Water-Energy Nexus 3 (2020) 46–61

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Water-Energy Nexus
CHINESE ROOTS
GLOBAL IMPACT
journal homepage: www.keaipublishing.com/en/journals/water-energy-nexus/

Photocatalytic degradation of pharmaceutical and pesticide compounds

(PPCs) using doped TiO2 nanomaterials: A review
Kiran S. Varma a, Rajesh J. Tayade b, Kinjal J. Shah c, Pradyuman A. Joshi a, Atindra D. Shukla a,⇑,
Vimal G. Gandhi a,⇑
a
Department of Chemical Engineering & Shah Schulman Center for Surface Science and Nanotechnology, Dharmsinh Desai University, College Road, Nadiad 387 001, Gujarat, India
b
Discipline of Inorganic Materials and Catalysis, Central Salt and Marine Chemicals Research Institute, Council of Scientific and Industrial Research (CSIR), G. B. Marg,
Bhavnagar 364002, Gujarat, India
c
College of Urban Construction, Nanjing Tech University, Nanjing 211800, China

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

Article history: Alarming level water pollution is a serious concern in heavily industrialized countries. The development
Received 29 November 2019 of advanced waste water treatment techniques and their utilization is sought for effective removal of pol-
Revised 14 March 2020 lutants especially pharmaceutical and pesticide compounds (PPCs). Doped TiO2 nanomaterials mediated
Accepted 31 March 2020
photocatalytic degradation of waste water has shown great potential in removing these complex organic
Available online 8 April 2020
pollutants. Improvement in properties of doped TiO2 nanomaterials resulted in the effective utilization of
visible light and solar light as light source. Doped TiO2 nanomaterials show great potential to water and
Keywords:
energy concerns by fulfilling two key features i.e., effective in removing pollutants which are persistent in
Doped TiO2 nanomaterials
Pharmaceutical and pesticide compounds
nature and cost-effective energy consumption. In this context, doped TiO2 nanomaterials mediated waste
(PPCs) water treatment process and its role in water energy nexus is briefly addressed. Application of doped TiO2
Advanced waste water treatment nanomaterials against PPCs under different light sources are also discussed in this review.
Photocatalytic degradation Ó 2020 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
Visible light This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-
Solar light nd/4.0/).
Water energy nexus

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
2. Development of doped TiO2 nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.1. Overview of TiO2 nanomaterial as photocatalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.2. Doped TiO2 nanomaterials as photocatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
2.2.1. Mechanism of metal doped TiO2 nanomaterials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.2.2. Mechanism of non-metal doped TiO2 nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
2.3. Methods for synthesis of doped TiO2 nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
3. Doped TiO2 photocatalyst for degradation of pharmaceutical and pesticide compounds (PPCs) under different light sources . . . . . . . . . . . . . . . 50
3.1. Photocatalytic degradation of PPCs under UV light source. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
3.2. Photocatalytic degradation of PPCs under visible light source . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
3.3. Photocatalytic degradation of PPCs under natural solar light source. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4. Water-energy nexus factors allied with doped TiO2 photocatalyst mediated advanced waste water treatment . . . . . . . . . . . . . . . . . . . . . . . . . . 53
4.1. Parameters affecting aqueous pollutant stream . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4.2. Visible light active doped TiO2 nanophotocatalyst materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4.3. Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
5. Future challenges and concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
CRediT authorship contribution statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58

⇑ Corresponding authors.
E-mail addresses: atindra.sscssn@ddu.ac.in (A.D. Shukla), vggandhi.ch@ddu.ac.in (V.G. Gandhi).

https://doi.org/10.1016/j.wen.2020.03.008
2588-9125/Ó 2020 The Authors. Production and hosting by Elsevier B.V. on behalf of KeAi Communications Co., Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 K.S. Varma et al. / Water-Energy Nexus 3 (2020) 46–61
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
1. Introduction
Water pollution and its adverse impact on aquatic ecosystem
and human health are found in all over the world. Toxic and haz-
ardous pollutants like detergents, pesticides and heavy metals
are found in rivers of Egypt and similar type of situation is
observed in rivers in India (Abdel-Shafy, 2002; Agrawal, 2010).
Impact of water pollution in China is so high that millions of people
have suffered and many of them have died due to various diseases
resulted from water contaminants (Wang and Yang, 2016). The
pollutants which mainly affect the water resources are organic in
nature. Many types of organic pollutants are present in water bod-
ies such as pharmaceuticals, pesticides, plasticizers, phenolic com-
pounds, industrial solvents and many others (Lapworth et al.,
2012; Naidu et al., 2016; Sharma et al., 2019).
Pharmaceuticals are widely utilized to control over the diseases
and to improve the health for humans, animals and other ecosys-
tems. Amongst various pharmaceuticals, the antibiotics are highly
consumed one due to their potent action against harmful microbes
and pathogens (Karthikeyan and Meyer, 2006; Santos et al., 2007).
The rapid consumption of antibiotics is observed in countries such
as India, China, Brazil, Russia and South Africa (Méndez et al.,
2017). The excess use of antibiotics has created adverse effects
on human health due to polluted water resources and also it is
developed antibiotic resistant microbes (Chatzitakis et al., 2008;
Giraldo et al., 2010). Non-steroidal anti-inflammatory drugs
(NSAIDs) are most widely used highly water soluble compounds
for treating various types of diseases such as pain relief, inflamma-
tory disorders and many others. These drugs are not degraded
easily and due to that it is reported to show harmful impact on
human health and water resources (Dawod et al., 2008; Kuo
et al., 2010). Demand of pesticides is increased due to excessive
usage for agriculture purpose. Industries associated with these
types of pesticides manufacturing are facing challenges in com-
plete removal of pesticides from the waste water. Consequently,
pesticide pollutants have highly affected the water resources due
to their persistent and toxic nature. (Agrawal, 2010; Fernández-
Alba et al., 2001; Mitsika et al., 2013). Phenol and phenolic chem-
icals are commonly used raw materials in manufacturing of phar-
maceuticals, pesticides, textile, plastic, pulp and paper industries
(Sable et al., 2018). These phenolic chemicals have highly affected
the environment due to their carcinogenic and toxic nature
(Naeem and Feng, 2009; Sarkar et al., 2003; Wang et al., 1999).
One of the most widely used phenol derivative is bisphenol A
(BPA), which is utilized in production of epoxy resins, drinking
water bottles, and consumer products. BPA as pollutant is consid-
ered an endocrine disruptive chemical (EDC) which creates imbal-
ance in hormones function and adversely impact on living
organisms (Sin et al., 2012; Teh and Mohamed, 2011).
The removal of diverse contaminants from industrial waste
water, efficient waste water treatment techniques should be uti-
lized. Physicochemical and biological treatment processes are
widely used in industries due to their simple design and their abil-
ity to treat the waste water with higher capacity (Crini and
Lichtfouse, 2019). However, commonly used waste water treat-
ment techniques have addressed issues related to removal of com-
plex organic pollutants from waste water up to some extent as
their design and strategies did not evolve considerably (Surenjan
et al., 2019). Also, conventional waste water treatment consumes
47
higher energy which is one of the major impediments for the
industry. Water energy nexus approach has substantial capability
to improve the performance of waste water treatment process by
equally focusing on two interconnected aspects i.e., water and
energy resources (Maktabifard et al., 2018; Scott et al., 2011).
There are many feasible options for application of water energy
nexus in waste water treatment such as optimizing major process
parameters (pH, temperature and raw materials), energy genera-
tion through waste, design modification in reactor and many
others (Artsupho et al., 2016; Barwal and Chaudhary, 2014;
Gilbert et al., 2015; Maspolim et al., 2015). These strategies must
be applied to existing waste water treatment stages. However,
improvement in existing treatment stages alone are not sufficient
to function the treatment plant effectively. So, it is necessary to
develop efficient treatment processes for targeting contaminants
which are difficult to remove and consume much energy in con-
ventional treatment techniques. There is need for developing
advanced treatment process for waste water which must have
incorporated water and energy efficient features. Moreover, to
intensify the advanced waste water treatment processes, emphasis
must be given for developing robust raw materials which are cap-
able in removing the various types of aqueous pollutants from
waste water.
Various advanced waste water treatment techniques such as
membrane-based processes, advanced oxidation processes (AOPs)
and UV illuminated processes are utilized for removal of organic
pollutants (Abdel-Fatah, 2018; Munter, 2001; Zhou and Smith,
2002). The main advantage of AOPs is that it effectively degrades
aqueous pollutants with in situ highly reactive hydroxyl radical
(HO), whereas primary conventional processes and activated
carbon-based adsorption processes are only involved in the physi-
cal transformation of pollutants without any degradation (Ali and
Gupta, 2006; Andreozzi et al., 1999; Cheng et al., 2016; Krishnan
et al., 2017; Oturan and Aaron, 2014). Many AOPs such as UV/
H2O2, ozone-based, Fenton-based and semiconductor based photo-
catalytic processes are employed for effective degradation of
organic pollutants (De la Cruz et al., 2012, 2013; García-Araya
et al., 2010; Tambosi et al., 2009). Semiconductor based photocat-
alytic process is extensively used compared to other AOPs due to
less input of chemical components and it utilizes oxygen from air
as oxidant compared to others AOPs where relatively expensive
oxidizing agents are necessary such as H2O2 and O3 (Anandan
et al., 2010; Dalrymple et al., 2007).
TiO2, CeO2, ZnO, CdS, WO3, Fe2O3 and many other semiconduc-
tor nanomaterials are employed as photocatalyst for different
applications like environment, energy and chemical synthesis
(Rajaraman et al., 2019; Dhananjay et al., 2001; Carp et al., 2004;
Shah and Chang, 2018). Amongst these various photocatalysts,
Titanium dioxide (TiO2) is widely used for different applications
as it is chemically stable, non-toxic and also comparatively eco-
nomical (Kumar and Devi, 2011; Lazar et al., 2012; Rauf et al.,
2011). Although, wide band gap TiO2 semiconductor materials
are less active under visible light source. Under solar light, the exci-
tation of TiO2 barely occurs as solar spectrum comprises only 5%
UV radiation (Devi et al., 2010; Molla et al., 2017; Xiong et al.,
2013; Zheng et al., 2017). Presently, many researchers are devel-
oped visible light active TiO2 photocatalyst by employing different
strategies like metal doping (Djurišić et al., 2014; Pongwan et al.,
2012), non-metal doping (Azami et al., 2017), metal/metal codop-
48 K.S. Varma et al. / Water-Energy Nexus 3 (2020) 46–61
ing and metal/non-metal codoping (Neville et al., 2012; Yang et al.,
2010), codoping with other semiconductor (Li et al., 2015), and dye
sensitization (Chowdhury et al., 2012). Parangi and Mishra (2019)
have comprehensively reviewed the different modification strate-
gies in TiO2 nanoparticles for improving photocatalytical activity
under visible light along with role of various synthesis methods.
Strategies like metal and non-metal doping onto TiO2 is
emerged as effective strategies to develop nanophotocatalyst as
it facilitates charge carriers separation and enhances photocatalyst
performance under visible and solar light source (Teoh et al., 2012).
Metal doping onto TiO2 are created intra-band gap states due to
integration of metal dopants. Thus, band gap energy is decreases
mainly due to lowering conduction band of TiO2 nanomaterials
(Dubey and Singh, 2017; Rauf et al., 2011). In non-metal doping,
narrowing band gap at desired level with incorporation of non-
metal doping ions are even better and it is created oxygen vacan-
cies which enhanced the performance of photocatalyst (Han
et al., 2009; Hu et al., 2012; Zaleska-Medynska, 2008).
For utilization of advanced waste water treatment processes at
industrial scale, it is necessary that it should be economical and
environmentally sustainable. UV light mediated Photocatalytic
degradation of pollutants is effective but the energy utilization is
high compared to visible light and natural light source. Also, con-
tact of UV light source is caused skin cancer (Matsumura and
Ananthaswamy, 2004; Wittlich et al., 2016). Visible Light emitting
diodes (LEDs) are environment friendly and consumed less energy
compared to conventional UV bulbs. Moreover, cooling water cir-
culation is required in UV based photocatalytic process to maintain
the temperature. Thus, operating cost is also reduced in visible LED
based waste water treatment processes (Mosleh et al., 2016; Zheng
et al., 2017).
Doped TiO2 nanomaterials mediated advanced waste water
treatment technique has considerable potential for removal of var-
ious types of complex organic pollutants from waste water under
visible, solar and UV light sources (Abdelhaleem and Chu, 2017;
Hinojosa-Reyes et al., 2019; Sood et al., 2015; Yi et al., 2019;
Zhang et al., 2015). Application of various metal doped TiO2 and
non-metal doped TiO2 nanomaterials against pharmaceutical and
pesticide compounds (PPCs) under different light sources have dis-
cussed. Role of doped TiO2 nanomaterials in photocatalytic degra-
Fig. 1. Photocatalytical degradation of pollutant using TiO2 nanomaterial.
dation of pollutants and its application towards water energy
nexus has briefly addressed. Moreover, energy consumption in var-
ious types of TiO2 based photocatalytic waste water treatment is
also outlined in this review.
2. Development of doped TiO2 nanomaterials
2.1. Overview of TiO2 nanomaterial as photocatalysts
TiO2 is an extensively used material by many researchers for
degradation of various pollutants like Benzofuran, 2,4-
dichlorophenoxyaceticacid (Herrmann et al., 1998), nitrobenzene
(Tayade et al., 2006), thiram (Kaneco et al., 2009), benzoic acid,
o-chlorobenzoic acid, o-nitrobenzoic acid, phthalic acid (Gandhi
et al., 2011, 2012a) and many others. Photocatalysis is a light dri-
ven degradation mechanism, triggered when photon is excited suf-
ficiently to overcome the band gap energy value of TiO2 of 3.2 eV
(for anatase TiO2). Thus, electron (e ) is excited from valence band
(VB) to conduction band (CB), this ejection of electron, gives rise to
a void (vacancy of e ), which is referred as hole (h+) and subse-
quently some of electron-hole pairs are recombined at highly
instantaneous rate (Ahmed et al., 2010; Gandhi et al., 2012b;
Herrmann, 1999). Excitation and recombination mechanism
involved in TiO2 photocatalyst with pollutant degradation stage
is illustrated in Fig. 1. Generally, photocatalytic degradation of
aqueous pollutants is done in presence of air which helps the for-
mation of superoxide ions (O2 ) at CB through interactions of free
electrons and O2 whereas hydroxyl radical (HO) is generated at VB
due to existence of H2O. The degradation of pollutants is occurred
at the reactive sites of TiO2 nanomaterials resulted the CO2, H2O
and other intermediate products mainly because of highly reactive
hydroxyl radicals (Gaya and Abdullah, 2008; Kositzi et al., 2004).
2.2. Doped TiO2 nanomaterials as photocatalyst
Doping in TiO2 has involved the incorporation of atoms of
dopant into structure of TiO2 (Mogal et al., 2013). Utilization of
metal dopant with TiO2 is reported to alter the charge carrier
recombination rate, band gap energy and physical properties.
Metal dopant is played vital role in trapping of electron, which
 K.S. Varma et al. / Water-Energy Nexus 3 (2020) 46–61
Fig. 2. Metal doped TiO2 mediated photocatalytic degradation of organic pollutants (M: Metal dopant).
helps in separation of charge carriers and delay the recombination
process. The incorporation of metal dopant has shifted band gap
edge towards higher wavelength. Many times, metal doped TiO2
nanomaterials work better under visible and solar light compared
to undoped TiO2 (Connelly et al., 2012; Kamat, 2007; Sathishkumar
et al., 2011; Sung-Suh et al., 2004; Vega et al., 2018). Doping of
non-metal significantly narrows down the energy band gap of bare
TiO2 by altering the VB energy level towards lower VB values. Sub-
stitution of oxygen by non-metal dopant is created oxygen defect
which decreases energy band gap of non-metal doped TiO2 nano-
materials (Ansari et al., 2016; Humayun et al., 2018).
2.2.1. Mechanism of metal doped TiO2 nanomaterials
Many Transition metals like Fe, Ni, Cr, Cu, Mn, Co, and Zn are
utilized as dopant for improving photocatalytic degradation
against aqueous pollutants under the visible light irradiation
(Devi et al., 2009; Krishnakumar et al., 2016; Narayana et al.,
2011; Nakhate et al., 2010; Yadav et al., 2016). Noble metals such
as Ag, Au, Pt and Pd played vital role in improving the photocat-
alytic efficiency under visible light illumination by assistance in
electron trapping and enhancing interfacial charge transfer which
delayed the charge carrier recombination rate (Kim et al., 2005;
Li and Li, 2001; Mogal et al., 2014; Pelaez et al., 2012).
In Fig. 2, metal doped TiO2 mechanism is schematically
explained, where it is shown that with doping of metal onto
TiO2, which shifted fermi level towards the positive value of CB
compared to TiO2. This shifting of fermi level in metal doped
TiO2 nanomaterials is increased the absorption of higher wave-
length from emitted light source. Hence, metal doped TiO2 semi-
conductor nanomaterials are promising candidates for utilization
under visible and solar sources along with UV irradiation. The gen-
eration of superoxide ions (O2 ) through oxygen and hydroxyl rad-
ical (HO) through water are attributed to photoreduction and
photooxidation processes respectively. With complete photocat-
alytical degradation of organic pollutants, CO2, H2O and other
intermediate products are formed at the end of the process
(Mahlambi et al., 2015; Shah et al., 2018).
49
2.2.2. Mechanism of non-metal doped TiO2 nanomaterials
Non-metal doped TiO2 nanomaterials are synthesized by vari-
ous dopants like C, N, I, B and S individually for removal of vari-
ous pollutants from water (Barkul et al., 2017; Sun et al., 2008;
Xu et al., 2009; Yang et al., 2012; Bu et al., 2012). Generally, dop-
ing of non-metal onto TiO2 is altered the VB by creating new VB
level at upward side. In non-metal doped TiO2 nanomaterial,
higher surface area and lower crystalline size are achieved com-
pared to bare TiO2 nanomaterial (Marschall and Wang, 2014;
Tan et al., 2011).
Effect of non-metal dopant onto TiO2 and its application for
organic pollutant degradation is shown as in Fig. 3, where due
to shifting of VB towards higher energy in non-metal doping
level, light sources like solar and visible excited electrons from
VB to CB in higher proportion compared to UV light source. In
non-metal doped TiO2 nanaomaterials, the effective separation
of electron and hole occurs which enhances the degradation per-
formance. Both superoxide ions (O2 ) and hydroxyl radical (HO)
are engaged in degradation of aqueous pollutants and converted
into simpler forms like CO2, H2O and other intermediate products
in presence of light irradiation (Bakar et al., 2016; Zhang et al.,
2012).
2.3. Methods for synthesis of doped TiO2 nanomaterials
Table 1 presents the synthesis of various metal and non-metal
doped TiO2 nanomaterials using different methods. Ag, Au, Fe,
Cu, Ni, Co, Bi, Mn, Zn and Mo are commonly used metal dopants,
and N, C, B. P, S and F are mostly used as a non-metal dopants.
Widely used methods for synthesis of doped TiO2 nanomaterials
are sol-gel, hydrothermal, and wet impregnation (Ali et al., 2018;
Asiltürk et al., 2009; Grabowska et al., 2009; Natarajan et al.,
2013; Ren et al., 2007; Tayade et al., 2006). Some modified synthe-
sis methods are also utilized such as reverse micelle mediated sol-
gel, microwave mediated sol-gel method and microwave mediated
hydrothermal (Chiang and Doong, 2014; Krejčíková et al., 2012;
Nasi et al., 2019; Niu et al., 2014).
50 K.S. Varma et al. / Water-Energy Nexus 3 (2020) 46–61

Fig. 3. Non-metal doped TiO2 mediated photocatalytic degradation of organic pollutants (NM: Non-metal dopant).

Table 1
Synthesis of various metal and non-metal doped TiO2 nanomaterials using different methods.

Doped TiO2 Synthesis method Precursors/Dopant Source Dopant concentration References

nanomaterial
Ag-TiO2 Sol-gel Ti{OCH(CH3)2}4, AgNO3 2, 4, 6, 8 mol % Ali et al. (2018)
Ag-TiO2 Reverse micelle mediated sol–gel Ti{OCH(CH3)2}4, AgNO3 0.7, 2.4, 3.4, 5.2 wt.% Krejčíková et al. (2012)
Ag-TiO2 Wet impregnation Ti{OCH(CH3)2}4, AgNO3 0.5 % Tayade et al. (2006)
Ag-TiO2 Chemical reduction TiO2 powder, AgNO3 0.25, 0.5, 1.0, 3.0, 5.0 wt.% Ng et al. (2016)
Ag-TiO2 Microemulsion Ti{OCH(CH3)2}4, AgNO3 1.5, 4.5, 6.5, 8.5 mol% Zielińska et al. (2010)
Au-TiO2 Sol-gel (Ti(OC4H9)4, HAuCl4
4H2O 0.25, 0.5, 1.0, 2.0, 4.0, 5.0 atomic Li and Li (2001)
%
Fe-TiO2 Wet impregnation Ti{OCH(CH3)2}4, FeCl3 0.5 % Tayade et al. (2006)
Fe-TiO2 Hydrothermal Ti{OCH(CH3)2}4, Fe (NO3)3
9H2O 0.3, 7 mol (%) ratio Asiltürk et al. (2009)
Cu-TiO2 Sol-gel Ti{OCH(CH3)2}4, CuCl2 5, 9, 13 mol% Krishnakumar et al. (2016)
Cu-TiO2 Wet impregnation Ti{OCH(CH3)2}4, Cu(CO2CH3)2 0.5 % Tayade et al. (2006)
Cu-TiO2 Microwave mediated sol–gel TiO2 (Degussa P25), Cu(NO3)2 0.4, 2, 7, 20 wt.% Chiang and Doong (2014)
Ni-TiO2 Sol-gel TiCl4, C2NiO4 0.02, 0.08, 0.1 at.% Devi et al. (2010)
Ni-TiO2 Hydrothermal Commercial TiO2, Ni(NO3)2
6H2O 5, 7 % Nakhate et al. (2010)
Ni-TiO2 Wet impregnation Ti{OCH(CH3)2}4, Ni(OCOCH3)2
4H2O 0.5 % Tayade et al. (2006)
Co-TiO2 Hydrothermal CoSO4, TiOSO4 0.1, 0.3, 0.5, 1, 2, 3% Jiang et al. (2015)
Co-TiO2 Wet impregnation Ti{OCH(CH3)2}4, CoCl2 0.5 % Tayade et al. (2006)
Bi- TiO2 Sol-gel & hydrothermal Ti{OCH(CH3)2}4, Bi (NO3)3
5H2O 0.5 wt.% Natarajan et al. (2013)
Mn-TiO2 Sol-gel TiCl4, C2MnO4 0.02, 0.06, 0.1 at.% Devi et al. (2010)
Zn-TiO2 Sol-gel TiCl4, C2ZnO4 0.02, 0.06, 0.1 at.% Devi et al. (2010)
Mo-TiO2 Reverse micelle mediated sol–gel Ti(OC4H9)4, (NH4)6Mo7O24
4H2O 1.0, 5.0, 10.0 wt.(%) ratio Nasi et al. (2019)
N-TiO2 Sol-gel Ti{OCH(CH3)2}4, CO(NH2)2 0.5, 2, 3 molar ratio Abdelhaleem and Chu
(2017)
N-TiO2 Flame spray pyrolysis Ti{OCH(CH3)2}4, HNO3 0.8, 1.0, 1.5, 2.0, 3.0, 4.0 M Boningari et al. (2018)
C-TiO2 Hydrothermal Ti{OCH(CH3)2}4, C6H12O6 4.5 wt.% Ren et al. (2007)
B-TiO2 Sol-gel Ti{OCH(CH3)2}4, B(OCH2CH3)3, 0.5, 1, 2, 5, 10 wt.% Grabowska et al. (2009)
BH3O3
P-TiO2 Microwave mediated Ti(OC4H9)4, NaH2PO4 0.012 molar ratio Niu et al. (2014)
hydrothermal
S-TiO2 solvothermal Ti(OC4H9)4, CH4H2S 0.5, 1.0, 1.5 molar ratio Yang et al. (2012)
F-TiO2 Sonochemical Ti{OCH(CH3)2}4, NH4F 0.7, 1.3, 2.4 mol% Yu et al. (2012)

3. Doped TiO2 photocatalyst for degradation of pharmaceutical
and pesticide compounds (PPCs) under different light sources
3.1. Photocatalytic degradation of PPCs under UV light source
UV light mediated photocatalytic degradation of organic pollu-
tants viz. chloramphenicol (Shokri et al., 2013), metronidazole
(Malakootian et al., 2019), amoxicillin trihydrate (Mohammadi
et al., 2012), bisphenol A (Gao et al., 2010), naproxen sodium
(Hinojosa-Reyes et al., 2019), and malathion (Kadam et al., 2014)
by using metal/non-metal doped TiO2 nanomaterials are summa-
rized in Table 2.
Shokri et al. (2013) synthesized Ag doped TiO2 nanomaterials
through photodeposition method where silver ion is doped onto
 K.S. Varma et al. / Water-Energy Nexus 3 (2020) 46–61
Table 2
Photocatalytic degradation of PPCs using doped TiO2 nanomaterial under UV light source.
Doped TiO2 Targeted pollutant & its Irradiation time
Nanomaterial concentration (min)
Ag-TiO2 Chloramphenicol (20 mg/L) 30
Fe-TiO2 Metronidazole (80 mg/L) 120
Sn-TiO2 Amoxicillin trihydrate (10– 30
40 mg/L)
Zr-TiO2 Bisphenol A (15–60 mg/L) 80
Ni-TiO2 Naproxen sodium (10 mg/L) 360
Cu-TiO2 Naproxen sodium (10 mg/L) 360
Fe-TiO2 Naproxen sodium (10 mg/L) 360
N-TiO2 Malathion (15 mg/L) 150
a 1
Rate constant for pseudo first order kinetics, min .
TiO2-P25 (Degussa) with different silver concentration from 0.32 to
1.6 wt.%. They have found almost complete degradation of chlo-
ramphenicol with Ag-TiO2 nanomaterial at optimum silver doping
which is synthesized at lower calcination temperature.
Malakootian et al. (2019) synthesized Fe doped TiO2 nanomate-
rials through sol-gel method and they are checked UV light medi-
ated photocatalyst performance against model metronidazole
aqueous solution and industrial pharmaceutical waste water. At
acidic pH of 3 and alkaline pH of 11, higher photocatalytic degrada-
tion of metronidazole is found compared to neutral pH of 7. High-
est photocatalytic degradation against aqueous pollutant is
achieved at alkaline pH. Performance of Fe-TiO2 photocatalyst
against industrial pharmaceutical waste water is also checked,
where 69.85% degradation is achieved at optimum pH and photo-
catalyst amount under 120 min UV light irradiation.
Mohammadi et al. (2012) utilized sol–gel method for synthesiz-
ing TiO2 and Sn-TiO2 nanomaterials for degradation of amoxicillin
trihydrate in laboratory quartz photoreactor under UV illumina-
tion. Band gap energy is increased slightly with Sn doping onto
TiO2, which suggested that synthesized Sn doped TiO2 photocata-
lyst is more active under the UV-C source compared to TiO2. High-
est photocatalytic performance against antibiotic is achieved in 1.5
mole% Sn-TiO2 which mainly due to altered photocatalyst proper-
ties like lower crystallite size, high specific surface area and higher
amount of hydroxyl radical.
Gao et al. (2010) prepared undoped TiO2 and Zr doped TiO2
nanomaterials with Zr concentration range in molar ratio from
0.05 to 0.35 by using sol–gel method. Photocatalysis performance
is checked against bisphenol A under UV light illumination. From
synthesized nanomaterials, Zr-TiO2 with 0.2 molar ratio of Zr is
shown removal of total organic carbon (TOC) of about 90% in 2
hrs, whereas only 60% TOC is removed by using TiO2 nanomaterial.
Zr doped TiO2 nanomaterials calcined at higher temperature are
shown enhancement in TOC removal compared to calcined at
lower temperature.
Hinojosa-Reyes et al. (2019) synthesized Ni-TiO2, Cu-TiO2 and
Fe-TiO2 nanomaterials through sol–gel method. Photocatalytical
performance against naproxen sodium aqueous solution using syn-
thesized metal doped TiO2 nanomaterials are checked individually
under UV light source. The metal dopant is altered the crystallite
size by hindered the crystal growth of TiO2, which is observed in
all transition metal doped TiO2 nanomaterials. Compared to
undoped TiO2 nanomaterial, BET surface area is increased in both
cases of 1wt.% Ni-TiO2 and 1wt.% Fe-TiO2 nanomaterials, whereas
surface area is decreased in 1wt% Cu-TiO2 nanomaterial. Highest
photocatalytic degradation is achieved at optimum dopant concen-
tration for all metal doped TiO2 nanomaterials. Fe doped TiO2
51
Optimized photocatalyst/reaction conditions Performance of References
photocatalyst
0.96 wt% Ag; calcined at 300 °C ~100% Shokri et al. (2013)
Photocatalyst: 500 mg/L; pH: 11 97% Malakootian et al.
(2019)
1.5 mol% Sn; photocatalyst:400 mg/L; 0.25a Mohammadi et al.
pollutant:10 mg/L (2012)
0.2 molar ratio Zr/Ti; calcined at 700 °C; ~100% Gao et al. (2010)
pollutant:15 mg/L
1wt.% Ni; photocatalyst: 2 g/L 84% Hinojosa-Reyes et al.
(2019)
1wt.% Cu; photocatalyst: 2 g/L 87% Hinojosa-Reyes et al.
(2019)
1wt.% Fe; photocatalyst: 2 g/L 99% Hinojosa-Reyes et al.
(2019)
pH: 6; photocatalyst: 1 g/L 97% Kadam et al. (2014)
nanomaterial with 1wt.% dopant concentration has shown highest
photocatalytic performance compared to all synthesized undoped
and transition metal doped TiO2 nanomaterials which may be
due to delaying in recombination of charge carriers through incor-
poration of Fe into TiO2 structure.
Kadam et al. (2014) synthesized N-TiO2 nanomaterial through
microwave mediated method. With doping of nitrogen, bang gap
edge is shifted towards higher wavelength region. Synthesized
photocatalyst is utilized for degradation of malathion aqueous pol-
lutant under UV light illumination. Effect of photocatalyst amount
is checked with range of 0.5–2 g/L, where initially degradation effi-
ciency is increased with increment in photocatalyst from 0.5 to 1 g/
L. However, further increment in N-TiO2 photocatalyst has affected
the degradation efficiency. Highest degradation efficiency found
against pollutant was when pH increased to 6, significant photo-
catalyst performance of N-TiO2 nanomaterial is achieved under
the optimized conditions.
From various researchers work on photocatalytic degradation of
doped TiO2 nanomaterials under UV light source, it is noted that
with metal and non-metal dopants incorporation onto TiO2 struc-
ture has helped for development of doped TiO2 nanomaterials with
improved properties such as lower crystallite size, higher specific
area and lower recombination rate of charge carriers. It is found
that, higher degradation efficiency against organic pollutant is
achieved due to these improved properties in doped TiO2 photocat-
alyst at optimum dopant amount. Stability of photocatalyst and
adsorption capacity of pollutant by photocatalyst are changed with
change in pH of the pollutant solution. Zirconium doped TiO2
nanomaterials has shown excellent results in TOC removal com-
pared to undoped TiO2 nanomaterials. Iron doped TiO2 nanomate-
rials has shown better photocatalysis performance compared to
nickel and copper doped TiO2 nanomaterials. It is also observed
that alternation of pH has played vital role in enhancement of pho-
tocatalyst performance. Moreover, Calcination temperature at post
synthesized stage of the nanomaterials is important for enhancing
the photocatalyst performance.
3.2. Photocatalytic degradation of PPCs under visible light source
Under visible light source, performance of metal/non-metal
doped TiO2 nanomaterials against various organic pollutants viz.
4-nitrophenol (Sood et al., 2015), metronidazole (Boxi and Paria,
2015), amoxicillin (Leong et al., 2014), 2,4-dichlorophenol (Tian
et al., 2012), bisphenol A (Blanco-Vega et al., 2017), diclofenac (Yi
et al., 2019), 4-chlorophenoxyacetic acid (Abdelhaleem and Chu,
2017), and 2,4,6-trichlorophenol (Malghe and Lavand, 2015) are
presented in Table 3.
52 K.S. Varma et al. / Water-Energy Nexus 3 (2020) 46–61
Table 3
Photocatalytic degradation of PPCs using doped TiO2 nanomaterial under visible light source.
Doped TiO2 Targeted pollutant & its Irradiation time
Nanomaterial concentration (min)
Fe-TiO2 4-nitrophenol (10 mg/L) 300
Ag-TiO2 Metronidazole (15–30 mg/L) 120
Ag-TiO2 Amoxicillin (20 mg/L) 300
Cr-TiO2 2,4-dichlorophenol (100 mg/L) 480
Ni-TiO2 Bisphenol A (10 mg/L) 120
S-TiO2 Diclofenac (10 mg/L) 240
N-TiO2 4-chlorophenoxyacetic acid 360
(0.01–0.1 mM)
C-TiO2 2,4,6-trichlorophenol (10– 90
40 mg/L)
Sood et al. (2015) synthesized visible light active Fe doped TiO2
nanomaterials through ultrasonic mediated hydrothermal method.
Photocatalytic degradation experiment is carried out against 4-
nitrophenol in batch photoreactor under 150 W CFL bulb as visible
light source. Due to Fe ion doping, band gap energy is decreased
compared to undoped TiO2 nanomaterials. From photolumines-
cence (PL) analysis, it is observed that PL intensity is decreased
with increment in Fe dopant upto 0.075 mol% which indicates that
Fe dopant has enabled the charge carriers separation. However, at
higher Fe doping amount, PL intensity is increased which may be
due to fast recombination of charge carriers. Highest photocat-
alytic degradation efficiency is observed in 0.05 mol% Fe doped
TiO2 nanomaterials compared to other nanomaterials because of
optimum conditions such as shifting of band gap edge towards vis-
ible light wavelength and lower PL intensity.
Boxi and Paria (2015) prepared silver doped hollow TiO2
nanoparticles through sol–gel method with AgBr as the sacrificial
core. Photocatalytic performance study is checked against metron-
idazole under 125 W mercury lamp with UV cut-off filter as visible
light source. Due to Ag doping, shifting of absorption wavelength
towards the higher wavelength is achieved which makes it suitable
for working under visible light source. Synthesized Ag doped hol-
low TiO2 nanomaterials have shown significantly higher BET sur-
face area compared to solid TiO2 nanomaterials which is resulted
due to generation of hollow nanoparticles. Synthesized silver
doped hollow TiO2 nanoparticles has shown higher photocatalytic
degradation performance compared to undoped TiO2 nanomateri-
als. Recyclability is also checked for synthesized Ag doped hollow
TiO2 nanomaterials against metronidazole and it is observed that
around 10% decrease in degradation after six cycle.
Leong et al. (2014) utilized non-hydrolytic sol–gel method for
synthesizing TiO2 nanomaterials and Ag doped TiO2 nanomaterials
is prepared by using ethylene glycol and silver nitrate as raw con-
stituents. Synthesized photocatalytic Ag-TiO2 nanomaterials is
used for degradation of amoxicillin under 500 W tungsten-
halogen lamp with UV cut-off filter as visible light source. Based
on diffused surface reflectance spectra, bare TiO2 nanomaterials
has shown absorption in UV region. However, due to localized sur-
face plasmon resonance effect formed by silver dopant, shifting of
absorption edge in visible region is found in Ag doped TiO2 nano-
material. The visible light active Ag doped TiO2 nanomaterials with
3wt.% Ag doping concentration has shown the significantly higher
photocatalytic activity against the amoxicillin aqueous pollutants
compared to undoped TiO2 nanomaterials.
Tian et al. (2012) synthesized Cr doped TiO2 nanomaterials by
using flame spray pyrolysis method. Photocatalytic degradation
against 2,4-dichlorophenol is employed in quartz photocatalytic
reactor under 1000 W halogen lamp with UV cut-off filter as visible
light source. The chromium ion doping onto TiO2 has altered the
crystalline phase of TiO2, where both anatase and rutile phase
Optimized photocatalyst/reaction Performance of References
conditions photocatalyst
0.05 mol% Fe 92% Sood et al. (2015)
Ag doped hollow TiO2; pollutant:15 mg/L 96.55% Boxi and Paria (2015)
3wt% Ag 63.48% Leong et al. (2014)
1at.% Cr 83% Tian et al. (2012)
1wt.% Ni; pH: 9 93% Blanco-Vega et al.
(2017)
Calcined at 300 °C 93% Yi et al. (2019)
2 molar ratio N/Ti; photocatalyst: 1 g/L; ~100% Abdelhaleem and
pollutant: 0.01 mM Chu (2017)
Calcined at 300 °C; pollutant: 20 mg/L ~98% Malghe and Lavand
(2015)
are observed as per XRD characterization. In Cr-TiO2 nanomateri-
als, with increment in Cr dopant amount from 1 to 5 atom%, more
shifting of band gap edge is observed towards visible light region.
Among the synthesized nanomaterials, 1atom% Cr-TiO2 nanopho-
tocatalysts has shown almost three times higher photoactivity
against aqueous pollutant compared to undoped TiO2
nanomaterial.
Blanco-Vega et al. (2017) synthesized undoped and Ni doped
TiO2 nanomaterials with different Ni dopant concentration (0.5–1
weight%) through microwave mediated sol–gel method. Photocat-
alyst performance of undoped and Ni-TiO2 nanomaterials are
checked against Bisphenol A under 25 W lamp as visible light
source. Increment in surface area is observed with increasing Ni
dopant concentration onto TiO2. Band gap wavelength edge of
undoped TiO2 nanomaterial is under UV light region and signifi-
cant red shift in band gap wavelength is observed in case of 1wt.
% Ni doped TiO2 nanomaterials. For evaluating microwave medi-
ated sol–gel method and sol–gel method, 1wt.% Ni-TiO2 nanomate-
rial is also synthesized using sol–gel method and it is found that
photocatalytic performance is higher in microwave mediated
sol–gel method compared to sol–gel method.
Yi et al. (2019) used sol–gel method for synthesizing S-TiO2
nanomaterials at three different calcination temperature (i.e.,
300, 350 and 400 °C). They have compared the photocatalytic per-
formance against diclofenac aqueous pollutant under white LED
lights as visible light source. Based on PL analysis, it has observed
that PL intensity is lower in case of S-TiO2 nanomaterials which is
calcined at lowest temperature. Highest photocatalytic degrada-
tion efficiency is found in S-TiO2 nanomaterials which is calcined
at 300 °C mainly due to lower band gap energy. Increment in pho-
tocatalytic performance is observed at high photocatalyst amount
for S-TiO2 calcined at 300 °C and photocatalytical performance is
declined rapidly when pH is increased towards alkaline region.
Abdelhaleem and Chu (2017) are synthesized N doped TiO2
nanomaterials through sol–gel method and photocatalytic degra-
dation against 4-chlorophenoxyacetic acid aqueous solution is car-
ried out using two 100 W white LED lamps as visible light source.
Visible light absorption by N doped TiO2 nanomaterial (with molar
ratio of 2) is higher compared to undoped TiO2 because of lower
band gap energy. With increment in pollutant concentration, there
is a considerable decrease in photocatalytic degradation efficiency
at constant photocatalyst amount. Rate of degradation of pollu-
tants is higher in acidic pH range, while there is much declination
in degradation performance in alkaline pH. With using N doped
TiO2 nanomaterials, 73% mineralization of TOC of pollutant is
achieved under visible light irradiation.
Malghe and Lavand (2015) prepared C doped TiO2 nanomateri-
als by using reverse microemulsion method at different calcination
temperature range from 300 to 500 °C. Photocatalytic degradation
of 2,4,6-trichlorophenol is carried out under 65 W CFL bulb
 K.S. Varma et al. / Water-Energy Nexus 3 (2020) 46–61
(k > 420 nm) as visible light source. Carbon dopant has decreased
the band gap energy, where lowest band gap energy is found in
case of C-TiO2 nanomaterial which is calcined at 300 °C. Perfor-
mance of C doped TiO2 nanomaterial calcined at different temper-
ature is checked, where highest degradation of pollutant is found
in case of 300 °C calcined sample. During recyclability test, it is
found that no significant decline of photocatalyst performance
after three times cycle of C-TiO2 nanomaterials.
Based on various approaches proposed and reported by
researchers for enhancing the performance of doped TiO2 nanoma-
terials against pollutant under visible light source, it is observed
that using metal and non-metal dopants individually, both band
gap energy and PL intensity are decreased which enhanced the
degradation performance under visible light source. Synthesis
method is also a governing factor for enhancing the performance
of photocatalyst against pollutants. It is found that through sacrifi-
cial core agent in sol–gel method, hollow nanomaterials with sig-
nificant higher surface area is synthesized compared to solid
nanomaterials. In another case of comparison where doped TiO2
nanomaterials is synthesized separately by using two synthesis
methods and it is found that performance of nanomaterials by
using microwave mediated sol–gel method is better than sol–gel
method. In silver doped TiO2 nanomaterials, higher photocatalytic
performance is achieved due to surface plasmon resonance effect.
Nitrogen doped TiO2 nanomaterials have shown good ability in
mineralization of pollutants under visible light. After recycling of
photocatalyst for multiple times, carbon doped TiO2 nanomaterial
has shown decent stability in photocatalytical performance.
3.3. Photocatalytic degradation of PPCs under natural solar light
source
Table 4 presents the photocatalytic degradation of organic
aqueous pollutants viz. ofloxacin (Kundu et al., 2014), ibuprofen
(Bhatia and Dhir, 2016), carbendazim, propiconazole (Kaur et al.,
2016), and acephate (Zhang et al., 2015) under natural solar light
irradiation by using metal/non-metal doped TiO2 nanomaterials.
Kundu et al. (2014) synthesized Ni doped TiO2 nanomaterial
through hydrothermal method. The synthesized nanomaterial
has shown peaks related to anatase TiO2 phase as per XRD charac-
terization. Photocatalytic degradation against ofloxacin is checked
in double walled photocatalytic reactor under natural solar light,
where it is found that considerable degradation of aqueous pollu-
tant is observed with utilization of Ni-TiO2 nanomaterial. Effect
of pH is also checked, where slight decrease in photocatalytic
degradation efficiency at pH 4 and pH 9 compared to neutral pH.
Bhatia and Dhir (2016) synthesized Bi-TiO2 and Ni-TiO2 nano-
materials individually through sol–gel method with different Bi
and Ni dopant concentration of 0.25, 0.5 and 1 wt.%. With incre-
ment in Bi doping amount, increase in crystallite size and slight
decrease in surface area is observed. In Ni-TiO2 nanomaterials,
lowest crystallite size and higher surface area is found at 0.5wt%
Ni doping amount. Highest band gap shifting towards visible light
Table 4
Photocatalytic degradation of PPCs using doped TiO2 nanomaterial under natural solar light source.
Doped TiO2 Targeted Pollutants & its Irradiation
Nanomaterial concentration time (min)
Ni-TiO2 Ofloxacin (25 mg/L) ~180
Bi-TiO2 Ibuprofen (25 mg/L) 360
Ni-TiO2 Ibuprofen (25 mg/L) 360
Fe-TiO2 Carbendazim (8 mg/L) 300
Fe-TiO2 Propiconazole (25 mg/L) 300
N-TiO2 Acephate (8  10 4 mol/L) 120
53
region is found in 0.25wt% Bi-TiO2 and 0.5wt% Ni-TiO2 nanomate-
rials. Under natural solar light illumination, significant photocat-
alytic degradation efficiency against aqueous ibuprofen solution
is found in 0.25wt% Bi-TiO2 and 0.5wt% Ni-TiO2 nanomaterials
which may be due to improved properties like lower crystalline
size and band gap energy.
Kaur et al. (2016) synthesized Fe doped TiO2 nanomaterials
with different Fe doping concentration ranging from 1-4 wt.%
through impregnation method. Photocatalytic degradation perfor-
mance is checked against two model aqueous pollutants i.e., car-
bendazim and propiconazole. Under natural solar light
illumination, highest photocatalytic performance against two
model aqueous pollutants is found at optimum Fe doping of 2wt
% because of low band gap energy. For individual degradation of
carbendazim and propiconazole, requirement of optimized Fe-
TiO2 (2wt%) is 1 g/L and 0.25 g/L respectively. Highest photocat-
alytic degradation is observed at natural pH solution of targeted
pesticides compare to other pH.
Zhang et al. (2015) prepared N doped TiO2 nanotube arrays via
two stages. TiO2 nanotube films are formed by anodic oxidation
method followed by annealing of N2, where N doped TiO2 nanotube
arrays is fabricated. Synthesized nanotube arrays is utilized for
photocatalytic degradation of acephate under natural solar light
illumination. H2O2 is also used in degradation experiment as oxi-
dizing agent along with nanophotocatalyst. N doped TiO2 nanotube
arrays are calcined at 400 and 500 °C, where substantial absorption
wavelength shift towards higher wavelength is observed for 500 °C
calcined photocatalyst. It is observed that N-TiO2 nanotube arrays
has shown noticeably higher photocatalytic performance than
undoped TiO2 nanotube arrays.
Degradation performance of various metal and non-metal
doped TiO2 nanomaterials are compared with undoped TiO2 nano-
material and it is observed that doped TiO2 nanomaterials have
shown better performance under natural solar light source. Effect
of dopant amount, post synthesis temperature and pH are key fac-
tors which influenced the photocatalyst performance. Bismuth
doped TiO2 nanomaterials has shown higher degradation perfor-
mance compared to nickel doped TiO2 nanomaterials.
4. Water-energy nexus factors allied with doped TiO2
photocatalyst mediated advanced waste water treatment
For removing organic pollutants from waste water by using
doped TiO2 nanophotocatalyst is one of the most promising
advanced waste water treatment technique. Here, literature is
scrutinized based on three aspects. First aspect is water, where
characteristics of waste water and associated process parameters
like pH and addition of ions have explained. Second aspect is doped
TiO2 nanomaterials, where development of doped TiO2 nanomate-
rials through various synthesis methods, and its applicability to
pollutant degradation have discussed. In last aspect, details of
energy consumption scenario are explained. Utilization of doped
TiO2 nanomaterials and LED light source has briefly exemplified
Optimized photocatalyst/reaction conditions Performance of References
photocatalyst
3wt.% Ni; photocatalyst: 1 g/L; pH: 7 70% Kundu et al. (2014)
0.25 wt.% Bi; pH: 6; photocatalyst: 2 g/L 89% Bhatia and Dhir (2016)
0.5wt.% Ni; pH: 6; photocatalyst: 2 g/L 78% Bhatia and Dhir (2016)
2wt.% Fe 98%, Kaur et al. (2016)
2wt.% Fe 90% Kaur et al. (2016)
calcined at 500 °C 84% Zhang et al. (2015)
54 K.S. Varma et al. / Water-Energy Nexus 3 (2020) 46–61
as effective strategies to reduce the energy consumption during
waste water treatment. Therefore, with utilization of these aspects,
water energy nexus approach is significantly addressed. The key
factors of water energy nexus associated with doped TiO2 photo-
catalyst mediated advanced waste water treatment is illustrated
in Fig. 4.
4.1. Parameters affecting aqueous pollutant stream
Industrial waste water is contained various types of cationic
and anionic contaminants. Integration of nanomaterials and its
photocatalytic performance is strongly depended on nature of
waste water. To analyse the performance of TiO2 nanomaterial at
different pH, it is necessary to identify the favourable pH range.
Moreover, types of contaminants and nanomaterials has unique
relationship with ions present in waste water. So, identification
of optimized pH range is required for enhancing the photocatalytic
based waste water treatment processes.
Xiao et al. (2008) observed that photocatalytic degradation of
methylene blue (MB) dye is highly influenced by pH values in dif-
ferent region. C doped TiO2 nanomaterials is employed as photo-
catalyst and it is found that in alkaline pH of 10, highest
photocatalytic degradation efficiency is achieved which is mainly
because of interaction of cationic MB dye with anioic C doped
TiO2 nanomaterials. At pH of 10, highest adsorption of dye pollu-
tant on photocatalyst surface is found. Suwarnkar et al. (2014)
checked the effect of pH on photocatalytic performance of Ag
doped TiO2 nanomaterials against methyl orange (MO) under UV
light source. Highest photocatalytic performance is observed for
pH 3. While further increment in pH from acidic region to alkali
is affected the degradation performance of positively charged Ag-
TiO2 nanomaterials. Thu et al. (2016) found that the individual
adsorption of MO and MB on surface of Cu doped TiO2 nanomate-
rials behaved differently. In acidic condition (pH = 3), adsorption
capacity of MO on photocatalyst surface is higher due to interac-
tion of negatively charged dye pollutant with positively charged
Cu doped TiO2 nanophotocatalyst. However, due to cationic nature
of for MB dye, there is hardly any adsorption occurred at acidic
condition at pH 3 and higher MB dye is adsorbed on photocatalyst
surface for pH near 9. Shetty et al. (2017) have shown that the
change in photocatalytic degradation efficiency against ciprofloxa-
cin HCl at different pH of 3, 7 and 9. Highest photocatalytic perfor-
Fig. 4. Key factors of water-energy nexus associated with doped TiO2 photocatalyst mediated advanced waste water treatment.
mance of N doped TiO2 nanomaterials is found at pH of 7. At acidic
and alkaline pH, photocatalyst performance is affected due to sim-
ilar charge on photocatalyst and pollutant.
Mohammadi et al. (2012) reported photocatalytic performance
of Sn doped TiO2 nanomaterials and checked the mineralization of
amoxicillin trihydrate in both distilled water and municipal raw
water consists mainly minerals like carbonates, bicarbonates and
sulphates. Ions present in photocatalytic reactor have lowered
the mineralization performance compared to distilled water,
resulting in the retardation of the adsorption of pollutants to the
nanomaterial reactive sites. Gao et al. (2010) utilized Zr doped
TiO2 nanomaterials for degradation of bisphenol A and they
checked the effect of inorganic ions on photocatalytic degradation.
Four types of inorganic ions are added individually in form of
sodium salt. Nitrate and chloride ions increased the rate of degra-
dation of bisphenol A, while phosphate and sulphate ions impaired
the photocatalyst performance.
Change in pH of solution has altered the adsorption capacity of
pollutant on surface of photocatalyst. Generally, degradation effi-
ciency is increased at high adsorption of pollutant. Addition of ions
has either improved or declined the degradation efficiency of
doped TiO2 nanomaterials which depends upon types of ions and
their interactions with pollutant solution and photocatalyst. So,
modification of parameters such as effect of pH and addition of
ions in aqueous pollutant stream are effective strategy to enhanced
the photocatalyst performance.
4.2. Visible light active doped TiO2 nanophotocatalyst materials
Role of various metal and non-metal dopants onto TiO2 nano-
materials is different and it also depends on calcination tempera-
ture. Here, we have mentioned different study which consist the
relationship of characteristics of doped TiO2 nanomaterials with
pollutant degradation under visible light.
Asiltürk et al. (2009) synthesized Fe doped TiO2 nanomaterials
through hydrothermal synthesis method, it is observed that Fe
doped TiO2 thin film is appeared as better photocatalyst compared
to undoped TiO2 thin film. Venkatachalam et al. (2007) observed
that with increment in Zr doping amount onto TiO2 has resulted
in decrease in crystallite size and increment in surface area of
the nanomaterials. Photocatalytic degradation efficiency is found
higher in case of Zr-TiO2 compared to undoped TiO2 and Degussa
 K.S. Varma et al. / Water-Energy Nexus 3 (2020) 46–61
P-25 TiO2 nanomaterials. Bu et al. (2012) found that compared to
undoped TiO2 nanomaterials, N doped TiO2 nanomaterial has
shown better control over the increment in growth of nanoparti-
cles with increment in calcination temperature. At optimum cal-
cined temperature, N-TiO2 nanomaterial has shown higher
photocatalytic degradation performance under visible light source
due to pertinent crystallinity and shifting of band gap edge. Feng
et al. (2012) observed that degradation efficiency of Mn doped
TiO2 nanomaterials is decreased when doping concentration and
annealing temperature exceeds the 3% and 450 °C respectively.
At higher annealing temperature, due to agglomeration of particles
and overgrowth of crystallite size is leads the decrease in perfor-
mance of photocatalyst.
Types of dopant and its concentration are critically important
while using it for photocatalytic degradation against pollutants
and the presence of dopant either enhances or retard the photocat-
alyst performance. For different dopants, optimum doping amount
is also varied where highest photocatalytic degradation efficiency
is achieved. Devi et al. (2010) synthesized Ni, Mn and Zn doped
TiO2 separately using sol–gel method with different dopant con-
centration. The band gap shifting towards the higher wavelength
is observed in all synthesized transition metal doped TiO2 nanoma-
terials. Photocatalytic degradation performances for Ni, Mn and
Zn-TiO2 nanomaterials (at optimum doping concentration) against
aqueous pollutants under solar light source was found higher than
undoped TiO2 nanomaterial. Amongst these metal doped TiO2
nanomaterials, Mn-TiO2 nanomaterials shown highest degradation
efficiency mainly because of bicrystalline phase resulted from rear-
rangement of ions and structure reorganization. Feng et al. (2012)
synthesized various metal doped TiO2 nanomaterials by using
metal ion dopant viz. Ag+, Cu2+, Mn2+, Ce3+, Fe3+ and Zr4+ separately
through hydrothermal method. In both under visible and solar
light irradiation, Mn-TiO2 nanomaterial showed maximum photo-
catalytic performance against model dye pollutant compared to
pure TiO2 and other metal doped TiO2 nanomaterials.
Gnanasekaran et al. (2016) synthesized undoped and three differ-
ent metal doped (Mn, Co and Zn) TiO2 nanomaterials through
widely used sol–gel synthesis method. They checked the photocat-
alytic performance of all synthesized nanomaterials against aque-
ous pollutants under visible light irradiation. Mn doped TiO2
nanomaterial showed highest photodegradation efficiency com-
pared to others because of low crystallite size, lower band gap
energy and high surface area. Colón et al. (2006) have shown effect
of Cu dopant states with respect to enhancement in photocatalyst
performance against the aqueous pollutant where they found that
Cu-TiO2 nanomaterial with Cu1+ has noticed higher photocatalytic
performance against aqueous pollutant compared to Cu doped TiO2
samples with Cu2+ state.
Nanomaterials with lower crystallite size, high surface area
have exhibited the enhanced photocatalytic performance in envi-
ronmental application. Change in calcination temperature during
synthesis of doped TiO2 nanomaterials has altered the properties
of nanomaterials, which is either enhanced or receded the degra-
dation performance against pollutants. Moreover, different
dopants have shown unique characteristics when incorporated
into TiO2 structure and exhibited properties like band gap shifting
in visible light region, bicrystalline phase and many others. These
improved properties of doped TiO2 nanomaterials enhanced the
photocatalyst performance compared to undoped TiO2
nanomaterials.
4.3. Energy
Based on various manufacturing industries scenario, it has been
observed that extensive amount of energy is required in many
stages of production. In addition, huge amount of energy consump-
55
tion is required in removing the pollutants from generated indus-
trial waste water. Therefore, it is important to develop the energy
efficient advanced waste water treatment processes which have
considerable potential in removal of pollutants from waste water.
We have focused on TiO2 and doped TiO2 nanomaterials based
photocatalytic degradation processes to rationalize the energy con-
sumption features.
Doping of metal in TiO2 nanomaterials and its importance is
known because of its improvement in the performance of photo-
catalytic degradation process. Doping of metal onto TiO2 nanoma-
terials has favoured the charge carriers separation and also altered
the nanomaterials properties. Energy consumption during photo-
catalytic degradation through pure TiO2 nanomaterials and metal
doped TiO2 nanomaterial is compared and revealed here.
Divya et al. (2013) have selected orange II as dye pollutant for
study the photocatalytic degradation under UV light source by
employing the three individual studies i.e., UV/H2O2 degradation
process, Degussa TiO2 P-25 and copper doped TiO2 P-25 nanomate-
rials mediated photocatalytic degradation process. Relative electric
energy per order (EEO) for Cu doped TiO2 P-25 for color removal
and COD removal are estimated as 0.640 and 0.082 with compared
to UV/H2O2 process with unit relative EEO. Comparison of energy
consumption for UV/H2O2, TiO2 and Cu-TiO2 photocatalytic process
in terms of relative EEO is illustrated in Fig. 5(a). Cu doped TiO2 P-
25 nanomaterials is shown higher photocatalytic performance as
well as consuming lesser electric energy in dye degradation.
Mohammadi et al. (2014) have synthesized TiO2, Sn doped TiO2
and Zn doped TiO2 as well as Sn/Zn doped TiO2 nanomaterials
through sol–gel method for targeting amoxicillin trihydrate using
black light lamp with k = 365 nm. Compared to pure TiO2, Sn-
TiO2 and Zn-TiO2 nanomaterials have also shown higher degrada-
tion against the antibiotic aqueous pollutant. Electric energy con-
sumption is estimated for all cases, where it has found that Sn-
TiO2 has EEO of 21.71 kWh/m3/order which is less compared to
Zn-TiO2 and TiO2 mediated photocatalytic degradation. EEO com-
parison for TiO2, Zn-TiO2 and Sn-TiO2 photocatalytic process is
shown in Fig. 5(b).
Photocatalytical activity of TiO2 nanomaterials depends on light
absorbed by photocatalyst. Therefore, light source intensity and
wavelength have its individual important role in photocatalytic
degradation of pollutants (Behnajady et al., 2011a; Subagio et al.,
2010). Energy consumption by TiO2 nanaomaterials in degradation
of contaminants under conventional UV light and UV-LED is eval-
uated here. Energy consumption of Solar and UV bulb mediated
photocatalytic process is also discussed.
Davididou et al. (2017) have utilized two different UV light
sources i.e., conventional blacklight fluorescent lamp (UV-BL) and
light-emitting diode (UV-LED) for removing pollutant. The targeted
pollutant in this study is artificial sweetener saccharin (SAC) and
TiO2 is chosen as photocatalyst. UV-LED mediated photocatalytic
process has better efficient than UV-BL mediated. Also, the pres-
ence of humic acid (HA) in aqueous pollutant solution has checked
where degradation efficiency is decreased with increment amount
of HA. Energy consumption in UV-LED based photocatalytic degra-
dation process is 8.2 kWh/m3/order which is very less compared to
UV-BL mediated process. Comparison of energy consumption for
UV black and UV LED for humic acid degradation is shown in
Fig. 6(a).
Davididou et al. (2018) have checked effect of light sources
(UV-LED, UV blacklight lamp and solar) on performance of photo-
catalytic degradation of bisphenol-A (BPA) with using Aeroxide
TiO2 P25 photocatalyst. Degradation of BPA is highest in case of
UV-LED and lowest in case of UV blacklight lamp, while solar light
mediated photocatalytic degradation of BPA is shown moderate
degradation performance result. UV energy consumption in UV
blacklight in terms of EEO is estimated as 43.067 kWh/m3/order
56
Relative EEO
1 0.905
UV/ H2O2 TiO2 P-25
(a)
Fig. 5. Effect of dopants on energy consumption of TiO2 based photocatalytic degradation of pollutant (a) Comparison of UV/H2O2, TiO2 and Cu-TiO2 photocatalytic process,
(b) Comparison of TiO2, Zn-TiO2 and Sn-TiO2 photocatalytic process.
EEO (kWh m−3 order−1)
134.4
UV Black UV LED
(a)
Fig. 6. Effect of light source on energy consumption of TiO2 based photocatalytic degradation of pollutant (a) Comparison of UV black and UV LED for humic acid degradation,
(b) Comparison of UV black and UV LED for bisphenol-A degradation.
which is much higher than EEO for UV-LED system. Energy con-
sumption for degradation of BPA under UV black and UV LED is
illustrated in Fig. 6(b).
Natarajan et al. (2011b) have utilized TiO2 nanotube for degra-
dation of Congo red dye using UV-LED light. They have compared
the degradation performance UV-LED with other earlier reported
work where tungsten, mercury, xenon types of lamps were utilized
for same dye pollutant and it is observed that UV-LED was utilizing
lowest power compared to others. Jo et al. (2014) are utilized UV
and blue LED light source for degradation of malachite green dye
in spiral shaped photocatalytic reactor using P25 Degussa TiO2 as
photocatalyst. In comparison to earlier work on degradation of
malachite green dye, it is observed that with energy efficient LEDs
is shown significant potential compared to other high energy con-
sumed halogen and mercury lamps. Dai et al. (2013) utilized UV-
LED for degrading MB dye in presence of P25 Degussa TiO2 nano-
materials. They are also compared for degradation performance
with other reported work on MB dye and it is found that low
energy consumed UV-LED is promising alternative to high energy
consumed UV lamps.
Dalrymple et al. (2007) compared solar vs UV lamps for photo-
catalytic degradation application. They mentioned that replace-
ment of conventional UV lamps by UV LEDs which are relatively
safer during handling, efficient and longer life span. However,
energy cost in UV mediated photocatalytic processes is high as
compared to solar mediated process. Utilization of solar energy
for photocatalytic degradation of pollutants is found as best option
at industrial level as solar light is clean, safe and most economical
light source.
Many types nanomaterials are employed as photocatalyst for
treating waste water. Interaction of pollutant molecules on active
sites of the nanomaterials is influenced the photocatalyst perfor-
K.S. Varma et al. / Water-Energy Nexus 3 (2020) 46–61
EEO (kWh m−3 order−1)
0.64
40.66
28.36
21.71
TiO2 P-
25/Cu TiO2 Zn/TiO2 Sn/TiO2
(b)
EEO (kWh m−3 order−1)
43.067
7.171
8.2
UV Black UV LED
(b)
mance. Therefore, degradation ability of photocatalyst against var-
ious pollutants are different. Pollutant which is easily degraded by
utilizing photocatalyst has consumed less energy in photocatalytic
degradation. Energy consumption scenario for different types of
pollutants is explained here.
Natarajan et al. (2011a) have utilized UV-LED mediated photo-
catalytic degradation of three diverse dye pollutants methylene
blue (MB), malachite green (MG) and rhodamine B (RhB) in immo-
bilize type photocatalytic reactor consist the TiO2 coated quartz
tube. The coated TiO2 nanomaterials has shown highest degrada-
tion of MG around 99% in 6 hrs. EEO is estimated based on degrada-
tion of all three dyes and it has observed that minimum electric
energy consumption in case of MG dye degradation is about
789.47 kWh/m3/order. Energy consumption for three dye pollu-
tants is represented in Fig. 7(a).
Behnajady et al. (2011b) have synthesized TiO2 nanoparticles
using sol–gel method. The synthesized TiO2 has utilized for degra-
dation of 4–nitrophenol (4–NP), methyl orange (MO), C.I. acid red
27(AR27) and malachite green (MG) under UV light irradiation.
Kinetics of degradation is suggested that highest and lowest photo-
catalytic degradation in MG and 4-NP is found respectively. The
energy consumption in terms of EEO is assessed where 4-NP is con-
sumed considerably much electric energy for degradation com-
pared to MG dye pollutant. Energy consumption in photocatalytic
degradation of different dyes and phenolic pollutants is shown in
Fig. 7(b).
Zatloukalová et al. (2017) have compared photocatalytic degra-
dation performance against various synthetic hormones in an
immobilized UV photocatalytic laboratory reactor setup by utiliz-
ing NnF Ceram TiO2 nanomaterials. Among the targeted endocrine
disrupting aqueous pollutants, progesterone is consumed least EEO
is of about 30 kWh/m3/order and electric energy consumed in pho-
 K.S. Varma et al. / Water-Energy Nexus 3 (2020) 46–61
Fig. 7. Effect of various pollutants on energy consumption of TiO2 based photocatalytic degradation of pollutant (a) Comparison of different dye pollutants, (b) Comparison of
different dye and phenolic pollutants, (c) Comparison of different synthetic hormones pollutants.
tocatalytic degradation of estrone is observed as lager compared to
others targeted hormone compounds. Comparison of energy con-
sumption for different synthetic hormones pollutants are illus-
trated in Fig. 7(c).
Development of different photocatalytic reactor designs for
effective utilization of light sources, interactions between pollutant
and photocatalyst and other allied parameters must be incorpo-
rated for devising efficient photocatalytic process for the removal
of pollutants. Kamble et al. (2003) utilized Degussa P-25 TiO2 pho-
tocatalyst for degradation of benzenesulfonic acid (BSA) under the
solar light source. They compared parabolic and spherical reflector
for degradation of BSA, where parabolic reflector is highly efficient
compared to spherical because of effective photo penetration
inside photocatalytic reactor. McCullagh et al. (2011) have briefly
explained about various types of photocatalytic reactors applicable
to pollutant degradation with focusing on their effectiveness, feasi-
bility for scale up at industrial level. They observed that slurry type
reactor is significantly capable to degrade the pollutants effectively
at laboratory scale, but at industrial scale this type of reactor has
shown limitation in scale-up due to its poor light penetration
capacity and separation of catalyst. Fluidized bed reactor is also
compared where they are found to be useful for both gaseous
and aqueous pollutant degradation, however, the losses of nano-
materials during the fluidization operation must be taken care of
for its utilization. Immobilized type reactor is also associated
where it is suggested that surface area exposed to aqueous pollu-
tant is challenging area of research and therefore scale up of this
type of reactor is required special design attention. Surenjan
et al. (2019) have performed degradation of pharmaceutical pollu-
tants i.e., diclofenac, ibuprofen and carbamazepine in a fluidized
bed reactor which consists nanomaterials coated supports. Carbon
57
doped TiO2 nanomaterials is used as photocatalyst. Treatment cost
per m3 of carbamazepine solution is compared with other treat-
ment techniques and it has found that by utilizing this type of vis-
ible light mediated fluidized bed reactor is economically more
proficient than UV based H2O2 and persulfate treatment processes.
Change in light source especially from UV to visible or solar for
activation of photocatalyst has saved significant energy consump-
tion during the degradation of pollutants. Jo and Tayade (2014)
noted that light emitting diodes (LEDs) has achieved a good atten-
tion as promising resources in various photocatalytic based mech-
anisms due to its less utilization of electric energy and
environment friendly approach. Photocatalytic performance of
doped TiO2 nanomaterials changed under different light sources.
Under diverse light intensity where degradation efficiency is asso-
ciated with excitation wavelength of nanomaterials, appropriate
selection of light source for enhancement of photocatalytic mech-
anism in doped TiO2 nanomaterials is significant.
5. Future challenges and concluding remarks
Mitigation of the water pollution is a huge challenge for entire
world due to rapid industrialization. One of the main concerns
regarding the commonly used waste water treatment techniques
is the efficiency in terms of complete removal of pollutants and
energy consumption. The complementarity between water treat-
ment and energy consumption is imminent and therefore this
nexus of water and energy should be in focus while devising new
approaches. Advanced waste water treatment process to conserve
water resources especially from pharmaceutical and pesticide
compounds (PPCs) is sought to be efficient in both the aspects
58 K.S. Varma et al. / Water-Energy Nexus 3 (2020) 46–61
i.e., pollutant removal and energy efficiency. Doped TiO2 nanoma-
terials based photocatalytic process has appeared as potential con-
tender among the other various advanced waste water treatment
processes owing to features viz. physical and chemical stability,
reusability, broad spectrum activity under variety of light sources
including solar and visible, and many others. Here in, a combined
approach has been proposed which consist the design and utiliza-
tion of doped TiO2 nanomaterials mediated advanced waste water
treatment process and simultaneously addressing the energetics
aspect.
To cultivate the concept of water energy nexus in waste water
treatment is a huge challenge for industry. Large quantity, diverse
quality and huge energy consumption in waste water treatment
are crucial challenging factors which must be concerned for devel-
oping doped TiO2 nanomaterials based advanced waste water
treatment processes. One of the challenges is to enhance the per-
formance of photocatalyst, where in the research is directed
towards band gap engineering through variety of dopants and
hybrid nanomaterials. Another important area is to achieve higher
surface area and narrow particle size distribution (PSD) in order to
ensure sufficient active sites. Research is also progressing on incor-
poration of additional photosensitizers to the photocatalyst to
accomplish amplified photooxidation. Moreover, enhancement in
photocatalyst performance by calcination temperature, pH and
many other process parameters give a plethora of control in
designing the desired doped TiO2 nanomaterials. Thus, the novel
photocatalysts with improved photodegradation efficiencies in vis-
ible light sources are expected outcome of research and
development.
Energy (light) source is equally important for exciting the doped
TiO2 nanomaterials and it is essential to utilize energy efficient
light source in order to render the process economical over the
existing approaches. Light emitting diodes (LEDs) are good options
for utilization in pollutant degradation as these LEDs are robust
and environment friendly. Also, LEDs consume lesser energy and
have longer life cycle than conventional light sources. At industrial
scale, the reactor design should ensure effective light penetration
to degrade the large quantity of waste water through photocat-
alytic treatment. Therefore, reactor design is one of the main chal-
lenges faced by proposed technique, concerning to address the
optimization of interaction between pollutants and photocatalyst,
uniform distribution of photon energy and residence time.
Overall, this review throws light on the energetics aspect of
waste water treatment using TiO2 based nanomaterials. To the best
of our knowledge, this is one of the first compilation of literature to
highlight the water energy nexus for advanced waste water treat-
ment aligned with environmental sustainability.
CRediT authorship contribution statement
Kiran S. Varma: Conceptualization, Writing - original draft.
Rajesh J. Tayade: Data curation, Methodology. Kinjal J. Shah: Data
curation, Methodology. Pradyuman A. Joshi: Visualization, Super-
vision. Atindra D. Shukla: Writing - review & editing, Validation,
Supervision. Vimal G. Gandhi: Writing - review & editing, Valida-
tion, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
Authors deeply acknowledge the Gujarat Pollution Control
Board (GPCB), Gandhinagar, Gujarat (India) for providing financial
assistance ship under the scheme of ‘‘Gujarat Pollution Control
Board Research & Development, and Ph.D. encouragement
Scheme” with grant ID: Ph.D./R&D/05/444437.
References
Abdel-Fatah, M.A., 2018. Nanofiltration systems and applications in wastewater
treatment: review article. Ain Shams Eng. J. 9, 3077–3092.
Abdelhaleem, A., Chu, W., 2017. Photodegradation of 4-chlorophenoxyacetic acid
under visible LED activated N-doped TiO2 and the mechanism of stepwise rate
increment of the reused catalyst. J. Hazard. Mater. 338, 491–501.
Abdel-Shafy, H., 2002. Water issue in Egypt: Resources, pollution and protection
endeavors. Central Eur. J. Med. 8, 1–21.
Agrawal, A., 2010. Water pollution with special reference to pesticide
contamination in india. J. Water Resour. Prot. 2, 432–448.
Ahmed, S., Rasul, M.G., Martens, W.N., Brown, R., Hashib, M.A., 2010. Heterogeneous
photocatalytic degradation of phenols in wastewater: A review on current
status and developments. Desalination 261, 3–18.
Ali, P.I., Gupta, V., 2006. Advances in Water Treatment by Adsorption Technology.
Nat. Protoc. 1, 2661–2667.
Ali, T., Ahmed, A., Alam, U., Uddin, I., Tripathi, P., Muneer, M., 2018. Enhanced
photocatalytic and antibacterial activities of Ag-doped TiO2 nanoparticles under
visible light. Mater. Chem. Phys. 212, 325–335.
Anandan, S., Ikuma, Y., Niwa, K., 2010. An overview of semi-conductor
photocatalysis: modification of TiO2 nanomaterials. Solid State Phenom. 162,
239–260.
Andreozzi, R., Caprio, V., Insola, A., Marotta, R., 1999. Advanced oxidation processes
(AOP) for water purification and recovery. Catal. Today 53, 51–59.
Ansari, S.A., Khan, M.M., Ansari, M.O., Cho, M.H., 2016. Nitrogen-doped titanium
dioxide (N-doped TiO2) for visible light photocatalysis. New J. Chem. 40, 3000–
3009.
Artsupho, L., Jutakridsada, P., Laungphairojana, A., Rodriguez, J.F., Kamwilaisak, K.,
2016. Effect of temperature on increasing biogas production from sugar
industrial wastewater treatment by UASB process in pilot scale. Energy
Procedia 100, 30–33.
Asiltürk, M., Sayılkan, F., Arpaç, E., 2009. Effect of Fe3+ ion doping to TiO2 on the
photocatalytic degradation of Malachite Green dye under UV and vis-
irradiation. J. Photochem. Photobiol. A. 203, 64–71.
Azami, M.S., Nawawi, W.I., Jawad, A.H., Mohd Ishak, M.A.B., Ismail, K., 2017. N-
doped TiO2 synthesised via microwave induced photocatalytic on RR4 dye
removal under LED light irradiation. Sains Malays. 46, 1309–1316.
Bakar, S.A., Byzynski, G., Ribeiro, C., 2016. Synergistic effect on the photocatalytic
activity of N-doped TiO2 nanorods synthesised by novel route with exposed
(110) facet. J. Alloys Compd. 666, 38–49.
Barkul, R.P., Patil, M.K., Patil, S.M., Shevale, V.B., Delekar, S.D., 2017. Sunlight-
assisted photocatalytic degradation of textile effluent and Rhodamine B by
using iodine doped TiO2 nanoparticles. J. Photochem. Photobiol. A 349, 138–
147.
Barwal, A., Chaudhary, R., 2014. To study the performance of biocarriers in moving
bed biofilm reactor (MBBR) technology and kinetics of biofilm for retrofitting
the existing aerobic treatment systems: a review. Rev. Environ. Sci. Bio/Technol.
13, 285–299.
Behnajady, M., Alizade, B., Modirshahla, N., 2011a. Synthesis of Mg-doped TiO2
nanoparticles under different conditions and its photocatalytic activity.
Photochem. Photobiol. 87, 1308–1314.
Behnajady, M., Eskandarloo, H., Modirshahla, N., Shokri, M., 2011b. Influence of the
chemical structure of organic pollutants on photocatalytic activity of TiO2
nanoparticles: Kinetic analysis and evaluation of electrical energy per order
(EEO). Dig. J. Nanomater. Biostruct. 6, 1887–1895.
Bhatia, V., Dhir, A., 2016. Transition metal doped TiO2 mediated photocatalytic
degradation of anti-inflammatory drug under solar irradiations. J. Environ.
Chem. Eng. 4, 1267–1273.
Blanco-Vega, M.P., Guzmán-Mar, J.L., Villanueva-Rodríguez, M., Maya-Treviño, L.,
Garza-Tovar, L.L., Hernández-Ramírez, A., Hinojosa-Reyes, L., 2017.
Photocatalytic elimination of bisphenol A under visible light using Ni-doped
TiO2 synthesized by microwave assisted sol-gel method. Mater. Sci. Semicond.
Process. 71, 275–282.
Boningari, T., Inturi, S.N.R., Suidan, M., Smirniotis, P.G., 2018. Novel continuous
single-step synthesis of nitrogen-modified TiO2 by flame spray pyrolysis for
photocatalytic degradation of phenol in visible light. J. Mater. Sci. Technol. 34,
1494–1502.
Boxi, S.S., Paria, S., 2015. Visible light induced enhanced photocatalytic degradation
of organic pollutants in aqueous media using Ag doped hollow TiO2
nanospheres. RSC Adv. 5, 37657–37668.
Bu, X., Zhang, G., Zhang, C., 2012. Effect of nitrogen doping on anatase-rutile phase
transformation of TiO2. Appl. Surf. Sci. 258, 7997–8001.
 K.S. Varma et al. / Water-Energy Nexus 3 (2020) 46–61
Carp, O., Huisman, C.L., Reller, A., 2004. Photoinduced reactivity of titanium dioxide.
Prog. Solid State Chem. 32, 33–177.
Chatzitakis, A., Berberidou, C., Paspaltsis, I., Kyriakou, G., Sklaviadis, T., Poulios, I.,
2008. Photocatalytic degradation and drug activity reduction of
chloramphenicol. Water Res. 42, 386–394.
Cheng, M., Zeng, G., Huang, D., Lai, C., Xu, P., Zhang, C., Liu, Y., 2016. Hydroxyl
radicals based advanced oxidation processes (AOPs) for remediation of soils
contaminated with organic compounds: a review. Chem. Eng. J. 284, 582–598.
Chiang, L.F., Doong, R., 2014. Cu-TiO2 nanorods with enhanced ultraviolet- and
visible-light photoactivity for bisphenol A degradation. J. Hazard. Mater. 277,
84–92.
Chowdhury, P., Moreira, J., Gomaa, H., Ray, A., 2012. Visible-solar-light-driven
photocatalytic degradation of phenol with dye-sensitized TiO2: parametric and
kinetic study. Ind. Eng. Chem. Res. 51, 4523–4532.
Colón, G., Maicu, M., Hidalgo, M.C., Navío, J.A., 2006. Cu-doped TiO2 systems with
improved photocatalytic activity. Appl. Catal. B 67, 41–51.
Connelly, K., Wahab, A.K., Idriss, H., 2012. Photoreaction of Au/TiO2 for hydrogen
production from renewables: a review on the synergistic effect between
anatase and rutile phases of TiO2. Mater. Renew. Sustain. Energy 1, 3.
Crini, G., Lichtfouse, E., 2019. Advantages and disadvantages of techniques used for
wastewater treatment. Environ. Chem. Lett. 17, 145–155.
Dai, K., Lu, L., Dawson, G., 2013. Development of UV-LED/TiO2 device and their
application for photocatalytic degradation of methylene blue. J. Mater. Eng.
Perform. 22, 1035–1040.
Dalrymple, O., Yeh, D., Trotz, M., 2007. Removing pharmaceuticals and endocrine-
disrupting compounds from wastewater by photocatalysis. J. Chem. Technol.
Biotechnol. 82, 121–134.
Davididou, K., McRitchie, C., Antonopoulou, M., Konstantinou, I., Chatzisymeon, E.,
2017. Photocatalytic degradation of saccharin under UV-LED and blacklight
irradiation. J Chem. Technol. Biotechnol. 93.
Davididou, K., Nelson, R., Monteagudo, J.M., Durán, A., Expósito, A., Chatzisymeon,
E., 2018. Photocatalytic degradation of bisphenol-A under UV-LED, blacklight
and solar irradiation. J. Cleaner Prod. 203.
Dawod, M., Breadmore, M.C., Guijt, R.M., Haddad, P.R., 2008. Electrokinetic
supercharging for on-line preconcentration of seven non-steroidal anti-
inflammatory drugs in water samples. J. Chromatogr. A 1189, 278–284.
De la Cruz, N., Esquius, L., Grandjean, D., Magnet, A., Tungler, A., de Alencastro, L.F.,
Pulgarín, C., 2013. Degradation of emergent contaminants by UV, UV/H2O2 and
neutral photo-Fenton at pilot scale in a domestic wastewater treatment plant.
Water Res. 47, 5836–5845.
De la Cruz, N., Giménez, J., Esplugas, S., Grandjean, D., de Alencastro, L.F., Pulgarín,
C., 2012. Degradation of 32 emergent contaminants by UV and neutral photo-
fenton in domestic wastewater effluent previously treated by activated sludge.
Water Res. 46, 1947–1957.
Devi, L.G., Kottam, N., Kumar, S.G., 2009. Preparation and characterization of Mn-
doped titanates with a bicrystalline framework: correlation of the crystallite
size with the synergistic effect on the photocatalytic activity. J. Phys. Chem. C
113, 15593–15601.
Devi, L., Kottam, N., Murthy, B., Kumar, S., 2010. Enhanced photocatalytic activity of
transition metal ions Mn2+, Ni2+ and Zn2+ doped polycrystalline titania for the
degradation of Aniline Blue under UV/solar light. J. Mol. Catal. A Chem. 328, 44–
52.
Dhananjay, B., Pangarkar, V., Beenackers, A., 2001. Photocatalytic degradation for
environmental application-a review. J. Chem. Technol. Biotechnol. 77, 102–116.
Divya, N., Bansal, A., Jana, A.K., 2013. Photocatalytic degradation of azo dye Orange II
in aqueous solutions using copper-impregnated titania. Int. J. Environ. Sci.
Technol. 10, 1265–1274.
Djurišić, A.B., Leung, Y.H., Ching Ng, A.M., 2014. Strategies for improving the
efficiency of semiconductor metal oxide photocatalysis. Mater. Horiz. 1, 400–
410.
Dubey, R.S., Singh, S., 2017. Investigation of structural and optical properties of pure
and chromium doped TiO2 nanoparticles prepared by solvothermal method.
Results Phys. 7, 1283–1288.
Feng, H., Zhang, M.H., Yu, L.E., 2012. Hydrothermal synthesis and photocatalytic
performance of metal-ions doped TiO2. Appl. Catal. A. 413–414, 238–244.
Fernández-Alba, A.R., Guil, L.H., López, G.D., Chisti, Y., 2001. Toxicity of pesticides in
wastewater: a comparative assessment of rapid bioassays. Anal. Chim. Acta 426,
289–301.
Gandhi, V., Mishra, M., Joshi, P.A., 2012b.. Titanium dioxide catalyzed photocatalytic
degradation of carboxylic acids from waste water: a review. Mater. Sci. Forum.
712, 175–189.
Gandhi, V.G., Mishra, M., Meka, S., Kumar, A., Joshi, P., Shah, D., 2011. Comparative
study on nano-crystalline titanium dioxide catalyzed photocatalytic
degradation of aromatic carboxylic acids in aqueous medium. J. Ind. Eng.
Chem. 17, 331–339.
Gandhi, V.G., Mishra, M.K., Joshi, P.A., 2012a. A study on deactivation and
regeneration of titanium dioxide during photocatalytic degradation of
phthalic acid. J. Ind. Eng. Chem. 18, 1902–1907.
Gao, B., Lim, T.M., Subagio, D.P., Lim, T.T., 2010. Zr-doped TiO2 for enhanced
photocatalytic degradation of bisphenol A. Appl. Catal A. 375, 107–115.
García-Araya, J., Beltrán, F., Aguinaco, A., 2010. Diclofenac removal from water by
ozone and photolytic TiO2 catalysed processes. J. Chem. Technol. Biotechnol. 85,
798–804.
Gaya, U.I., Abdullah, A.H., 2008. Heterogeneous photocatalytic degradation of
organic contaminants over titanium dioxide: a review of fundamentals,
progress and problems. J. Photochem. Photobiol. C 9, 1–12.
59
Gilbert, E.M., Agrawal, S., Schwartz, T., Horn, H., Lackner, S., 2015. Comparing
different reactor configurations for Partial Nitritation/Anammox at low
temperatures. Water Res. 81, 92–100.
Giraldo, A.L., Peñuela, G.A., Torres-Palma, R.A., Pino, N.J., Palominos, R.A., Mansilla,
H.D., 2010. Degradation of the antibiotic oxolinic acid by photocatalysis with
TiO2 in suspension. Water Res. 44, 5158–5167.
Gnanasekaran, L., Hemamalini, R., Saravanan, R., Ravichandran, K., Gracia, F., Gupta,
V.K., 2016. Intermediate state created by dopant ions (Mn, Co and Zr) into TiO2
nanoparticles for degradation of dyes under visible light. J. Mol. Liq. 223, 652–
659.
Grabowska, E., Zaleska, A., Sobczak, J.W., Gazda, M., Hupka, J., 2009. Boron-doped
TiO2: Characteristics and photoactivity under visible light. Procedia Chem. 1,
1553–1559.
Han, F., Kambala, V.S.R., Srinivasan, M., Rajarathnam, D., Naidu, R., 2009. Tailored
titanium dioxide photocatalysts for the degradation of organic dyes in
wastewater treatment: a review. Appl. Catal. A 359, 25–40.
Herrmann, J.M., 1999. Heterogeneous photocatalysis: fundamentals and
applications to the removal of various types of aqueous pollutants. Catal.
Today 53, 115–129.
Herrmann, J.M., Disdier, J., Pichat, P., Malato, S., Blanco, J., 1998. TiO2-based solar
photocatalytic detoxification of water containing organic pollutants. Case
studies of 2,4-dichlorophenoxyaceticacid (2,4-D) and of benzofuran. Appl.
Catal. B 17, 15–23.
Hinojosa-Reyes, M., Camposeco-Solis, R., Ruiz, F., Rodríguez-González, V.,
Moctezuma, E., 2019. Promotional effect of metal doping on nanostructured
TiO2 during the photocatalytic degradation of 4-chlorophenol and naproxen
sodium as pollutants. Mater. Sci. Semicond. Process 100, 130–139.
Hu, C.C., Hsu, T.C., Kao, L.H., 2012. One-step cohydrothermal synthesis of nitrogen-
doped titanium oxide nanotubes with enhanced visible light photocatalytic
activity. Int. J. Photoenergy.
Humayun, M., Raziq, F., Khan, A., Luo, W., 2018. Modification strategies of TiO2 for
potential applications in photocatalysis: a critical review. Green Chem. Lett.
Rev. 11, 86–102.
Jiang, P., Xiang, W., Kuang, J., Liu, W., Cao, W., 2015. Effect of cobalt doping on the
electronic, optical and photocatalytic properties of TiO2. Solid State Sci. 46, 27–
32.
Jo, W.K., Tayade, R.J., 2014. New generation energy-efficient light source for
photocatalysis: leds for environmental applications. Ind. Eng. Chem. Res. 53,
2073–2084.
Jo, W., Park, G., Tayade, R., 2014. Synergetic effect of adsorption on degradation of
malachite green dye under blue LED irradiation using spiral-shaped
photocatalytic reactor. J. Chem. Technol. Biotechnol. 90, 2280–2289.
Kadam, A.N., Dhabbe, R.S., Kokate, M.R., Gaikwad, Y.B., Garadkar, K.M., 2014.
Preparation of N doped TiO2 via microwave-assisted method and its
photocatalytic activity for degradation of Malathion. Spectrochim. Acta Part A
133, 669–676.
Kamat, P.V., 2007. Meeting the clean energy demand: nanostructure architectures
for solar energy conversion. J. Phys. Chem. C 111, 2834–2860.
Kamble, S., Sawant, S., Pangarkar, V., 2003. Batch and continuous photocatalytic
degradation of benzenesulfonic acid using concentrated solar radiation. Ind.
Eng. Chem. Res. 42, 6705–6713.
Kaneco, S., Li, N., Itoh, K., Katsumata, H., Suzuki, T., Ohta, K., 2009. Titanium dioxide
mediated solar photocatalytic degradation of thiram in aqueous solution:
kinetics and mineralization. Chem. Eng. J. 148, 50–56.
Karthikeyan, K.G., Meyer, M.T., 2006. Occurrence of antibiotics in wastewater
treatment facilities in Wisconsin, USA. Sci. Total Environ. 361, 196–207.
Kaur, T., Sraw, A., Toor, A.P., Wanchoo, R.K., 2016. Utilization of solar energy for the
degradation of carbendazim and propiconazole by Fe doped TiO2. Sol. Energy
125, 65–76.
Kim, S., Hwang, S.J., Choi, W., 2005. Visible light active platinum-ion-doped TiO2
photocatalyst. J. Phys. Chem. B 109, 24260–24267.
Kositzi, M., Poulios, I., Malato, S., Caceres, J., Campos, A., 2004. Solar photocatalytic
treatment of synthetic municipal wastewater. Water Res. 38, 1147–1154.
Krejčíková, S., Matějová, L., Kočí, K., Obalová, L., Matěj, Z., Čapek, L., Šolcová, O.,
2012. Preparation and characterization of Ag-doped crystalline titania for
photocatalysis applications. Appl. Catal B 111–112, 119–125.
Krishnakumar, V., Boobas, S., Jayaprakash, J., Rajaboopathi, M., Han, B., Louhi-
Kultanen, M., 2016. Effect of Cu doping on TiO2 nanoparticles and its
photocatalytic activity under visible light. J. Mater. Sci.: Mater Electron. 27,
7438–7447.
Krishnan, S., Rawindran, H., Sinnathambi, C., Lim, J., 2017. Comparison of various
advanced oxidation processes used in remediation of industrial wastewater
laden with recalcitrant pollutants. IOP Conference Series: Materials Science and
Engineering 206.
Kumar, S.G., Devi, L.G., 2011. Review on modified TiO2 photocatalysis under UV/
visible light: selected results and related mechanisms on interfacial charge
carrier transfer dynamics. J. Phys. Chem. A 115, 13211–13241.
Kundu, P., Kaur, A., Mehta, S., Kansal, S., 2014. Removal of ofloxacin from aqueous
phase using Ni-doped TiO2 nanoparticles under solar irradiation. J. Nanosci.
Nanotechnol. 14, 6991–6995.
Kuo, Y.L., Liu, W.L., Hsieh, S.H., Huang, H.Y., 2010. Analyses of non-steroidal anti-
inflammatory drugs in environmental water samples with microemulsion
electrokinetic chromatography. Anal. Sci. 26, 703–707.
Lapworth, D.J., Baran, N., Stuart, M.E., Ward, R.S., 2012. Emerging organic
contaminants in groundwater: a review of sources, fate and occurrence.
Environ. Pollut. 163, 287–303.
60 K.S. Varma et al. / Water-Energy Nexus 3 (2020) 46–61
Lazar, M.A., Varghese, S., Nair, S.S., 2012. Photocatalytic water treatment by
titanium dioxide: recent updates. Catalysts 2, 572–601.
Leong, K.H., Gan, B.L., Ibrahim, S., Saravanan, P., 2014. Synthesis of surface plasmon
resonance (SPR) triggered Ag/TiO2 photocatalyst for degradation of endocrine
disturbing compounds. Appl. Surf. Sci. 319, 128–135.
Li, H., Zhou, Y., Tu, W., Ye, J., Zou, Z., 2015. State-of-the-Art progress in diverse
heterostructured photocatalysts toward promoting photocatalytic
performance. Adv. Funct. Mater. 25, 998–1013.
3+
Li, X.Z., Li, F.B., 2001. Study of Au/Au -TiO2 Photocatalysts toward visible
photooxidation for water and wastewater treatment. Environ. Sci. Technol.
35, 2381–2387.
Mahlambi, M., Ngila, J., Mamba, B., 2015. Recent developments in environmental
photocatalytic degradation of organic pollutants: the case of titanium dioxide
nanoparticles-a review. J. Nanomater., 1–29
Maktabifard, M., Zaborowska, E., Makinia, J., 2018. Achieving energy neutrality in
wastewater treatment plants through energy savings and enhancing renewable
energy production. Rev. Environ. Sci. Bio/Technol. 17, 655–689.
Malakootian, M., Olama, N., Malakootian, M., Nasiri, A., 2019. Photocatalytic
degradation of metronidazole from aquatic solution by TiO2-doped Fe3+ nano-
photocatalyst. Int. J. Environ. Sci. Technol. 16, 4275–4284.
Malghe, Y., Lavand, A., 2015. Nano sized C-Doped TiO2 as a visible-light
photocatalyst for the degradation of 2,4,6- Trichlorophenol. Adv. Mater. Lett.
6, 695–700.
Marschall, R., Wang, L., 2014. Non-metal doping of transition metal oxides for
visible-light photocatalysis. Catal. Today 225, 111–135.
Maspolim, Y., Zhou, Y., Guo, C., Xiao, K., Ng, J., 2015. The Effect of pH on
solubilization of organic matter and microbial community structures in sludge
fermentation. Bioresour. Technol. 190, 289–298.
Matsumura, Y., Ananthaswamy, H.N., 2004. Toxic effects of ultraviolet radiation on
the skin. Toxicol. Appl. Pharmacol. 195, 298–308.
McCullagh, C., Skillen, N., Adams, M., Robertson, P., 2011. Photocatalytic reactors for
environmental remediation: a review. J. Chem. Technol. Biotechnol. 86, 1002–
1017.
Méndez, E., González-Fuentes, M.A., Rebollar-Perez, G., Méndez-Albores, A., Torres,
E., 2017. Emerging pollutant treatments in wastewater: cases of antibiotics and
hormones. J. Environ. Sci. Health Part A: Toxic/Hazard. Subst. Environ. Eng. 52,
235–253.
Mitsika, E.E., Christophoridis, C., Fytianos, K., 2013. Fenton and Fenton-like
oxidation of pesticide acetamiprid in water samples: kinetic study of the
degradation and optimization using response surface methodology.
Chemosphere 93, 1818–1825.
Mogal, S.I., Gandhi, V.G., Mishra, M., Tripathi, S., Shripathi, T., Joshi, P.A., Shah, D.O.,
2014. Single-step synthesis of silver-doped titanium dioxide: influence of silver
on structural, textural, and photocatalytic properties. Ind. Eng. Chem. Res. 53,
5749–5758.
Mogal, S.I., Mishra, M., Gandhi, V.G., Tayade, R.J., 2013. Metal doped titanium
dioxide: synthesis and effect of metal ions on physico-chemical and
photocatalytic properties. Mater. Sci. Forum 734, 364–378.
Mohammadi, R., Massoumi, B., Eskandarloo, H., 2014. Preparation and
characterization of Sn/Zn/TiO2 photocatalyst for enhanced amoxicillin
trihydrate degradation. Desalin. Water Treat.
Mohammadi, R., Massoumi, B., Rabani, M., 2012. Photocatalytic decomposition of
amoxicillin trihydrate antibiotic in aqueous solutions under UV irradiation
using Sn/TiO2 nanoparticles. Int. J. Photoenergy.
Molla, M., Tateishi, I., Furukawa, M., Katsumata, H., Suzuki, T., Knaeco, S., 2017.
Photocatalytic decolorization of dye with self-dye-sensitization under
fluorescent light irradiation. ChemEngineering 1, 8.
Mosleh, S., Rahimi, M.R., Ghaedi, M., Dashtian, K., 2016. Sonophotocatalytic
degradation of trypan blue and vesuvine dyes in the presence of blue light
active photocatalyst of Ag3PO4/Bi2S3-HKUST-1-MOF: central composite
optimization and synergistic effect study. Ultrason. Sonochem. 32, 387–397.
Munter, R., 2001. Advanced oxidation processes-current status and prospects. Proc.
Estonian Acad. Sci. Chem. 50, 59–80.
Naeem, K., Feng, O., 2009. Parameters effect on heterogeneous photocatalysed
degradation of phenol in aqueous dispersion of TiO2. J. Environ. Sci. 21, 527–
533.
Naidu, R., Arias Espana, V.A., Liu, Y., Jit, J., 2016. Emerging contaminants in the
environment: risk-based analysis for better management. Chemosphere 154,
350–357.
Nakhate, G.G., Nikam, V.S., Kanade, K.G., Arbuj, S., Kale, B.B., Baeg, J.O., 2010.
Hydrothermally derived nanosized Ni-doped TiO2: a visible light driven
photocatalyst for methylene blue degradation. Mater. Chem. Phys. 124, 976–981.
Narayana, R.L., Matheswaran, M., Aziz, A.A., Saravanan, P., 2011. Photocatalytic
decolourization of basic green dye by pure and Fe, Co doped TiO2 under daylight
illumination. Desalination 269, 249–253.
Nasi, R., Esposito, S., Freyria, F.S., Armandi, M., Gadhi, T.A., Hernández, S., Rivolo, P.,
Ditaranto, N., Bonelli, B., 2019. Application of reverse micelle sol–gel synthesis
for bulk doping and heteroatoms surface enrichment in Mo-Doped TiO2
nanoparticles. Materials 12, 937.
Natarajan, K., Natarajan, T.S., Bajaj, H.C., Tayade, R.J., 2011a. Photocatalytic reactor
based on UV-LED/TiO2 coated quartz tube for degradation of dyes. Chem. Eng. J.
178, 40–49.
Natarajan, T.S., Natarajan, K., Bajaj, H.C., Tayade, R.J., 2011b. Energy efficient UV-LED
source and TiO2 nanotube array-based reactor for photocatalytic application.
Ind. Eng. Chem. Res. 50, 7753–7762.
Natarajan, T.S., Natarajan, K., Bajaj, H., Tayade, R., 2013. Enhanced photocatalytic
activity of bismuth-doped TiO2 nanotubes under direct sunlight irradiation for
degradation of Rhodamine B dye. J. Nanopart. Res. 15, 1–18.
Neville, E.M., Mattle, M.J., Loughrey, D., Rajesh, B., Rahman, M., Don MacElroy, J.M.,
Sullivan, J.A., Thampi, K.R., 2012. Carbon-doped TiO2 and carbon, tungsten-
codoped TiO2 through sol–gel processes in the presence of melamine borate:
reflections through photocatalysis. J. Phys. Chem. C 116, 16511–16521.
Ng, K.H., Lee, C.H., Khan, M.R., Cheng, C.K., 2016. Photocatalytic degradation of
recalcitrant POME waste by using silver doped titania: photokinetics and
scavenging studies. Chem. Eng. J. 286, 282–290.
Nguyen Thi Thu, T., Nguyen Thi, N., Tran Quang, V., Nguyen Hong, K., Nguyen Minh,
T., Le Thi Hoai, N., 2016. Synthesis, characterisation, and effect of pH on
degradation of dyes of copper-doped TiO2. J. Exp. Nanosci. 11, 226–238.
Niu, J., Lu, P., Kang, M., Deng, K., Yao, B., Yu, X., Zhang, Q., 2014. P-doped TiO2 with
superior visible-light activity prepared by rapid microwave hydrothermal
method. Appl. Surf. Sci. 319, 99–106.
Oturan, M.A., Aaron, J.J., 2014. Advanced oxidation processes in water/wastewater
treatment: principles and applications. a review. Crit. Rev. Environ. Sci. Technol.
44, 2577–2641.
Parangi, T., Mishra, M.K., 2019. Titania nanoparticles as modified photocatalysts: a
review on design and development. Comments Inorg. Chem. 39, 90–126.
Pelaez, M., Nolan, N.T., Pillai, S.C., Seery, M.K., Falaras, P., Kontos, A.G., Dunlop, P.S.
M., Hamilton, J.W.J., Byrne, J.A., O’Shea, K., Entezari, M.H., Dionysiou, D.D., 2012.
A review on the visible light active titanium dioxide photocatalysts for
environmental applications. Appl. Catal. B 125, 331–349.
Pongwan, P., Inceesungvorn, B., Wetchakun, K., Phanichphant, S., Wetchakun, N.,
2012. Highly efficient visible-light-induced photocatalytic activity of Fe-doped
TiO2 nanoparticles. Eng. J. 16, 13–16.
Rajaraman, T.S., Parikh, S.P., Gandhi, V.G., 2019. Black TiO2: a review of its properties
and conflicting trends. Chem. Eng. J. 389, 123918.
Rauf, M.A., Meetani, M.A., Hisaindee, S., 2011. An overview on the photocatalytic
degradation of azo dyes in the presence of TiO2 doped with selective transition
metals. Desalination 276, 13–27.
Ren, W., Ai, Z., Jia, F., Zhang, L., Fan, X., Zou, Z., 2007. Low temperature preparation
and visible light photocatalytic activity of mesoporous carbon-doped crystalline
TiO2. Appl. Catal. B 69, 138–144.
Sable, S.S., Shah, K.J., Chiang, P.C., Lo, S.-L., 2018. Catalytic oxidative degradation of
phenol using iron oxide promoted sulfonated-ZrO2 by advanced oxidation
processes (AOPs). J. Taiwan Inst. Chem. E 91, 434–440.
Santos, J.L., Aparicio, I., Alonso, E., 2007. Occurrence and risk assessment of
pharmaceutically active compounds in wastewater treatment plants. A case
study: seville city (Spain). Environ. Int. 33, 596–601.
Sarkar, M., Acharya, P.K., Bhattacharya, B., 2003. Modeling the adsorption kinetics of
some priority organic pollutants in water from diffusion and activation energy
parameters. J. Colloid Interface Sci. 266, 28–32.
Sathishkumar, P., Anandan, S., Maruthamuthu, P., Swaminathan, T., Zhou, M.,
Ashokkumar, M., 2011. Synthesis of Fe3+ doped TiO2 photocatalysts for
the visible assisted degradation of an azo dye. Colloids Surf A 375, 231–
236.
Scott, C.A., Pierce, S.A., Pasqualetti, M.J., Jones, A.L., Montz, B.E., Hoover, J.H., 2011.
Policy and institutional dimensions of the water-energy nexus. Energy Policy
39, 6622–6630.
Shah, K. J. and Chang, P. C., 2018. Shape-Control Synthesis and Photocatalytic
Applications of CeO2 to Remediate Organic Pollutant Containing Wastewater: A
Review, in Tayade, R. J., Gandhi, V. (Eds.), Photocatalytic nanomaterials for
environmental applications. Materials Research Forum LLC, USA, (27) pp 316–
342.
Shah, K. J. Pan, Y. A., Gandhi, V., Chiang, P. C., 2018. Photo electrochemical reduction
of CO2 to solar fuel: a review, in Tayade, R. J., Gandhi, V. (Eds.), Photocatalytic
nanomaterials for environmental applications. Materials Research Forum LLC,
USA, (27) pp. 211–235.
Sharma, B.M., Bečanová, J., Scheringer, M., Sharma, A., Bharat, G.K., Whitehead, P.G.,
Klánová, J., Nizzetto, L., 2019. Health and ecological risk assessment of emerging
contaminants (pharmaceuticals, personal care products, and artificial
sweeteners) in surface and groundwater (drinking water) in the Ganges River
Basin, India. Sci. Total Environ. 646, 1459–1467.
Shetty, R., Chavan, V.B., Kulkarni, P.S., Kulkarni, B.D., Kamble, S.P., 2017.
Photocatalytic degradation of pharmaceuticals pollutants using N-doped TiO2
photocatalyst: identification of CFX degradation intermediates. Indian Chem.
Eng. 59, 177–199.
Shokri, M., Jodat, A., Modirshahla, N., Behnajady, M., 2013. Photocatalytic
degradation of chloramphenicol in an aqueous suspension of silver-doped
TiO2 nanoparticles. Environ. Technol. 34, 1161–1166.
Sin, J.C., Lam, S.M., Mohamed, A., Lee, K.T., 2012. Degrading endocrine disrupting
chemicals from wastewater by TiO2 photocatalysis: a review. Int. J.
Photoenergy.
Sood, S., Umar, A., Mehta, S.K., Kansal, S.K., 2015. Highly effective Fe-doped TiO2
nanoparticles photocatalysts for visible-light driven photocatalytic degradation
of toxic organic compounds. J. Colloid Interface Sci. 450, 213–223.
Subagio, D.P., Srinivasan, M., Lim, M., Lim, T.T., 2010. Photocatalytic degradation of
bisphenol-A by nitrogen-doped TiO2 hollow sphere in a vis-LED photoreactor.
Appl. Catal B 95, 414–422.
Sun, J., Qiao, L., Sun, S., Wang, G., 2008. Photocatalytic degradation of Orange G on
nitrogen-doped TiO2 catalysts under visible light and sunlight irradiation. J.
Hazard. Mater. 155, 312–319.
 K.S. Varma et al. / Water-Energy Nexus 3 (2020) 46–61
Sung-Suh, H.M., Choi, J.R., Hah, H.J., Koo, S.M., Bae, Y.C., 2004. Comparison of Ag
deposition effects on the photocatalytic activity of nanoparticulate TiO2 under
visible and UV light irradiation. J. Photochem. Photobiol. A 163, 37–44.
Surenjan, A., Pradeep, T., Philip, L., 2019. Application and performance evaluation of
a cost-effective vis-LED based fluidized bed reactor for the treatment of
emerging contaminants. Chemosphere 228, 629–639.
Suwarnkar, M.B., Dhabbe, R.S., Kadam, A.N., Garadkar, K.M., 2014. Enhanced
photocatalytic activity of Ag doped TiO2 nanoparticles synthesized by a
microwave assisted method. Ceram. Int. 40, 5489–5496.
Tambosi, J.L., de Sena, R.F., Gebhardt, W., Moreira, R.F.P.M., José, H.J., Schröder, H.F.,
2009. Physicochemical and advanced oxidation processes-a comparison of
elimination results of antibiotic compounds following an MBR treatment.
Ozone: Sci. Eng. 31, 428–435.
Tan, Y.N., Wong, C.L., Mohamed, A.R., 2011. An Overview on the photocatalytic
activity of nano-doped-TiO2 in the degradation of organic pollutants. ISRN
Mater. Sci.
Tayade, R.J., Kulkarni, R.G., Jasra, R.V., 2006. Photocatalytic degradation of aqueous
nitrobenzene by nanocrystalline TiO2. Ind. Eng. Chem. Res. 45, 922–927.
Teh, C.M., Mohamed, A.R., 2011. Roles of titanium dioxide and ion-doped titanium
dioxide on photocatalytic degradation of organic pollutants (phenolic
compounds and dyes) in aqueous solutions: a review. J. Alloys Compd. 509,
1648–1660.
Teoh, W.Y., Scott, J.A., Amal, R., 2012. Progress in heterogeneous photocatalysis:
from classical radical chemistry to engineering nanomaterials and solar
reactors. J. Phys. Chem. Lett. 3, 629–639.
Tian, B., Li, C., Zhang, J., 2012. One-step preparation, characterization and visible-
light photocatalytic activity of Cr-doped TiO2 with anatase and rutile
bicrystalline phases. Chem. Eng. J. 191, 402–409.
Vega, M.P.B., Reyes, M.H., Ramírez, A.H., Mar, J.L.G., González, V.R., Reyes, L.H., 2018.
Visible light photocatalytic activity of sol-gel Ni-doped TiO2 on p-arsanilic acid
degradation. J. Sol-Gel Sci. Technol. 85.
Venkatachalam, N., Palanichamy, M., Arabindoo, B., Murugesan, V., 2007. Enhanced
photocatalytic degradation of 4-chlorophenol by Zr4+ doped nano TiO2. J. Mol.
Catal. A Chem. 266, 158–165.
Wang, K.H., Hsieh, Y.H., Chou, M.Y., Chang, C.Y., 1999. Photocatalytic degradation of
2-chloro and 2-nitrophenol by titanium dioxide suspensions in aqueous
solution. Appl. Catal B 21, 1–8.
Wang, Q., Yang, Z., 2016. Industrial water pollution, water environment treatment,
and health risks in China. Environ. Pollut. 218, 358–365.
Wittlich, M., Westerhausen, S., Kleinespel, P., Rifer, G., Stöppelmann, W., 2016. An
approximation of occupational lifetime UVR exposure: algorithm for
retrospective assessment and current measurements. J. Eur. Acad. Dermatol.
Venereol. 30 (Suppl 3), 27–33.
61
Xiao, Q., Zhang, J., Xiao, C., Si, Z., Tan, X., 2008. Solar photocatalytic degradation of
methylene blue in carbon-doped TiO2 nanoparticles suspension. Sol. Energy 82,
706–713.
Xiong, J., Cheng, G., Qin, F., Wang, R., Sun, H., Chen, R., 2013. Tunable BiOCl
hierarchical nanostructures for high-efficient photocatalysis under visible light
irradiation. Chem. Eng. J. 220, 228–236.
Xu, J., Ao, Y., Chen, M., Fu, D., 2009. Low-temperature preparation of Boron-doped
titania by hydrothermal method and its photocatalytic activity. J. Alloys Compd.
484, 73–79.
Yadav, H.M., Kolekar, T.V., Barge, A.S., Thorat, N.D., Delekar, S.D., Kim, B.M., Kim, B.J.,
Kim, J.S., 2016. Enhanced visible light photocatalytic activity of Cr3+-doped
anatase TiO2 nanoparticles synthesized by sol–gel method. J. Mater. Sci.: Mater.
Electron. 27, 526–534.
Yang, G., Yan, Z., Xiao, T., 2012. Low-temperature solvothermal synthesis of visible-
light-responsive S-doped TiO2 nanocrystal. Appl. Surf. Sci. 258, 4016–4022.
Yang, X., Ma, F., Li, K., Guo, Y., Hu, J., Li, W., Huo, M., Guo, Y., 2010. Mixed phase
titania nanocomposite codoped with metallic silver and vanadium oxide: new
efficient photocatalyst for dye degradation. J. Hazard. Mater. 175, 429–438.
Yi, C., Liao, Q., Deng, W., Huang, Y., Mao, J., Zhang, B., Wu, G., 2019. The preparation
of amorphous TiO2 doped with cationic S and its application to the degradation
of DCFs under visible light irradiation. Sci. Total Environ. 684, 527–536.
Yu, C., Fan, Q., Xie, Y., Chen, J., Shu, Q., Yu, J., 2012. Sonochemical fabrication of novel
square-shaped F Doped TiO2 nanocrystals with enhanced performance in
photocatalytic degradation of phenol. J. Hazard. Mater. 237–238, 38–45.
Zaleska-Medynska, A., 2008. Doped-TiO2: a review. Recent Pat. Eng. 2, 157–164.
Zatloukalová, K., Obalová, L., Kočí, K., Čapek, L., Matěj, Z., Šnajdhaufová, H.,
Ryczkowski, J., Słowik, G., 2017. Photocatalytic degradation of endocrine
disruptor compounds in water over immobilized TiO2 photocatalysts. Iran. J.
Chem. Chem. Eng. 36, 29–38.
Zhang, X., Zhou, J., Gu, Y., Fan, D., 2015. Visible-light photocatalytic activity of N-
doped TiO2 nanotube arrays on acephate degradation. J. Nanomater., 1–6
Zhang, Y., Zhang, P., Huo, Y., Zhang, D., Li, G., Li, H., 2012. Ethanol supercritical route
for fabricating bimodal carbon modified mesoporous TiO2 with enhanced
photocatalytic capability in degrading phenol. Appl. Catal. B 115–116, 236–244.
Zheng, X., Shen, Z.-P., Shi, L., Cheng, R., Yuan, D.-H., 2017. Photocatalytic membrane
reactors (PMRs) in water treatment: configurations and influencing factors.
Catalysts 7, 224.
Zhou, H., Smith, D.W., 2002. Advanced technologies in water and wastewater
treatment. J. Environ. Eng. Sci. 1, 247–264.
Zielińska, A., Kowalska, E., Sobczak, J.W., Ła˛cka, I., Gazda, M., Ohtani, B., Hupka, J.,
Zaleska, A., 2010. Silver-doped TiO2 prepared by microemulsion method:
surface properties, bio- and photoactivity. Sep. Purif. Technol. 72, 309–318.