ABSTRACT

Water contamination is a major cause of several diseases. Here, detoxification of paper mill
wastewater was carried out by newly investigated visible light driven Heterogenous
photocatalysts. Here, synthesis of pure and composite nanoscaled cobalt oxide and calcium
oxide as well as their photocatalytic behaviour under visible light illumination were reported.
Nanoparticles were synthesized by simple sol-gel technique and grown on gravels which then
characterized by scannning electron microsope, X-ray diffractometer and Fourier transform
infrared spectrophotometer. Detoxification of paper mill wastewater was studied at lab scale
and it was found that maximum 90% photocatalytic degradation of conaminants achieved
using composite CoO-CaO. Photocatalytic degradation of paper mill pollutant was studied by
considering variability in pH, oxidant concentration, sunlight irradiation time and initial
concentration of pollutants. The described variables were optimized statistically by response
surface methodology. Photocatalytic effeciency was found maximum at pH 7, oxidant
concentration 40 ppm, sunlight irradation 2 hours and initial concentration of pollutants 200
ppm. Water quality parameters (WQPs) such as chemical oxygen demand (COD), biological
oxygen demand (BOD) and total organic carbon (TOC) were studied before and after
treatment. It was found that COD, BOD and TOC was reduced by 80%, 76% and 82% with
respect to initial values. Nanocomposite was recycled twelve times to determine its
reusability, it was found effective to degrade the pollutants (60%) even at 12th cycle.

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CHAPTER 1
INTRODUCTION
Water is one of the basic essentials of life to sustain but its need is not limited to just
for drinking purpose. It has several other usages in daily life routines, which are essential for
living standards. Unfortunately, fresh water makes a small fraction of total water i.e. only 3%
of total water. Human activities and development in recent century demand excessive usage
of clean water to carryout their operations and excessive wastewater is produced. This
wastewater is dumped into limited freshwater resources without purification. As a result of
which fresh water contaminates and becomes inappropriate to drink. Growing population is
another major challenge of the century. Nature is providing freshwater still to ensure life on
the planet, but growing population disturbed the natural balance, as a result of which water
scarcity occurs. Now it is major problem for the scientists and researchers round the globe to
develops an alternative to costly wastewater treatments techniques, in order to treat the
wastewater using available resources such as sunlight. According to world health
organization, more than 2 million people die every year due to lack of fresh water.
There are several industries such as textile, paper, tannery, petroleum, and
pharmaceuticals, pesticides etc., are working day and night and use freshwater in their
operations and produce huge amount of dirty water, which is then drained and injected to
freshwater without proper treatment. Industrial wastewater may be microbial, organic and
inorganic in nature. Microorganisms such as protozoa are common water pollutants, which
are commonly found in municipal wastewater. Textile, petroleum and pesticide industries
injects huge number of organic contaminants in freshwater such as detergents, greases, azo
dyes, proteins, hydrocarbons, fats etc. On other hand, tannery industry injects a large number
of inorganic pollutants into freshwater such as hexavalent chromium, sulfur, sulfides and
nitrates. Paper mill effluent is variable in nature containing huge amount of organic and
inorganic waste. Paper mills effluent is inappropriate to treat to with biological treatment
method, because pollutants in it, react with bacteria to kill them, as a result of which water
becomes more dangerous. There are several acids and basis are using in paper making
operations which are hazardous for drinking. Environment is badly affected because of air

ii
pollution. A common cause of thermal pollution is the use of water as a coolant by power
plants and industrial manufacturers
One of the most polluting industries is the pulp and paper industry, which in terms of
water consumption has the third place after chemical industries. It generates 30 to 180 m 3 of
wastewater per every ton of pulp production and 20 to 70 m 3 of wastewater per every ton of
paper production. Paper industry injects heavy metals and persistent organic pollutants into
freshwater it contains very complex organic and inorganic pollutants like tannins, chloro-
phenolic compounds, dioxins, furans, biocide, fatty acids, and resin acids along with chloro-
lignin compounds as persistent organic pollutants (POPs). These pollutants are discharged
during pulping and bleaching process in paper manufacturing which needs special attention
for water discharge to rivers and lacks. The presence of such non-common toxic waste traces
in ground make, make it unsanitary. Industries are continuously enhancing their production
as a result of increase in population to meet population demand. Industrial operations such as
mining operations, electro-coating of metals, leather production etc., make use of excessive
clean water in their operations. Industries also use huge amount of clean water to drain their
wastes into nearby wastewater stream. As a result of which several carcinogenic substances
add to pure water, causing health problems. It becomes necessary to treat the wastewater
before its discharge to environment reserves.
There are several wastewater cleanup methods have been studied throughout the century,
some of them are biological, physical and chemical in nature. Commonly used physical and
chemical treatment methods are electrocoagulation, ultrasound, reverse osmosis,
photocatalytic systems using titanium dioxide (TiO 2) and zinc oxide (ZnO) under UV-solar
irradiation, hydrogen peroxide, Fenton’s reagent (H 2O2/Fe2+), UV, UV/ H2O2, Photo-Fenton
(UV/ H2O2/Fe2+), ozonation and peroxon (ozone/ H 2O2)/. These methods have some
limitations associated with them like requirement of huge area, high operational cost,
produced secondary pollutant, by-products formation and maintenance issues etc. Despite the
development of various technologies for water treatment and reclamation, economic,
effective and rapid water treatment and reclamation at a commercial level is still a
challenging problem. The management of the removed pollutant should be kept in mind. The
systematic approach of water treatment and recycling technologies involves the

iii
understanding of the technology that includes construction and operational cost, along with
the maintenance and management of removed pollutants.
Water treatment and recycling technologies have been classified under the following
headings.
1. Primary water treatment technologies
2. Secondary water treatment technologies
3. Tertiary water treatment technologies
In this category, water is treated at the primary level using screening, filtration,
centrifugation, sedimentation, coagulation, gravity and flotation methods. Normally, these
methods are used when water is highly polluted. Paper mills effluent usually involves
primary treatment, including neutralization, screening and precipitation to remove the
suspended solids, which are then dewatered to the sludge which needs secondary treatment to
detoxify. Less often, secondary and tertiary treatment involves reducing the amount of
organic matter in wastewater and destroying toxic organic substances and colors. The sewage
treatment process produces sludge that must be managed In the recent studies,
nanotechnology has received attention for wastewater treatment which can easily degrade the
toxic substances. It works by converting long chain hydrocarbons and dyes rings into low
molecular weight substances such as water and CO 2. Nanoparticles have size less than 100
nm at least in one dimension, they have very small surface area, large number of active sites
and a much greater surface to volume ratio. Nanoparticles have several applications in
electronics, medicines, chemistry and physics etc. Nanoscience has got attention toward
wastewater treatment because several semiconductor oxides with verities of band gaps have
been investigated throughout the years. Most of semiconductor oxides show activity in
ultraviolet region because of higher band gap. Composite formation adds several impurity
levels between valance band to conduction band to enhance their photo-catalytic activity
toward visible region of spectrum.
Photocatalysis is a science of absorption of electromagnetic radiations by
semiconductor materials followed by transfer of electrons from valance band to conduction
band. As soon as photon of energy equal or greater to band gap energy of semiconductor
materials absorbs, excitation of electrons takes place, which results in photo-generated
electron hole pairs i.e. holes in valance band while electrons in conduction band. The holes

iv
are than used to oxidize the water molecules adsorbs in the surface of semiconductor
materials to produce hydroxyl radicals, which will used for further oxidation of organic
pollutants present in water while electrons are used to reduce heavy metals and other
inorganic pollutants. Still, the purposed mechanism of photocatalysis is under modification
but major reactions taken place during detoxification have been understood well. Major
problem encountered during the course of photocatalysis is the wide band gap of
semiconductor materials which make them to absorb higher energy photons such as
ultraviolet photons, which is only 3% of the total solar spectrum. Therefore, it was felt by the
researchers and engineers that band gap should be modified in such a way that semiconductor
materials should capable to absorb low energy photons such as visible light photons. Several
photocatalysts have been investigated in this regard such as pure zinc oxide, titanium oxide,
iron oxide, copper oxide, tin oxide, cobalt oxide, zirconium oxide etc., but they all were
proved to be less effective to absorb visible light. Therefore, doping and composite formation
were practiced by the scientist of the era, results in higher photocatalytic activity toward
visible light.
Response surface methodology is a statistical tool to optimize the response with
respect to affecting variables i.e. response of dependent variable is optimized by the suitable
conditions for independent variables. Here in this study, pH, oxidant concentration, sunlight
irradiation time, and initial concentration of pollutants are taken as independent variables for
optimization of percentage degradation of pollutants which is taken as response variable. In
this study, composite cobalt oxide and calcium oxides were investigated to mineralize paper
mill wastewater. It was proved an efficient visible light driven photocatalyst.

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OBJECTIVES

 Fabrication of pure and composite CaO/CoO nanoparticles by sol-gel method to

determine photocatalytic activity
 Degradation of pollutants present in paper mill effluent especially 2,2-
dichlorophenol.
 Evaluation of photocatalytic degradation by UV/visible spectroscopy

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CHAPTER 2
REVIEW OF LITERATURE
2.1. Fresh water contamination and industrial development
Fresh water is essential source of life on our planet but unfortunately, fresh mater
makes very small percentage of total water i.e. only 2.9%. Fresh water is usually extracted
from ground, excessively used in daily routine. Industrial development, on one side, makes
life standards and essential for sustaining them, but on other side it is responsible for excess
water usage and water contamination. Industries such as textile, paper, tannery, petroleum,
pharmaceuticals and drugs & agriculture use excess of clean water, contaminate it with
hazardous chemicals such as dyes, carcinogenic substances, heavy metals, organic pollutants,
lignin and persistent organic pollutant. These industries harshly pollute freshwater quality,
such as water quality parameters chemical oxygen demand, biological oxygen demand, pH,
density, total suspended solids and total organic carbon. There are several wastewater
treatments technologies assessed thoroughly from filtration to advanced oxidation process
throughout the decades.
2.2. Chemistry and processes of paper mills operations

The pulp and paper industry occupy a challenging position w.r.t the natural
environment. On the positive side, the industry is based on the usage of renewable,
photosynthetic resources. On negative side, this industry discharges huge quantities of
aqueous effluents. Large volumes (up to 70 m3) of wastewater are generated for each metric
ton of paper produced, depending on the nature of raw material, the type of finished product,
and the extent of water reuse, the paper and pulp industry uses about 70% of its massive
water intake as process water. Reducing water consumption, by increasing internal water
recirculation after the implementation of internal cleaning processes, saves money and also
decreases the use of scarce environmental resources. Since the main unit operations
associated with pulping and papermaking are carried out in aqueous media, the application of
various chemical additives can considerably alter the properties of the produced effluents,
making it harmful for the receiving environments. The total closure of the water circuits is
limited by the accumulation of contaminants in the process water, which can give rise to
corrosion, deposits, and odors and alter the runnability of the paper machine and the quality

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of the final product. If further closure is required, then the effluent has to be extensively
treated so that it can be used again in the process.

Paper mill effluent is variable in nature. The pulp and paper industry effluents contain
a variety of toxic organic compounds and its untreated discharge may cause deleterious
environmental impacts to water bodies. Among the various sections, the effluents from pulp
bleaching are responsible for most of the color, organic matter, and toxicity of the water
discharges of this industry. The pulp produced by chemical pulping requires bleaching to
produce bright pulps. The use of chlorine gas and chlorine compounds as bleaching
chemicals is known to generate various toxic and bio-refractory chlorinated organics
(phenols, resin and fatty acids, dioxins and furans) in the paper mill effluents. Some of them
are toxic, mutagenic, and resistant to biodegradation.

A pulp mill is a manufacturing plant that transforms wood chips or another source of
fiber into a thick fiber board that can be delivered to a paper mill for further processing. The
pulp can be manufactured using mechanical, semi-chemical or purely chemical methods
(kraft and sulfite processes). The final product can be either bleached or bleached according
to the client's requirements. Plant materials such as wood utilized in paper manufacturing
have three main components other than water which are cellulose fibers (required for paper
making), lignin (a three-dimensional polymer that binds cellulose fibers together) and
hemicellulose (carbon fibers) which is shorter branched polymer). The purpose of pulping is
to destroy the structure of the fibrous material, whether it in pieces, than binds these
constituents together it to form a long continuous structure which is finally resulted in paper
formation. Chemical pulp production process this by converting lignin and hemicellulose into
water soluble small fractions which can be washed away and removed from cellulose fibers
without degrading cellulose fiber polymerization (chemically depolymerizing the cellulose
weakens the fibers). Various methods of mechanical pulp, such as ground wood and refiner
mechanical pulping, physically tear cellulose fibers from each other. Much of the lignin
remains attached to the fibers. Related mixed pulp methods use a mixture of chemical and
thermal treatment to initiate the abbreviation for core chemistry, followed immediately by
mechanical treatment for the separation of fibers. Related hybrid pulping methods use a
combination of chemical and thermal treatment to begin an abbreviated chemical pulping

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process, followed immediately by a mechanical treatment to separate the fibres. These hybrid
methods include thermomechanical pulping (TMP) and chemo-thermo mechanical pulping
(CTMP). The chemical and thermal treatments reduce the amount of energy subsequently
required by the mechanical treatment, and also reduce the amount of strength loss suffered by
the fibers. Table 1.1 characterize the paper mill effluent and shows impact of various
treatment methods toward treatment of paper mill effluents with reference.

Table 1.1. Processes in paper mills, impact of wastewater treatment methods

2.3. Chemistry of paper mills wastewater and its toxicity

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 The processes involved in paper formation are discussed in detail in section 1.2. No
doubt, all the treatments form initial step to final step involves excessive usage of fresh
water, that contains excess of chemicals, rich in biological oxygen demand, chemical oxygen
demand, highly turbid and colored, nitrogen, phenolic compounds, phosphorous, sulfates,
total suspended solids, total dissolved solids, chlorine and various inorganic metallic cations
such as potassium, sodium, iron, copper, manganese, nickel and zinc usually acidic. This
effluent when drains into freshwater resources such as ground water and lacks, it will harshly
affect water quality, drinking it will cause several painful diseases, danger to water bodies. It
contains lignin waste, non-biodegradable cations in concentration more than permissible
limits.

Discharged effluents have toxic effect on reproductivity of aquatic species due to long
chain fatty acids. There are carcinogenic chlorinated organic compounds and dioxin present
in paper mill wastewater. Water contamination with toxic organic as well as inorganic
substances causes health issues and a serious danger to aquatic life. Therefore, it is necessary
to detoxify industrial wastewater before its discharge. There are several wastewater treatment
technologies among which some of physical, chemical and biological in nature such as
adsorption, membrane filtration, coagulation flocculation, precipitation, adsorption, ion-exchange
and electro-chemical deposition introduced to treat industrial and municipal wastewater .
Organic natured pollutants which resist biodegradation are of great concern, they just not resist
biodegradation but kill the beneficial bacteria that play a very important role in degradation of
organic pollutants. There are several efforts have been reported to remove such type of
recalcitrant pollutants, Recently, advanced oxidation processes have reported to produce reactive
species to degrade non-biodegradable substances.

2.4. Advanced oxidation processes.

Advanced oxidation processes (AOPs) are the set of various chemical reactions aimed
to produce highly reactive radicals via oxidation of water and other substances. There are
several treatments joins in AOPs such as Ultraviolet (UV) treatment, treatments using
oxidants such as hydrogen peroxide and ozone, combined ozone and peroxide, Ultraviolet
enhanced oxidation such as UV/Fenton or photo-Fenton, UV/hydrogen peroxide, UV/ozone,
UV/air wet air oxidation and catalytic wet air oxidation (where air is used as the oxidant),
Fenton and photo-Fenton reactions, treatment via combination of oxidants and UV light, and

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photo-catalysis. Advanced oxidation processes are categorized in environmental friendly
processes because of zero sludge production. It has got attention of researchers worldwide
because of smaller time to degrade pollutants and smaller usage of chemicals. AOPs are
widely using to degrade organic natured pollutants present in effluents because organic
pollutants have sufficient potential to undergo oxidation reaction, but now a days
photocatalysis, A treatment in AOPs, are using to reduce the pollutants side wise oxidation at
ambient temperature and pressure. It is a newly investigated trend to oxidize and reduce the
pollutants present in wastewater via photocatalysis treatment of AOPs. That is why, in our
treatment, we select photocatalysis as AOPs treatment for paper mill wastewater. Various
chalcogenides (oxides such as TiO 2, ZnO, ZrO2, CeO2, etc., or sulfides such as CdS, ZnS,
etc.) have been applied and modified as photocatalysts in the photocatalytic process and the
process is found suitable for degradation of a wide range of organic pollutants
2.4.1. Ozonation
Ozonation is a well-known advanced oxidation processes to degrade the organic
pollutants present in wastewater. This is a process in which ozone molecule is added into
wastewater containing harmful and recalcitrant organic pollutants such as coloring agents,
surfactants, Organo-halogens and organic pesticides to carry out oxidation of these
pollutants. Ozone acts as a power full oxidizing agent which have chemical oxidation
potential 2.07eV that of 2.8eV for hydroxyl radical. Ozone can effectively degrade the
dissolved organic compounds especially at low pH there are two reactions of ozone with
organic contaminants can easily be distinguished. It has advantage of giving selective
oxidation of persistent organic pollutants and it oxidizes the water to produce hydroxyl
radical which helps to enhance the oxidation process.
There are some limitations associated with ozonation process such as the use of
electricity in its production process. An electric discharge is used to produce ozone and
produced ozone has short lifetime as compared to other oxidants and it must be used quickly
as it forms. Its instability can cause it to decompose it into oxygen. The use of electricity for
large scale generation of ozone is a cost full process which limits the ozone usage for
wastewater treatment technologies.

2.4.2. Ozone/oxidant treatment

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 The combination of ozone with hydrogen peroxide is also known as peroxone. It is a
bitter fact that there are still problems related to efficiency in oxidation and degradation of
pollutants present in wastewater by a single one technique. Therefore, combination of the
two or more than two types of treatments leads to a considerable destruction of wastewater
pollutants. The mechanism behind the degradation of pollutants is the production of hydroxyl
radical which further react to mineralize the pollutants present in the wastewater. Hydrogen
peroxide is considered as a strong oxidant that of ozone itself behaves as oxidant. So, there is
much higher oxidation rate can be achieved as compared to the individual use of these
oxidants.

2.4.3. O3/UV treatment (Photolytic ozonation)

According to the Environmental protection Agency (EPA), there are several methods
available for the effective wastewater treatment, two of the methods are ozonation and use of
UV light (Chin and Bérubé, 2005). Both treatment processes have been widely used to kill
the pathogenic bacteria present in water. When they are using in combination with each other
than UV source provides energy for the ozone molecule to decompose into atomic oxygen
which on further reaction with water molecule produces reactive hydroxyl radical. The
oxidant produced is a key specie in the advanced oxidation processes. Ozone/UV treatment
can effectively disinfect the water because of the higher oxidizing potential of the ozone that
is 2.07eV that of oxidizing potential of the hydroxyl radical 2.8eV. it can effectively destroy
the organic pollutants.

2.4.4. O3/catalyst treatment

Ozone is a strong oxidant which is used to adsorbs the pollutant materials on the surface of
the photocatalysts such as ZnO, Fe2O3, MnO2, TiO2 etc. The adsorption of the pollutants on
the catalyst surface enhanced the pollutants degradation rate with the help of redox reaction
carried out using photo-active catalyst. The photo-active material can also oxidize the water
surrounds it and adsorbs on its surface leading to production of hydroxyl radical. The
production of hydroxyl radical enhanced several times in presence of ozone. Therefore,
ozone in combination with catalyst can effectively be used to decontaminate the wastewater
(Tanaka et al., 1992).

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2.4.5 H2O2/UV treatment

Process of using H2O2 oxidant along with the use of ultraviolet radiations is known as
Photolysis. Oxidation of pollutants exist in wastewater observed with only hydrogen
peroxide is not as efficient as compared to the oxidation with H 2O2 under UV irradiation.
Actually, the UV radiations make the hydrogen peroxide to decompose quickly into hydroxyl
radicals.

2.4.6. O3/H2O2/UV Treatment

The combination of oxidants of high chemical oxidation potential with the UV radiations can
enhance the water purification. It is a fact that no single one process is efficient in degrading
the pollutants, so the combination of the processes makes the reaction to occur at much
higher rate. The production of hydroxyl radical increases as the wastewater containing O3
and H2O2 irradiated with UV source. There is production of very short lived ∙OH2 entities
which are also constituted to produce hydroxyl radical. The hydroxyl radical is a key specie
produced in advanced oxidation processes and essential one to carry out the whole oxidation
reaction because of its oxidation potential 2.8eV. The combination of these oxidants and UV
is widely used in textile industries to eliminate the excess chemical oxygen demand (COD)
present in their effluent. The process can enhance the COD elimination rate from 15 to 62%
form industrial wastewater.

2.5. Nanoscience and photocatalysis

Nanoscience is a science to study the materials which are less than 100 nm in size, at
least in one dimension. Particles of which size is less than hundred nanometer in at least one
dimension out of three are regarded as nanoparticles. Nanoparticles possesses extended
properties with respect to their bulk materials. They have large number of active sites,
adsorption sites and large surface area with smaller volume. Semiconductor oxides can be
grounded to nanoscale by different methods to enhance their photocatalytic activity as
number of active sites increases while bulk properties of semiconductors do not affect.
Photocatalysis is a process that accounts for absorption of photon by catalyst, excitation of
electrons from valance band to conduction band to create holes in valance band by
transferring electrons to conduction band. Photocatalyst only absorbs the photons which

xiii
possess minimum amount of energy to cross the energy gap between valance band and
conduction band. Photocatalysis now a days extensively investigated by scientist for
photocatalytic degradation of pollutants and water splitting. Water splitting used to produce
hydrogen gas which is an excellent energy carrier. Photocatalysis is environmental friendly
and non-toxic treatment which can give fruitful results. During photocatalytic process, the
electrons in conduction band and holes in valance band transfer to the surface of catalyst to
react with adsorbs species. There are contaminants present in wastewater which adsorbed on
the catalyst surface to accept electrons and holes to get reduced and oxidized, finally
converted into low molecular weight substances such as water and carbon dioxide. In fresh
water, holes in conduction band oxidize the water molecules to hydrogen ions and electrons
in conduction band used to reduce hydrogen ions to hydrogen gas. The whole process
surmises in figure 1.1.

Figure 1.1: Photocatalysis process and mechanism of degradation of pollutants

2.5.1. Synthesis of CaO/CoO and its applications for wastewater treatment

The effectiveness of the photocatalytic process was studied by the degradation of azo
dye X6G present in wastewater using CaO/CoO doped with titanium dioxide. The electron
beam evaporation method was used to synthesize the thin films of the metal oxides which
than deposited on glass substrates. X-ray diffraction (XRD) and atomic force microscopy

xiv
(AFM) were used to characterize the film’s samples and UV-Visible spectroscopy was used
in evaluation of degradation. Indium CaO/CoO was proved to be efficient photocatalyst to
degrade the azo dye present in wastewater of several textile industries under UV-irradiation.
Different reaction parameters such as film thickness, concentration of dye, H 2O2 volume and
ethanol and pH of solution were optimized. It is revealed that with the increase in
concentration of H2O2 enhanced the oxidation rate.

Amino acids chelate were used to fabricate. the CaO/CoO. nanoparticles. By

precipitation. method. to degrade rhodamine. dyes. and organic pollutants present. in.
wastewater. The. results revealed that there was 100% degradation of the rhodamine complex
under UV irradiation. in the presence of CaO oxide. The TOC degradation checked after dye
degradation and it was found that the TOC decreased and degraded to 83.3%. A similar work
was done by the Wu et al., (2009) to prepare CaO/CoO by the amino acid assisted
hydrothermal process the degradation of the rhodamine B dye present in wastewater was
checked to determine the photocatalytic efficiency of the composite metal oxide
nanoparticles. The results showed that there were compete degradation after 150 mints of
irradiations

The nanostructured CoO nanoparticles were prepared by the thermal decomposition

of the cobalt hydroxide and used an egg shall membrane. The metal oxide particles were
characterized by the transmission electron microscopy (TEM), XRD, FT-IR and UV-Visible
spectrophotometry. The degradation of the rhodamine B dye was checked and there was
94.48% degradation recorded according to the author under exposure to ultra violet light for
60 minutes (Sangami and Dharmaraj, 2012).

Oesin Y, red Congo and methylene blue degradation was checked by the CaO/CoO
nanoparticles under UV- irradiations. Green synthesis of the CaO/CoO nanoparticles was
firstly reported by the Diallo et al., (2016) in which they used the Asplathus linearis extract
which is a good chelating agent. This biological environment friendly method produced the
single-phase CaO/CoO nanoparticles which are characterized by the high resolution
transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED).
They carried out J-analysis for imaging forces and EDX for elemental analysis. The dye

xv
degradation was checked, optimized and found that it can be degraded to 95% with
CaO/CoO under UV irradiation (Diallo et al., 2016).

Biochemical technique was used to synthesize the CaO/CoO nanoparticles which is

environment friendly. The aqueous extract of catunaregam spinosa root barks were used to
prepare CaO/CoO nanoparticles which was then used to degrade the Cango red organic dye.
Because of the presence of the aromatic rings in high concentrations the Cango red dye is
carcinogenic and persistent. The method is completely non-toxic and environment green. The
evaluation of degradation was carried out using UV-Visible spectroscopy and analysis shows
that there are 80% dye degradation under UV illumination (Haritha et al., 2016).

Photocatalytic degradation of the azo dye can be improved by the combination of the
CaO/CoO nanoparticles with titanium oxide nanoparticles. The thin film of CaO/CoO doped
with TiO2 was formed by the hydrothermal method coated on glass plates. The operational.
parameters. such. as. irradiation time and concentration. of the. dye. in ppm were optimized
and it was observed that the degradation rate enhanced as the time increased. Rapid and full.
degradation. of the azo dye was observed by. the. use of nano-crystalline metal oxide and the
UV radiations. The higher degradation rate is due to improvement in the charge separations
in CaO/TiO2 Nano composite (Vinodgopal and Kamat, 1995).

A homogenous co-precipitation method was used to synthesize the Zinc oxide doped
CaO/CoO nanoparticles for efficient degradation of the methyl orange dye present in textile
effluent. XRD and TEM were used to characterize the material and the degradation of the
dye was observed in aqueous system under UV irradiations. It is found that the coupled ZnO
with CaO/CoO exhibit higher photo-activity than the ZnO and CaO alone and the photo
catalytic reaction of the methyl orange obey the first order kinetics (Zhang et al., 2005).

Han et al., (2009) synthesized nano-sized Tin dioxide using hydrothermal process.
The precursor calcium chloride pentahydrate hydrolyzed to nanosized CaO/CoO and pH was
adjusting by adding HCl. The material was obtained by heating the CuCl 4.5H2O solution to
200oC for 12h and the particles obtained were characterized by X-ray diffraction (XRD) and
scanning electron microscopy (SEM). XRD pattern shows that the obtained CaO/CoO was
octahedral structure having rutile phase and SEM shows that obtained material was of high

xvi
purity. The CaO/CoO nanoparticles have applications in photocatalysis, rechargeable lithium
batteries and in gas sensing (Han et al., 2009).

The usefulness of heterogeneous photocatalysis is estimated by the CaO/CoO

electrode doped with the nickel and antimony for the direct electrochemical degradation of
the 4-chalorophenol which is a model toxic organic pollutant used in the production of dyes,
pesticides and drugs. Direct electrochemical degradation is a useful advanced oxidation
process. CaO/CoO doped with the nickel and antimony coated by pyrolysis method on anode
(metal substrate) to efficiently evaluate oxygen in form of ozone which can further react with
organic pollutants to oxidize them. The. effects. of the. reaction and operational parameters
like concentration of dopant w.r.t CaO/CoO and pH have also been investigated (Wang et al.,
2006).

Thermal deposition technique was used to synthesize CaO nanoparticles and this
technique was used to deposit the CaO/CoO nanoparticles on the titanium dioxide electrode.
The effectiveness of the process is checked by the electrochemical oxidation process to
degrade of the 2-chlorophenol present in textile effluent. During the process, samples were
collected at different time intervals and COD values checked for each sample. There was
maximum of COD was removed is 1000mg/dm 3. The result shows that there was effective
degradation of the 2-chlorophenol present in textile effluent using CaO/TiO 2 nanocomposite
(Polcaro et al., 1999).

A ternary mixture of the three metal oxides was prepared by the Wang et al., ( 2005)
in which they prepare mixture of ZnO, TiO 2 and CoO to check the enhanced photo-activity
as compared to the individual catalysts. The characterization was carried out using XRD,
thermogravimetric and differential thermal analysis (TG-DTA) and diffuse reflectance
UV/visible spectroscopy. The results revealed that there was maximum dye degradation
when the calcination temperature was 500 oC and above this temperature there was decrease
in the dye degradation observed. The ternary mixture was proving efficient photo catalyst to
degrade the methylene blue exist in textile waste (Wang et al., 2005).

Zakeritabar et. al., (2018) was made an effort to synthesize ZrO2/CoO nanocomposite for
pharmaceuticals wastewater treatment. The effectiveness of the properties presents in the

xvii
membrane of Nano-composite such as photocatalytic activity, anti-fouling behavior,
hydrophilicity and pharmaceutical wastewater permeability was studied. The sample was
characterized by XRD, Field emission scanning electron microscopy (FESEM), EDX and
FT-IR in order to determine crystallinity, morphology and surface properties. Nano-
composite membrane proved to be efficient long-term solution to treat the pharmaceutical
effluent under UV irradiations. There was maximum 90% removal for the COD achieved.

2.6. Response surface methodology

There are several mathematical techniques and designs available to optimize the
operational parameters regarding photocatalysis. Operational conditions of different
parameters in which concentration. of the pollutants, irradiation time, pH, catalyst loading,
surface area of photocatalyst, temperature of substrate and irradiation temperature can be
optimized to get maximum efficiency by different techniques such as response surface
methodology (RSM) and genetic algorithm (GA). RSM is commonly used by the researchers
because easy to understand design of the experiments and graphical representation of the
data.

Liu and Chiou, (2005) used RSM to optimize the parameters to degrade the reactive
red 239 (RR-239) dye by TiO2 under the action of UV radiations. The decolonization of the
azo dye RR-239 in batch reactor under UV-irradiations by TiO 2 was studied. RSM was used
to optimize the four independent parameters, Concentration of photocatalyst, stirring speed,
intensity of UV light and initial pH were optimized by using the 2 4 full factorial central
composite design. The design show that concentration of the TiO 2 and initial pH was
significance effect on the decolorization of the RR-239 and there was maximum of 99.82%
degradation of RR-239 was achieved under optimized conditions.

Zhang. et. al., (2010) was investigated. the chloramphenicol removal by TiO 2 under
the action of UV light. The experimental parameters with different conditions such. as. initial
pH, loaded concentration. of TiO2 and initial concentration of chloramphenicol were
optimized by the RSM to achieve maximum degradation. The maximum degradation of
85.97% of chloramphenicol was achieved under optimized condition.

xviii
 Sohrabi and Akhlaghian, (2016) studied the phenol degradation over copper doped
titanium dioxide under UV irradiation. They observed the degradation of phenol by
optimizing different operational parameters conditions such as catalyst doses, phenol
concentration and reaction time. The result indicated that catalyst doses was the most
significant effect on the degradation of the phenol and the initial phenol concentration was
of the least significance.

Fu. et. al., (2007) investigated the oxidation. of the fulvic acid into low molecular
weight substances by photo electro-catalytic process and optimized the operational
parameters with response surface methodology. Effect of reaction parameters on the
oxidation of fulvic acid was studied using response surface methodology. The Box Behnken
design was used to optimize the variables such as pH, potassium peroxide disulfate and
MATLAB software was used to study interactions between these variables and optimum
conditions. Under optimized conditions, the maximum degradation of the Fulvic acid was
found to be 57.06% by using TiO2 electrode in photo-reactor under UV irradiation.

Photo catalytic degradation of poly brominated diphenyl ether (BDE) was studied
under the action of UV light and at high temperature the catalyst absorbed visible light. Here,
a tri-metallic oxide CoO/NiO/TiO2 was used to degrade BDE-47, BDE-99, BDE-100, BDE-
153 and BDE-154 under optimized conditions. The catalyst was characterized by the Xx-ray
diffraction, X-ray photoelectron spectroscopy, photoluminescence and diffused reflectance
ultraviolet visible spectroscopy. The gas chromatography-electron capture detector was used
to study the degradation results and the key parameters such as catalyst dosage, TiO 2 loading
and calcination temperature optimized by the response surface methodology. The BDE-47
degradation was found to be maximum 64.63% under optimized conditions.

Salehi et al., (2017) was studied the degradation of the aromatic direct blue 71 dye
using CoO-ZnO nanocomposite under optimized conditions by the action of UV radiations.
Central composite design in response surface methodology was used to optimize the
parameters which are pH, catalyst amount, amount of dye and the reaction time. A quadric
polynomial model in response surface methodology was used to evaluate relation between
photo-activity of catalyst and operational parameters. The maximum degradation for the
direct blue 71 dye was found to be 89.58% under optimized conditions.

xix
CHAPTER 3
MATERIALS AND METHODS
The whole research and scientific work in this thesis were practiced in radiation chemistry
laboratory, university of Agriculture, Faisalabad. Analytic grade chemicals were used as they
received and used without further purification.
3.1. Chemicals required
 Calcium chloride
 Cobalt chloride anhydrous
 Sodium hydroxide
 Hydrogen peroxide
 Sulfuric acid
 Hydrochloric acid
 Potassium dichromate
 Silver sulfate
 Murcury sulfate
3.2. Glassware used
 Beakers (50-1000 mL)
 Measuring cylinder (10-500 mL)
 Pipette (10 mL)
 Test tubes
 Filter paper
 Funnel
 Thermometer
 Test tube stand
 Spectula
3.3. Instruments
 Analytical balance (Sartorius TE, 214 S)
 Magnetic stirrer, hot plate (DHPs-1)
 UV/visible spectrophotometer (CE Cecil 7200, Germany)
 pH meter (Loviband Senso Direct150, Germany)

xx
  COD meter (Lovibond PCCHECKIT COD vireo with Lovibond incubator)
 BOD meter (Lovibond Senso Direct 150)
3.4. Wastewater collection
Wastewater was collected from paper mills located in Faisalabad and Lahore, Punjab,
Pakistan. Wastewater was collected in plastic cans and immediately bring to radiation
chemistry laboratory, department of chemistry, university of Agriculture, Faisalabad.
3.5. Reagent Preparation
3.5.1. 0.0125M calcium chloride solution
0.125M calcium chloride solution was prepared by dissolving 1.8875g of it in 200
mL of distilled water.
3.5.2. 0.0125M cobalt chloride solution
0.125M copper sulfate pentahydrate solution was prepared by dissolving 1.35g of it in
200mL of distilled water.
3.5.3. 0.5M NaOH solution
0.5M sodium chloride solution was prepared by dissolving 8g of NaOH in 400mL of
disstiled water
3.6. Methodology
All the reseatch work comparises of following steps.
 Preparation of pure and composite cobalt oxide-calcium oxide powder nanoparticle
 Characterization of nanoparticles by XRD, SEM, and FT-IR.
 pH optimization
 Optimization of oxidant concentration
 Optmization of irradiation time
 Optimization of initial concentration of pollutant
 Calculation of percentage degradation of pollutants
 Measurment of percent degradation of pollutants by UV/visible spectrophotometer
3.6.1. Synthesis of pure calcium oxide, pure cobalt oxide and calcium oxide/cobalt oxide
nano-composite
Pure calium oxide was prepared by dissolution of calcium chloride in water,
precipiataing calcium hydroxide by the action of NaOH. Calcium hydroxide was filtered, air
dired and calcinated at 6000C for 3 hours in muffle furnace for decomposition of O-H

xxi
(hydroxide) bond. The resulting powder of calcium oxide (CaO) was grinded with piston
mortor to nanoscale and these nanoparticles of CaO were used for characterization and
wastewater treatment applications. Cobalt oxide was prepared in similer way by dossolving
cobalt chloride anhydrous in water. Sodium hydroxide was used as precipitating agent, and
precipitates of cobalt hydroxide was filtered and air dired, calcinated at 600 0C for 3 hours to
ensure cobalt oxide formation. The powder was grinded to nanoscale by piston mortor.
Nanocomposite was prepared by mixing the as prepred solutions of calcium chloride
and cobalt chloride anhydrous. The hydroxide of composite metals was precipitated using
sodium hydroxide having concentration double as compred to its concentration used in pure
solutions of each precursor. The composite hydroxide was seperated from solution via
filteration with filter paper, dried using air currents, calcinated at 600 0C for 3 hour for CaO-
CoO formation, grinded to nanoscale with piston mortor. As prepared sample of
nanocomposite and pure metal oxide were used for further pollutant degradation and
characterization purpose.
3.6.2. Wastewater treatment
The prepared samples of pure and composite nanoparticles were checked for their
photocatalytic activity. Photocatalytic activity of nano metal oxides were estimated as a
result of degradation of pollutants present in wastewater. Paper mills effluent was analyzed
before treatment and reanalyzed with spectrophotometer to check maximum pollutant
degradation
3.7. Instrumintation
Paper mill wastewater samples were analyzed for pollutants, chemical oxygen
demand using COD meter, biological oxygen demand (BOD) by the digital BOD meter
(Lovibond Oxi Direct, Germany) and total organic carbon using COD meter. pH of the
samples was checked by the digital pH meter (Lovibond Senso Direct150, Germany).
Analytical balance at Radiation lab, UAF was used for weighing the chemicals. Double beam
UV/visible spectrophotometer (CE Cecil 7200, Germany) at radiation chemistry lab, UAF
was used to take absorbance and for spectral studies of the wastewater. Magnetic stirrer
linked with thermostat assembly was used make the solution homogenous by mixing the two
solutions at the rate of 600 rpm . The wastewater samples and treated samples were analyzed
by UV/Vis double beam spectrophotometer at radiation chemistry lab while atomic

xxii
absorption spectroscopy at Hi- Tec lab UAF used to conform the reduction of pollutants.
Characterization of nanoparticles of calcium oxide/cobalt oxide was done by X-ray
diffraction (JEOL JDX-3532 diffractometer, Japan) for structural study, scanning electron
microscopy SEM (Quanta 250. FEG, USA) for surface studies, and Fourier transform
infrared spectroscopy (FT-IR) at National Textile University, Faisalabad.

3.7.1 Digital pH meter

pH of the effluent and solutions used during the experimentation was calibrated using
digital pH meter (Lovibond Senso Direct 150, Germany) at Radiation chemistry laboratory
UAF. Standard buffer solution of pH 4,7,10 was used to calibrate pH meter. The pH meter tip
was carefully and completely washed with de-ionized water for each treatment.

Fig. 3.1: Digital pH meter (Lovibond Senso Direct 150, Germany)

3.7.2. Analytical balance

Analytical balance of model Sartorius TE 214S with weighing range from 0.1 mg to
212g was used in the research study thoroughly.

xxiii
 Fig. 3.2: Analytical balance, (Sartorius TE. 214S)

3.7.3. COD meter.

A digital COD meter of model Lovibond PCCHECKIT COD vario with Loviond
incubator was utilized to determine COD and TOC of effluent at radiation chemistry lab,
UAF. Calibration of COD meter was carried out by the solution of known COD. The COD
tubes were washed using de-ionized water prior to each treatment

Fig.3.3: COD meter, (Lovibond PCCHECKIT COD vireo with Lovibond incubator)

3.7.5. BOD meter

xxiv
 For BOD measurments a digital BOD meter of model Lovibond Senso Direct 150
was used at Radiation chemistry lab UAF. Solutions of known BOD values was used to
calibrate the BOD meter

Fig.3.4: BOD meter, (Lovibond Senso Direct 150)

3.8. Characterization

X-ray diffraction, scanning electron microscopy, energy dispersive X-ray, Fourier transform
infrared spectroscopy were used to characterize the nano samples.

3.8.1. Scanning electron microscopy (SEM)

Scanning Electron microscope can take image the surface of sample by scanning it
with the high energy beam of electrons. SEM makes use of electron beam to interact with the
sample followed by the production of X-rays, back scattered electron, auger electrons and
secondary electrons to examine surface features and morphology of the respective samples.
SEM is a powerful analytical tool to examine surface morphology of the nanoparticles which
have set on primary detection mode ranging from the few nanometers to several hundred
nanometers. There is a stable electronic system present in the sample particles which is
disturbed and imbalanced by the beam of electron having high energy. The atom goes to
stability and in balanced state by ejecting the radiations such as secondary electrons and X-
rays. Examination of these electrons and X-rays can give fruitful information about surface
morphology and particle size of the nanosized sample (Preacher et al., 2011). SEM (Quanta

xxv
250 FEG (US) at Nataional Textile University, Faislabad was utilized for imaging of
nanoparticles

Fig. 3.5: Scanning electron microscope, (Quanta 250. FEG (USA))

3.8.2. XRD analysis

The XRD is powerful techniques used for the crystallographic analysis of sample by
making use of finely divided specimens in form of powder and ensure the random orientation
of crystalline planes. Angel and respective intensity of the diffracted beam can be detected by
current generation XRD instrument using inherent radiation counter. A recorder connected to
the XRD system automatically deals with the intensity of different beams. The particle
distribution angles and their associated intensities can be recorded by this method of crystal
analysis at the same time. If there will destructive interference than it will be removed but if
scattered rays reinforce each other to exhibits constructive phenomena than crystallographic
planes of crystal separated by interplanar distance ‘d’ were investigated. Crystalline
materials always exhibit specific angles of diffraction indicating that the material possess
crystalline properties and percentage purity. Temperature and stress on the crystalline
material make it to change the crystalline phase which are well designated by variation
observed in angle of diffraction followed by the Brag’s law (Bunaciu et al., 2015).

Jeol JDX-3532 diffractometer with Cu-Ka radiation, Japan at National Textile University,
Faisalabad was employed to get X-ray diffractogram of fabricated nanoparticles (Cullity,

xxvi
2001).

Fig. 3.6: X-ray diffractometer, (Jeol JDX- 3532, Japan)

3.8.3. FT-IR Analysis

Working principle of FT-IR spectrophotometer is in accordance with the Michelson

interferometer which employed a beam splitter to split the light into two parts. FT-IR
spectrophotometer works in vacuum at a pressure of 0.01 mbar and optically it consists of IR
source, interferometer itself, sample covets and detector. There are different sources available
to emit IR radiations but three commonly used IR sources for spectroscopic studies are (i)
high pressure mercury lamp, (ii) a globe or lamp at 1100K temperature and (iii) an external
light source. IR beam passes through the beam splitters. Several beam splitters are available
such as KBr, CaF2 and quartz beam splitters that can divide the incoming beam. The two
beams recombine at the axis of the interferometer than the beam is focused on another
circular aperture by using an optical filter. Sample containing chamber is mounted and
equipped with the absorption cells where recombined beam comes and interact with the
sample. The IR beam goes to the detector which converts the numerical data into electrical
signals (Palmer and Smith, 1986).

xxvii
 Fig. 3.7: Fourier Transform Infrared Spectrophotometer, (Bruker IFS 125HR, Japan)

3.9. Photocatalytic treatment of model pollutant under solar radiations

Following useful methods are employed for treatment and reduction of waste materials.

3.9.1. Solar photocatalytic treatment

In this method, pure metal oxides and nanocomposite was used as photocatalyst and
wastewater treatment was carried out by exposing nanocomposite to solar radiation for
different time intervals.

3.9.2. Parameters optimization

Operational parameters include pH, oxidant concentration, initial concentration of

2,2-dichorophenol and irradiation time were optimized to check maximum degradation of
pollutants. pH was adjusted in the range 3-11 using 10% HCl and dilute base 0.1M NaOH
while other parameters kept constant. Volume % range for H 2O2 selected for optimization
was 100-700 ppm. Irradiation time under visible source was ranging from 36 minutes to 7
hours for estimation of the optimum exposure time.

3.10. Extent of pollutant degradation

The extent of photocatalytic degradation of contaminants of selected model compound was

evaluated by following techniques.

xxviii
3.10.1. UV/Vis spectrophotometric analysis

UV/Vis double beam spectrophotometer was used in order to measure absorbance

and record spectra of tannery effluent at radiation chemistry lab, UAF. Absorption spectra
was recorded before and after treatment of effluent to check the percentage reduction in
metal concentration. The treated and untreated effluent samples of different concentration
were scanned from 200 to 800 nm range in UV-visible spectrophotometer and photocatalytic
degradation was calculated mathematically.

Fig. 3.8: Double beam UV/VIS Spectrophotometer, (CE Cecil 7200, Germany)
3.10.2. Percentage degradation of contaminants.

Percentage degradation of contaminants can be calculated in term of absorbance using

formula,

Percentage degradation = (initial absorbance – final absorbance)/(initial absorbance) ×100.

3.11. Water quality parameters analysis

xxix
The water quality parameters include COD, BOD, TOC and pH were analyzed by COD,
BOD and pH meters respectively, all instruments were calibrated properly before use.

3.11.1. TOC analysis

TOC was measured by double beam spectrophotometer (CECIL CE 7200)

Reagent Preparation

Preparation of potassium dichromate solution: 2N K2Cr2O7 solution was prepared in 250

mL solution.

Preparation of standard glucose solution: 250 ppm glucose solution was prepared in 500
mL solution.

Procedure: 1.6 mL of H2SO4 mixed with 1 mL of 2N K2Cr2O7 solution in screw cap vial.
After shaking, 4mL sample was added. The mixture was set to incubate for 110 °C for 1.5h.
Similarly, standard glucose solution was incubate instead of effluent sample. TOC was
calculated using formula

conc . of glucose(mg/ L)
Standard factor =
absorbance after incubation

TOC (mg/L) = (Standard factor) × (absorbance after incubation)

3.11.2. COD analysis:

Standard method number 5220 C, 17th edition, Page number 5 was followed to determine
COD (Eaton et al., 2005).

Reagent preparation

Preparation of digestive solution: Dissolution of 2.61 g K2Cr2O7 and 8.34g HgSO4 in 42 ml

(98%) H2SO4, diluted to 250 mL using distilled water.

Preparation of catalyst solution: Dissolution of 2.5 g Ag2SO4 was dissolved in 250 mL

(98%) H2SO4 and left for 24 hours to ensure digestion of Ag2SO4.

xxx
Preparation of potassium hydrogen phthalate (KHP) solution: 425 ppm solution of KHP
was prepared in distilled water which have 500 mg/L COD.

Procedure: Clean screw cap COD vials was filled with 1.5 mL digestive and 3.5 mL catalyst
solution then 2.5 mL effluent sample was mixed well with them. Similar conditions were
followed for KHP incubation. COD meter was set to incubate at 150 °C for 2h. COD was
calculated using formula

COD of standard KHP

Standard factor =
absorbance after incubation

COD (mg/L) = Standard factor × absorbance after incubation

3.11.3. Measurement of Biological Oxygen Demand

Lovibond Senso Direct 150 BOD meter was used to analyze the wastewater for BOD at
Radiation Chemistry lab UAF.

Procedure involved
BOD bottles were cleaned by washing and rinsing using deionized water. First bottle
was filled with 57 mL of deionized water which was used as blank. Remaining bottles were
filled with the effluent samples of different concentrations having volume equal to the
standard solution. Standard KOH solution was added to bottles containing standard solution
and sample solutions added dropwise (7 drops) before capping them. The bottles were placed
at their fixed positions in BOD meter which was set for 5 days for BOD measurement. The
BOD of untreated and treated samples has been measured in the same way.

3.9. Response surface methodology:

Response surface methodology (RSM) is frequently used statistical procedure for
optimization of the different experimental conditions to achieve maximum results. Response
surface methodology (RSM) is a collection of mathematical and statistical techniques for
empirical model building. By careful design of experiments, the objective is to optimize a
response (output variable) which is influenced by several independent variables (input
variables). In my research work, percentage reduction was taken as response variable while
pH, oxidant concentration, irradiation time and initial concentration of 2,2-dichorophenol

xxxi
were taken as independent variables. The levels of independent variables employed was
depicted by Table 3.1.

Table 3.1: Independent variables and their levels employed in CCD

Factors Variables Units Lower Upper
value Value

A pH - 5 9

B Irradiation time Hours 1 5

C Oxidant Conc. milimolar 10 20

D Initial conc. of 2,2-dichlorophenol ppm 50 200

CHAPTER 4

xxxii
 RESULTS AND DISCUSSION

4.1. Nanoparticles synthesis route

In this study, pure CaO, CoO and CaO-CoO nano-sized composite was prepared by
the sol-gel technique. Calcium chloride and cobalt chloride were used as precursors for
nanoparticles formation. Equimolar clear solutions of both minerals were prepared
separately, for composite formation a sufficient volume of pure solutions of each precursor
was mixed homogenously with magnetic stirrer at the rate of 300 rounds per minute at
temperature 250C. Sodium hydroxide was used as precipitating agent. A small volume of
NaOH solution was poured into three solutions, pure CaO solutions, pure CoO solution,
mixture of CaO-CoO solutions, which in turn react with NaOH solution to form water
insoluble hydroxides of each metal present in solution. The hydroxide precipitates were
filtered, dried, and calcinated to 600 0C for 2 hours for the formation of oxides of respective
metal ions, i.e. CaO, CoO and CaO-CoO composite. All three samples were grinned to
nanoscale using ceramic mortar.

Figure 4.1. Synthesis of pure and composite CaO, CoO, Cao-CoO nanoparticles

4.2. Characterization of CaO, CoO and CaO/CoO composite

The samples were characterized by X-ray diffraction (XRD) to confirm

crystallinity of samples, scanning electron microscopy (SEM) to confirm surface morphology

xxxiii
of samples while Fourier transform infrared spectroscopy (FT-IR) to investigate vibrational
frequencies of metal oxide bonds

4.2 XRD analysis

4.2.1. XRD of CaO nanoparticles

XRD pattern observed for CaO can be shown in figure 4.1. Its comparison with standard
JCPDS card number 01-077-2010 confirms the synthesis of CaO crystalline particles. It
confirms its cubic geometry where all three angels are of 90 o and a=b=c with cell parameter a
= 4.6770 Å. Pattern shows the peaks at 33.08o (111), 37.69o (200), 54.2o (202), 62.41o (311)
and 65.92 (222 ) were due to CaO particles. Debye Scherrer formula was used to calculate
average crystallite size, which was given as

D = 0.9λ/βCosθ

Where,

D = average crystallite size

λ = wavelength of X-rays (1.54060Å)

β = full width half maximum (FWHM) of the most intense peak and

Theta (θ) = θ/2

The average crystallite size of nanoparticles was found to be 9.84 nm

xxxiv
 Fig. 4.2: XRD analysis of CaO nanoparticles.

Fig. 4.3: Tetragonal arrangement of Ca and O molecules in lattice with planes

xxxv
 Fig.4.4: Tetragonal growth of Ca and O molecules in crystal lattice

4.2.2. XRD analysis of cobalt oxide

XRD pattern observed for Cobalt oxide is shown in figure 4.5., its comparison with standard
JCPDS card number 80-1545 confirms the formation of cobalt oxide (Co 3O4) crystalline
material. Strong diffraction peaks at 2θ values 32.68o, 38.39o, 40.89o, 46.66o, 57.63o, 60.23o
and 66.78o associated with planes (220), (311), (222), (400), (422), (511) and (440)
confirmed for cobalt oxide. The obtained unit cell is cubic in structure with a =b=c while a=
β=γ=90o related to space group C 1 2/c 1 (15) having cell parameters α= 4.6830. The bond
distance of oxygen and copper in crystal lattice was calculated using VESTA software, found
to be 1.8 Å. Debye Scherrer formula was used to calculate average crystallite size, which was
given as

D = 0.9λ/βCosθ

Where,

D = average crystallite size

λ = wavelength of X-rays (1.54060Å)

xxxvi
β = full width half maximum (FWHM) of the most intense peak and

Theta (θ) = θ/2

The average crystallite size of nanoparticles was found to be 17.5nm.

Fig. 4.5: XRD pattern of Co3O4 nanoparticles.

Fig. 4.6: Arrangement of Co and O throughout cubic lattice with specific planes

xxxvii
 Fig. 4.7: Growth pattern of Cu and O throughout the cubic lattice

4.2.3. X-ray diffraction of CaO/CoO

Synthesized nanocomposite sample was characterized by XRD which determined its

crystallinity and purity. Figure 4.8 shows the sharp and strong X-ray diffraction peaks
pertaining nanocomposite crystallinity and almost zero noise which indicates the high
percentage purity of the synthesized CaO/CoO nanoparticles. Peaks comparison with their
standard JCPDS numbers (JCPDS for CaO 32-105-4372 and 76-135-5643) can readily be
indexed for its cubic structure (a=b=c and a=β=γ=90o). It has cell parameter a=5.3526Å,
β=93.3o having space group p 121 c 1 (14). Pattern peaks and respective miller indices for
CaO at 2θ values 33.08o, 37.69o, 54.2o, 62.41o and 65.92 are (111), (200), (202), (311), and
(222) while peaks at 2θ values 32.68o, 38.39o, 40.89o, 46.66o, 57.63o, 60.23o and 66.78o
associated with planes (220), (311), (222), (400), (422), (511) and (440) were confirmed for
the CoO nanoparticles. The average crystallite size was calculated using Debye Scherrer
formula, given by

D = 0.9λ/βCosθ

Where,

D = average crystallite size

xxxviii
λ = wavelength of X-rays (1.54060Å)

β = full width half maximum (FWHM) of the most intense peak and

Theta (θ) = θ/2

The average crystallite size of nanoparticles was found to be 33.31nm.

Fig. 4.8: XRD pattern of CaO-CoO nanocomposite

Fig. 4.9: (a) cubic structure of the CaO and Cubic structure of CoO in crystal lattice

xxxix
 Fig 4.10: Nanocomposite growth in cubic geometry

4.3. FT-IR analysis of calcium oxide, cobalt oxide and their composite

Fourier transform infrared spectroscopy used to determine vibrations of bonds in

molecules. It makes use of infrared radiations, which on interaction with molecules, makes
the molecule to vibrate with specific frequency. The vibrational frequencies obtained as a
result of Fourier transform infrared can give useful information regarding the bond presence
in sample. FT-IR spectrograms for CaO, CoO, and their composite are discussed below in
detail

4.3.1. FT-IR of CaO

Figure 4.11 is representing the FT-IR spectrogram of pure calcium oxide nanoparticles. It
shows several peaks at different wavenumbers such as 3214.24 cm -1, 1657.67 cm-1, 1392.60
cm-1, and 720.68 cm-1. The peak at 3214.24 cm-1 is relatively broad and is present due to
present of O-H bond stretching vibrations. O-H bond is present as impurity because of use of
sodium hydroxide as precipitating agent in formation mechanism of nanoparticles. This O-H
shows bending vibrations at 1657.67 cm-1. The peaks at 1392.60 cm-1 and 720.68 cm-1 is due
to metal oxide stretching vibrations.

xl
 102
100

90 1392.60cm-1, 94.06%T
720.68cm-1, 92.84%T

80

70
1657.66cm-1, 70.22%T
2836.73cm-1, 68.42%T
%T

2909.79cm-1, 65.41%T
60

50
1108.84cm-1, 51.03%T

40

30 3214.24cm-1, 26.54%T

25
4000 3500 3000 2500 2000 1500 1000 600
cm-1
Figure 4.11. FT-IR spectra of CaO nanoparticles

4.3.2. FT-IR of CoO

Figure 4.12 represents FT-IR spectrogram of pure cobalt oxide nanoparticles. As the
synthesis procedure involves usage of sodium hydroxide as precipitating agent, so a broad
peak at 3375.47 cm-1 and a sharp peak at 1529.27 cm-1 appear due to stretching and bending
vibrations of O-H bond. Meanwhile, peaks at 1256.47 cm-1 and 1134.07 cm-1 was due to
metal oxide stretching and bending vibrations i.e. peak at 1256 cm-1 was due to stretching
vibrations of O-Co-O bonds while its bending vibrations appeared at 1134.07 cm-1.

xli
 Figure 4.12. FT-IR spectra of Cobalt oxide

4.3.3. FT-IR of CaO/CoO

Figure 4.13 shows result for vibrational frequencies associated with polar bonds
present in CaO/CoO nanocomposite. it shows vibrational frequencies in form of sharp peaks
at 1992.3 cm-1, 1420.1 cm-1, 1217 cm-1, 872.2 cm-1, 853.6 cm-1, and 713.8 cm-1. Composite
contains several bonds such as Co-O bond, O-Co-O bond, Ca-O bond, Ca-O-Co bonds which
make a complex bonding structure throughout the crystalline sample, it is because the peaks
below 1000 cm-1 can be assigned to metal oxide stretching vibrations in fingerprint region.
The peaks at 1992.3 cm-1 and 1420.1 cm-1 can be assigned to the bending vibrations of some
polar organic molecules such as O-H because of use of NaOH as precipitating agent. Their
may be some presence of sodium impurity, that is why the peak at 1217 cm -1 may be
assigned to sodium associated bonds.

xlii
 Figure 4.13. FT-IR spectra for composite CaO-CoO

4.5. SEM characterization

Scanning electron microscopy uses to determine surface morphology of samples as

well as size distribution of particles. SEM analysis of pure and composite CaO and CoO can
be observed in subsequent section

4.5.1. SEM analysis of CaO nanoparticles

SEM is microscopic technique to get surface images of particles and gives useful
information about size distribution of nanoparticles. SEM images of CaO shows
agglomerated structure and it was depicted grain (spherical) type morphology with average
size distribution 68 nm with width 17 nm. Average particles size was calculated using
ImageJ, analyzed by the origin software to get size distribution by statistical histogram and
scattered plot. Spherical nanoparticles have potential applications in photocatalysis. Figure
4.13, 4.14 and 4.15 are showing SEM images of CaO nanoparticles, size distribution
statistical histogram and size distribution scatter plot with gaussian fit to calculate average
particle size and average width respectively.

xliii
Figure 4.13. SEM images of CaO powder at a distance of 20 um and 50 um

Figure 4.14. Nanoparticles size distribution statistical histogram

xliv
 Figure 4.15. Nanoparticles size distribution scatter plot with average particles size, width
and area
4.5.2. SEM analysis of CoO nanoparticles

SEM images of CoO nanoparticles are clearly showing disc type morphology, which
is very effective for contaminants adsorption on it. Contaminants can easily get adsorbed on
disc type structure and can be degraded via electron channeling as a result of light absorption.
Average particle size was found by gaussian analysis in origin, which was 51 nm. Figure
4.16, 4.17 and 4.18 are showing CoO morphology, size distribution statistical histogram and
gaussian fit scattered plot with average size and average width of nanoparticles respectively.

xlv
Figure 4.16. SEM images of CoO powder at a distance of 10 um and 20 um

Figure 4.17. Nanoparticles size distribution statistical histogram

xlvi
 Figure 4.18. Nanoparticles size distribution scatter plot with average particles size, width
and area

4.5.2. SEM analysis of CaO-CoO nanoparticles

SEM images for composite CaO-CoO are showing heterogenous structure, mixture of
spherical and disc type particles. It is porous structure to facilitates for pollutant adsorption
on light (photons) induced reactive particles. Average particle size was calculated by
gaussian model, found to be 60 nm with average with 13 nm. Figure 4.19, 4.20 and 4.21
represents SEM images (surface morphology) of composite, statistical histogram and
scattered plot with gaussian fit to calculate average size and width.

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Figure 4.19. SEM images of composite CaO-CoO powder at a distance of 10 um and 20 um

Figure 4.20. Nanoparticles size distribution statistical histogram

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 Figure 4.21. Nanoparticles size distribution scatter plot with average particles size, width
and area

4.6. Response surface methodology (RSM)

Design expert (7.0.1, Stat-Ease Inc., Minneapolis, MN, USA) was used to optimize
the percentage degradation of the 2,2-dichlorophenol. Independent variables such as pH,
sunlight irradiation time, concentration of oxidant was tested to optimize the response,
whereas, light intensity and catalyst loading were considered as constant. Central composite
design was used to carryout 30 trails with different conditions. Percentage degradation of
2,2-dichorophenol was calculated using formula (Equation No. 4.1) below

Percentage degradation = (initial absorabance – final absorbance)/initial absorbance (Eq.

4.1.)

Table 4.4. Represents experimental conditions and percentage degradation

Run pH Irradiation time Oxidant Initial Percentage
(hours) concentration concentration degradation
(millimole) of pollutant
1 7 1 15 200 50
2 9 2 20 300 64
3 9 2 10 300 53

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4 7 3 15 0 61
5 5 4 20 300 62
6 7 3 5 200 52
7 3 3 15 200 25
8 7 3 15 200 90
9 9 4 20 100 68
10 5 2 10 100 37
11 5 4 10 300 46
12 7 3 15 200 90
13 5 2 10 300 35
14 5 4 10 100 61
15 7 3 25 200 97
16 7 3 15 200 95
17 7 3 15 200 96
18 9 2 20 100 58
19 9 2 10 100 40
20 5 2 20 100 58
21 5 4 20 100 81
22 7 5 15 200 70
23 7 3 15 200 85
24 7 3 15 400 60
25 9 4 10 100 59
26 7 3 15 200 87
27 11 3 15 200 45
28 5 2 20 300 65
29 9 4 10 300 57
30 9 4 20 300 75

4.6.1. Model preparation

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Central composite design in RSM was used to optimize the response i.e. degradation by
varying independent variables A= pH, B= sunlight irradiation, C= oxidant concentration and
D= initial concentration of 2,2-dichlorophenol. Analysis of variance calculations show that
probe is less than 0.0005 which represents that degradation of 2,2-dichlorophenol strongly
depends upon pH, light exposure time, oxidant concentration and initial concentration of 2,2-
dichlorophenol. P-value is less than 0.0001 showing the accuracy of the model. Model
appropriateness is shown by R- values, where R2 = 0.9736 and adjusted R2 = 0.9443. Basic
model equation used in RSM is

Y= β0 + β1A + β2B + β3C + β4D + β12AB + β13AC + β14AD + β23BC + β24BD + β34CD + β11A2
+ β22B2 + β33C2 + β44D2 (Eq.4.2)

Y= 90.50 + 2.87A + 5.79B + 9.71C – 0.29D – 0.69AB – 1.94C + 3.31AD – 1.06BC –

3.31BD + 0.44CD – 13.89A2 –7.64B2 – 4.01C2 –7.51D2 (Eq.4.3)

In both equations “Y” is percentage degradation of pollutants while β 0, β1, β2, β3, β4, β12, β13,
β14, β23, β24, β34, β11, β22, β33, and β44 is multiple regression coefficient and A, B, C and D shows
independent variables.

4.6.2. Sequential model sum of squares

Sequential model sum of squares is used to corelate the P-value with error sum of squares
and regression sum of squares. A larger p-value indicates a higher change in response
variable due to error while a smaller p-value indicates that independent variables are
responsible for the change in response variable. A model is considered as best if its p-value is
less than 0.0001 because this 0.0001 represents that there is very small variability in “Y” of
equation 4.3 due to error. Here, in our model quadratic model has p-value < 0.0001 which
shows significance of the model.

Table 4.5. Sequential model sum of squares

Sum of Mean P-value
Source squares df squares F-Value Probe > 5
Mean VS
total 1.23E+05 1 1.23E+05
Linear VS
mean 3267.5 4 816.88 2.69 0.0542

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2FI VS
linear 439.88 6 73.31 0.19 0.9744
Quadratic
VS 2FI 6861.41 4 1715.35 89.63 < 0.0001 Suggested
Cubic VS
quadra 141 8 17.63 0.84 0.5949 Aliased
Residual 146.08 7 20.87
Total 1.34E+05 30 4466.4

4.6.4. Lack of fit test

Lack of fit test in statistics explains the inadequateness of the model to evaluate the
functional relationship between the independent variables and response variable. F-value for
the lack of fit is 1.04 which confirms that it is not significant when p value is 0.5171.

Table. 4.6: Lack of Fit Test

Sum of Mean P-value
Source squares df squares F-Value Probe>5
Linear 7.49E+03 20 3.75E+02 20.04 0.0018

2FI 7054.99 14 503.93 26.95 0.0009

Quadratic 193.58 10 19.36 1.04 0.5177

Cubic 52.58 2 26.29 1.41 0.3277 Suggested

Pure error 93.5 5 18.7 Aliased

4.6.5 Model summary statistic

Model summary statistic provides the calculation of standard deviation and R-

squared. According to our design and data, quadratic model has standard deviation 4.37, least
one deviation as compared to others with R-squared 0.9736. R-squared represent the
percentage of variation of response variable w.r.t independent variables in case where

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independent variables are two or less than two, which is 97.36% in our model while 2.64%
variation in response may be due to noise. When independent variables are more than 2 (just
like 4 in our case), than R-squared automatically increases just because of larger number of
intendant variables. Therefore, Adjusted R-squared introduced which subtract the bogus
percentage from actual one. Just as in our quadratic model, adjusted R-squared is 0.9489, i.e.
94.89% variations in response variable (percentage degradation of pollutants in our case) was
due to four independent variables described earlier, while 3.11% variations (degradation) was
due to noise. Table 4.7 shows the standard deviations, R-squared and adjusted R-squared
values of linear, cubic and quadratic model, as well as their press.

Table. 4.7: Quadratic model summary statistic

Source Standard R- Adjusted Predicted Press
deviation Squared R- R-
Squared Squared

Linear 17.42 0.301 0.1891 0.1022 9746.72

2FI 1.94E+01 0.3415 -5.10E-03 -0.1407 12383.64

Quadratic 4.37 0.9736 0.9489 0.8849 1249.68 Suggested

Cubic 4.57 0.9865 0.9443 0.2901 7706.64 Aliased

4.6.6. Analysis of variance (ANOVA)

ANOVA provides very efficient calculations regarding acceptance or rejection of null
hypothesis in statistics. A large F-value corresponds to significance of the model, just in
effect of pH, irradiation time, concentration of oxidant F-values are large. For our model, p-
value is less than 0.0001 significance while lack of fit is not significance. Coefficient of
variance (C.V) of our model is 6.83% which represents a best degree of agreement between
dependent variable (percentage degradation) and independent variables (A, B, C, D)
Table. 4.8: ANOVA for response surface quadratic model
Analysis of variance table [Partial sum of squares - Type III]
Sum of Mean P-value
Source Df F-Value
squares squares Probe>5
Model 1.06E+04 14 7.55E+02 39.44 < 0.0001 significant

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A-pH 198.37 1 198.37 10.37 0.0057

B-Irradiation
time 805.04 1 805.04 42.06 < 0.0001

C-Conc.of
oxidant 2262.04 1 2262.04 118.19 < 0.0001

D-initial
concentration
of pollutant 2.04 1 2.04 0.11 0.7485

AB 7.56 1 7.56 0.4 0.5391

AC 6.01E+01 1 60.06 3.14 0.0968

AD 175.56 1 175.56 9.17 0.0085

BC 18.06 1 18.06 0.94 0.3467

BD 175.56 1 175.56 9.17 0.0085

CD 3.06 1 3.06 0.16 0.6948

A^2 5288.36 1 5288.36 276.31 < 0.0001

B^2 1599.07 1 1599.07 83.55 < 0.0001

C^2 441.15 1 441.15 23.05 0.0002

D^2 1547.15 1 1547.15 80.84 < 0.0001

Residual 287.08 15 19.14

not
Lack of Fit 193.58 10 19.36 1.04 0.5177 significant

Pure Error 93.5 5 18.7

Cor Total 10855.87 29

Cv= 6.83%

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4.7. Independent factors affecting photocatalytic degradation

Here, in our study, four independent dominants variables were chosen to optimize the
photocatalytic degradation process, that are pH, sunlight irradiation time, concentration of
oxidant (H2O2) and initial concentration of pollutant (2,4-dichlorophenol was selected as
model pollutant). All the parameters are important and that is why, all they fully explained
and evaluated by RSM, their interactions make easy to understand the photocatalytic
degradation process.

4.7.1. Collaborative effect of pH and sunlight irradiation time

Both the pH and sunlight irradiation are important independent variables and can
impart worth able degradation in 2,2-dichlorophenol level. Its 2D contour clearly shows that
maximum photocatalytic degradation of model pollutant 75.6707% achieved at natural pH
and 3 hours irradiation, while 86.36% degradation was achieved at natural pH. It is clear that
photocatalytic degradation depends upon pH and sunlight irradiation time. When the pH was
increased from 1 to 7, i.e. from acid to neutral, there is enhancement observed in
photocatalytic degradation. On other side, when the pH goes beyond neutral region, i.e.
toward basic region, there is detraction observed in photocatalytic degradation process.
Sunlight irradiation is another important factor to determine photocatalytic degradation.
When the sunlight irradiation time was increased, photocatalytic degradation was also
increased. It is because more the sunlight photons absorbed by the photocatalyst, more
photocatalytic degradation was observed. Figure 4.15 clearly depict the collaborative effect
of both on degradation.

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lvi
Figure 4.22. 2D contour and 3D surface for collaborative effect of pH and sunlight
irradiation on photocatalytic degradation of 2,2-dichlorophenol

4.7.2. Collaborative effect of pH and oxidant concentration

pH is an important factor which determine the photocatalytic degradation of

pollutants. When pH raised from acidic to neutral, photocatalytic degradation was improved.
Similarly, this improvement was reversed when pH was raising from neutral to basic region.
It is because photocatalyst works better at neutral pH. At neutral pH, it was able to absorbs
more and more photons to excite its electrons and produce holes to carry out the whole
degradation process. Oxidant is another most important parameter, which oxidize the matter
just like photocatalyst. In other words, it facilitates photocatalyst by improving charge
separations, provides several holes for pollutants to degrade. Figure 4.16 clearly shows that
maximum photocatalytic degradation was observed at pH 7 and oxidant concentration 15
millimolar.

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Figure 4.23. 2D contour and 3D surface for collaborative effect of pH and concentration of
oxidant on photocatalytic degradation of 2,2-dichlorophenol

4.7.3. Collaborative effect of pH and initial concentration of pollutant

Importance of pH is cleared from sections 4.7.1 and 4.7.2., because it effects the
nature of photocatalyts. Some catalysts are working efficiently at acidic pH, some on neutral
pH and some catalysts worked best in basic region. In our study, CaO-CoO works efficiently
at neutral pH, clearly depicts by figure 4.17. Initial concentration of pollutant is another one
important independent variable. Its 2D contour and 3D surface shows that how pH and effect
the highly concentrated solution of pollutant or how the both pH and concentration effect the
photocatalytic degradation phenomenon. It was observed from figure 4.17 that maximum
photocatalytic degradation of 2,2-dichlorophenol (85%) was achieved at pH 7 and when
initial concentration of pollutant is 200 ppm.

lviii
lix
Figure 4.24. 2D contour and 3D surface for collaborative effect of pH and initial
concentration of pollutant on photocatalytic degradation of 2,2-dichlorophenol

4.7.4. Collaborative effect of sunlight irradiation time and oxidant concentration

Sunlight irradiation is important because working of photocatalyts depends upon

energy and wavelength of photons. Sunlight is mega source of photons of all types but
majorly 70% of photons have energy and wavelength in visible region. Photocatalyst make
use of these photons and generate reactive radicals to degrade the pollutant. More the
irradiation time, higher will be the degradation. Oxidant is another reactive reagent and
independent variable which oxidize the water to produce hydroxyl radical and oxidize the
pollutants to low molecular weight substances, in combination with photocatalyst it
facilitates electron hole separations, it facilitates the whole degradation process. Increasing
the concentration of oxidant, there is enhancement in photocatalytic degradation observed.
Figure 4.18 shows that maximum 91% photocatalytic degradation was achieved when the
solution was irradiated for 3 hours at 15 millimolar concentration of oxidant.

lx
lxi
Figure 4.25. 2D contour and 3D surface for collaborative effect of irradiation time and
concentration of oxidant on photocatalytic degradation of 2,2-dichlorophenol

4.7.5. Collaborative effect of sunlight irradiation time and initial concentration of

pollutant

Figure 4.19 shows the collaborative effect of irradiation time and initial concentration
of pollutant. Sunlight radiations contains several photons but especially photons of UV and
Visible light. Photo-catalyts make use of these photons to excite its electrons from valance
band to conduction band. More the photons, more will be the production of electrons and
holes, which in turn stands for higher degradation of pollutant. Initial concentration of
pollutant is another one important independent variable. Figure 4.19 shows that maximum
87% of photocatalytic degradation was achieved when the wastewater was irradiated for 3
hours and when the initial concentration of pollutant is 200 ppm.

lxii
Figure 4.26. 2D contour and 3D surface for collaborative effect of irradiation time and initial
concentration of pollutants on photocatalytic degradation of 2,2-dichlorophenol

4.7.5. Collaborative effect of oxidant concentration and initial concentration of

pollutant

Oxidation of hazardous substances by oxidant is a chemical treatment leads to

detoxification, if oxidant was used in small quantity. In case where oxidant concentration
cross certain concentration threshold, wastewater becomes poisonous. In collaborative effect,
maximum 70% of degradation of pollutants achieved using oxidant. When initial
concentration of pollutants was rises, more and more degradation of pollutants was observed
but when initial concentration was rises to higher level, solution becomes colorful,
degradation was hindered because small percent of light passage. Figure 4.20 represents the
percent degradation of pollutants in 2D and 3D mode.

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lxiv
Figure 4.27. 2D contour and 3D surface for collaborative effect of oxidant and initial
concentration of pollutants on photocatalytic degradation of 2,2-dichlorophenol

4.8. Water quality parameters

Chemical oxygen demand, biological oxygen demand and total organic carbon was
measured in standard solutions of wastewater and solutions of unknown concentrations. The
treatments was repeated two times before and after the analysis to confirm the accuracy of
results.

4.8.1. Chemical oxygen demand (COD)

COD was determined before and after the analysis using digital COD meter
(Lovibond PCCHECKIT COD vireo with Lovibond incubator). For measurement of COD of
wastewater, standard dichromate method was applied, and absorbance was determined using
UV-Visible spectrophotometer. COD was calculated using following formulas

Standard factor = COD of standard KHP(potassium hydrogen phosphate)/absorbance after

incubation (eq. 4.4.)

COD (mg/L) = Standard factor × absorbance after incubation (eq. 4.5.)

Table 4.9. COD of standard solutions, untreated and treated solutions

Sr. No. Samples COD (mg/L)
1 300 ppm 2,2-dichlorophenol
untreated 1538.462
2 200 ppm 2,2-dichlorophenol
untreated 961.5385
3 100 ppm 2,2-dichlorophenol
untreated 625
4 300 ppm untreated effluent 1826.923
5 200 ppm untreated effluent 1365.385
6 100 ppm untreated effluent 1038.462
7 300 ppm 2,2-dichlorophenol
treated 200.9615

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8 200 ppm 2,2-dichlorophenol
treated 169.2308
9 100 ppm 2,2-dichlorophenol
treated 129.8077
10 300 ppm treated effluent 355.7692
11 200 ppm treated effluent 259.6154
12 100 ppm treated effluent 169.2308

Chemical oxygen demand

Before and After
2000
1800
1600
1400
1200
1000
800
600
400
200
0
300 ppm 2,2-dichlorophenol untreated

300 ppm 2,2-dichlorophenol treated

200 ppm 2,2-dichlorophenol untreated

200 ppm 2,2-dichlorophenol treated

100 ppm 2,2-dichlorophenol untreated

100 ppm 2,2-dichlorophenol treated

300 ppm effluent untreated

300 ppm effluent treated

200 ppm effluent untreated

200 ppm effluent treated

100 ppm effluent untreated

100 ppm effluent treated

COD (mg/L) COD (mg/L) COD (mg/L) COD (mg/L) COD (mg/L) COD (mg/L)
Figure 4.28. COD of treated and untreated solutions

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4.8.2. Total organic carbon (TOC)

Total organic carbon is another water quality parameter. Several samples of standard
solutions, untreated and treated solutions were analyzed for TOC and TOC was calculated
using following formulas

Standard Factor = concentration of glucose (mg/L)/ absorbance after incubation

TOC (mg/L) = Standard factor × absorbance after incubation (eq. 4.6.)

TOC for various samples are shown by table 4.10

Table 4.10. TOC of standard solutions, untreated and treated solutions

Sr. No. Samples COD (mg/L)
1 300 ppm 2,2-dichlorophenol
untreated 1278.846
2 200 ppm 2,2-dichlorophenol
untreated 956.7308
3 100 ppm 2,2-dichlorophenol
untreated 682.6923
4 300 ppm untreated effluent 1826.923
5 200 ppm untreated effluent 1592.788
6 100 ppm untreated effluent 1322.596
7 300 ppm 2,2-dichlorophenol
treated 282.6923
210.5769
8 200 ppm 2,2-dichlorophenol
treated 140
9 100 ppm 2,2-dichlorophenol
treated 280
10 300 ppm treated effluent 192.7885
11 200 ppm treated effluent 139.9038
12 100 ppm treated effluent 1278.846

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 Total organic carbon
Before and After
2000

1600

1200

800

400

0
300 ppm 2,2-dichlorophenol untreated

300 ppm 2,2-dichlorophenol treated

200 ppm 2,2-dichlorophenol untreated

200 ppm 2,2-dichlorophenol treated

100 ppm 2,2-dichlorophenol untreated

100 ppm 2,2-dichlorophenol treated

300 ppm effluent untreated

300 ppm effluent treated

200 ppm effluent untreated

200 ppm effluent treated

100 ppm effluent untreated

100 ppm effluent treated

TOC (mg/L) TOC (mg/L) TOC (mg/L) TOC (mg/L) TOC (mg/L) TOC (mg/L)

Figure 4.29. TOC of treated and untreated solutions

4.8.3. Biological oxygen demand (BOD)

BOD of different samples were determined using digital BOD meter and shown in
table 4.11 below.

Table 4.11. BOD of standard solutions, untreated and treated solutions

Sr. No. Samples BOD (mg/L)
1 300 ppm 2,2-dichlorophenol untreated 1086
2 200 ppm 2,2-dichlorophenol untreated 730
3 100 ppm 2,2-dichlorophenol untreated 670
4 300 ppm untreated effluent 1230
5 200 ppm untreated effluent 921

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6 100 ppm untreated effluent 640
7 300 ppm 2,2-dichlorophenol treated 110
8 200 ppm 2,2-dichlorophenol treated 70
9 100 ppm 2,2-dichlorophenol treated 40
10 300 ppm treated effluent 75
11 200 ppm treated effluent 39
12 100 ppm treated effluent 27

Biological oxygen demandBOD (mg/L)

Before and After
1400
1200
1000
800
600
400
200
0
300 ppm 2,2,dichlorophenol untreateed

200 ppm 2,2,dichlorophenol untreateed

100 ppm 2,2,dichlorophenol untreateed

300 ppm 2,2,dichlorophenol treateed

200 ppm 2,2,dichlorophenol treateed

100 ppm 2,2,dichlorophenol treateed

300 ppm effluent untreated

200 ppm effluent untreated

100 ppm effluent untreated

300 ppm effluent treated

200 ppm effluent treated

100 ppm effluent treated

1 2 3 4 5 6 7 8 9 10 11 12
BOD BOD BOD BOD BOD BOD
(mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L)

Figure 4.30. BOD of treated and untreated solutions

CHAPTER 5

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 SUMMARY

This research work is started by powder synthesis of the pure and composite CaO/CoO using
sol-gel method, a cost-effective method to produce powder. cobalt chloride and calcium
chloride were used as precursors while sodium hydroxide was used as precipitating agent.
Water contaminants such as 2,2-dichlorophenol is a carcinogenic pollutant and can be
effectively treated/degraded by the photocatalysis which is an emerging technology in
advanced oxidation process. It provides 99% degradation of pollutants and detoxify the
wastewater for its reuse in agricultural scenario. The nanocomposite CaO/CoO was found the
most effective and efficient material for the pollutant degradation because of its mild reaction
conditions and high photochemical reactivity as compared to other conventional methods
available for wastewater treatment. Therefore, photocatalysis using nanocomposite CaO/CoO
has proved to be an effective alternative route for the chromium reduction. Both the separate
metal oxides and nanocomposite CaO/CoO was characterized by the X-ray diffraction,
scanning electron microscopy and Fourier transform infrared spectroscopy. The
nanocomposite CaO/CoO shows maximum photo-activity to degrade pollutant up to 83%
present in paper mills wastewater at optimized conditions of the pH, irradiation time,
concentration of oxidant and initial concentration of 2,2-dichlorophenol as estimated by UV-
visible spectroscopy. According to UV-Visible spectroscopy, Maximum 97% degradation
was achieved. The optimization of the four independent variables was carried out using
response surface methodology (RSM) which tells us about percentage degradation, providing
ANOVA calculation, lack of fit test and model summery along with the interactive effects of
independent variable. At optimized conditions i.e. 7 pH, 3 hours irradiation time, 25-mile
molar oxidant and 200 ppm initial concentration of pollutants maximum 97% degradation
was observed with only 6.83% CV of the process. Therefore, at these optimized conditions,
paper mill effluent was treated, and more than 80% degradation was observed. Photocatalytic
treatment of wastewater was proved effective and more work can be carried out on this in
term of material engineering to make them more and more light harvester.

lxx