INTRODUCTION

Water scarcity has emerged as one the biggest threats presently due to multiple factors including
environmental pollution and non-availability of water due to regional limitations. To overcome this
issue, a conventional solution is to install water desalination plants but they have a major economic
drawback of being very expensive to run. At present, one of the most likely solution is to desalinate
water by harvesting solar energy (Huang et al., 2017). Although treating water by harvesting solar
energy seems very promising, there are number of factors such as poor light absorption of water make
this process inefficient(Higgins et al., 2018). Despite these problems, researchers have put forwarded
many solar based prototypes which are claimed to be efficient. One such solar evaporator was
designed for a single household which used both solar and wind energy and had an output efficiency
of 53% (Soni et al., 2017). Likewise, another prototype uses candle soot coated cotton as a floating
absorber improved output efficiency to 80 % (Wilson et al., 2019). However, the study didn’t focused
on treating bacteria’s which differed with the origin of water.

In this research, the use of carbon and its derivates especially TiO2 are studied especially in their role
as photocatalysts for not only desalinating water, but also for degradation of different organic
contaminants like dyes and antibiotics which are mostly present in wastewater (Rabé et al., 2019). A
study used 3D printed graphene-based solar system and managed 80% efficiency under 1 sun
illumination. The treated water had ion concentrations under WHO limits (Li et al., 2017b). However,
the fabrication of the catalyst seems difficult to be applied on commercial scale. Another research
proposed purification of water by using calcinated melamine-derived carbon sponges in a solar steam
generator which produced efficiency of 92% under one sun illumination (Gong et al., 2019). The results
encourages to find new ways to improve evaporation rates of different types of water. Another article
focused on solar steam generator comprising of double layer structure of reduced graphene oxide
sheets and cellulose membrane managed to produce evaporation 4 times higher than pure
water(Wang et al., 2017). The efficiency was increased by decreasing heat transfer as a result of
reduced graphene oxide sheets. Similarly, researchers fabricated a Ag-TiO2 based nanoparticle
membranes which had 69% efficiency under one sun irradiation (Li et al., 2017a). Similarly, a research
proposed a composite photothermal membrane including carbon nanotubes and polysulfone which
showed efficient separation under solar-assisted simulator(Song et al., 2019). The solar assisted
composite membrane managed to maintain a high temperature which led to low energy consumption
and higher permeate output.

Apart from desalination, TiO2 based photocatalysts have tremendous applications in degradation of
organic pollutants. These organic pollutants include dyes like Rhodamine B dye, antibiotic resistant
bacteria’s which are difficult to remove in conventional wastewater treatment. A research used
carbon fabric as photocatalyst for solar steam generation which removed almost 87% of organic
impurities from brackish water (Higgins et al., 2018). The research also focused on using titanium-
nanorods (TiO2) grown on carbon fabric to eradicate organic impurities especially dyes (Higgins et al.,
2018). The outcome showed efficiency of TiO2 in eliminating organic contaminants. Another study
used TiO2 as a heterogeneous photocatalyst for degrading different chemicals like dyes and pesticides
in water treatment(Cheriyan et al., 2017). However, the procedure required further filtration of
treated water to remove powdered catalyst. Similarly, a comparative study on effective
photocatalytic degradation showed nano-sized TiO2 as a capable contender in biological treatment of
organic impurities in wastewater due to its simple structure and easy removal from aqueous
solution(Murgolo et al., 2015). Another article focussed on combined process of solar photo-Fenton
reaction followed by granular activated charcoal to eliminate antibiotic mixtures from wastewater
which was proved effective in not only eliminating antibiotic mixtures but also in reducing toxicity
(Michael et al., 2019). The Fenton reactions led to the formation of oxidation products due to toxicity
which requires further treatment of water to remove acidity which may affect the economic feasibility
of the process on industrial level. Another research used GO-TiO2 composite catalyst to specifically
degrade bisphenol-A which resulted in 84% reduction in TOC of the sample (Monteagudo et al., 2018).

The aim of this study is to focus on the use of TiO2 as a photocatalyst in desalination of saline water
along with degradation of microbial organic contaminants and to find different ways to optimize the
performance thereby resulting in increased efficiency of the system. However, there are number of
parameters which need to be factored in before defining and evaluating the efficiency of the system.
The efficiency of solar assisted desalination system will be calculated by determining the weight loss
during evaporation. However, for degradation analysis there are various other parameters such as
total organic content (TOC), coliform removal rate using quanti tray method, chloride analysis, pH and
effect on alkalinity and total hardness of the aqueous sample. By calculating these parameters, the
efficiency of the system will be calculated for comparing different system and to find out various ways
to increase the overall efficiency.

Literature Review
One of the biggest threats presently faced by humankind is water scarcity. There are multiple factors,
which lead to this danger including regional limitations, water pollution etc.; however, one of the
biggest and challenging factor is the presence of organic pollutants in wastewater. These organic
pollutants comes from various domestic, agricultural and industrial activities. Some of the most
common pollutants are dyes, antibiotics from pharmaceutical industries and chemicals that are very
resilient to conventional processes. This has led to release of these chemicals in natural water bodies
like lakes and rivers. Since the composition of wastewater differs due to use of different complex
processes in different industries, it is almost impossible to devise a universal strategy to treat
wastewater. Multiple researchers have put forwarded various approaches to remediate wastewater
such as physiochemical techniques that have drawbacks of low efficiency especially with industrial
dyes and high cost of equipment. Another approach is biological solutions, which generate
comparatively less sludge and are cost effective, however, there implementation requires a large land
area along with very high operation time. (Garcia-Segura and Brillas, 2017).

Over the past decades, advanced oxidation processes (AOP) have developed to be one of the most
effective methods in treating organic pollutants as it is produces highly reactive hydroxyl radicals (OH)
that are able to degrade organic compounds. Advanced oxidation processes are very effective in
degradation of organic pollutants originating from pharmaceutical industries such as antibiotics.
Fenton reactions are AOP based process, which produce radical hydroxyl ions OH that can also be
enhanced when irradiated with light, which promotes oxidation as well as mineralization of pollutants.
A major drawback for these reactions is the formation of oxidation products, which are toxic and are
derived from dissolved effluent organic pollutants. One of the ways to counter these products is the
use of granular activated charcoal that has the ability to absorb these derivations. This principle was
applied by researchers to degrade antibiotic resistance bacterias, which were present in a stock
solution prepared with antibiotics and effluents collected from two wastewater plants. Photocatalytic
(SPF) and adsorption experiments were performed in a compound parabolic collector pilot plant with
solar irradiation data monitored on daily basis. Initial and final concentrations of stock solutions as
well as their pH was assessed which showed a pseudo-kinetics pattern in degrading antibiotic bacteria
(Michael et al., 2019). However, further treatment of toxicity by GAC makes this process costly and
the study also didn’t took into account the influence of change in pH while applying GAC treatment
process.
Apart from Fenton reactions in AOPs, heterogeneous photocatalytic reaction use semiconductors like
TiO2 to degrade organic pollutants. One of the most persistent organic pollutant is endocrine
disrupting chemical (EDC) bisphenol-A (BPA) that generally come from plastic industries. A study put
forwarded by researchers effectively degraded EDC by solar activation of graphene based TiO2
photocatalyst. Titanium dioxide is one of the most promising photocatalyst for the degradation of
organic impurities in industrial wastewater. TiO2 is an n type semiconductor with three main
crystalline structure that are brookite, rutile and anatase with anatase having highest band gap value
of 3.32 eV. TiO2 are cost effective and chemically stable with no absorption in the visible region. The
chemical stability of TiO2 holds in dark only however its use under sunlight in degradation of fabrics
containing TiO2 has shown similar stability(Garcia-Segura and Brillas, 2017). In the study,
photocatalyst was synthesized using graphene oxide (GO) obtained by Hummers method. GO was
then treated in ethanol solution, TiO2 nanoparticles were later added and stirred and then
hydrothermal process was applied to get TiO2/GO composite samples for photocatalytic activity. For
the photocatalytic experiment, BPA solution was prepared by dissolving BPA in deionize water and
then it was place inside a reservoir for some time with the prepared catalyst added in it to attain
equilibrium. The mixture was then subjected to photocatalytic oxidation in a reactor. Afterwards, the
sample was withdrawn and chemical analysis along with TOC, DO were performed to evaluate
degradation of BPA. The chemical analysis showed that the hydroxyl ion concentration increased in a
rapid manner and then remained constant, however, with the variable concentration of BPA, the
behaviour of OH ion changed. However, for the smaller concentration of BPA, a high radical ion
concentration was obtained which resulted in higher degradation in terms of TOC removal
(Monteagudo et al., 2018). One of the drawbacks specific to this proposed design is the complexity in
the process of synthesizing photocatalyst on a commercial level while its effectiveness against other
organic pollutants also need to be tested.

A study put forwarded by S. Murgolo utilized TiO2 to fabricate a photocatalyst nano-sized TiO2 grown
on carbon nanotubes to degrade organic pollutants by heterogeneous photocatalysis in water. The
conventional photocatalyst TiO2 has a major drawback that the photocatalyst is difficult to recover at
the end of treatment due to micrometric size of the pollutants. Another disadvantage is called
shadowing effect in which photocatalyst suspension has a reduced solar intensity due to suspension.
One of the means to overcome these challenges proposed by the authors is the use of nanostructured
photocatalysts. Since, the major advantage of using advance oxidation processes is high energy costs
due to use of ozonizers and UV lamps, the presented work opted for solar based reactions. The authors
synthesized a nano-sized single walled carbon nanotube to obtain anatase TiO2 nanorod.
Photocatalytic degradation reactions were performed, and afterwards total organic content of sample
was measured at scheduled times which showed an adequate degradation (Murgolo et al., 2015).
However, a further coupling of the proposed design with adequate biological setups for focussed
removal of organic contaminants should also be studied to increase efficiency.

Besides conventional organic pollutants, researchers have used TiO2 in very focused manner to treat
specific organic contaminants like antibiotics and industrial dyes in wastewater that are normally very
resilient to conventional methods. A study by Kané Rabé used chemical reduction process to fabricate
a TiO2 based heterostructure photocatalyst g-C3N4/Fe0(1%)/TiO2 and then characterized it using
different techniques such as X-Ray diffraction (XRD), Transmission electron microscopy (TEM) and
energy dispersive spectrum (EDS). The author then performed photocatalytic reactions by simulating
light using halogen bulbs in deionized water sample which contained Rhodamine dye and TC. The
degradation performance of the photocatalyst was evaluated by taking the difference between initial
and final concentrations of contaminants. The results showed an excellent degradation performance
of fabricated catalyst when compared with conventional TiO2 photocatalyst. A possible explanation
of performance enhancement of fabricated photocatalyst is the presence of doping ion Fee in TiO2
along with further presence of graphitic carbon nitride (Rabé et al., 2019). However, the performance
of photocatalyst against varying pH of sample must also be studied.

Since TiO2 has emerged as the most promising photocatalyst, extensive research has been made by
researchers to enhance its photocatalyst activity. One of the works developed is floating photocatalyst
which has some considerable advantages such as it increases solar light utilization process and
enhances the oxygenation by the proximity with air/water interface. F. Magalhães applied this
concept to remediate remotely located contaminated wastewater and degradation of industrial dyes
and insoluble suspended organic pollutants like oil spills. The authors fabricated the photocatalyst by
grafting commercially available TiO2 P25 on floating substrate expanded polystyrene (EPS) beads. The
prepared photocatalyst was then characterized by BET surface area in a quantachrome and by
thermogravimetric analysis. Photocatalyst reactions were then initiated in a photocatalytic reactor
used for surface illumination. Solar light intensity of wavelengths measured during experiments was
almost 250 to 400nm. The subjects degraded were industrial dyes drimaren red (DR), indigo carmine
(IC) and methyl blue (MB). The results were later analysed spectrophotometrically and by TOC
readings which showed discoloration of dyes and significant TOC removal. The trend showed
considerable good in the first use but remained constant in the later uses (Magalhães and Lago, 2009).
Even though the preparation of catalyst seems simple and low cost, further study to increase TOC
removal efficiency in the reuse of catalyst should be made to make it suitable for remote locations.

In another research, F. Magalhães fabricated a floating photocatalyst using commercially

available TiO2 P25 and low density polyethylene (LPDE). LPDE is a hydrophobic material and helps in
enhancing oxidation efficiency by organic pre-concentration. The floating photocatalyst was prepared
by a suspension of TiO2 in LDPE while using different contents of TiO2 in terms of weight percentage
for results comparison. After fabrication, the catalyst was characterized using XRD analysis, density
measurements and SEM analysis. The photocatalytic reactions were carried out by using a MB dye in
a photoreactor which provided surface illumination and under UV and solar illumination. The results
showed that no discoloration o dye took place without catalyst, while the presence of photocatalyst
caused discoloration of dye in a 240 min test. In terms of TiO2 weight percentage, pure TiO2 showed
very low discoloration of about 20%, while, the photocatalyst TiO2 (82)/LPDE and TiO2 (68)/LPDE
showed complete discoloration of organic dyes after 240 mins test. The TOC removal rate while using
this catalyst was found out to be 35% (Magalhães et al., 2011). Since the experiment only focused on
MB dye, a study to evaluate the performance of photocatalyst against other industrial dyes like IC and
DR should also be done while trying to increase TOC removal rate.

Mouheb Sboui also conducted a similar research in which the authors coupled TiO2 with
semiconductor PANI (polyaniline) polymer and cork to investigate the feasibility of TiO2-PANI/Cork as
a floating photocatalyst. The catalyst was prepared by a direct impregnation method and then
characterized by using XRD and SEM analysis. Photocatalytic reactions were then carried out using a
photoreactor that provided surface illumination and by using solar illumination on textile dye ME. The
degradation was later measured using initial and final concentration of dye which showed complete
discoloration (Sboui et al., 2017). However, TOC removal rate and effect of photocatalyst in removing
other dyes and organic contaminants must also be evaluated before studying feasibility on a
commercial level.

The objective of this study is to study photocatalytic degradation using TiO2 while trying to design a
TiO2 based photocatalyst experiment that degrades organic contaminants found in typical industrial
wastewater efficiently and also economically low cost and the degradation can be verified by using
different chemical parameters. At this point, floating photocatalysts have appeared to be most
promising in terms of research area and their application in remote locations while still keeping the
cost down. Another advantage is the relative simple process of photocatalyst fabrication which does
not involve complex processes and still manage to effectively degrade organic contaminants.

Research Design
The research question outlined is the use of TiO2 photocatalyst in effectively degradation of organic
contaminants in wastewater in an economical manner and validating the results by different chemical
parameters such as total organic content TOC, discoloration of dyes and chloride analysis. It has been
quite evident from literature review that TiO2 base photocatalyst offer many research areas of
improvement along with their benefits of simple fabrication process, relatively low cost and their
ability to treat wastewater in a remote location.

Higgins M. Wilson designed an experiment for water purification in which a floating absorber was first
synthesized using candle soot and then characterized using scanning electron microscopy and XRD
analysis. The floating absorber was placed over water surface inside a solar simulator and a digital
balance was used to record weight loss over time. An infrared camera was used to evaluate thermal
condition of absorber. For water desalination study a trapezoidal box with two compartments was
used. The floating absorber was placed over polluted water surface and the setup was exposed to sun.
The evaporated vapours were then condensed in other compartments and later collected for chemical
analysis to find out concentration of pollutants. The design has various advantages including low cost,
mobility and almost 80% photothermal efficiency. The chemical analysis showed considerable removal
of microbial pollutants (Wilson et al., 2019). However, the design has its limitation includes
performance against other organic impurities like bacteria that differ by the nature of water source.
Also, the setup is designed for a very specific organic pollutants and its effect on degrading other
organic contaminants is unknown but important as the setup is designed for human consumption and
the water source might contains organic contaminants coming from industrial waste.

F. Magalhães put forwarded a design based on the concept of using floating photocatalyst to treat
specific organic contaminants found in industrial wastewater like industrial dyes. A composite
photocatalyst was synthesized using TiO2 P25 and a low density polyethylene (LDPE) as a floating
substrate. The author fabricated the catalyst with different weight percent of TiO2 to evaluate its
effect on degrading organic contaminants and then characterized by using XRD analysis and SEM
analysis. Photocatalyst reactions were then carried out on methylene blue (MB) dye in a photocatalytic
reactor used for surface illumination. Solar light intensity of wavelengths were measured during
experiments. The results showed that no discoloration o dye took place without catalyst, while the
presence of photocatalyst caused discoloration of dye in a 240 min test. The TOC removal rate while
using this catalyst was found out to be 35% (Magalhães et al., 2011). The advantages of design include
low cost, simple fabrication and ability to degrade organic contaminants in a remote location.
However, the limitations of design include its effect on other contaminants such as antibiotics,
bacterias remain unknown. Also, the TOC removal rate is not adequate and design needs modification
for an increased efficiency.

The research design being proposed has a very ambitious prospect of treating organic contaminants
as well as microorganisms to enhance the quality of water as high as possible. The design involves
fabrication of TiO2 based floating photocatalyst with organic polymer substrate. The experiments aims
to degrade common industrial dyes such as methylene blue (MB) and microorganisms in water so that
the treated water can be used for different industrial or medical purposes.
  The photocatalyst will be synthesized using TiO2 and organic polymer such as methyl
methacrylate as a floating substrate. The composite photocatalyst can be fabricated by using
microemulsion method.
 A number of photocatalysts will be fabricated which will differ by the varying weight
percentage of TiO2 to evaluate the effect on degradation performance.
 A special trapezoidal box with two compartments will be made.
 One compartment will hold a weighted amount of wastewater with floating photocatalyst
placed on its surface.
 The sides of the box will be painted black to avoid any stray light except for the side exposed
to the sun.
 The vapours form as a result of evaporation will be collected and condensed in the other box
for further analysis.
 Evaporation performance will be evaluated by measuring weight loss.
 The degradation performance will be evaluated by examining the discoloration of dyes and
total organic content TOC.
 The antibacterial activity will be evaluated by using Kirby–Bauer method to find out degree
of photocatalytic destruction on specific bacteria such as Escherichia coli.

Finally, the results of different samples can then be compared to find out best weight percent of TiO2
that gives highest efficiency in combination with organic polymer substrate in degrading organic
contaminants.

The proposed design has several advantages such as low cost, simple fabrication of composite floating
catalyst and a possibility to execute the process in a remote location with limited resources. The design
efficiently manages to treat multiple contaminations such as dyes and microorganisms.

The design limitations include studying the effect of pH on the degradation performance. Also, the
performance of photocatalyst on contaminants such as antibiotics needs to be assessed. Another
limitation is that the experiment is designed for laboratory scale and a feasibility study is required for
any modifications to implement on a plant or industrial scale.

CHERIYAN, A. J., SHAIK, F., ALI BAAWAIN, M. S. & SARKAR, J. P. 2017. A STUDY ON THE REMOVAL OF
CONTAMINANTS FROM SECONDARY TREATED MUNICIPAL WASTEWATER BY SOLAR
PHOTOCATALYSIS. Environmental Engineering & Management Journal (EEMJ), 16, 1451-1456.
GARCIA-SEGURA, S. & BRILLAS, E. 2017. Applied photoelectrocatalysis on the degradation of organic
pollutants in wastewaters. Journal of Photochemistry and Photobiology C: Photochemistry
Reviews, 31, 1-35.
GONG, F., LI, H., WANG, W., HUANG, J., XIA, D., LIAO, J., WU, M. & PAPAVASSILIOU, D. V. 2019. Scalable,
eco-friendly and ultrafast solar steam generators based on one-step melamine-derived
carbon sponges toward water purification. Nano Energy, 58, 322-330.
HIGGINS, M. W., SHAKEEL RAHMAAN, A. R., DEVARAPALLI, R. R., SHELKE, M. V. & JHA, N. 2018. Carbon
fabric based solar steam generation for waste water treatment. Solar Energy, 159, 800-810.
HUANG, J., HE, Y., WANG, L., HUANG, Y. & JIANG, B. 2017. Bifunctional Au@TiO2 core–shell
nanoparticle films for clean water generation by photocatalysis and solar evaporation. Energy
Conversion and Management, 132, 452-459.
LI, H., HE, Y., LIU, Z., JIANG, B. & HUANG, Y. 2017a. A flexible thin-film membrane with broadband
Ag@TiO2 nanoparticle for high-efficiency solar evaporation enhancement. Energy, 139, 210-
219.
LI, Y., GAO, T., YANG, Z., CHEN, C., KUANG, Y., SONG, J., JIA, C., HITZ, E. M., YANG, B. & HU, L. 2017b.
Graphene oxide-based evaporator with one-dimensional water transport enabling high-
efficiency solar desalination. Nano Energy, 41, 201-209.
MAGALHÃES, F. & LAGO, R. M. 2009. Floating photocatalysts based on TiO2 grafted on expanded
polystyrene beads for the solar degradation of dyes. Solar Energy, 83, 1521-1526.
MAGALHÃES, F., MOURA, F. C. C. & LAGO, R. M. 2011. TiO2/LDPE composites: A new floating
photocatalyst for solar degradation of organic contaminants. Desalination, 276, 266-271.
MICHAEL, S. G., MICHAEL-KORDATOU, I., BERETSOU, V. G., JÄGER, T., MICHAEL, C., SCHWARTZ, T. &
FATTA-KASSINOS, D. 2019. Solar photo-Fenton oxidation followed by adsorption on activated
carbon for the minimisation of antibiotic resistance determinants and toxicity present in urban
wastewater. Applied Catalysis B: Environmental, 871-880.
MONTEAGUDO, J. M., DURÁN, A., CHATZISYMEON, E., SAN MARTÍN, I. & NARANJO, S. 2018. Solar
activation of TiO2 intensified with graphene for degradation of Bisphenol-A in water. Solar
Energy, 174, 1035-1043.
MURGOLO, S., PETRONELLA, F., CIANNARELLA, R., COMPARELLI, R., AGOSTIANO, A., CURRI, M. L. &
MASCOLO, G. 2015. UV and solar-based photocatalytic degradation of organic pollutants by
nano-sized TiO2 grown on carbon nanotubes. Catalysis Today, 240, 114-124.
RABÉ, K., LIU, L., NAHYOON, N. A., ZHANG, Y., IDRIS, A. M., SUN, J. & YUAN, L. 2019. Fabrication of high
efficiency visible light Z-scheme heterostructure photocatalyst g-C3N4/Fe0(1%)/TiO2 and
degradation of rhodamine B and antibiotics. Journal of the Taiwan Institute of Chemical
Engineers, 96, 463-472.
SBOUI, M., NSIB, M. F., RAYES, A., SWAMINATHAN, M. & HOUAS, A. 2017. TiO2–PANI/Cork composite:
A new floating photocatalyst for the treatment of organic pollutants under sunlight irradiation.
Journal of Environmental Sciences, 60, 3-13.
SONG, X., WANG, Y., WANG, C., HUANG, M., GUL, S. & JIANG, H. 2019. Solar-Intensified Ultrafiltration
System Based on Porous Photothermal Membrane for Efficient Water Treatment. ACS
Sustainable Chemistry and Engineering, 7, 4889-4896.
SONI, A., STAGNER, J. A. & TING, D. S. K. 2017. Adaptable wind/solar powered hybrid system for
household wastewater treatment. Sustainable Energy Technologies and Assessments, 24, 8-
18.
WANG, G., FU, Y., MA, X., PI, W., LIU, D. & WANG, X. 2017. Reusable reduced graphene oxide based
double-layer system modified by polyethylenimine for solar steam generation. Carbon, 114,
117-124.
WILSON, H. M., RAHMAN A.R, S., PARAB, A. E. & JHA, N. 2019. Ultra-low cost cotton based solar
evaporation device for seawater desalination and waste water purification to produce
drinkable water. Desalination, 85-96.