A review on an application of photo catalytic degradation for organic pollutant in textile

effluent by using TiO2 Nano particles

Janmay Singh Hada1, Manoj Tiwari2

1. Assistant Professor, Department of Fashion Technology, National Institute of Fashion Technology (NIFT), Jodhpur, India,
janmay.hada@nift.ac.in

2. Associate Professor, Department of Fashion Technology, National Institute of Fashion Technology (NIFT), Jodhpur,
India, manoj.tiwari@nift.ac.in
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Abstract : A significant quantity of effluents is disposed in Textile and Garments industry due to usage of dyes,
chemicals and other materials. Such effluents are eventually disposed in treatment plants. If these effluent
disposed without treatment it causes significant environmental issues. In present scenario textile plants are
intending to use sustainable approach to recover water and chemicals from these effluents. Nano technology is
one of the most sought after technology in this field of water purification. Recent Nano technological
advancements suggest that metal oxides such as Titanium dioxide and Zinc Oxide in Nano particles form is
being used for the removal of organic pollutants and Xeno biotics from textile effluents. This Nano catalyst is
also used for photo catalytic self cleaning properties of cotton fabrics. This paper discusses the mechanism of
the self cleaning effect of cotton, photo catalytic degradation, cleaning of organic pollutant in textile effluents.

Keywords: Textile Effluents, Nano particles, Titanium oxide Nano particles, Xeno biotics , photo catalytic
degradation, self cleaning fabrics..

Introduction:

Textile industry convert fibres into yarns, convert yarns into fabrics or other related products. Further dyeing,
printing and finishing of these fibres, yarn, fabrics and garments is performed at various stages of production.
This results into value addition as per the market demand. These processes include different types of dyes and
chemicals for pre-treatment, dyeing, printing and finishing operations. Manufacturing processes generate
chemical effluents which set out in treatment plant. The meaning of the effluent treatment, management and its
disposal has gradually got significant and importance in modern times. Now a days, it is treated as a major
concern for public health as well as scientific interests. If this effluents disposed in sewerage without treatment
it create serious environmental problems. There are 2324 textiles plants in India (including composites and
process house). Textile effluents including dyes, pigments, dissolved solids, toxic materials (metal contents),
residual chlorine and non bio-degradable organics termed as refractory materials [1].

In recent times, the semiconductor heterogeneous photo catalysis such as TiO2/ZnO has emerged as an
alternative economical and harmless technology for taking away of toxic organic pollutants. Titanium dioxide
(TiO2) is considered as an one of an important nano particles (NPs) for photo catalysis activity.

Nano Particles

The prefix Nano mean a billionth (10-9). Nano technology is concerned with the creation of particles or materials
whose minimum dimension are in nano metric scale, though normally less than 100nm. These materials may be
produced from structured organisation of atoms groups molecules or by reducing macroscopic materials to a
nano-metric scales [2]. In October 2011 the European union defined nano materials as a natural, incidental or
manufactured material containing particles, in an unbound state or as an aggregate or agglomerate where 50%
of more particles exhibited, one or more external dimensions in size range 1-100 nm. Others have defined NPs
as object with at least one of their three dimensions range of 1-100 nm [3].

There are two general approaches to produce nano materials. The first approach is to start with the bulk material
and then break it into smaller pieces using mechanical, chemical or other form of energy. A reverse approach is
to synchronise the material from atomic or molecular species via chemical reactions, allowing for the precursor
particles to grow in size. Both approaches can be applied in either gas, liquid, supercritical fluids, solid states, or
in vacuum also. There are several physico-chemical methods for preparation of NPs such as vapour phase
reaction, chemical vapour deposition, inert gas condensation, laser ablation, plasma spraying, spray conversion
and sputtering. To build up new NPs including emulsion preparation, Nano structures fabrication. In each step
it is critical to characterize the morphological features and properties of particles to obtain real functional
performance [4]. Nano particles and Nano technologies do not simply represent another steps towards
miniaturization. At the "Nano" level, the performance of particles is dominated by quantal effects. The particles
may be confined to small composition distributed over large surfaces or exhibit an entire series of exclusive
phenomenon and properties not encountered in larger materials [5]. Large specific area and high reaction
activity and other novel properties broaden attention of Nano materials. Titanium dioxide as nano material has
been used as cosmetic functional additives to fight aging based on its ability to ultraviolet light [6].

Latest technological advances suggest that metal oxide nano particles (NPs) have been expected to be used in
various fields, ranging from catalysis and opto-electronic materials to sensors, environmental remediation, and
biomedicine.

Titanium di oxide Nano particles:

Titanium di oxide is inorganic non combustible, white odourless powder with molecular weight of 79.9 g/mol,
boiling point of 2972ºC, melting point of 1843ºC and relative density of 4.26 g/cm3 at 25ºC. Due to its
brightness and very high refractive index it is among the top 5 NPs used in nano Products Due to its affinity to
oxygen and other elements, it is used for photo catalytic degradation of textile effluents. Ti does not exist in the
metallic state in environment. The most common oxidation state of Ti is 4, but 3 & 2 states also do exist.
Metallic Ti, TiO2 (Titanium dioxide/ titanic acid anhydride, Titania, Titanic anhydride), and TiCl4 are the
common compounds used in the industrial applications. These NPs possess different physio chemical properties
compared to the fine particles (FPs) analogs, which might alter their bio activity. The smaller size of Nps certify
that large portion of atom is on the particle surface. Since surface properties, such as energy level, electronic
structure and reactivity are quite different from interior states, the bioactivity of NPs likely differ from that of
the fine analogue [7].

TiO2 NPs are constructed and used extensively because of their high stability, anticorrosive and photo catalytic
properties[8]. TiO2 NPs can be used in catalytic reactions, such as semiconductor photo catalysis, in the
treatment of water contaminated with hazardous industrial products [9]. As one the most recent development of
TiO2 NPs is act as catalyst that help break down of carbon based molecules and require only sunlight to trigger
the action. The photo catalytic effect of TiO2 NPs can use for industrial applications like self-cleaning and anti-
fogging purposes such as self-cleaning tiles, self-cleaning windows, self-cleaning textiles, and anti-fogging car
mirrors. The fabrics could be made into self cleaning clothes that tackle dirt, environment pollutant and harmful
microorganism.[10]. Titanium dioxide is found in 3 crystalline forms normally anatase, rutile and brookite. The
anatase is the most active and simple form to produce in semiconductor photochemistry. The photo catalytic
activity of TiO2 depends upon diameter of its particles. A NPs below 100 Aº show high photo catalytic activity
due to large surface area per unit mass and volume as well as diffusion of the electrons and holes before
recombination.

Photo catalytic degradation:

Semiconductor catalyst TiO2 has been widely used to mineralize harmful organic components in waste water
into less damaging inorganic non toxic compounds like Carbon dioxide(CO2), HCl and H2O [11]. TiO2 is more
superior due to its photo catalyst activity, large chemical stability, low price and robustness against photo
corrosion. The ultra violet light and visible light are used for catalytic oxidation of organic substance for colour
removal. The free radicals disintegrate organic pollutants and Xeno Biotics from textile effluents with help of
oxidising agents. Xeno biotics are the organic substance which have higher concentration of chemical substance.
The use of a heterogeneous photo catalyst is a usual method for water purification which includes reduction and
oxidation reactions from adsorbed waste water, oxygen molecules and hydroxyl anions, or other organic
molecules. Uses of semiconductors likes TiO2 and ZnO etc. in photo catalysis employs semiconductors in
suspension [9]. Titanium dioxide has proved to be an excellent catalyst in the photo degradation of colorants
and the other organic pollutants.

Mechanism:
The basic mechanism of photo catalytic reaction occurs on the surface of the photo catalytic materials. Photo
catalytic reaction is controlled by the generation of electron hole pair into the semiconductor surface and its
transformation to its destination. When a photo catalytic surface is exposed by radiation of energy equal or
greater than the band gap energy of the material , it creates positively charged holes in the valence bond (VB)
and negative charged electron in the conduction band (CB) by exciting the electrons from CB to VB.[12]. The
promotion of electron is achieved by absorption of ultra violet light from VB to the CB. The energy difference
between the electrons in the VB and the CB is EBG≈ 3.2 eV. The electron hole pair, e- h+ created due to electron
transfer from VB to CB determines largely the photoconductivity of conductor materials [13]. In the presence of
oxygen and water hydroxyl and superoxide's, radicals are formed which attack on adsorbed organic species on
the surface of TiO2 and decomposed them. Many of the modern commercial economic systems utilize the
semiconductor photo catalyst TiO2 to oxidise organic pollutants by oxygen, i.e.

𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷 𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄 (𝑻𝑻𝑻𝑻𝑶𝑶𝟐𝟐 ) + 𝒉𝒉𝒉𝒉 → 𝒆𝒆− + 𝒉𝒉+

𝒉𝒉+ + 𝒘𝒘𝒘𝒘𝒘𝒘𝒘𝒘𝒘𝒘 → 𝑯𝑯+ + 𝑶𝑶𝑶𝑶−
𝒆𝒆− + 𝑶𝑶𝟐𝟐 → 𝑶𝑶𝟐𝟐−
𝑻𝑻𝑻𝑻𝑶𝑶𝟐𝟐
𝑶𝑶𝑶𝑶𝑶𝑶𝑶𝑶𝑶𝑶𝑶𝑶𝑶𝑶 𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝒂𝒂𝒂𝒂𝒂𝒂 + 𝑶𝑶𝑶𝑶− + 𝑶𝑶𝟐𝟐 �⎯� 𝑪𝑪𝑪𝑪𝟐𝟐 + 𝑯𝑯𝟐𝟐 𝑶𝑶 + 𝑶𝑶𝑶𝑶𝑶𝑶𝑶𝑶𝑶𝑶 𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷𝑷

Fig. 1 Degradation by semi conductor Nano particles (10)

The positively charged holes oxidize the organic pollutants in textile effluent directly or indirectly in to water to
provide hydroxyl free radicals. On the other end free electrons are adsorbed to TiO2 surface. Semiconductors
also used as photo catalyst for purifying action. Here the free radicals (OH-) and super oxide ions (O2-) act as
powerful oxidiser to disintegrate the organic textile effluents and convert into carbon dioxide and water. TiO2 in
the presence of UV irradiation can disintegrate the pollutant dyes in to non toxic simple compounds like CO2,
HCl and water. The band gap energy of TiO2 is 3.03 volt [14]. The most fundamental component for a photo
catalytic system are light source photo catalyst. The photo catalytic oxidation reaction depend on generation and
recombination of electrons.

These processes have limitations which can potentially affect degradation efficiency through control pH range,
rapid load variations and also the effluents photochemical behaviour [15]. The Nano catalysts have larger
surface area then normal photo catalyst. the reason behind this are as below-

Quantum size effect: The particle size of NP have less then certain critical limit, that gives rise to quantum size
effect. The oxidation and reduction potential of the electrons and holes is increased, therefore oxidation activity
of Nano sized TiO2 is increased.

Higher specific surface area: The adsorption capacity towards organic pollutants of NPs increased due to more
number of atoms on the surface. Due to miniature size of NPs charge carriers moving very fast from inside to
outside and start redox reaction. Higher to the surface volume ratio , smaller the particle diameter and smaller
time may be used by charge carriers diffusing to the surface inside. This can provide lesser chance of electron
and holes combination [16].

Effect of Temperature, Dye concentration , catalyst loading and type of catalyst:

Temperature: The decolourization of waste water dyes increased with increasing temperature and time. Higher
temperature is helpful decompose of the pollution in wastewater [17].

Dye concentration: The less dye in pollutant waste water reduce the time of decomposition of the waste water.

Photo catalyst loading: Konstantinou and his co-workers found in their research that , for azo dyes in aqueous
solution were directly proportional to TiO2 assisted photo catalyst [18]. Advance studies have also revealed that
the decolourization efficiency increase with increase in catalyst loading. The photo catalytic activity increase
with concentration of photo catalyst due to accessibility of more sites and diminish due to saturation region at
the photo catalyst sites.

Type of catalyst: Rutile and anatase are more common structure for photo catalyst . Anatase phase of TiO2 is
superior photo catalyst than rutile phase while there are not much reports on brookite phase study [19].

Self Cleaning properties.:

The nano technology finishes create carefree fabrics that minimize stains, offer superior liquid repellence and
provide additional wrinkle resistance. When mercerised cotton fabrics are treated with ultraviolet radiations a
significant number of functional groups like carboxylic acid, per carboxylic acid, epoxide and peroxide groups
are formed. The Titanium dioxide can be used in various forms like as colloidal TiO2, Titanium tetra chloride
(TiCl4) or TTIP ( Titanium tetra isopropoxide) [20].

The studies done at Suntest solar simulator (Hanau, Germany) by Bozzi shown that fabrics or garments reacted
by Titanium dioxide can marginalised stains coffee/ red wine more effectively than without treated fabrics. The
organic parts of the stain leading ultimately to carbon dioxide (CO2) and Di hydrogen oxide or water (H2O) as
shown in fig. 2.

Fig. 2 Discolouration of stain by visible sun light radiation by TiO2 (10)

Mechanism:

The organic compound or stain of materials such as coffee, blood or wine are decomposed in organic
compounds like carbon dioxide. The electron generated in the process is injected into TiO2 and the conduction
band starts the oxidative radical chain, leading to stain discoloration as shown in fig. 2.

Conclusion:
Different aspects of TiO2 NPs as discussed in the paper make it as one of the most efficient photo catalyst used
for the degradation of organic dyes and pollutants in waste-water. Various other parameters such as light
source, pH of the chemical reaction, temperature, dye concentration, catalyst loading and type of catalyst also
play a critical role in degradation of waste-water dyes.

By using Ultra violet (UV) light degradation efficiency of organic dyes may be improved. Metal and Non metal
doped Nano structured TiO2 may further improve degradation rate due to modified band gap energy for visible
and solar radiation. TiO2 NPs have a great potential for the practical application in photo catalytic oxidation of
waste water for the removal of organic pollutants and anti bacterial properties. The new concepts exploited for
the development of TiO2 NPs have opened up stimulating prospect for cleaning of organic pollutant in textile
effluents with anti bacterial properties.

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