CHAPTER I

INTRODUCTION

1.1 Environmental pollution

Pollution is the introduction of contaminants into the natural environment that
causes adverse changes. Pollution can take the form of chemical substances or energy,
such as noise, heat or light. Pollutants, the components of pollution, can be either
foreign substances/energies or naturally occurring contaminants. The major forms of
pollution are listed below along with the particular contaminant relevant to each of
them:
ƒ Air pollution, the release of chemicals and particulates into the atmosphere.
Common gaseous pollutants include carbon monoxide, sulfur dioxide,
chlorofluorocarbons (CFCs) and nitrogen oxides produced by industry and
motor vehicles. Photochemical ozone and smog are created as nitrogen oxides
and hydrocarbons react to sunlight.
ƒ Light pollution, includes light trespass, over illumination and astronomical
interference.
ƒ Noise pollution, which encompasses roadway noise, aircraft noise, industrial
noise as well as high-intensity sonar.
ƒ Soil contamination occurs when chemicals are released by spill or
underground leakage. Among the most significant soil contaminants are
hydrocarbons, heavy metals, MTBE, herbicides, pesticides and chlorinated
hydrocarbons.
ƒ Radioactive contamination, resulting from 20th century activities in atomic
physics, such as nuclear power generation and nuclear weapons research,
manufacture and deployment.
ƒ Thermal pollution, is a temperature change in natural water bodies caused by
human influence, such as the use of water as coolant in a power plant.
ƒ Water pollution, by the discharge of wastewater from commercial
and industrial waste (intentionally or through spills) into surface water;
discharges of untreated domestic sewage and chemical contaminants, such

1
 as chlorine, from treated sewage; release of waste and contaminants into
surface runoff flowing to surface water [1-3].

1.2 Water pollution

Water pollution is the contamination of water bodies (e.g. lakes, rivers, oceans
and groundwater). Water pollution occurs when pollutants are discharged directly or
indirectly into water bodies without adequate treatment to remove harmful
compounds. Water pollution affects plants and organisms living in these bodies of
water.

1.3 Control of water pollution

Some industrial facilities generate ordinary domestic sewage that can be
treated by municipal facilities. Industries that generate wastewater with high
concentrations of conventional pollutants (e.g. oil and grease), toxic pollutants
(e.g. heavy metals and volatile organic compounds) or other nonconventional
pollutants such as ammonia, need specialized treatment systems. Some of these
facilities can install a pre-treatment system to remove the toxic components and then
send the partially treated wastewater to the municipal system. Industries generating
large volumes of wastewater typically operate their own complete on-site treatment
systems [4-7].

1.4 Dyes
A dye is a colored substance that has an affinity to bind the substrate to which
it is being applied. The dye is generally applied in an aqueous solution and requires
a mordant to improve the fastness of the dye on the fiber. By the nature of
their chromophore, dyes are divided as follows [8, 9].
ƒ Acridine dyes, derivates of acridine
ƒ Anthraquinone dyes, derivates of anthraquinone
ƒ Arylmethane dyes
ƒ Diarylmethane dyes, based on diphenyl methane
ƒ Triarylmethane dyes, derivates of triphenyl methane
ƒ Azo dyes, based on -N=N- azo structure
ƒ Diazonium dyes, based on diazonium salts

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 ƒ Nitro dyes, based on a -NO2 nitro functional group
ƒ Nitroso dyes, based on a -N=O nitroso functional group
ƒ Phthalocyanine dyes, derivatives of phthalocyanine
ƒ Quinone-imine dyes, derivatives of quinone
ƒ Azin dyes
ƒ Eurhodin dyes
ƒ Safranin dyes, derivates of safranin
ƒ Indamins
ƒ Indophenol dyes, derivates of indophenol
ƒ Oxazin dyes, derivates of oxazin
ƒ Oxazone dyes, derivates of oxazone
ƒ Thiazin dyes, derivatives of thiazin
ƒ Thiazole dyes, derivatives of thiazole
ƒ Xanthene dyes, derived from xanthene
ƒ Fluorene dyes, derivatives of fluorene
ƒ Pyronin dyes
ƒ Fluorone dyes, based on fluorone
ƒ Rhodamine dyes, derivatives of Rhodamine

The wastewater generated by the textile industries is rated as one of the most
polluting effluents among the entire industrial sectors. It is estimated that 1±20 % of
the total world production of dyes is lost during synthesis and dyeing processes. The
discharge of highly pigmented synthetic dye to the ecosystem causes aesthetic
pollution, eutrophication and perturbations in aquatic life [10].

1.5 Nitrophenols
Phenol and its derivatives constitute an important class of water pollutants
because of their stability and solubility in water. Nitrophenol compounds are common
toxic, industrial and persistent pollutants. It is desirable to reduce their concentration
to less than 20 ppb in water reservoirs. Direct photolysis was not effective [11]. The
destruction and mineralization of wastewaters contaminated with nitrophenols by
traditional methods is extremely arduous, since nitrophenols are resistant due to their
high stability and solubility in water.

3
 Various treatments with their inherent limitations and merits are available.
Some of these include activated carbon adsorption, solid membrane filtration and
biological degradation. At the same time, physico-chemical processes of pollutant
removal transferring pollution to another waste medium are not much desired forms
of wastewater treatment. During the past two decades Advanced Oxidation Processes
(AOPs), which involve hydroxyl radicals as oxidanizing agent, have been shown to be
potentially advantageous in treatment of wastewater pollutants. The most advanced
technique nowadays is the photocatalytic oxidation of pollutants using
semiconducting metal oxides [12].

1.6 Redox reactions

Redox (reduction-oxidation) reactions include all chemical reactions in
which atoms have their oxidation state changed. In other words, redox reactions are
concerned with the transfer of electrons between speces. This can be either a simple
redox process, such as the oxidation of carbon to yield carbon dioxide (CO2) or the
reduction of carbon by hydrogen to yield methane (CH4) or a complex process such as
the oxidation of glucose (C6H12O6) in the human body through a series of
complex electron transfer processes.
The term redox comes from two concepts involved with electron transfer: viz.,
reduction and oxidation, which can be explained in simple terms.
x Oxidation is the loss of electrons or an increase in oxidation state by
molecule, atom or ion.
x Reduction is the gain of electrons or a decrease in oxidation state by a
molecule, atom or ion.
A good example is the reaction between hydrogen and fluorine in which
hydrogen is being oxidized and fluorine is being reduced:
H2 + F2 ĺ+)
The overall reaction can be written as two half-reactions:
The oxidation reaction:
H2 ĺ H+ + 2 eí
and the reduction reaction:
F2 + 2 eí ĺ Fí

4
 Analyzing each half-reaction in isolation can often make the overall chemical
process clear. Because there is no net change in charge during a redox reaction, the
number of electrons in excess in the oxidation reaction must equal the number
consumed by the reduction reaction (as shown above) [13].

1.7 Redox processes on semiconductor nanocomposites

The band theory of solids and electronic theory of catalysis have proved to be
useful in the understanding of photo-processes that have been studied on
semiconductor nanocomposites. According to the band model, the occurrence and
efficiency of various photoredox processes are initiated related to the location of the
valence band and conduction band edges. Absorption of light energy E > Ebandgap leads
to the generation of electron-hole pairs and those under the influence of an electric
field move in the conduction band and valence band, respectively. The resulting
non-equilibrium distribution of electrons and holes leads to reduction and oxidation
processes. Often, because of the high absorption coefficients, the incident photons are
attenuated within a short distance from the surface and hence surface properties of
catalysts play a dominant role.

The main advantages of semiconductor nanocomposites systems are given as

follows.
™ The work-up of the reaction mixture is easier since the powder can be
separated by centrifugation.
™ They are simpler, less expensive and relatively easy to fabricate and can be
recycled.
™ Since a very large surface area is exposed to the reactants, their efficiency is
high.

5
1.8 Redox properties of surfaces
The surfaces of metal oxides possess redox sites whose nature, number and
strength are often required to be known to correlate to the catalytic behaviour. This is
possible using charge transfer reactions leading to charge transfer of a single electron
between the solid surface (S) and electron acceptor (A) as well as between the solid
surface (S) and electron donor (D) organic molecules, usually dissolved in benzene.

(S) + A (S)+ + A-

(S) + D (S)- + D+

The ability of the surface to result such reactions depends on the electron
affinity of the acceptor and on the ionization potential of the donor. It is possible to
estimate these redox sites by forming a charge transfer complex with molecules
having varying ionization potential and electron affinity. The molecules with high
electron affinity such as tetracyanoethylene, dinitrobenzene and trinitrobenzene were
used as probe molecules. Surface hydroxy and/or oxygen ions act as electron donor
centers and oxidized forms of surface cations and molecular oxygen adsorbed on the
surface act as electron acceptor sites [13, 14].

1.9 Photocatalysis
Photocatalysis is the acceleration of a photoreaction in the presence of
a catalyst. In catalyzed photolysis, light is absorbed by an adsorbed substrate. In
photogenerated catalysis, the photocatalytic activity (PCA) depends on the ability of
the catalyst to create electron±hole pairs, which generate free radicals (hydroxyl
radicals: ‡OH) able to undergo secondary reactions. Its comprehension has been made
possible ever since the discovery of water electrolysis by means of the TiO2.
Commercial application of the process is called AOP. There are several methods of
achieving AOPs that can but do not necessarily involve TiO2 or even the use of UV
light. Generally the defining factor is the production and use of the hydroxyl radical
[15, 16].

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1.10 Photocatalytic effect
To induce photochemical redox reactions, a catalyst is required, because
energy of photons is often not sufficient to excite simple molecules to higher excited
states. The role of photocatalyst is essentially, the same as the role as photosensitizers.
Photoredox reactions between a semiconductor and redox species in solution take
place vectorically and unidirectionally and are, in general, not reversible.
Heterogeneously dispersed semiconductor surface provides a fixed
environment that influences the chemical reactivity of adsorbates. Upon
photoexcitation, simultaneous oxidation and reduction occur. The incident light that
initiates these sequences is in a wavelength region (visible or low energy range of the
ultraviolet region) absorbed by the semiconductor rather than by the substrate of
interest. Thus, these reactions involve photosensitization, i.e., an indirect
photoactivation of the dispersed semiconductor rather than the direct formation of an
excited state of the substrate. In addition, another point of relevance is that the
photocatalyst is often stable under photolysis conditions (particularly when metal
oxides such as TiO2 and ZnO are employed) and unusually a large number of
conversions per active site on the catalyst can be realized. Initial interest on these
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water can be split on illuminating a TiO2 single crystal to which an electrochemical
bias had been applied [13].

1.11 Semiconductor systems as photocatalysts

Photocatalysis on a semiconductor nanocomposite is essentially a redox
reaction. During a photocatalytic reaction, the irradiated surface of the
semiconductors will act as a sink for the electrons (or holes) depending upon the
direction of band bending. The other charge carrier will move under the influence of
the electric field into the bulk of the semiconductors or to the surface that receives the
lowest intensity of incident light radiation. Thus, the separation of the charge carriers
namely the electrons and holes determines the efficiency of any photocatalytic
reaction. Sometimes, effective charge separation can be achieved by metallization,
doping, by coupling two semiconductors and surface modification by
supramolecules [15].

7
1.12 Semiconductor photocatalysis
Photoreactions do not occur effectively on illumination with light alone. These
reactions often require the use of photocatalyst. In the case of semiconductor material
the role of photons (light energy) is to generate electron (eí) ± hole (h+) pair
(Scheme 1.1) that takes part in subsequent dark (thermal) redox reactions with the
surface adsorbed molecules to yield the ultimate product(s).

Scheme 1.1 Generation of electron-hole pair

The process of semiconductor photocatalysis basically involves the following

stages. Light energy of a certain wavelength is made to fall onto a semiconductor. If
the energy of the incident light is equivalent to the band gap energy of the
semiconductor, electrons would be excited from the valence band (VB) to the
conduction band (CB) of the semiconductor and holes would be left in the valence
band. These electrons and holes could undergo subsequent oxidation and reduction
reactions with any species, which might be adsorbed on the surface of the
semiconductor to give the necessary products. In homogeneous reacting system the
major disadvantage is the energy-wasting back-electron transfer reaction to give back
the starting material. Although heterogeneous semiconductor particulate/colloidal
systems which act as light absorbing units offer an excellent route to overcome this
problem, strong eí±h+ pair recombination process (Scheme 1.2) is also a formidable
obstacle or realizing high efficiency in the photocatalytic processes.

8
 Scheme 1.2 eí± h+ pair recombination

The development of effective means to suppress back-electron transfer or

í
e ±h recombination process is vital for increasing chemical conversion efficiency.
+

Thus the eí±h+ generated can be used to drive chemical reactions provided:
a) The energy separation (band gap) between eí and h+ is larger than the energy
required for the desired reaction.
b) The redox potentials of the eí and h+ (that is the position of CB and VB) are
suitable for inducing redox processes.
c) The rates of these redox reactions are faster than or at least fast enough to
compete with the eí±h+ recombination.
Therefore, development of efficient redox catalysts capable of making product
formation more competitive against these recombination processes is recognized to be
important in the field photocatalytic degradation of organic pollutants [17-22].

1.13 Titanium dioxide and the photocatalytic processes

Titanium dioxide (TiO2) is a metal, which is multiply present in nature. TiO2
has three different molecule structures: viz., rutile, anatase and brookiet. Rutile is
known as pigment in white paints but shows up till now low photocatalytic reactivity.
Anatase is preferable if used as photocatalytic cell. To use anatase in heterogenic
photocatalysis, UV-light with a wavelength lower than 387 nm has to be present. Also
the intensity of the light is important to optimize the photocatalytic activity. Normal
daylight can be used for the photocatalytic reaction. Research is focusing now on the
application of nanoparticles of TiO2 active in the visible light range [23].

9
1.14 Applications of Zinc Oxide (ZnO) as a photocatalyst
Recently ZnO has attracted much attention within the scientific community as
a future material. It can be used in a large number of areas and unlike many of the
materials with which it competes. ZnO is inexpensive, relatively abundant, chemically
stable, easy to prepare, low cost and non-toxic. Most of the doping materials that are
used with ZnO are also readily available. One of the benefits of ZnO is that it can be
used both as a conductor and a semiconductor. ZnO is a good semiconductor because
of its environmental stability, low resistivity and high transparency, not to mention its
low cost and abundance. Since the semiconductors are transparent to light with energy
less than the band gap, they only absorb photons with energy greater than the band
gap. ZnO has a band gap of 3.37 eV leaving very little of the solar spectrum able to be
absorbed [24, 25].

1.15 Role of cyclodextrins in the modification of photocatalytic activity of

nanomaterials
Cyclodextrins (CDs) are cyclic oligosaccharides of six to eight Į-D-glucose
units connected via JO\FRVLGLFĮ-1,4 bonds and are composed of hydrophobic internal
cavity and hydrophilic external surface [26-28]. The three most important members of
the &'V IDPLO\ DUH Į-&' ȕ-&' DQG Ȗ-CD (with 6, 7 and 8 glucose units
respectively). This kind of special molecular structure allows them to form host/guest
inclusion complexes with various guest molecules with suitable polarity and
dimensions. In the field of environmental research, CDs have been applied to promote
degradation of hazardous pollutants discharged into aqueous environment, because of
their non-toxicity and biodegradability. CDs have been applied to promote
degradation of hazardous pollutants discharged in the aqueous environments [29, 30].
These materials present several advantages in wastewater treatment like high stability,
low cost, reutilization and recovery [31].
Recently, CDs have been modified as electron-donating and molecular-
recognizing agents on semiconductor nanoparticles. In general, the chemisorption of
CDs onto semiconductors increases the stability of particles against aggregation and
enhances the yield of photo-induced charge-transfer reactions. Thus, the modification
of CDs on the photocatalysts shows a significant enhancement effect on degradation
processes of a pollutant [32].

10
 CD modified nanomaterial, a typical type of host modified nanomaterial, has
attracted considerable interest because of its unique properties. As one of the most
common host molecules, CD does not only alter the external morphology of the
nanomaterial, but also affect/change the intrinsic properties including photoactivity,
photoelectric activity, energy transfer, etc. More importantly, nanomaterials can be
endowed with the recognition ability for certain guest molecules after the
modification with CD, which can lead to more guest-targeting and efficient functions
of the nanomaterials. CD can play a role as a channel or bridge between the guest
molecules and the surface of the nanomaterial. The size/shape-fit relationship between
CD and the guest molecule, a general rule to predict the possibility of forming a
complex in aqueous solution, is usually adopted in the design of CD modified
nanomaterial. On the other hand, once CD, whose primary ring side has smaller
dimensions than its secondary ring side, is attached onto the surface of the
nanomaterial, the relationship between its orientation onto the nanomaterial (through
which side cyclodextrin attaches) and its inclusion routes of the guest (through which
side the guest can enter into the cavity of cyclodextrin) can be a potential factor
affecting the approach of the guest to the nanomaterial [33].

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