RESEARCH PROPOSAL

Project Tittle: Nano – photocatalyst for Treating Emerging Contaminant.

Research Supervisor: Professor Srinivasan Madapusi.

Department of Chemical and Environmental Engineering

Introduction

Rapid development of technology in nanomaterials and increasing demand in its usage has
merged a new crisis such as nano – toxicology. Conventional methods such as chlorination and
ozonation, are crucial in centralized wastewater treatment. Previous works have coupled
magnetic graphic oxide properties to Titanium Dioxide (TiO2) due to its high catalytic activity,
low toxicity, chemically stable and efficient separation. However, TiO2 only capable to react
within limited ultraviolet range which is 3% - 5% of total sunlight. Moreover, photo – oxidation
rate of TiO2 is limited to the low electron transfer rate and high rate of electron recommendation
(Chang et al. 2015). Therefore, this work will investigate new combination of nanocomposite
prepared in simple method, by introducing Cu – TiO2 into alginate carboxymethyl cellulose
(CMC) reinforced barium nitrate nanocomposite hydrogels. Transition metal – TiO2
modification provides cost efficient and excellent degradation alternative under visible light
(Han et al. 2009). Recently, hybrid hydrogels derived from biopolymers has become the centre
of attention as the advantages such as porosity, macro – structure, mechanical and degradation
stability (Balakrishnan & Banerjee 2011). So far, all these studies on nano – photocatalyst for
treating emerging contaminants were conducted in individual organic contaminant under
controlled laboratory conditions (Chang et al. 2015). Moreover, Ag+ modified TiO2 was not
much effective in salt water and wastewater environment (Han et al. 2009). Therefore, more
complex surroundings need to be investigated to identify the real effect of this nanocomposite
on the multiple organic contaminants.

Problem Statement & Objectives

Besides the advantageous of titanium oxide as semiconducting materials, it is also obliged for
its internal problems, such as difficulty in separation and recycling efficiency as it’s reduced in
degradation ability due to nanoparticle loss. Moreover, visible irradiation is more favourable
for easier deployment. Therefore, the objectives of this study are 1) efficient degradation of
organic contaminants under visible solar spectrum. 2) easy aggregation of nanocomposite. 3)
excellent reduplicative photocatalytic efficiency after regeneration.
Hypothesis

Incorporating nanocomposites photocatalyst into hydrogels will increase separability of the

materials form aqueous solutions. Nanocomposite combination, Cu – TiO2 nanocomposite
hydrogels has excellent organic contaminants degradation under visible irradiation. In fact,
those materials in combine will yield consistent photocatalytic organic contaminants
degradation efficiency after being used for several times in treating emerging contaminants.

Background Study

Organic contaminants discharged to water bodies from textile industries are considered as
major source of water pollution. It is estimated that almost to the quarter of global industrial
pollution are caused by textile industry (Zhou & Srinivasan 2015). The mentioned industry
extensively utilises complex synthetic organic dyes which excessive dyes that is not adsorbed
by fabrics and textile fibres cause problems to aquatic life and mutagenic to humans as released
to environments (Lucas et al. 2013).

Semiconductor photocatalyst is an advanced technology in water purification and disinfection.

In particular, Titanium dioxide has been widely used as catalyst in photochemical and
photocatalytic processes due to its nontoxicity and stability (Khalid et al. 2013). Upon
excitation of photon by light, energy is generated electron – hole pairs on the catalyst surface,
hence react with oxygen and water molecules producing hydroxyl radicals which are strong
oxidants for organic matter degradation (Chang et al. 2015).

Gels that are strongly enough to swell in aqueous solutions and hydrophilic organic composed
polymer which cross – linked component turn into network by either non – covalent or covalent
bond are called hydrogels (Nayak & Lyon 2005). Conventionally, nanoparticles of titanium
dioxide have been used for degradation of emerging contaminants due to its high surface, and
photocatalytic ability. However, the suspended catalysts are difficult to recover, therefore
immobilized nanoparticles have been introduced to various substrate such as polymer, carbon
nanotube and stainless steel (Thomas et al. 2016). Many research groups have used fabricating
method by utilising carbon nanocrystals (CNC) as fillers to poly (vinyl alcohol), epoxy resin
and poly (lactic acid). Based on this concept, synthesis of nanocomposite hydrogels composed
of PEG matrix reinforced with varying the volume fraction of CNC fillers which acted as
multifunctional cross - links. It is also identified that the swelling ratio depends on the CNC
concentration which means more CNC provided more cohesive force to avoid swelling and
reduced the absorption capacity of water (Yang et al. 2013).
Methodology (Thomas et al. 2016)

Materials: Sodium alginate and carboxymethyl cellulose (CMC) from Sigma- Aldrich.
Barium nitrate from Fluka. Congo red (CR) and Methylene Blue (MB) dye from Merck.

Preparation of Ba/Alg/CMC/Cu – TiO2 nanocomposite hydrogels: Ba/Alg/CMC/Cu – TiO2

composites is prepared by dissipative convective process followed by freeze drying method. A
homogeneous solutions of 2% w/v of sodium alginate (2 g in 100 mL deionized water) and 3%
w/v of carboxymethyl cellulose (CMC) (3 g in 100 mL water) is prepared. Mix 20 mL solution
of alginate with 20 mL solution of CMC and stir it for about 20 min. Subsequently, Cu – TiO2
nanoparticles is carefully added into the solution. The resultant solution is then crosslinked
with Ba2+ ions (2% w/v) in a cylindrical mould and the above system hold for 48 h under
stagnant conditions at room temperature to allow the crosslinking of barium ions. Afterward,
gel body is taken out from the mould, cut it 5 mm form the top and washed several times with
water to remove unbounded Ba2+ ions from the gel. After that the gel body is immersed in 1 M
methyl formate for 2 h to exchange the metal ions for protons to further induce densification of
the gel bodies followed by dipping the gel in acetone-water mixture (1:5 v/v) for 3 h to remove
excess acid and water. Furthermore, the gel body is placed in liquid nitrogen for about 30 min
to protect the dissipative convective structures which produced self-organized sponges using
freeze drying process.

Characterization: Fourier transform infrared spectrometer is used to characterize crosslinking

in composite gels. XRD patterns of the nanocomposite gels is recorded with an advanced X –
ray diffractometer. The UV– vis – DRS of catalysts are performed using spectrophotometer
from the wavelength range of 200 – 800 nm and BaSO4 is used as a reference. Surface area
analysis of nanocomposite gels are performed by nitrogen adsorption – desorption isotherm
analysis at 196°C using a sorptometer. Prior to analysis the samples are degassed at 473 K for
2 h under vacuum and surface area and pore size distributions are calculated using BET method.
The surface morphology of prepared nanocomposite gels is determined using scanning electron
microscope. The morphology of the composite is further confirmed by transmission electron
microscopy (TEM). The gel body is cut into a rectangular shape before measurements.

Photocatalytic degradation of organic dyes: The photocatalytic degradation efficiency of as-

synthesized Ba/Alg/CMC/Cu – TiO2 catalyst is evaluated by performing the organic dye
degradation reaction under direct sunlight irradiation. Prior to degradation reaction sunlight
intensity is determined. It is validated throughout the reaction of dyes degradation process.
Prior to photocatalytic degradation reaction, 1.2 g/L of synthesized photocatalyst and 30 mL
of aqueous solution of organic dye (30 mg/L) are put in a flask, ultrasonicated for 2 min and
stir under dark atmosphere for 30 min to determine the adsorption capacity of the photocatalyst.
Subsequently the reaction mixture is irradiated direct sunlight and it is continuously stirred to
prevent the sedimentation of photocatalyst, and intermittently sampling is performed up to 4 h
of photocatalytic degradation reactions for absorbance measurement. Prior to UV analysis,
catalyst is separated by centrifugation and filtered using membrane filter and absorbance at is
determined using spectrophotometer. Subsequently the concentration of organic dye in the
degraded dye solution is determined using calibration curve of that particular dye. The
influence of operational parameters like catalyst amount, initial concentration of dye and pH
of dye solution on the photocatalytic degradation of dye are studied to determine the optimum
conditions for higher photocatalytic degradation efficiency. Moreover, the pseudo – kinetic and
isotherm study of degradation process are investigated using time – based analysis and
Langmuir and Freundlich isotherm model respectively.

Significant of Study and Impact

Safe drinking water and water scarcity have been a major global issue in recent years. The
reuse of treated water would be the best solution for the future of sustainable water management
in water – deprived countries (Miranda-García et al. 2011). Therefore, this study aims to
provide cheaper and effective wastewater treatment for water recycling as well as improving
drinking water quality from harmful contaminants. Moreover, efficiency of the filter treatment
will be designed to a low cost and portable filters that could be used by people without access
to clean water to remove pollutants in matter of minutes.
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