Journal of Water Process Engineering 36 (2020) 101300

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Journal of Water Process Engineering

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A review on floating nanocomposite photocatalyst: Fabrication and T

applications for wastewater treatment
Atikah Mohd Nasir, Juhana Jaafar, Farhana Aziz*, Norhaniza Yusof, Wan Norhayati Wan Salleh,
Ahmad Fauzi Ismail, Madzlan Aziz
Advanced Membrane Technology Research Centre (AMTEC), School of Chemical and Energy Engineering, Faculty of Engineering, Universiti Teknologi Malaysia, 81310
UTM Skudai, Johor Darul Ta‘zim, Malaysia

A R T I C LE I N FO A B S T R A C T

Keywords: The illumination of source light and oxygenation are two fundamental factors for superior photocatalytic per-
Floating composite photocatalyst formance in waste water treatment. Powder form of existing photocatalyst reduced the performance of the
Surface coating photocatalyst due to lowering active surface area, reduce light utilization and limiting contact area with the
Fabrication pollutants. A number of researchers came out with fresh and novel ideas on immobilizing potential photocatalyst
Application
on floatable substrate to form floating composite photocatalyst. The floating composite photocatalyst is an at-
Wastewater treatment
tractive option for waste water treatment due to utilization of full solar irradiation of non-oxygenated and non-
stirred reservoir. This makes development of floating photocatalyst is significant to be reviewed. This review
highlights the most recent fabrication and application of floating photocatalyst for wastewater treatment.
Fabrication techniques such as sol-gel, surface coating, hydrothermal, solvent casting, surface modification,
three-dimensional printing and low temperature ultrasonic were reviewed. Moreover, the perspective on future
direction to improve the photocatalytic performances were discussed at the end of the review.

1. Introduction photogeneration of charge carriers, (2) separation of charge carrier and

“A drop of water is worth more than a sack of gold to a thirsty man”
is a famous quote describing the significance values of clean and pure
water rather than luxurious materials. The past few decades have wit-
nessed to rapid development in agriculture and industrialization ac-
tivities that generated increased volume of untreated wastewater.
Contaminants such as dye, phenolic compounds, humic substances,
pesticides, heavy metal and pharmaceutical wastes have found in the
untreated wastewater and regarded as the main culprit of the surface
water pollution. Exposure to those organic contaminants could disrupt
the physiological system in human and living organisms. Currently,
there are various conventional methods were introduced to treat the
wastewater contaminant such as chemical coagulation, flocculation, ion
exchange, membrane filtration and adsorption [1–6]. However, those
methods only converting the contaminants to other different phase and
they are not fully destroyed or eliminated [7]. Although organic con-
taminants are difficult to biologically degrade due to their complex
organic structure, but they can be easily degraded by induced photo-
chemical treatment.
Photocatalytic process involved three main steps which are; (1)
diffusion to the surface of the photocatalyst and (3) redox reaction on
the surface of the photocatalyst. Compared to other conventional
method, removal of contaminant through photocatalytic offer friendly
by product due to mineralization capability to produce CO2 and H2O.
Furthermore, photocatalyst like TiO2 and ZnO were acknowledged as
cheap, chemically stable, non-toxic, high efficiency and reusable [8].
Despite the promising achievement of photocatalyst like titania (TiO2),
zinc oxide (ZnO), cadmium sulphide (Cds), calcium titanate (CaTiO3),
bismuth ferrite (BiFeO3), lanthanum ferrite (LaFeO3) and others as
photocatalyst, there are several limitations suffered when applied in
real waste water treatment [9–16]. The major limitation of currently
used semiconductor photocatalyst is their wide band gap. Therefore,
they required high power UV irradiation to excite the electron from
valence band to conduction band. Previous studies proposed coupling
the semiconductor photocatalyst with other semiconductors that have
smaller band-gap to form heterostructures to capture photons from the
visible light and generate stable electron-hole pairs [17,18]. Most re-
cently, many new and innovative photocatalytic materials offering
highly efficient photocatalytic have been developed to further improve
the photocatalytic performance on wastewater contaminants. They are

⁎
Corresponding author.
E-mail addresses: farhana@petroleum.utm.my, farhanaaziz@utm.my (F. Aziz).

https://doi.org/10.1016/j.jwpe.2020.101300
Received 13 January 2020; Received in revised form 12 April 2020; Accepted 14 April 2020
2214-7144/ © 2020 Elsevier Ltd. All rights reserved.
A.M. Nasir, et al.
including metal-selenide and their composites as the photocatalytic
materials with high efficient has been attended [19–22]. There also
graphene and g-C3N4 could do a revolution in the photocatalytic ma-
terials such as semiconducting nanostructures [23–25]. In addition,
there also advanced photocatalyst like bismuth sulphide nanorod [26],
gallium-doped zinc sulphide quantum dots [27], carbon-bismuth sul-
phide core-shell heterostructures [28] and g-C3N4/ niobium pentoxide
[29] were developed for enhancing photocatalytic performance.
However, as they present in powder form, they tend to agglomerate,
sinks or suspends in the solution and very difficult to be separated from
the solution. These conditions reduce the performance of the photo-
catalyst due to lowering active surface area, reduce light utilization and
limiting contact area with the pollutants. Hence, immobilizing the
photocatalyst on substrate to form composite materials could overcome
those limitations. Most recently, development of various hybrid com-
posite materials by impregnated onto potential substrate has attracted
much attention to tackle the environmental issues [8,20,25,30,31].
Researchers come out with fresh and novel idea on development of
floating composite photocatalyst by immobilizing the photocatalyst on
the floatable substrate. In order to achieve highest photocatalytic effi-
ciency, the substrate need to be well designed to utilize the maximum
source light and retain the pollutants close to the surface of photo-
catalysts. The floating composite photocatalyst is an attractive option
for waste water treatment due to utilization of full solar irradiation of
non-oxygenated and non-stirred reservoir. This is due to the max-
imization of light utilization and oxygenation would result in higher
rates of radical formation and oxidation efficiencies hence enhance the
photocatalytic performance [32]. Furthermore, the floating photo-
catalyst can be independently utilized in remote areas under local solar
remediation without any special installation or equipment [33]. For
example, they can be used for the more efficient destruction of sus-
pended insoluble organic contaminants such as in in oil-spill accidents
area [34]. Fig. 1 illustrated the schematic diagram of photocatalytic
degradation of pollutants over floating composite photocatalyst.
Basically, the ability of the photocatalyst to float on the water sur-
face allows more efficient irradiation and oxygenation which are fun-
damental for the photocatalytic degradation of contaminated waste
water. Generally, in the presence of solar or ultraviolet (UV) irradiation,
Fig. 1. Schematic diagram of photocatalytic degradation by floating nanocomposite photocatalyst.
2
Journal of Water Process Engineering 36 (2020) 101300
electrons are promoted from the valence band (VB) to the conduction
band (CB) of the semiconductor oxide to give electron-hole pairs [33].
The valence band hole (hvb+) is positive enough to form hydroxyl ra-
dicals (O%H) at the surface of the photocatalyst. Then, electron at
conduction band (e¯) is negative enough to reduce O2 molecules to
generate superoxide radicals ion (O%2¯). Both superoxide and hydroxyl
radicals are responsible for degradation of pollutants. Subsequently,
large numbers of radicals were generated by the hydrolysis of water in
the presence of O2. Recent studies reported floating photocatalyst can
be fabricated by impregnating photocatalyst onto various floating ma-
terial such as palm trunk, perlite, wood cork, vermiculite, canvas and
etc [33,35–39]. They also called as buoyant photocatalyst. In this re-
view, we discussed the recent advances on the fabrication, performance
as well as application of floating composite membrane for waste water
treatment.
The development of floating photocatalysts received considerable
attention as they could overcome the limitation of non-floating pho-
tocatalysts such as agglomeration, recovery and flexibility. The most
important issue of non-floating photocatalyst is the accessibility of
oxygen and sunlight to the bottom of the water is a really big challenge
[40]. By immobilizing photocatalyst onto a floatable support, the
maximal oxygenation and optimal solar irradiation can be achieved as
the photocatalyst localized on the interface of the water and the air.
Consequently, the oxidation efficiency and radical generation rate are
highly improved [41]. Moreover, the floating photocatalyst do not re-
quire stirring process especially contaminated wastewater reservoir
that located in remote areas like river or lakes since stirring is not
available under that kind of condition. Particularly, all these reasons
show the importance of the floating photocatalyst over non-floating
photocatalyst.
2. Fabrication of floating-nanocomposite photocatalyst
Over the past decades have witnessed development of floating
composite photocatalyst as a newly emerging and innovative solution
for wastewater treatment. In the literature, various techniques have
been introduced for immobilizing photocatalyst onto floatable mate-
rials such as sol-gel, dip coating, spray coating, solvothermal,
 Table 1
Summary of the recent fabrication technique of floating composite photocatalyst and their photocatalytic degradation performance for various contaminants.
Floating composite photocatalyst Fabrication method Fabrication parameters Contaminant Source light Photodegradation Degradation time References
performance (%)
A.M. Nasir, et al.

CuFeO2/ expanded perlite Solvothermal 180 °C Methylene blue Visible light 99.0 30 min [32]
24 h
TiO2- polyaniline (PANI)/ cork Suspension coating Vigorous stirring 30 min Methyl orange Solar light 95.2 210 min [41]
Salicylic acid-TiO2/palm trunk Suspension coating Vigorous stirring 30 min. Congo red Visible light 98.2 210 min [33]
Graphitic carbon nitride/ polyetherimide (PEI- Centrifugation Rotating speed :4000 rpm Methyl orange Visible light 80.0 68 h [40]
gC3N4) Time: 10 min
Cadmium sulphide (Cds)/expanded perlite Liquid phase deposition Stirring time: 30 min Rhodamine B Visible light 70.0 2h [42]
Mixing time: 2 h at room temperature
TiO2/ hollow glass microspheres (HGMST) Surface modification and Stirring and mixing time: 2 h Rhodamine B UV 21.0 6 h [43]
calcination Drying: 100 °C Visible light 46.0 4 h
Calcination: 550 °C for 4 h Phenol UV 16.0 6 h
Visible light 22.0 4 h
Hollow TiO2 / hollow glass microspheres Rhodamine B UV 85.0 6 h
(HGMSHT) Visible light 96.0 4 h
Phenol UV 68.0 6 h
Visible light 73.0 4 h
TiO2/ expanded perlite Direct hydrolysis Calcination temperature 500 °C Phenol UV 36.0 1 h [44]
precipitation and
calcination
TiO2/ autoclaved cellular concrete composite Dip coating Contact time: 20 s Indigo carmine UV 100.0 350 min [45]
Drying: 60 °C for 30 min
Calcination: 550 °C for 2 h.
TiO2-triethylamine (TEA) 12/ polypropylene Hydrothermal 150 °C Methyl orange UV 93.4 20 min [46]
10 h Visible light 32.0 100 min

3
TEA treatment time: 12 h
TiO2-TEA 48 /polypropylene 150 °C UV 93.8 20 min
10 h Visible light 43.0 100 min
TEA treatment time: 48 h
TiO2-TEA 160/ polypropylene 150 °C UV 96.3 20 min
10 h Visible light 66.3 100 min
TEA treatment time: 160 h
TiO2- low-density-polyethylene 3D printing Extrusion temperature: 235.0 °C Methylene blue UV 14.0 120 min [47]
(LDPE)/ cylinder mixture (CM) mesh Nozzle temperature: 194.0 °C
TiO2-LDPE/ O-xylene mesh Nozzle diameter: 1.75 mm 9.0
TiO2-LDPE/ surfactant mesh Extrusion speed: 4 cm/min 10.0
Printing speed: 1000 mm/min
Reduced graphene-oxide quantum-dots bismuth Liquid-phase deposition Contact time: 18 h Rhodamine B Visible light 95.0 15 min [35]
bismuth tungstate (rGO QDs Bi-Bi2WO6)/ process Vacuum dried:65.0 °C for 8 h. Phenol 93.0
expanded perlite Calcination temperature: 300 °C, 3 h.
Iron oxide/ polypropylene non-woven fabric canvas Dip coating Contact time: 1 h Rhodamine-B UV 6.2 90 min [48]
(NWFC) Drying temperature: 150 °C, 12 h.
Strewn Ag doped TiO2 /polystyrene (PSt) Strewing solvent casting Contact time: 30 min Methylene blue UV 86.0 5h [49]
Evaporation time: 2.5 h Visible light 68.0 6h
Mesh opening size: 0.5 mm.
Evaporation: 36 h
Drying: 100 °C for 1 h.
Impregnated Ag doped TiO2/ polystyrene Impregnating solvent Contact time: 30 min (high speed UV-C 94.0 5h
casting stirring). Visible light 83.0 6h
Evaporated at room temperature 24
h.
Bi-N-TiO2 / expanded graphite C/C (EGC) Sol-gel Aging time: 24 h Diesel oil Visible light 83.8 300 min [50]
Heating: 80 °C for 8 h.
Calcination: 550 °C for 2 h.
(continued on next page)
Journal of Water Process Engineering 36 (2020) 101300
 Table 1 (continued)

Floating composite photocatalyst Fabrication method Fabrication parameters Contaminant Source light Photodegradation Degradation time References
performance (%)
A.M. Nasir, et al.

Ni-N-TiO2/ porous EGC Sol-gel Aging time: 24 h Diesel oil Visible light 95.9 300 min [51]
Heating: 80 °C for 8 h.
Calcination: 550 °C for 2 h.
Addition of polyvinyl butyral (PVB)
as porogen and methenamine as
hardener.
Ni-N-TiO2 / EGC Sol-gel Aging time: 24h Diesel oil 63.0 300 min
Heating: 80 °C for 8 h.
Calcination: 550 °C for 2 h.
TiO2/ glass plate Dip coating Contact time: 30 min Phenol 125 W UV 92.2 4h [52]
Calcination: 350 °C lamp
80 W UV 41.6
lamp
TiO2/ perlite Contact time: 30 min 125 W UV 83.3
Calcination: 450 °C for 30 min. lamp
80 W UV 39.7
lamp
TiO2/ steel fiber Contact time: 30 min 125 W UV 73.2
Calcination: 350 °C lamp
80 W UV 35.5
lamp
TiO2-ZnO/ light expanded clay aggregate (LECA) Dip coating Contact time: 30 min Ammonia UV-C 95.2 120 min [8]
Calcination 350 °C for 30 min.
Well-ordered mesoporous TiO2/ polyurethane foam Low temperature ultrasonic Ultrasonic vibration: 30 min at 80 °C Hexavalent chromium, Cr (VI) with Visible light 97.4 [38]
(OMT/PUF) and deposition Drying: 60 °C for 24 h presence of rhodamine B

4
Cr(VI) with presence of methyl 94.3
orange
Cr(VI) with presence of methylene 94.8
blue
Rhodamine B with presence of Cr 95.2
(VI)
Methyl orange with presence of Cr 99.2
(VI)
Methylene blue with presence of Cr 90.4
(VI)
TiO2/ LECA Dip coating Drying temperature: 120 °C for 12 h. Ammonia Solar 42.2 180 min [53]
Calcination 550 °C for 30 min UV 58.1
TiO2/ expanded perlite (EP) Direct hydrolysis Pre-treatment: Sieved by 40 mesh Sulfamethoxazole (SMX) UV 100.0% 120 min [37]
screen, immersed in water 12 h. Dry
60 °C
Contact time: 15 min. Vacuum dry:
100 °C
Calcination: 500 °C
Journal of Water Process Engineering 36 (2020) 101300
A.M. Nasir, et al.
hydrothermal, liquid phase deposition, sol-carbonization, surface
modification, centrifugation as well as three-dimensional (3D) printing
as summarized in Table 1. There are also different kind of floating
materials have been identified as potential substrate for fabrication of
floating composite photocatalyst such as cork, glass beads, silica, palm
trunk, perlite, polymer, light expanded clay aggregate (LECA), con-
crete, graphite, canvas and etc [36].
Table 1 summarizes the fabrication techniques of the floating
composite photocatalyst, fabrication parameters, type of contaminants
and their performances based on the solar or UV irradiation. In the
following sections, we describe the fabrication methods of floating
nanocomposite photocatalyst in more details.
2.1. Sol-gel
Sol-gel is the most popular technique to fabricate floating composite
photocatalyst. This is due to the compatibility of the formation of in-
organic photocatalyst on the organic substrate under mild condition
while enhance the chemical, thermal and mechanical stability of the
composite photocatalyst [54]. Generally, during sol-gel process, the
floatable substrate is immersed in alcohol solution of precursor pho-
tocatalyst. Alcohol promote good dispersion of photocatalyst particles.
Then the solution is heated up to certain temperature for some time by
forming gel-like mixture. The amorphous photocatalyst can directly
precipitated and coated on the surface of the floating substrate through
hydrolysis then followed by calcination process respectively [43]. Sol-
gel technique is acknowledged as the most appropriate technique to
deposit photocatalyst on floating materials such as expanded graphite
and organosilica due to high temperature resistance during calcination
[51,54,55].
Zhang et al., fabricated floating photocatalyst by sol-gel technique
to treat the diesel polluted water area [50]. Initially, the tetrabutyl ti-
tanate, bismuth nitrate and expanded graphite were vigorously stirred
in absolute alcohol and HNO3 to form solution A. Then solution B which
formed by dissolution of urea as the nitrogen, N precursor was added
dropwise into solution A under vigorous stirring to form a gel pre-
cipitate. In order to ensure the mixture completely hydrolyze, the gel
precipitate was aged for 24 h before heated at 80˚for 8 h and calcinated
at temperature of 550 °C for 2 h in the N2. The fabricated composites
were rinsed with ethanol and deionized water three times before dried.
In the presence of 500 W xenon lamp as visible light source, the Bi-N-
TiO2/ expanded graphite exhibited the promising photodegradation
efficiency of 83.8 % towards high initial concentration of diesel (500
mg/L) under visible light irradiation for 300 min. This finding also
evidenced that Bi-N-TiO2/ expanded graphite that fabricated by sol-gel
technique are stable photocatalyst for the in-situ treatment of diesel
contaminated water due to floatation and regeneration of this compo-
site photocatalyst.
Expanded graphite is recognized as an excellent adsorbent due to
the porosity and light properties. However, previous study reported the
structure of the expanded graphite was unstable and tends to collapse
by external force [51]. Hence, the researchers found it was crucial to
develop expanded graphite C/C composite (EGC) and porous expanded
graphite C/C composite (pEGC) to improve the stability of expanded
graphite (EG) structure to be suitable floating substrate as photocatalyst
carrier. Wang et al., fabricated EGC by dispersing expanded graphite
and phenol-formaldehyde resin into absolute alcohol while stirring at
60 °C for 8 h [51]. Then the mixture was heated at 105 °C for 8 h then
calcined at 550 °C for 1 h in N2 atmosphere. Then, they fabricated Ni-N-
TiO2 on both EGC and pEGC by sol-gel technique with gel precipitate
aging of 24 h, drying at 80 °C for 8 h and calcined at 550 °C. In order to
fabricate pEGC, the fabrication procedure was extended by addition
polyvinyl butyral and methenamine as porogen and hardener respec-
tively. The photocatalytic degradation performance of diesel oil by EG,
N-TiO2/EGC, Ni-N-TiO2/ EGC and Ni-N-TiO2/ pEGC were compared
favorably. The results revealed, the Ni-N-TiO2/ pEGC exhibited higher
5
Journal of Water Process Engineering 36 (2020) 101300
diesel removal rate of 95.9 % under visible light irradiation for 5 h in
contrast to N-TiO2/EGC which recorded removal rate of 63.0 %. Ex-
cellent performance of the Ni-N-TiO2/ pEGC composite might be at-
tributed to (1) the porous structure of the substrate refine the excellent
electron acceptor and transporter which could reduce the recombina-
tion of the photo-induced hole-electron pairs, (2) larger surface active
area could increase the reaction, (3) synergistic adsorption -photo-
catalytic on the surface of the floating composite, (4) floatable prop-
erties of pEGC induced maximum utilization of light energy and (5) the
variant channel structure of the composite photocatalyst offer the diesel
adsorption with different carbon constitutions.
Post treatment of floating composite photocatalyst by calcination at
high temperature ranging from 300−400 °C could promote the strong
interaction and compatibility between the photocatalyst particle and
the floating substrate. However, very high calcination temperature
could deteriorate the floating properties of the substrate. As reported by
Maki et al., 2016, they fabricated floating TiO2 photocatalyst support
from organosilica through sol-gel reactions of organosilanes; which are
octyl- and methyl-silyl trichlorides and 3-aminopropyltrimethoxysilane
then dried at 50 °C and denoted as TiO2-SN-50 [54]. Calcination of the
sample TiO2-SN-50 at 400 °C (TiO2/SN-400), resulted on formation of
TiO2-polymethylsiloxane by oxidative decomposition of octyl and 3-
aminopropyl groups while retaining the floatability properties. They
also found that calcination at optimum temperature led to the en-
hancement of the total specific surface area from 88.0 to 230.0 m2/g
and the growth of anatase crystallites. Fig. 2(a–d) showed the digital
image of the floatability of the photocatalyst at different calcination
temperature. The sample SN-50, TiO2/SN-50, and TiO2/SN-400 particles
floated on water. However, the sample TiO2/ SN-600 sank when the
sample was calcined at 600 °C. This is due to the absence of organic
groups in the TiO2/organosilica. Fig. 2(e–f) showed the water contact
angles of TiO2/ SN-50 and TiO2/ SN-400 were 129˚ and 139˚ indicates
that the surface of the composite is hydrophobic which make them
floatable in water.
2.2. Surface coating
Basically, there are three types of surface coating that have been
employed by researchers for fabrication of floating composite photo-
catalyst which are dip coating, spray coating and spin coating
[34,40,45]. Surface coating technique is an alternative route to alter the
surface of the floating materials in order to deposit the photocatalyst
particles on them. However, this technique does not involve direct at-
tachment of chemical functional group like chemical surface mod-
ification technique do. Hence, usage of binding agent is crucial to im-
prove the deposition of photocatalyst on the floating substrate.
Furthermore, post treatment like calcination at higher temperature is
necessary to guarantee the crystallization of amorphous photocatalyst
precursor which could enhance the photocatalytic performance of the
floating composite photocatalyst.
2.2.1. Dip coating from suspension
Dip coating is one of the simple, economic and efficient technique to
immobilize photocatalyst onto the floating materials. This technique
allows the immersion of floating materials in the photocatalyst sus-
pension or slurry and thereafter allowed for drying and followed by
calcination. In the earlier research, Hosseini et al., successfully fabri-
cated floating composite photocatalyst by utilizing perlite as the
floating substrate and titania powder (P-25) as photocatalyst [52]. By
employed dip coating technique, titania successfully coated on the
floatable and porous structure of the perlite within 30 min contact time
and calcinated at 450 °C for 30 min. They also recommended in order to
remove excess unattached titania, the TiO2/perlite composite need to
be washed in deionized water and assisted by air bubbling in a vessel
for a few minutes twice.
Later, de Andrade et al., were prepared the floating photocatalyst by
A.M. Nasir, et al. Journal of Water Process Engineering 36 (2020) 101300

Fig. 2. Digital images of (a) SN-50, (b) TiO2/ SN-50, (c) TiO2/ SN-400, (d) TiO2/ SN-600, (e) water contact angle of TiO2/ SN-400, (f) water contact angle of TiO2/ SN-
600 [54].

Fig. 3. a) SEM image of ACC, (b) SEM image of floating TiO2/ACC composite, (c) expanded view of XPS spectrum of the floating TiO2/ACC composite, (d) digital
image of degradation of indigo carmine by floating TiO2/ACC composite and (e) plots of removal efficiency for indigo carmine as a function of reaction time for TiO2/
ACC composite, TiO2(P25)/UV and UV system [45].

6
A.M. Nasir, et al.
simply dip coating the cubes of autoclaved cellular concrete composite
(ACC) approximately 2 × 2 × 1 cm by mixture of titanium tetra-
chloride and isopropanol solution for only 20 s [45]. The coated cubes
then were dried in oven at 60 °C for 30 min before calcined at 550 °C for
2 h. High temperature during calcination treatment is important for
transformation of titanium tetrachloride into anatase form of TiO2
which promote the photocatalytic activity of the floating TiO2/ ACC
photocatalyst. They found TiO2 successfully deposited onto the ACC
based on Fig. 3(a–b) that displayed the scanning electron microscopy
(SEM) images of cork before and after deposition of TiO2 respectively.
Furthermore, X-ray photoelectron spectroscopy (XPS) also detected the
presence of TiO2 on the ACC. The binding energies of the Ti 2p1/2 and
2p3/2 doublets (464.3 ± 0.5 eV and 458.6 ± 0.4 eV, respectively) are
very close to values previously reported (464.34 eV and 458.8 eV, re-
spectively) thus indicating a minor chemical variation of Ti in the TiO2/
ACC composite which indicates weak interactions between TiO2 on the
ACC surface (Fig. 3c). This floating photocatalyst was tested for de-
gradation of indigo carmine under UV irradiation as shown in Fig. 3(d).
They revealed that the floating TiO2/ACC photocatalyst is far more
efficient of about 100 % rather than TiO2-P25/UV and UV with removal
rates of nearly 60 % as shown in Fig. 3(e).
Mohammadi et al., reported floating photocatalyst can be derived
from LECA granules. In their study, a novel hybrid TiO2-ZnO photo-
catalyst was deposited on the porous LECA [8]. Initially, TiO2 (P25)
powder was dispersed in the ethanol solution and striated to from the
slurry solution. In order to produce uniform dispersion TiO2 slurry
solution, dilute nitric acid (pH 3.5) was added in the solution. Zinc
acetate solution was added in the titania solution to form TiO2-ZnO
composite. Sonication under 50 kHz frequency also necessary to reduce
the flocculation of the mixture. Then, the porous LECA granules was
added to the synthesized solution to adsorb adequate amount of the
slurry before separated and dried at 120 °C for 12 h. The TiO2-ZnO/
LECA composite was calcinated for 30 min a 350 °C to ensure the ef-
fective and strong adhesion of the particles on the surface of LECA
granule. The floating TiO2-ZnO/ LECA composite photocatalyst then
was tested for degradation of ammonia under UV-C irradiation. The
results showed that 95.2 % of ammonia was degraded in 3 h reaction
time.
However, dip coating also can be performed without calcination
treatment. For example, Sboui et al. were successfully fabricated a
floating photocatalyst from TiO2-polyaniline (PANI) and cork through
dip coating technique without calcination at high temperature [41].
This is due to the TiO2-PANI nanocomposites particles are well syn-
thesized by surface modification technique before being coated on the
surface of the floating cork substrate. The cork was subjected to direct
Fig. 4. (a) SEM image of pure TiO2 nanoparticles, (b) SEM image of TiO2-PANI, (c) SEM image of TiO2-PANI/ cork nanocomposite, (d) TEM of TiO2-PANI nano-
particles (e) schematic diagram of proposed mechanism of photocatalytic activity of TiO2-PANI/ Cork nanocomposite under sunlight irradiation [41].
7
Journal of Water Process Engineering 36 (2020) 101300
deposition of TiO2-PANI nanocomposite with presence of commercial
vinyl as binder for the resultant mixture. In order to ensure the uniform
coating of TiO2 on floating substrate, the resultant mixture was vig-
orously stirred for 30 min. Fig. 4(a–d) showed SEM images of pure TiO2
nanoparticle, TiO2-PANI, TiO2-PANI/ cork nanocomposite and trans-
mission electron microscopy (TEM) image of TiO2-PANI respectively.
The TiO2-PANI/ cork floating photocatalyst showed very promising
photocatalytic performance by efficiently degrade methyl orange dye
up to 95.2 % within 210 min using solar irradiation without oxygena-
tion and stirring. This result is mainly reflected by the ability to float by
cork also ability to adsorb both UV and solar light by TiO2-PANI to
deliver the excited-state electrons of the highest occupied molecular
orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO) as
illustrated in Fig. 4(e). PANI not only improved the photocatalytic
performance of TiO2, but also other semiconductor like zinc selenide
nanoparticles [19].
The floating composite photocatalyst also can be fabricated through
immersing the canvas (non-woven textured) into iron precursor solu-
tion, Fe(NO3)3.9H2O [48]. The material was stirred for 1 h contact time
before dried in oven for 12 h at 150 °C. Fig. 5 concluded Fe successfully
coated on the canvas through dip coating process. Fig. 5(a–b) showed
the color change of the neat canvas from white to reddish-brown after
coated by iron nitrate solution. In order to further observe the mor-
phology of the coated iron on the canvas, SEM images of before and
after treatment were analysed. From Fig. 5(c–f), impregnation of iron
(III) oxide can be clearly observed by homogeneous distribution of the
particles throughout the microfibers structure of the canvas. Fig. 5(g)
indicated the removal of organic dye from the aqueous solution almost
completed due to the significant decrease in the band of 552 nm re-
present the character of the Rh-B pigment. Fig. 5(h) demonstrated in
the presence of the catalyst and UV light, the degradation of Rh-B is
almost 100 % after 90 min. These findings indicated the floating canvas
are promising solution for contaminant degradation by solar remedia-
tion through non-mechanically stirring and non-oxygenated reservoirs.
This is based on the maximum light utilization that obtained by the
entangled fibers that result in higher radical formation rates and oxi-
dation efficiencies.
2.2.2. Spin coating
Researcher also attracted on spin coating technique for fabrication
of floating composite photocatalyst. For example, Guo et al., fabricated
floating graphitic carbon nitride/ polyetherimide (gC3N4/ PEI) by spin
coating [40]. Firstly, they synthesized g-C3N4 from urea through heat
treatment. Then, they are simplified dissolved PEI particles within di-
chloromethane then mixed with the g-C3N4 powder by subsequent
A.M. Nasir, et al.
Fig. 5. a) Neat canvas before treatment, (b) Fe-treated canvas, (c) SEM image of neat canvas (500 μm magnification), (d) SEM image of neat canvas (100 μm), (e)
SEM image of 0.1 % Fe-canvas (500 μm magnification, (f) SEM image of 0.1 % Fe-canvas (100 μm magnification), (g) plot of removal profile of Rh-B at different times
of reaction, (h) plot of kinetic decay until 1.5 h [48].
ultrasonication and centrifugation for 10 min with the rotating speed of
4000 rpm. The fabricated gC3N4/ PEI was tested for degradation of
methyl orange under light irradiation of table lamp. They compared the
photodegradation efficiency of methyl orange by neat g-C3N4 powder
and gC3N4/ PEI composite with stirring and without stirring. The re-
sults showed methyl orange was degraded 91.0 % by g-C3N4 powder
and 80.0 % by gC3N4/ PEI composite with stirring. However, without
stirring condition the photodegradation of gC3N4 dropped to 37.0 %
which is lower than 55.0 % by gC3N4/ PEI composite. This finding
indicated the floating gC3N4/ PEI composite photocatalyst utilized
more solar energy for better photodegradation performance then the
submerged gC3N4 powder photocatalyst that require stirring process.
2.2.3. Spray-coating
Besides than fabricated floating photocatalyst using dip coating
technique, the floating photocatalyst also can be fabricated through
spray coating. Magalhães and Lago prepared floating photocatalyst by
spraying a polystyrene (PSt) solution in ethyl acetate on expanded
polystyrene (EPS) beads and TiO2 [34]. EPS beads were selected as
floating support is due their light and floatable properties. Furthermore,
EPS also having good chemical, thermal and mechanical stability. The
floating TiO2/ EPS composite was dried at 80 °C for 1 h to remove the
ethyl acetate before subjected to vigorous strring in water for 2 h to
remove any loosely attached TiO2 from the EPS surface. Spray coating
is suitable for short run fabrication because the process is fast and
simple. However, this kind of fabrication technique often leads to waste
of materials due to over-spraying. It is also very difficult to contol the
coating thickness on the surface of the floating materials.
2.3. Hydrothermal
Fabrication of floatable composite photocatalyst by hydrothermal is
8
Journal of Water Process Engineering 36 (2020) 101300
carried out in one-pot Teflon autoclaves which are tightly sealed in
stainless steel chamber that can withstand high pressure and tempera-
tures for a long duration time. The main fabrication parameters of this
method are the synthesis temperature, duration, pressure and initial pH
of the medium in the system [39]. This fabrication technique is one of
the great interest due to its potential to develop homogenous composite
photocatalyst in one-step process. Furthermore, this technique also af-
fordable and environmentally friendly. Numerous researchers applied
hydrothermal technique for coating TiO2 onto floatable materials such
as surface of woods [39,56,57].
Recently, Darkhosh et al., successfully developed a novel visible
light water-floating catalyst called as CuFeO2/ expanded perlite for
degradation of methylene blue [32]. In their study, the CuFeO2 was
directly deposited on the surface of expanded perlite through one-step
hydrothermal reaction at 180 °C within 24 h. The morphology char-
acterization analysis indicated that the rhombohedral CuFeO2 homo-
geneously distributed on the perlite surface as shown by Fig. 6(a–c). As
shown in Fig. 6(d) with the presence of visible light, the CuFeO2
composite photocatalyst was reported excellent photodegradation effi-
ciency of 99.0 % for degradation of methylene blue. The excellent
photocatalytic activity of this composite photocatalyst is resulted by the
synergistic influence and interaction between photocatalytic and floa-
table properties of CuFeO2 and perlite in the moderate hydrothermal
reaction that ensure the reaction at the surface of the composite pho-
tocatalyst as illustrated in Fig. 6(e).
Researchers also demonstrated that fabrication of floating compo-
site photocatalyst can be revealed by combination of hydrothermal and
liquid-phase deposition process. For example, Khan et al., 2019 re-
ported the floating reduced graphene-oxide quantum-dots bismuth-
bismuth tungstate (rGO QDS Bi-Bi2WO6)/ expanded perlite nano-
composite photocatalyst can be fabricated by hydrothermal technique
and followed by liquid-phase deposition process [35] as illustrated in
A.M. Nasir, et al. Journal of Water Process Engineering 36 (2020) 101300

Fig. 6. a) SEM image of expanded perlite, (b) SEM images of CuFeO2 particles, (c) SEM image of composite CuFeO2/ expanded perlite, (d) photodegradation of MB by
CuFeO2/ expanded perlite (e) schematic illustration of photocatalytic degradation mechanism by floating CuFeO2/ expanded perlite photocatalyst [32].

Fig. 7(a). The expanded perlite required pre-treatment by soaked
overnight in 10 wt.% HCL before being sieved uniformly through a 40-
mesh screen. Then the treated perlite was soaked in D-H2O for 1 h be-
fore dried in oven for 24 h at 80 °C. The reduced graphene-oxide
quantum-dots (rGO QDs) was firstly synthesized by Hummer’s method
and treated with strong acid. As illustrated in Fig. 7(b) they prepared
the floating Bi-Bi2WO6/expanded perlite nanocomposite by hydro-
thermal method. Hydrothermal synthesis was carried out by using
precursors bismuth nitrate, Bi(NO3)35%H2O and sodium tungstate,
Na2WO42%H2O with the presence of PVP K30 and citric acid at synthesis
temperature of 170.0 °C for 10 h. Then rGO-QDS was deposited on the
Bi-Bi2WO6/expanded perlite by the facile-liquid-phase deposition pro-
cess. Their result shows the significant photodegradation efficiency on
rhodamine B and phenol which recorded 95.0 and 93.0 % with the
presence of visible light irradiation.
Researchers have demonstrated solvothermal technique can be
employed to grow TiO2 photocatalyst on the graphene substrate to form
floatable photocatalyst in the water [58]. Schematic diagram of for-
mation floating TiO2/ graphene photocatalyst was demonstrated in
Fig. 8. In their study, expanded graphite was first heated at high tem-
perature with the presence of oleum to enlarge the distance between
adjacent graphitic layers also to enhance the number of surface groups.
Then, Ti precursor solution (tetrabutyl titanate in ethanol) was mixed
with oleum treated expanded graphite before filled in Teflon autoclave
and kept at 180 °C for 3, 6, 12 or 24 h. This solvothermal process al-
lowed in-situ growth of TiO2 nanoparticles in the interlayers of the
expanded graphite forming TiO2/ graphene composites.
Even though solvothermal offers fast and simple technique of fab-
rication of floating nanocomposite photocatalyst, but there are limita-
tions of this technique. One of them is low hydrothermal temperature is
not suitable for transformation of amorphous structure inorganic par-
ticles into crystalline structure which reduce the photocatalytic activity
of the particles. Then, the usage of photocatalytic precursor solution is
not recommended for this kind of fabrication technique. Secondly, high

Fig. 7. (a) Synthesis of Bi-Bi2WO6/ expanded graphite by hydrothermal technique, (b) synthesis of rGO QDs-Bi-Bi2WO6/ expanded graphite by liquid-phase de-
position technique [35].

9
A.M. Nasir, et al.
Fig. 8. Schematic diagram of formation of TiO2 –graphene composites by solvothermal process [58].
Fig. 9. The fabrication of floating composite photocatalyst via hydrothermal technique.
temperature of hydrothermal process is not suitable for organic floa-
table substrate such as polymeric-based materials. Due to lower thermal
stability, the structure of the polymeric substrate might deteriorate
during solvothermal process. Hence, selection of the substrate needs to
be strict and carefully analysed before proceed to fabrication. Third,
fabrication of floating composite photocatalyst might resulted in het-
erogeneous or diverse distribution of photocatalyst particles on the
surface of substrate. This is due to the floatability of the substrate and
hydrolysis process of development of the photocatalyst occurred at the
bottom of the autoclave flask which discrete the uniform deposition of
the photocatalyst on the floating substrate as illustrated in Fig. 9. Hence
continuous stirring is required to ensure homogeneous dispersion of
developed photocatalyst on the surface of the floating substrate.
2.4. Solvent casting
Another technique to fabricate floating composite photocatalyst
that attracted attention of researcher is solvent casting. Singh et al.,
introduced two routes called as (1) impregnation solvent-cast and (2)
strewing solvent-cast technique [49]. Fig. 10(a–b) showed the devel-
oped floating photocatalyst, Ag-TiO2 onto/into polystyrene (PS) fabri-
cated by impregnation solvent-cast and strewing solvent-cast respec-
tively.
10
Journal of Water Process Engineering 36 (2020) 101300
The fabricated composite photocatalyst films were subjected to
photodegradation of methylene blue in aqueous solution under both
solar and UV irradiation. They found the maximum photodegradation
of methylene blue irradiated by solar light by strewn solvent-cast
photocatalyst and impregnated solvent-cast photocatalyst were about
83.0 % and 68.0 % respectively. While, under UV irradiation the pho-
todegradation of methylene blue by strewn solvent-cast photocatalyst
and impregnated solvent-cast photocatalyst were about 94.0 % and
86.0 % respectively. This result indicated photocatalyst film that fab-
ricated by strewn solvent-cast having higher photodegradation perfor-
mance. This can be ascribed by the location of the TiO2 photocatalyst
particles that adhered externally onto the surface of PS as compared to
floating photocatalyst that fabricated via impregnated solvent-cast.
Strewn photocatalyst have a greater probability interacting with the
methylene blue molecules which enhance the photodegradation per-
formance.
2.5. Surface modification
Surface modification of the floating substrate could enhance the
interaction or deposition of photocatalyst particles onto the surface of
the substrate. Commonly the surfaces of the substrates were treated by
strong acid or alkaline to make the them became rougher before
A.M. Nasir, et al. Journal of Water Process Engineering 36 (2020) 101300

Fig. 10. Digital image of (a) impregnated solvent-cast TiO2/ PSt, (b) strewn solvent-cast TiO2/ PSt film floating composite photocatalyst [49].

deposition of the photocatalyst. According to Wang et al., 2015, they
used the method of surface modification to load hollow TiO2 onto the
surface of hollow glass microsphere (HGMS) [43]. This method offered
production of floating photocatalyst with larger specific surface area
and much better photocatalytic performance. Briefly, as demonstrated
in Fig. 11(a) they modified the surface of HGMS by hydrofluoric acid
(HF) and vinyl trimethoxysilane (VTMS) to make the surface became
rougher and appropriate to load PSt particles. PSt particles was used as
the template for precipitation of amorphous TiO2 through hydrolysis
process. Then, the crystallization of amorphous TiO2 was proceed
through calcination (550 °C) and directly removed PSt by combustion.
Fig. 11 show the SEM images of the (b) PSt, (c) HGMS corroded by HF
and modified by VTMS, (d) PSt loaded on HGMS, (e) HGMSHT after
calcination at 550 °C.
Based on previous studies, most of the floating photocatalysts were
prepared by coating the commercial photocatalyst within the floatable
substrate. Besides that, sol-gel and hydrothermal technique are often
used by mixing the substrate with the precursor solution of the pho-
tocatalyst. Commonly, in order to further enhanced the photocatalytic
activity of the photocatalyst, addition of activation agent during pre-
paration process was suggested. However, those techniques involved
physical interaction which limiting the stability and could be resulted in

Fig. 11. (a) Schematic diagram on fabrication of HGMSHT, (b) SEM image of PSt, (c) SEM image of HGMS treated by HF and VTMS, (d) SEM image of PSt loaded on
HGMS and (e) SEM image of HGMSHT after calcination at 550 °C [43].

11
A.M. Nasir, et al.
Fig. 12. (a) Schematic diagram of fabrication floating photocatalyst and (I) SEM surface images, (II) EDS mapping and (III) EDS analysis of the fabricated b) LDPE-
TiO2/ CM, (c) LDPE-TiO2/O-xylene, (d) LDPE-TiO2-surfactant [47].
leaking of the photocatalyst from the surface of the floating substrate.
Photocatalyst particles tend to peel off and shrink during the crystal-
lization and calcination process hence decline the photocatalytic per-
formance due to the reduction of active surface area. In order to
overcome the limitation, production of floating photocatalyst through
surface modification could be consider as promising alternative to load
photocatalyst on the surface of floating substrate materials.
2.6. Three-dimensional (3D) printing
Most recently, fabrication of floating photocatalyst by 3D printing
has attracted much attention due to the economical, efficient, easily
implantable and environmentally compatible process. According to
Martín de Vidales et al., they fabricated TiO2/LDPE by different
method; (1) mixing TiO2 and LDPE in a hot-cylinder-mixer, (2) using o-
xylene as dispersing and (3) using anionic surfactant as dispersing agent
[47]. The scheme of fabrication of the photocatalyst was illustrated in
Fig. 12(a) the mixture then was chopped and extruded as the three
different filaments called as LDPE-TiO2/CM, LDPE-TiO2/O-xylene and
LDPE-TiO2/surfactant respectively. The filaments were printed as me-
shes in a Fused-Deposition-Modelling 3D-printer. Fig. 12(b–d) showed
the (I) SEM surface images, (II) EDS mapping and (III) EDS analysis of
the fabricated b) LDPE-TiO2/ CM, (c) LDPE-TiO2/O-xylene, (dld[pe)
12
Journal of Water Process Engineering 36 (2020) 101300
LDPE-TiO2-surfactant. The observation can be made all the photo-
catalyst particles were highly dispersed and agglomerated on the sur-
face of meshes which indicated when an anionic surfactant or o-xylene
were used as dispersing media, no apparent improvement is achieved
and significant agglomerations can be observed.
From the results, they found the maximum degradation by photo-
catalyst in meshes form that obtained from 3D printing is significantly
higher than the plate geometry. The enhancement of the process effi-
ciency is attributed to the higher active surface available for oxidation
of pollutant. Furthermore, the adhesion of TiO2 photocatalyst and
polymer was improved by extrusion and 3D printing process. Hence,
fabrication of floating composite photocatalyst by 3D printing offer
promising solution for photodegradation of contaminant in aquous
system.
2.7. Low temperature ultrasonic and deposition
Even though researchers reported physical approach on deposition
of photocatalyst on floating substrate such as sol-gel, dip coating, hy-
drothermal is an efficient and cost effective. But most the mentioned
techniques are not suitable to be used for coating TiO2 on polymer
substrate. This is due to high-temperature calcination for transforma-
tion of photoactive anatase structure of TiO2 might destroyed the
A.M. Nasir, et al. Journal of Water Process Engineering 36 (2020) 101300

structure of the polymer substrate. Hence, Zhang et al., introduced a As shown in the schematic diagram, in the visible light region Ni-N
low temperature ultrasonic and deposition approach for efficiently codoping showed effective absorption which attributed to the charge
coated TiO2 onto the polyurethane foam (PUF) [38]. transfer between the orbital d of the dopants and band gap states of
Zhang et al., utilized PUF as substrate for the photocatalyst because TiO2. The synthesized Ni-N-TiO2/ EGC photocatalyst generates h+ and
of it has a rougher surface, high specific surface area, high porosity as photogenerated electrons in the presence of visible light (Eq. 1). The h+
well as light-weight. The OMT powders were used as precursor and react with water or OH¯ that adsorbed on the surface of photocatalyst to
dissolved in absolute alcohol with a little portion of concentrated nitric produce hydroxyl radicals (Eqs. 2 and 3). Meanwhile, the photo-
acid. The solution was vibrated by ultrasonic vibration for 30 min at 80 generated electrons can be trapped by the oxygen molecule that ab-
°C. Then PUF was added to the dispersed OMT-ethanol solution before sorbed on the surface of catalyst to produce superoxide (Eq. 4). Ad-
ultrasonic vibrated for another 30 min. The OMT-coated PUF then was ditionally, the superoxide can further react with water to generate
dried at 60 °C for 24 h to form TiO2/PUF floating composite photo- hydroxyl radicals (Eq. 5). These reactive oxygen radicals can react with
catalyst. This photocatalyst was analysed for the simultaneous de- diesel oil to mineralize the hydrocarbon components as shown in Eq. 6.
gradation of organic dyes (methylene blue, rhodamine B and methyl
Ni-N-TiO2 / PEGC + hv → Ni-N-TiO2/ PEGC + h+ + e¯ (1)
orange) and reduction of heavy metal hexavalent chromium Cr(VI) into
%
trivalent chromium Cr(III). They found with the presence of solar ir- h +
+ H2Oads → OH + H +
(2)
radiation, TiO2/PUF that fabricated via low temperature ultrasonic %
approach exhibited good adsorption performance and high photo- h +
+ OH¯ads → OH (3)
catalytic activity (90.4–97.4 %). e¯ + O2(ads) → O2¯ %
(4)
% %
3. Photocatalytic mechanism by floating photocatalyst O2¯ + 2H2Oads → 2 OH + 2OH¯ + O2 (5)
% %
Diesel oil + OH / O2¯ → CO2 + H2O (6)
3.1. Organic pollutants

Organic contaminants are the major pollutant in wastewater [59].

Primarily, organic contaminants composed of carbon, hydrogen and 3.2. Inorganic pollutants
other elements such as nitrogen, amine, amide, azo, aromatic com-
pound and etc. They could be various wastes like dye, phenols, alcohol, Inorganic pollutants of wastewater comprise of metalloid, heavy
diesel, aldehydes, antibiotics, pharmaceutical and etc. Fig. 13 shows the metal ions, nitrate, phosphate, etc. Heavy metal contamination in water
photocatalytic degradation mechanism of Rhodamine B (RhB) by CdS/ supplies has drawn global attention due to the toxicity and carcino-
EP floating photocatalyst [42]. The CdS nanoparticles were attracted to genicity effects towards living bodies. Recently, the treatment of
the partially positive charges on the surface of EP due to the content of harmful heavy metal like hexavalent Cr(VI) with the presence of dyes
alumina and silica. As the floatable properties of EP, the visible light were studied by Zhang et al. [38]. Fig. 15 shows the removal of Cr(VI)
irradiated the CdS to excite its electrons to the conduction band. The by photocatalytic activity of the floating OMT/PUF by reduction of Cr
presence of oxygen molecules in the atmosphere accept the photo- (VI) under sunlight in different coexisting dye systems.
generated electrons and superoxide is produced. Meanwhile, the h+ in The main photocatalytic reaction mechanism of the simultaneous
the valence band is captured by H2O molecules to form hydroxyl ra- dye oxidation and reduction of Cr(VI) was described in Eqs. (7, 8, 9, 10,
dicals. Formation of superoxides and hydroxyl radicals can degrade 11, 12, 13, 14 and 15) as expressed below:
RhB into CO2 and H2O. TiO2 + hv → hVB +
+ eCB ̶
(7)
In other study, Wang et al. successfully synthesized EGC based Ni-N-
TiO2 floating photocatalyst for adsorption and degradation of diesel oil eCB̶ + Cr VI
→ ... → Cr III
(8)
[51]. The proposed mechanism of photocatalytic degradation of diesel
hVB +
+ dye pollutants → …. → CO2 + H2O (9)
oil was depicted in Fig. 14.

Fig. 13. Schematic diagram of the photocatalytic degradation mechanism of RhB by CdS/EP floating photocatalyst [42].

13
A.M. Nasir, et al. Journal of Water Process Engineering 36 (2020) 101300

Fig. 14. Schematic diagram of photocatalytic degradation of diesel oil by Ni-N-TiO2/ EGC floating photocatalyst [51].

eCB̶ + O2 → O2%¯ (10) 4. Future directions and conclusions

O2%¯ + dye pollutants → …. → CO2 + H2O (11)

Basically, the ability of the composite photocatalyst to float on the
%
hVB +
+ H2O → OH + H +
(12) surface of water permits more efficient light illumination and oxyge-
nation which are fundamental for the photocatalytic process. In the
O2%¯ + H2O → %OH + OH¯ (13) future, more studies and research work on fabrication of floating
%
OH + dye pollutants → … → CO2 + H2O (14) composite photocatalyst are still required to enhance the performance
of the photocatalyst. This study can be a guideline to design and fab-
TiOH2 +
+ Cr2O72¯ → TiOH.Cr2O72¯ +H +
(15) ricate the superior materials with photocatalytic and floatable proper-
ties for wastewater treatment. First, an excellent, non-toxic and bio-
Briefly, from Eqs. (7–14) when the TiO2 that located in OMT/PUF is
degradable floatable substrate and photocatalyst need to be explored.
bombarded by sunlight irradiation, the electrons are released from the
This is due to the longer contact time on the contaminated water could
VB to CB to give electron-hole pairs. The electron at CB (eCB¯) could
deteriorate the floating properties of the substrate. Hence, utilization of
reduce the Cr(VI) into Cr(III). Additionally, the H+ ions adsorbed on
the biodegradable substrate could solve the environmental issue such as
the surface of TiO2 allows the adsorbed H+ to trap electrons to form
post-treatment issue by letting them settled down at the bottom of
Hads and facilitate the reduction of toxic Cr(VI) into less harmful Cr(III)
treatment tank. Second, adhesion of photocatalyst on the surface of the
as expressed in Eq. 15. Simultaneously, the dye pollutants were de-
of the floatable substrate must be further improved because it is the
graded by superoxide (O2%¯) and hydroxyl radicals (%OH) that generated
major key to down-to-earth application of the photocatalyst. Leaking of
by hydrolysis of water in the presence of O2.
photocatalyst from floatable substrate could led to secondary pollution
to environment. Third, more research work on development of visible
driven floating photocatalyst should be intensified rather than UV

Fig. 15. Schematic diagram of degradation of Cr(IV) in the dyes solution by floating photocatalyst OMT/PUF under sunlight [38].

14
A.M. Nasir, et al.
driven photocatalyst. This is due to visible light is more accessible
especially in local remote area. Modification of photocatalyst particle
by reduction of band gap could further enhance the photocatalytic
performance. Fourth, other potential semiconductor-based photo-
catalyst need to be explored that fulfilled practical application instead
of focusing on existing semiconductor-based photocatalyst.
Semiconductor like perovskite could overcome the limitation of the
common photocatalyst by having lower bandgap and utilized visible
light irradiation rather than UV irradiation. Last but not least, green
synthesis of floating photocatalyst by using plant-based or agricultural
waste as reducing or stabilizing agent should be further explored.
Commonly chemical additives were employed as stabilizing agent
which contribute to secondary pollution. As conclusion, more effort
should be devoted to deeper understanding on fabrication, utilization
and mechanism of floating composite photocatalyst on wastewater
treatment.
5. Declaration of interests
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
The authors would like to acknowledge the financial support pro-
vided by Ministry of Higher Education, Malaysia under Fundamental
Research Grant Scheme grant with vote number
R.J130000.7851.5F007, Malaysian Research University Network with
vote number R.J1300000.7813.4L874 and HICoE:
R.J090301.7851.4J431
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