl2N2O) Higarashi and Jardim
(2002)
TiO2 under UV light p,p’-DDT (C14H9Cl5) Quinn et al. (2005)
TiO2 and montmorillonite composite g-hexachlorocyclohexane (C6H6Cl6) (Zhao et al., 2007)
photocatalysts
Nano-TiO2 coated films under UV irradiation Hexachlorobenzene (BHC) (C6Cl6), dicofol (C14H9Cl5O) and cypermethrin (C22H19Cl2NO3) Yu et al. (2007)
LaFeO3@TiO2 heterojunction composites Myclobutanil pesticide Garcia-Mun ~ oz et al. (2020)
photocatalysis
Coupled ZnO/SnO2 photocatalysts Triclopyr (C7H4Cl3NO3) Yadav et al. (2019)
Solar photocatalytic with TiO2-rGO Alachlor (C14H20ClNO2) Luna-Sanguino et al.
nanocomposites (2020)
Nano- metal doped TiO2 with UV light 4-Chlorophenol (C6H5ClO) Venkatachalam et al.
(2007)
UV and visible light using N-doped TiO2 Lindane (C6H6Cl6) Senthilnathan and Philip
(2010)
TiO2 with Visible light-induced Carbon tetrachloride (CCl4) Cho et al. (2001)
Photoactivity of nanosized Bi2WO6 catalyst 4-Chlorophenol (C6H5ClO) Fu et al. (2008)
SrFeO3-x/g-C3N4 photocatalysts Chloramphenicol (C11H12Cl2N2O5) Lin et al. (2016)

1.18. Addition of oxidants 1.20. Coupling with other technologies

Another probable approach that may elevate the photo-
degradation rate is addition of oxidants like peroxymonosulfate
and persulfate. Adequate irradiance produced by oxidants causes
increase in number of reactive radical species generated. Therefore,
degradation efficiency of photocatalysis is enhanced (Nguyen et al.,
2020).
1.19. Composite system with carbonaceous nanomaterials
Besides, photocatalysts can be assist by hybridizing the carbo-
naceous nanomaterials such as fullerene, graphene nanosheets,
carbon nanotubes (CNTs) and multi-walled carbon nanotubes
(MWCNTs). The composite system of photocatalysts with carbo-
naceous nanomaterials showed longer effect in separating
electron-hole pairs, excellent reactants adsorption, higher electron
mobility and larger surface area (Nguyen et al., 2020). For instance,
99.2% of perfluorooctanoic acid removal efficiency is recorded
when reduced graphene oxide (rGO) and TiO2 combined together
for degradation (Panchangam et al., 2018).
10
Photocatalysis can also be coupled with other technologies to
achieve higher degradation rate of pollutants. Sonolysis that
transmit ultrasound waves through an aqueous solution produces
acoustic cavitation where radicals that are highly reactive are
formed. The presence of radicals is then utilized as the materials to
degrade organic pollutants with hydroxylation and oxidation.
Sonophotocatalysis that encompasses of both sonolysis and pho-
tocatalysis technologies proven to have higher decomposition rate
of pollutants (Anandan et al., 2020). Benefits of the sonophotoca-
talysis technology concluded by Kritikos et al. (2007), which in-
cludes: (1) elevated formation of hydroxyl radicals; (2) mass
transfer of organic molecules between the catalyst surface and
liquid phase increased; (3) catalyst excitation that overcome band
gap energy of catalyst; (4) catalytic activity enhanced; and (5) more
vacant active catalyst sites with acoustic micro-steaming that
cleans the catalyst surface.
Besides, the degradation of organic pollutants in photocatalysis
can also be accelerated with combination with electrochemical
treatment (Hakim Wirzal et al., 2020). Coupling of electrochemical
treatment assists the formation of electron-hole pairs and limits
the recombination of these pairs. Hence, the performance of
M.A. El-Sheikh, T. Hadibarata, A. Yuniarto et al.
photocatalyst is improved. This beneficial effects of coupling both
electrochemical and photocatalytic methods are recorded in the
remediation of dyes and pharmaceutically active compounds
(PhACs) (Hakim Wirzal et al., 2020; Tantis et al., 2016).
2. Conclusions
The photocatalysis technology that remediates water pollution,
especially the photodegradation of organic with semiconductor
nanophotocatalysts is reviewed in this study. Furthermore, limita-
tions as well as benefits of photocatalytic degradation compared to
existing conventional water treatment technologies are evaluated.
Vital factors that influence the photocatalysis mechanism and
several modifications to improve the photodegradation efficiency
were discussed briefly. Efficient and economical photocatalysis
technology capable of decomposing organic pollutants with no
hazardous by-products generation. In addition, photocatalytic ac-
tivity that makes use of solar energy is simple to operate at ambient
pressures and temperatures. Furthermore, semiconductor nano-
photocatalyst that is durable, less toxic, hydrophilic, cost-effective
and outstanding stability in chemical and photochemical means
is an effective catalyst to be applied in remediation of organic
pollutants. Additionally, photocatalytic efficacy in remediating a
wide range of pollutants can be boosted with modifications of
nanostructures, thus nanotechnology in photocatalysis has to be
further research and manufacture in real field applications. How-
ever, the toxicity risk originated from chemically synthesized
nanoparticles has to be clarified before establishment of this
technology in order for photodecontamination being prevented. In
short, environmental friendly photocatalysis technology is a prob-
able replacement for energy-intensive conventional technology
after drawbacks such as limited efficiency under sunlight, optimum
position of the photocatalyst, treatment medium and light source
and design of photocatalytic reactor are addressed adequately.
Credit author statement
Mohamed A. El-Sheikh, Conceptualization, Data curation,
Writing - original draft preparation. Tony Hadibarata, Conceptual-
ization, Data curation, Validation, Writing - original draft prepara-
tion, Resources, Supervision. Adhi Yuniarto, Data curation,
Validation, Writing - original draft preparation. Palanivel Sathish-
kumar, Writing-Reviewing and Editing. Eslam M. Abdel-Salam,
Resources, Supervision, Funding acquisition. Abdulrahman A. Ala-
tar, Resources, Supervision, Funding acquisition.
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.
Acknowledgements
The authors extend their appreciation to the Deanship of Sci-
entific Research at King Saud University for funding this work
through research group no. (RGP-1438-053).
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