I declare that this thesis entitled One-Pot Electrosynthesis of Silver Oxide deposited

on Egg Shell for Photocatalytic Degradation of Phenolic Compounds is the result of

my own research except as cited in the references. The thesis has not been
accepted for any degree and is not concurrently submitted in candidature of any
other degree.

Signature :
Name : MUHAMMAD YUSOF BIN MOHD ALI
Date :

ii
Special dedication to my family members that always inspire, love and stand beside
me, my supervisor, my teammate, my beloved friends the one who always help me
and who may know me.Thank you so much for all your love and support.

iii
 ACKNOWLEDGMENT

Alhamdulillah praise to Allah S.W. T and thanks to the Allah S.W.T that eases
all the difficulties that I have faced and bring the good health and wellbeing that was
necessary to complete this final year project successfully for the requirement to attain
Bachelor of Chemical Engineering Technology (Hons.) in Process. During two
semesters in order to complete the final project so many people offered me help that
I would like to express my sincere acknowledgements here. First and foremost, my
sincere thanks to my thesis supervisor, Dr. Norzahir Sapawe, who not only gave me
the opportunity to conduct research under his supervision, but also offered me
continuous supervisory, guidance, and support throughout my course of research
work.

Secondly, I would also like to express my grateful acknowledgement to the

UniKL MICET Organic and Chemistry Laboratorys technician Mr. Syukri and Mr.
Fadhil, whom teach me how to conduct UV-Vis and FT-IR. Last but not least, I want
to thank all my colleagues my partner Surendran for their knowledgeable and moral
support Umi Fakriyah, Fahmi, and Faiz. Special thanks to Faiz and Fahmi which also
taught me how read FT-IR table and taught me how to use the facilities in our lab.

iv
 TABLE OF CONTENTS

CHAPTER TITLE PAGE

TITLE PAGES I
ABTRACT II
ABSTRAK III
APPROVAL IV
DECLARATION PAGE V
DEDICATION PAGE VI
ACKNOWLEDGEMENT VII
TABLE OF CONTENT VIII
LIST OF TABLES XI
LIST OF SYMBOLS XIV
LIST OF ABBREVIATIONS XV

1 INTRODUCTION
1.1 Background of Research 1
1.2 Problem Statement and Hypothesis 2
1.3 Objectives of Research 3
1.4 Scopes of Research 3
2 LITERATURE REVIEW
2.1 Introduction 5
2.2 Phenol 5
2.2.1 Classification of Phenol 5
2.2.2 Problem associate with phenolic wastewaters 8
2.2.2.1 Phenol 8
2.2.3 Technologies of phenolic compounds removal 9
2.2.3.1 Adsorption onto Granular activated carbon 9
2.2.3.2 Biological treatments 10
2.2.3.3 Chemical oxidation l 10
2.3 Photocatalysis Degradation of phenol by AOPs 11
2.3.1 Photocatalysis 11

v
 2.3.2 Photocatalysis process parameter 12
2.3.2.1 Light intensity and wavelength 12
2.3.2.2 Contact time 12
2.3.2.3 pH of the solution 13
2.3.2.4 Catalyst dosage 13
2.3.2.5 Initial phenol concentration 14
2.3.2.6 Synthesis technique 14
2.3.3 Kinetics of the photocatalytic process 14
2.3.4 Mechanism degradation phenol by photocatalytic 15
Process
2.4 Photocatalysts Synthesis and Modification 15
2.4.1 Types of Photocatalysts 15
2.4.2 Method of preparation 16
2.4.2.1 Electrochemical process 16
2.4.2.2 Faradays law of electrolysis 16
2.4.3 Photocatalyst supports 17
2.5 Previous Studies 17

3 METHODOLOGY
3.1 Preface
3.2 Chemicals and Materials 21
3.3 Instrumentations 22
3.4 Photocatalysts Preparation Procedures 22
3.4.1 Support preparation 22
3.4.2 Preparation of electrogenerated metal oxide 23
nanoparticles
3.4.3 Preparation of electrogenerated metal 23
oxide supported husk
3.5 Photocatalyst Characterization Procedures 23
3.5.1 Vibration spectroscopy 23
3.5.2 Photocatalytic activity measurement 24
3.6 Photodegradation Performance Evaluations 24
Procedures
3.6.1 Phenolic compounds solution preparation 24
3.6.2 Photodegradation procedure 25
3.6.3 Photodegradation procedure for simulated phenolic 25

vi
 wastewater 25
3.6.4 A simple batch photoreactor system
3.7 Photodegradation Parameters Optimization procedure 26

3.7.1 Parameters evaluations 26

3.7.2 Kinetic experiments 27
3.8 Analytical Procedures 27
3.8.1 Phenol concentration determination 27
3.8.2 Biological oxygen demand 28
3.8.3 Chemical oxygen demand 28

4 RESULTS AND DISSCUSION 29

4.1 Preface 29
4.2 Characterization study 30
4.3 photocatalytic activity test 31
4.3.1 Performance test 32
4.3.2 Effect of pH 33
4.3.3 Effect of metal loading (wt %) 34
4.3.4 Effect of catalyst dosage 35
4.3.5 Effect of initial phenolic concentration 36

4.4 Kinetic study 37

4.5 Investigation on biodegradability 39

5 CONCLUSION
5.0 Preface 40
5.1 Summary 40
5.2 Recommendation 41

REFERENCES 42

vii
 LIST OF TABLE

Tables Titles Pages

2.1 Classification of Phenol and Uses 6
2.2 Types of phenolic compounds and its sector of industry 7
2.3 Previous studies adsorbent used and optimum conditions 18

viii
 LIST OF FIGURE

Figure Titles Pages

3.1 Research Methodology 21

4.1 FTIR analysis of CNS with different weight percent 30

4.2 Analysis result comparison FTIR for CNS before 31
and CNS after
4.3 Performance of CNS and AgO-CNS 32
4.4 Effect of pH water in degradation of phenol 33
4.5 Effect of weight percent on degradation of phenol 34
4.6 Effect of catalyst dosage on degradation of phenol 35
4.7 Effect of initial concentration to degradation of 36
phenol
4.8 Pseudo first-order kinetics model 38
4.9 COD and BOD5 before and after reaction 39
(condition: pH 7, 3wt%, 0.3 g/L, and 10mg/L)

ix
 LIST OF ABBREVIATION

AgO - Silver Oxide

Al2O3 - Aluminium oxide

COD - Chemical oxygen demand

Cl - Calcium

CNS - Coconut Shell

Cr2O3 - Chromium (III) oxide

CNS - Coconut Shell

FeO - Iron (II) oxide

g mol-1 - Gram per mole

g - Gram

g/cm3 - Gram per centimeter cube

g/L - Grams per litre

h - Hour

H2O2 - Hydrogen peroxide

H2SO4 - Sulfuric acid

HCl - Hydrochloric acid

mA cm-2 - Miliampere per centimeter square

mg/L - Miligrams per litre

min - Minute

mL - Mililiter

x
MnO - Manganase oxide

Na2SO4 - Sodium sulfate

NaCl - Sodium Chloride

NaOH - Sodium Hydroxide

nm - Nanometer

Pt - Platinum

S - Sulphur

SiO2 - Silicon dioxide

TiO2 - Titanium dioxide

xi
 LIST OF SYMBOLS

C - Celcius

AAS - Atomic absorption spectroscopy

AOPs - Advanced oxidation processes

BOD - Biological oxygen demand

CI - Colour index

DPV - Differential pulse voltammetry

FT-IR - Fourier transform infrared Spectrocopy

IC - Inorganic carbon

K - Kelvin

KLH - Adsorption equilibrium constant

KR - Reaction rate constant

MPa - Mega pascal

PCDDs - Polychlorinated dibenzodioxins

PCDF - Polychlorinated dibenzofurans

R2 - Correlation coefficient

UV-Vis - Ultraviolet-visible spectroscopy

xii
 CHAPTER 1

INTRODUCTION

1.1 Background of Research

Water is fundamental to maintain all living thing in our planet. Comprising

over 70% of the Earths surface, water is unquestionably the most valuable natural
resource that exists on our planet. Water pollution is a major problem in the global
context; water pollution has been suggested be the leading cause of deaths and
diseases worldwide (Kifferstein, 2009). Despite the fact that we as people know
about this, we disregard it by contaminating our streams, lakes, and seas. Hence, it
creates pollution through water and gave the bad consequences to us and flora and
fauna.

Water pollution can be defined as one or more substances have built up in

water to such an extent that they cause problems for animals or people. Water
pollution can be divided into two categories which is non-point source pollution and
point source pollution. Non-point source pollution refers to diffuse contamination that
does not come from a single discrete source (Woodford, 2009). Contaminated storm
water washed off from parking lots, streets and interstates, called urban overflow, is
here and there included under the classification of non-point source contamination.
Emerging contaminant from non-point sources represents a greater part of the
contaminants to streams and lakes.

Point source pollution refers to contaminants that enter a waterway through a

discrete passage, such as a pipe or ditch (Woodford, 2009). Examples of sources in
this category are sewage treatment plant, a factory, or a city storm drain. When point-
source pollution enters the environment, the place most affected is usually the area
directly around the source. Point source pollution is easier to control because the
authorities can identify which factory or plant responsible for the pollution. Sometimes
pollution that enters the environment in one place has an effect hundreds or even
thousands of miles away.

1
 Phenol and its derivative compounds are considered to be dangerous organic
compounds for the environment. Discharging of phenolic compound effluent into the
natural stream and rivers can cause several problems such as toxicity to aquatic life,
so water that contains phenolic compounds must be treated first before being
discharged. This industry consumes a large quantity of water and produces large
volumes of wastewater from different steps of end products or finishing process.
Discharging of phenolic compounds effluent into the natural stream and rivers can
cause several problems such as toxicity to aquatic life, so water that contains
phenolic compound must be treated first before being discharged.

There are various techniques to treat wastewater from industries that

generate phenolic compounds as effluent. Phenolic compounds wastewater can be
treated by using conventional methods which either treats the wastewater using
physical or chemical processes such as coagulation, flocculation, biosorption,
ultrafiltration, and oxidation (Nagda et al., 2007). However, researchers found that
adsorption using activated carbons is the preferable method and gives the best
results due to its versatility. Although activated carbon is preferred sorbent, its
widespread use is constrained due to high cost. Hence, the new technique is studied
in order to create new catalyst that simple and low cost.

1.2 Problem Statement and Hypothesis

Phenol and its derivative compounds can cause hazards to the environment
can also arise due to the presences of large number of contaminants such as toxic
organic residues, acids, bases, and inorganic contaminants. Phenolic compounds
are not easily biodegradable and often not fully removed in conventional biological
plants. Therefore, a phenolic compound removal from wastewater is very important in
order to solve the problems linked to phenolic compounds wastewater.

Generally, various techniques have been examined and recognized for the
removal of phenolic compounds from wastewater. The methods normally used is
electro-kinetic coagulation, coagulation, precipitation, nanofiltration, advanced
chemical oxidation, electrochemical oxidation, supported liquid membrane, liquid-
liquid extraction, biological process, adsorption and photo-catalytic degradation.

2
 Activated carbon is the most widely used adsorbent with a highly great
demand due to its large surface area, high adsorption capacity, micro-porous
structure etc. However, this type of adsorbent is proved to be uneconomical due to
the high cost and additional cost in regeneration (Cicek et al., 2006).

In the recent years, numerous approaches have been studied for the
development of cheaper and effective absorbents from agricultural wastes. The
release of phenolic compound assisted in the receiving environmental problems due
to various phenolic compounds assisted in the receiving water bodies. In present
studies, photocatalytic degradation is one of the most efficient methods to remove
phenolic compounds from wastewater due to its versatility characteristics such as low
cost, simple design, easy to operate and insensitive to toxic substance. Hence, this
study will introduce and explain about photocatalytic degradation in order to prove
the efficiency of photocatalytic degradation.

1.3 Objectives of Research

i. To electro synthesize of silver oxide deposited on Cocos Nucifera (coconut)

shell (CNS) catalyst using electrochemical method.
ii. To study the physicochemical properties of AgO/CNS catalyst.
iii. To study the potential of AgO/CNS catalyst.
iv. To study the kinetic and mechanism of photo degradation process.

1.4 Scope of Research

The AgO/CNS will be prepared by the electrochemical method in presence of

water in a normal compartment cell fitted with cathode and anode plate at constant
current density of 120 mA cm-2 under normal atmosphere at 273 K. The required
weight percentage and the time required for electrolysis completion was calculated
based on Faradays law of electrolysis.
The characterization will be investigated under physiochemical technique
such as Fourier Transform Infrared (FT-IR) to obtain information on the vibration of
any species through which the beam passes as well as determination of functional
group presence.

3
 The potential of the photo catalyst (AgO/CNS) in degradation phenolic
compound from aqueous solution using batch system under visible light radiation at
room temperature will be measured under various parameters such as effect of light
radiation at room temperature will be measured under various parameters such as
effect of light source, effect of contact time (1, 3, 5, and 7 h), effect of pH (3, 5, 7, 9,
11) effect of catalyst dosage (0.10, 0.20, 0.30, 0.40, 0.50 g/L) and effect of initial
concentration (10, 20, 30, 50, 70, 100 mg/L). The degradation of phenolic
compounds is then will evaluated by UV-Vis.

The kinetics study will be employed and rationalized in terms of the Langmuir-
Hinshelwood model to obtain to obtain the reaction rate constant (KR) and the
adsorption equilibrium constant (KLH). The mechanism of photo degradation process
will also be proposed. The reusability and mineralization of degradation of phenolic
compounds will measure using chemical oxygen demand (COD) and biological
oxygen demand (BOD).

4
 CHAPTER 2

LITERATURE REVIEW

2.1 Introduction

In industry, many different processes are used and almost all of them
generate wastewater. The effluents resulting from these processes differ greatly in
composition, due to differences in processes, used fabrics and machinery. Various
industries use phenolic compounds extensively in different operations such as textile,
paper, plastic, leather etc. In Asia Pacific petroleum refinery and agricultures is the
most usage of phenolic compounds (Basha et al., 2010).

2.2 Phenols

Phenols are aromatic alcohols that have an-OH group bonded to aryl ring.
They are more noted as water pollutants than air pollutants. Phenol and derivatives
compound is among the top 50 chemicals produced annually. It is most commonly
used in the manufacture of resins and polymer, such as bake lite, a phenol-
formaldehyde copolymer (Rahul & Sachin, 2014). Phenols are produced by the
pyrolysis of coal and are major by-products of coking. Thus, in local situations
involving coal coking and similar operations, phenols can be troublesome air
pollutants.

2.2.1 Classification of Phenols

There is various type of phenol. Each type of phenol have their own uses, the
uses of phenol are shown in Table 2.1. Phenol has been in production since the
1860s. Antiseptic was one of the early uses of phenol. Towards the end of the 19th
century, industrial scientists found new uses for phenol in the synthesis of dyes,

5
aspirin, and one of the first high explosives, picric acid. As early as 1872, it was
found that phenol could be condensed with aldehydes (for example methanal) to
make resinous compounds, a process still in use today. Phenol-methanal
(formaldehyde) resins are the basis of the oldest plastics, and are still used to make
low cost thermosetting plastics such as melamine and bake lite, used in electrical
equipment. These resins are also used extensively as bonding agents in
manufacturing wood products such as plywood and MDF (Molva, 2004).

Table 2.1: Classification of phenol and uses (Molva, 2004)

Types End uses/product
BIsphenol A Used to produce epoxy, resins for paints
coatings,and in polycarbonate plastics,
familiar in CDs and domestic electrical
appliances.
Carpolactam Caprolactam is used in the manufacture of
nylon and polyamide plastics for a wide
range of products, including carpets,
clothing, fishing nets, molded components
and packaging.
Phenlamine (anline) Used as an antioxidant in rubber
manufacture, and as an intermediate in
herbicides, dyes and pigments, and
pharmaceutical is used to make
isocyanates for the production of
polyurethanes, with a wide range of uses
from paints and adhesives to expanded
foam cushions.
Chloro-phenols Used in medical antiseptics and
bactericides such as TCP and Dettol. Also
used in fungicides for timber preservation
and as additives to inhibit microbial growth
in many products.
Salicylic acid Use for production of aspirin and other
pharmaceuticals.

6
 It should be noted each classes of phenol has their own properties, structure
and its way of bonding. Instead of classify the phenol according their uses. There is
several ways for phenol classification. As an example from the previous, according
to Molva, phenol and its compound can be divided into class according the sector of
industries that used phenol in their process. Table 2.2 shows the type of phenolic
compound used in sector of industry in Turkey.

Table 2.2: Types of phenolic compounds and its sector of industry (Molva, 2004)
Sector Phenolic compounds
Textile Phenol, 2, 4, 6-trichlorophenol, pentachlorophenol, benzene,1,1-
dichloroethylene, 1,1-dichloroethane, chloroform,
1, 1,-trichloroethane, trichloroasetilene, Tetrachloroethylene,
vinylchloride, toluene, ethylbenzene.
Leather Phenol, 2,4,6-trichlorophenol, pentachlorophenol, 1,1-
dichloroethylene, chloroform, 1,1-trichloroethane, trichloroasetilene,
tetrachloroethylene, benzene, toluene, ethylbenzene.
Coal & Phenol, benzene, toluene
petroleum
Tobacco Phenol and phenolic compounds
Wood 2,4,6-trichlorophenol, pentachlorophenol, 1,1,1-trichloroethane,
benzene, toluene, ethylbenzene
Paper Phenol, 2,4,6-trichlorophenol, pentachlorophenol, Chloroform,
1,1,1-trichloroethane.
Printing Phenol, pentachlorophenol, 1,1-dichloroethylene, chloroform, 1,1,1-
trichloroethane, trichloroasetilene, tetrachloroethylene, benzene,
toluene
Plastic Phenol, ethylbenzene, 1,2-dichloroethane,toluene
Non-metal Ethylbenzene, pentachlorophenol, toluene, benzene, 1,2-
industry dichloroethylene, 1,1-dichloroethane, chloroform, 1,1,1-
trichloroethane, hexachloroethane, trichloroasetilene.
Metal industry Phenol, 2,4,6-trichlorophenol, pentachlorophenol, 1,1-
dichloroethylene, 1,1-dichloroethane, 1,1,1-trichloroethane,
trichloroasetilene, tetrachloroethylene, benzene, toluene,
ethylbenzene.

7
Sector Phenolic Compound
Nonferrous Ethylbenzene, pentachlorophenol, toluene, benzene, 1,2-
dichloroethylene, 1,1-dichloroethane, chloroform, 1,1,1-
trichloroethane, hexachloroethane, Trichloroasetilene
Electricity 1,2-dichloroethylene, chloroform, trichloroasetilene,
tetrachloroethylene, 1,1,1-trichloroethane,1,2-dichloroethane
Medical Pentachlorophenol, 1,1-dichloroethylene, 1,1,1-trichloroasetilene,
tetrachloroethylene, benzene, toluene, 1,2-dichloroethane
Motor Phenol, 2,4,6-trichlorophenol, pentachlorophenol, benzene, 1,1-
transportation dichloroethylene, 1,1-dichloroethane, chloroform, 1,1,1-
trichloroethane, trichloroasetilene, tetrachloroethylene, vinyl
chloride, toluene, ethylbenzene
Motor vehicles Phenol, pentachlorophenol, benzene, toluene, chloroform, trans
1,2-dichloroethylene, 1,2-dichloroethane, 1,1,1-trichloroethane,
trichloroasetilene, tetrachloroethylene, ethylbenzene
Furniture Phenol, Pentachlorophenol, 2,4,6 trichlorophenol, chloroform, 1,1,1-
trichloroethane, benzene, toluene, ethylbenzene.

2.2.2 Problem associate with phenolic compound in wastewater

Phenol and derivatives of phenol is the most current organic water pollutants,
because of their varieties of applications and high production volumes. Phenol is an
aromatic alcohol with an acidic proton; it is soluble in water, highly mobile in surface
and ground waters and widely disposed from agricultural and industrial sources
(Barakat et al., 2005). Due to a wide variety of uses of phenolic compounds, their
incidence in source waters is very common especially in areas near human
settlements.

2.2.2.1 Phenol

Phenol is toxic even at low concentrations, and its presence in natural waters
can lead to the formation of substituted compounds during disinfection and oxidation
processes (Busca et al., 2008). Even at low concentrations, these organic pollutants
are a major health risk due to their very high endocrine disrupting potency and Geno
toxicity (Ahmed et al, 2010).

8
 Moreover, the toxic weak acid causes an unpleasant taste and colour in water
(Pdkoscielny & Laszlo, 2007). The major sources to the phenolic compounds are
wastewaters from paint, pesticide, coal conversion, polymeric resin and
petrochemicals industries. Globally, annual production rate of phenol is estimated at
6 million ton.

2.2.3 Technologies of phenolic compound removal

Nowdays, in Malaysia water pollution had recently caught the public attention.
The increasing of polluted river makes the impact and caught public attention. Kelang
River is one of the examples of polluted source of water.

In the past decade, the technologies are not yet discover to treat this kind of
pollution. These days, there are several methods of wastewater treatments that
already studies and apply. Methods of waste water treatment can be divided into
three categories which is physical treatment, biological treatment and chemical
treatment. Each of these categories has their own advantages and disadvantages.
The technologies can be chosen according to suitability of compound of wastewater
to be treated and depends on the type of industrial waste.

2.2.3.1 Adsorption onto granular activated carbon

Adsorption on activated carbon is the most typical procedure in order to

discharge organic material. Activated carbon is defined as a product that is made
from carbonaceous material such as wood, pulp-mill char, peat and lignite. The
efficiency is these materials are measured by its massive surface. By burning the raw
material anaerobically below 600C, carbon can be made which then is continued
with an activation step where it oxidizes partially. At 600C - 700C, Carbon dioxide
may act as an oxidizing agent as it could be oxidized at 800 C- 900C by water
(Molva, 2004). The reactions for oxidation can be referred below:
CO2 2CO (2.1)

H2O + C H2O + CO (2.2)

9
 These reactions lead to porosity, maximizing its surface area and isolate the
C atoms in arrangement that attracts organic compounds. Activated carbon can
appeared in two general types, which are granulated and powdered activated carbon.
It differs by the size of particle in diameter. Granular carbon has been extensively
used for water treatment, which can be used in fixed bed.

2.2.3.2 Biological Treatment

Phenolic compounds are known to be complicated to discharge by treatment

processes biologically used to their resistance of biodegradation (Molva, 2004).
However there is a treatment in which phenol can be eliminated from wastewater,
such as in the biological process (Molva 2004).

Biological treatment consists of the activity of living microorganism. Different

kinds of microorganism take the waste material as food and change it into incomplex
substances through natural metabolic process. Usually, petroleum industry generates
organic waste that can be treated in a biological way. As for the traditional biological
treatment systems, land farming and land treatment can take place by combining the
waste with surface soil, where microorganisms and nutrient can also be mixed, as
desired. The toxic material is divided between organic and inorganic, where organic
materials is degraded in a biological way whereas inorganic materials are treated by
adsorbing it in the soil (Molva, 2004). For biological treatment techniques, up to 500
mg/L of phenol concentration is accounted as acceptable (Metcalf & Eddy, 2003).

2.2.3.4 Chemical Oxidation

It has been proclaimed that chemical oxidation by ozone and chlorine is

efficient for some toxic organic, which in this study is phenol. By using ozone as an
oxidant reagent, 48% of phenolic compound can be discharged at pH 7 with a
concentration at 1000 mg/L. There are many factors that control the efficiency of the
oxidation process such as the ozone reactions with target compounds, reactivity rate,
the demand, for ozone to reach a certain degree of treatment, the area of irregular
striping due to the dispersion of ozone, and other treatment for parameters such as
pH and temperature. For example, in ozone treatment of phenol, treatment proceeds
at pH 11 at a rate approximately twice as fast as at pH 7 (Metcalf & Eddy, 2003).

10
2.3 Photocatalysis of Degradation Phenolic Compound by AOPs

AOP is a method that is applied in order to oxidize complex organic

components which are mainly originated found in wastewater. Biologically, these
organic components are hard to degrade into complex end products. Nitrogen or
phosphorus is mainly taken for the conversion of ammonia to nitrate as well as to
give rise to its efficiency of the plant at 85 95 % of pollutants discharge. Hydroxyl
free radical takes part in generating and making itself as a strong oxidant to eliminate
compounds which are unable to oxidize through conventional oxidant. This process
is considered operative due to use of modern technology for colour degradation.

Fentons oxidation is the most typical process that is being used in AOP. The
treatment for industrial wastes that contain varieties of organic compounds is usually
treated with Fentons reagent. Other that wastewater, this process can also be used
on sludge, or contaminated soils with its negative impacts such as destruction from
organic pollutant, reduction due to toxicity, odor and colour degradation. The free
radical of hydroxide that is produced from this process will respond by removing the
colour from the aqueous solution.

2.3.1 Photocatalysis

Photocatalysis is an acceleration of photoreactions by presence of a

catalyst. The semiconductor photocatalytic process is reported to occur due to the
adsorption of a photon of energy equal to or greater than the semiconductor bandgap
energy, which then leads to the promotion of an electron (e-) from the valence band
to the conduction band, while creating a hole (h+) in the valence band.

The photocatalytic detoxification of wastewater is a process that combines

heterogeneous catalysis with solar technologies. Semiconductor Photocatalysis,
recently focus on Ti02, has been applied to a variety of problems of environmental
interest in addition to water and air purification.

The photo-produced holes and electrons may migrate to the surface and are
available for oxidation and reduction reactions respectively or may be combining to
decrease the photocatalytic efficiency, as shown in the reaction 2.1 and 2.2 below.

11
hV + Ti0s h+ + e- (2.3)

h++ e - heat (2.4)

2.3.2 Photocatalysis process parameter

This part will elaborate the process of parameter for the experiment. In order
to achieve the objective several parameters have been set to know the effect of
photocatalytic degradation to remove phenolic compound in wastewater.

2.3.2.1 Light intensity and wavelength

In this research one of vital parameter for degradation of phenol in photo

catalytic process is the intensity of the fluorescent light irradiation. Based on previous
study, increment of irradiation intensity of black light lamps helps to enhance the
degradation of phenolic compound. The enhancement happen because more
radicals fall on the catalyst and more OH- were produced, when there is high
intensity of light that involving more radiation.

This will lead to an increasing of the degradation of phenolic compound

(Chanataworm et al. 2012). There are more photons at higher light intensity thus the
chances of photon activation on the photo catalyst surface also increase.

2.3.2.2 Contact time

Experiments on contact time were conducted by agitating with 50 ml of 250

mg/L phenolic compounds solution in different conical flasks with 0.2 g of coconut
shell at optimum pH. These studies need to be done at constant rpm and at room
temperature. Samples were analyzed for reduction in absorbance at different time
intervals of 1, 3, 5, and 7 h using UV-Vis (Chanataworm et al., 2012).

12
2.3.2.3 PH of the solution

Photo catalytic efficiency is well known to strongly depend on the pH of the

solution during the degradation process of waste water. PH of the solution is the
important parameter for metal oxides to act as photo catalysts, since it influences the
surface charge properties of the photo catalyst. In addition, ph is important because it
influence the rate of photo catalytic process. However, due to the multiple roles
including electrostatic interactions between the catalyst surface, solvent molecules
and substrate and charged radicals formed during the reaction, it makes the
interpretation of the effect of pH more difficult (Sapawe et al., 2012).

2.3.2.4 Catalyst dosage

Amount of photo catalyst is main factor of degrading efficiency. Theoretically,

the rate of degradation would be increased with the increase of catalyst dosage.
Despite, when the dosage exceeds the optimum limit the removal efficiency would be
decreased (Sapawe et al., 2012). Turbidity of solution that hindered the transmission
light might happen if amount of catalyst keep increasing cause of lack efficiency. The
amount of catalyst that will be tested is 0.10, 0.20, 0.30, 0.40 and 0.50 g/L.

2.3.2.5 Initial concentration

The effect of initial concentration also must be determined in this research.

The initial concentration is important aspects that need to be studied because the
photocatalytic reaction rate depends on the substrate concentration. Theoretically,
when the initial concentration of phenolic compound increase while, the efficiency will
be vice-versa. As the initial concentration of phenolic compound increased, the
solution colour will be more intense and the path length of the photons entering the
solution will be decreased, thereby fewer photons could reach the photocatalyst
surface (Chanataworm et al., 2012). Therefore, the degradation efficiency will be
reducing.

13
2.3.2.6 Synthesis Technique

Photocatalyst can be synthesized using various mechanisms according

previous study. The 1 wt% EGZrO2/HY catalyst will be prepared using DMF solution
(10 mL) which containing of 0.1 M TEAP, electrolyzed in the presence of a
napthelene mediator (6 mmol) and HY zeolite (1.5 g) in a normal one-compartment
cell fitted with a Pt plate cathode (22 cm2) and Ago plate anode (24 cm2) at a
constant current density of 120 mA/cm2 under a nitrogen atmosphere at 273 K. After
electrolysis, the mixture was impregnated, oven dried overnight at378 K, and
calcined at 823 K for 3 h to yield a white powder (1 wt% EGZro2), therefore ready for
characterization and photocatalytic testing. The required weight percent of the
EGZro2 supported on HY and time required for complete electrolysis was calculated
based on faradays law of electrolysis.

2.3.3 Kinetics of the photocatalytic process

In general, the influence of the initial concentration of the solution on the

photocatalytic degradation rate of the most organic compounds is described by
pseudo first kinetics, which is corresponding to the Langmuir-Hinshelwood model
(Sapawe et al., 2012). The equation for the rate of photodegradation of phenolic
compound can be expressed by

= + (2.5)

Where K is the pseudo first-order rate, and C0 and Ct are the concentrations of
phenol at the start and at time t, respectively. The integration of equation above
yields the equations below.

= (2.6)

The straight line (direct proportional graph) from a plot of ln (Co/Ct) as a

function of time would follows a pseudo first-order kinetics model, which is
corresponding to the Langmuir-Hinshelwood model. A lower concentration of phenol
results in higher first-order rate constant, demonstrating the suitability of the
photocatalytic process for phenolic compound concentrations.

14
2.3.4 Mechanism degradation phenol by photocatalytic process

Currently, there is a lot of mechanism degradation of phenolic compound is

being studied. One of the mechanisms applied in degradation of phenolic compound
is the electrical method. In this process, two types of plates will be synthesized in
medium such as deionized water for the further photocatalytic process. Next is
Fentonlike mechanism. OH radicals will be generated by using AgO and UV light so
it can occur without the addition of hydrogen peroxide (Rahmani et al., 2010).
Enzymatic mechanism also will be used in degradation of phenolic compounds
process.

2.4 Photocatalyst synthesis and modification

A photocatalyst is defined as substance which is activated by adsorbing a

photon. The catalyst is capable of accelerating a reaction without being consumed.
These substances are invariably semiconductors. Semiconducting oxide
photocatalyst have been increasingly focused in recent years due to their potential
applications in solar energy conversion and environmental purification (Rajabi &
Farsi, 2015). Semiconductor heterogeneous photocatalyst has enormous potential to
treat organic contaminants in water and air.

2.4.1 Type of photocatalyst

Various numbers of solids can be opted as photocatalyst. The most suitable

photocatalyst is silver oxide due to their photocorrosion resistance and wide band
gap energies.

AgO can be considered as the most effective photocatalyst because it is cost-

effective, thermally stable, on-toxic, chemically & biologically inert and is capable of
promoting oxidation of organic compounds. AgO has also been widely used in water
and wastewater treatment.

15
2.4.2 Method of preparation

This part will explain the preparation of method. This study consists of two
methods which are electrochemical and faradays law of electrolysis. The selection of
material for electrochemical will be stated in 2.4.2.1.

2.4.2.1 Electrochemical process

Electrochemical reaction is any process either caused or accompanied by the

passage of an electric current and involving the transfer of electron between two
substances (liquid and solid). In this study, two types of metals will be use which is
silver plate and platinum plate.

The preparation method for a silver plate and platinum plate by a simple and
rapid electrochemical process, which exhibited high photoactivity it the degradation of
phenolic compounds. The nano sized metal oxides were found to play important
roles in the enhancement of the reaction (Sapawe, 2013).

2.4.2.2 Faradays law of electrolysis

The chemical deposition due to the flow of current through electrolytes

directly proportional to the quantity of electricity (coulombs) passed through it.

, = = . (2.7)

Where Z is a constant of proportionality and is known as electrochemical equivalent

of the substance.

When Q=1 in the above equation so, Z = m which is implies that

electrochemical equivalent of any substances is the amount of the substance
deposited on passing of 1 coulomb through its solution. This constant of passing of
electrochemical equivalent is generally expressed in terms of milligram per coulomb
or kilogram per coulomb (Faradays First Law of Electrolysis).

16
2.4.3 Photocatalyst supports

There are various kinds of materials that can support the catalyst for the
degradation of phenolic compounds. The medium that will be used in this research
works is coconut shell (CNS).

2.5 Previous Study

Result that gained from the previous study has been reviewed, compared and
tabulated into a table. Based on the table, it showed that EGZrO2-EGZnOHY is the
best materials as photocatalyst since it has highest percentage of removal. The
removal of phenolic compounds depends on the situation and conditions of the
compound and amount of the photocatalyst.

Table 2.3 Previous studies adsorbent use and optimum conditions

No Photocatalyst Optimum Conditions & Efficiency Reference
1 EGZrO2- pH:7 Sunil et al., 2013.
EGZnOHY Time:2 h
Efficiency: 99.7% phenolic
compounds were removed
2 Tio2 Ag+ pH:7 Wing, 2007.
Ag+ - Tio2 Time:6 h
Efficiency: 96% was degraded
Initial concentration= 0.01mg/L
3 Zno pH:9 Kreufu, 2012.
nanoparticles Time: 4 h
Efficiency: 97% of phenols have
been degraded
4 Ag Zno Dosage = 0.4g/L Udom, 2014.
Nanowires Irradiation times = 4 h
Efficiency: About 96% of dyes
remove

17
No Photocatalyst Optimum Conditions & Efficiency Reference
5 Tio2 Dosage:2.0 g/L Naeem & Feng, 2008
pH = 5
Initial concentration= 35 mg/L
Efficiency: 94.5 % of phenol has
been removed.
6 UV/TiO2/H2O2 Time: 10 s Zhang et al., 2013
Efficiency: 98 % was degraded
Initial Concentration:20mg/L
7 Tio2 Dosage:5.0g/L Bamuza, 2014
Phenol = 100mg/L
of phenol 90% degrade after 15 min

8 Coconut Coir Dosage: 0.05 g Etim et al., 2012

pH= 6
Time:
Efficiency: 80% of were degraded
9 TIO2 pH : 6.8 Giwa et al.,2012
Nanoparticles Time: 4 h
Efficiency: 92 % of phenol were
degraded
initial concentration:50 g/L
10 ZnO/SnO2 pH: 12 Chiang and lin.,2013
Time: 4 h
Efficiency: 96 % of phenol were
remove

18
 CHAPTER 3

METHODOLOGY

3.1 Preface

This chapter consists of seven different parts. The first part covers the
particular of the chemical and the materials that will be used in the recent studies.
The equipment and apparatus are under the instrumentation part which is employed
during the handling of the research. Next is the description for the preparation of
photocatalyst and the characterization of the photocatalyst. After that, the procedures
of photodegradation performance is evaluate and lastly, the analytical procedure.
The photocatalyst is used in degradation of phenolic compound in aqueous solution.

19
 Characterization of the synthesized catalysts
The physico-chemical property of the catalysts will studied using
FT-IR.

Photocatalytic activity testing

The photoactivity of the catalysts will tested on removal ofphenolic
compounds under various parameters such as effect of pH,
catalyst dosage, and initial phenol concentration

Analysis
The concentration of phenol will determined using UV-Vis

Study the mechanism of synthesis of catalysts and kinetics

modelling of the photocatalyst degradation
The process by which a photochemical alteration occurs in one
molecular entity as a result of initial absorption of radiation by
another molecular entity. The kinetics pseudo first-order
rationalized Langmuir-Hinshelwood model will achieved and
mineralization was measured with COD, TOC, and BOD5
analyses.

Figure 3.1 Research Methodology

20
3.2 Chemicals and Materials

The chemicals used are ethanol from HmbG Chemical; sodium hydroxide
(Naoh), hydrochloric acid (HCL), phenol and its derivatives were purchased from
QReCTM. Platinum (Pt) and Silver (Ag) plate cell was obtained from Nilaco Metal,
Japan (>99.9% purity). All of the reagents were in analytical grade and were used as
received. Deionized water was used for the preparation of pH solution with
adjustment using 0.1 M HCL and Naoh solution (Sapawe, 2014).

3.3 Instrumentations

The catalyst needed is prepared using one pot of electrolysis supported with
Cocos Nucifera (coconut) shell (CNS). For the next step, the catalyst is dry in the
oven overnight and calcined using a muffle furnace (B180 Naberthem). The prepared
catalyst were subjected to Fourier transform infrared (FT-IR) (Nicolet is 10 FT-IR)
spectrometer).

In order to measure the absorbance of degrading phenol, need to be monitor.

The mineralization of degradation of phenolic compounds is measure using chemical
oxygen demand (COD) (HACH DR4000 and biological oxygen demand (BOD)b(YSI
model33).

3.4 Photocatalyst Preparation Procedures

In this part, procedures of photocatalyst preparation consist of preparation of

support, preparation of electrogenerated metal oxide nanoparticle and preparation of
electrogenerated silver oxide supported coconut shells.

3.4.1 Support Preparation

For the support preparation, 5 -10 pieces of Cocos Nucifera (coconut) shell
(NCS) are needed. The main procedure is to separate three part of coconut to gained
the shell. The first part is the husk, the husks are peeled from the coconut then the
coconut is cut into two sections in order to remove the copra from the shell. The shell

21
is then washed with tap waters and dried into the oven at 60C for 24hours. The dried
coconut shell will be blend using blender until it turns to powder. The weight
estimation of coconut shell powder needed is about 200 300 g.

3.4.2 Preparation of Electrogenerated metal oxide nanoparticles

A deionized water was electrolyzed in a normal one-compartment cell fitted

with a Pt plate cathode (22 cm2) and Ag plate anode (22 cm2) at 120 mA/cm2 of
constant current density under normal atmosphere at 273 K (Sapawe et al.,2013).

3.4.3 Preparation of electrogenerated metal oxide supported shell

The coconut shell powder will mixed with AgO that generated by
electrochemical by in-situ approach. The bare AgO will collect in order to compare
the behavior of bare and modified silver oxide towards degradation of phenolic
compound.

3.5 Photocatalyst Characterization Procedures

The physic-chemical property of the catalysts is determined by Fourier

transforms infrared spectroscopy (FT-IR) and Ultraviolet-visible spectrophotometry
(UV-Vis).

3.5.1 Vibration spectroscopy

Spectroscopic information on the vibration of species formed was examined

by Fourier transform infrared spectroscopy (FT-IR) (Nicolet iS10 FT-IR Spectrometer)
in the range 4004000 cm1. The functional groups of the catalyst were determined
using KBr pellet technique. The catalyst was grounded into powder thoroughly with
KBr at approximately 1 to 3% by weight before it was pressed in hydraulic press (8
tons) to form a thin pellet. The spectra were recorded at room temperature with a
spectral resolution of 8 cm1 and accumulation of 5 scans in open beam air
background.

22
3.5.2 Photocatalyst activity measurement

Prepared catalyst will be test for their activity of photocatalyst by degrading

the phenolic compound solutions. The photocatalytic activity of the prepared
catalysts was tested for the degrading of phenol solutions. An amount of 0.375 g/L
catalyst was dispersed in 200 mL of 10 mg/L phenolic solution. The adsorption-
desorption equilibrium was achieved under dark conditions after 2 h, and the mixture
was irradiated at room temperature for 6 h with constant stirring using a fluorescent
light. The distance between the light and the reaction vessel was 15 cm. At specific
time intervals, 2.5 mL of the sample solution was withdrawn and centrifuged (SIGMA
3-16 Centrifuge 100 to 14 500 rpm) prior measurements of the phenolic compounds
concentration by a Ultraviolet-visible spectrophotometry (UV-Vis).

3.6 Photodegradation performance Evaluations Procedures

In this part, its cover the preparation of phenolic compound solution,

procedure of photocatalyst degradation activity, and procedure for conducting
photocatalyst degradation of simulated phenolic compounds.

3.6.1 Phenolic compound solution preparation

The preparation of phenol solution was started by preparing the pH water.

The 1.5 L distilled water was placed in the beaker followed by continuous stirring by
using a magnetic stirrer. The hydrochloric acid (0.1 M HCl) was added in the water
to decrease the pH of water until the desired pH was obtained. On the other hand,
sodium hydroxide (NaOH) was used to increase the pH of the solution. The 0.01 g of
phenol and 2, 4, 6-trichlrophenol was placed into separate beaker followed by
addition of pH solution. Then, the beaker was sonicated to phenolic compound with
the solution. The concentrated phenol and 2, 4, 6-trichlrophenol solution was poured
into the 1 L volumetric flask. The step was repeated until phenol and 2, 4, 6-
trichlrophenol powder was well dissolved before adding the pH solution until marked
level. Lastly, the phenol solution was sonicated for 20 min to ensure the solution was
well-dissolved. The purity of prepared phenol and 2, 4, 6-trichlrophenol solution is
expected to be 100 %.

23
3.6.2 Photocatalyst degradation procedure

To know the photo catalytic activity of prepared catalyst, the catalyst will be
tested by degrading phenolic solution. The catalyst will be dispersed in 200 mL of 10
mg L-1 aqueous solution of phenolic compound. The solution will be stirred using
magnetic stirrer about 2 h to remove the adsorption effect. The solution will be
exposed to irradiation by fluorescent lamp with distance with approximately 15 cm.
The samples will be taken and treated in the same manner for every 15 min for 2 h
and every 30 min for 4 h. The sample will be centrifuged using centrifuge at 75,000
rpm for 10min. After the centrifuge, the concentration of phenolic compound in the
sample solution will be determined by measuring its absorbance at 664 nm and
phenol at 464 nm Ultraviolet-visible spectrophotometry (UV-Vis).

3.6.3 Photocatalyst degradation procedure for simulated phenolic wastewater

The simulated phenolic compound is prepared by using phenol and its

derivative compound. The stock of solution for phenolic compound is prepared with
the initial two types of phenolic compounds which are phenol and 2, 4, 6,-
trichlrophenol. The stock solutions of the phenolic compound were prepared with the
initial concentration each of the compound was 0.01 g/L. The preparation method of
the phenolic compound solution followed the step of phenol solution preparation.
The stock solutions of the phenolic compounds were mixed. The mixed phenolic
compounds solution was sonicated for 20 min to ensure the solution was well-
dissolved. The analysis of the results was followed to the previous procedure.

3.6.4 A simple batch photoreactor system

A simple batch of photo reactor system containing fluorescent lamp (Philips

Lifemax TLD 18W/54 daylight, 13000 h, 6200 K, 280-315 nm emission) and magnetic
stirrer will be used for testing the photo catalytic activity by the catalyst. The light
source is put approximately 15 cm above the solution. The photo catalytic
experiments were performed in batches consisting of 200 mL of Pyrex conical flask
place on the mechanical stirrer to uniformly disperse the catalyst into the solutions.
The photo catalytic is conducted in a box to increase the light radiation. In addition,
the aluminium foil will be used to wrap the internal box because it can help to reach

24
the maximum exposure for sample radiation when light radiation can reflect back into
the solution. The temperature was measure using the thermometer that place inside
the Pyrex conical flask.

3.7 Photodegradation Parameters Optimization Procedures

These parts cover, the parameters in evaluations, which is optimization by

response surface methodology and kinetic experiments. The photo degradation
activity will be optimized by using try and error method. This method will be done
under various parameters such as light intensity, contact time, pH, catalyst dosage,
and initial phenolic compound concentration.

3.7.1 Parameters and evaluation

The potential of the photo catalyst (AgO/CNS) in degradation

phenolic compound from aqueous solution using batch system under visible light
radiation at room temperature will be measured under various parameters such as
effect of light radiation at room temperature will be measured under various
parameters such as effect of light source, effect of contact time (1,3,5, and 7 hrs),
effect of pH (3,5,7,911), effect of catalyst dosage (0.10,0.20,0.30,0.40,0.50 g/L) and
effect of initial concentration (10,20,30,50,70,100 mg/L). The degradation of phenolic
compounds is then will evaluated by Ultraviolet-visible spectrophotometry (UV-Vis).

3.7.2 Kinetic experiments

The kinetics study will be employed and rationalized in terms of the Langmuir-
Hinshelwood model to obtain the reaction rate constant (KR) and the adsorption
equilibrium constant (KLH). To study the kinetics of phenolic compounds photo
degradation, a series of reactions at different initial concentrations of phenolic
compound ranging from 10-100 mg/L at pH 11 were perform. According to Langmuir-
Hinshelwood model, the photo catalytic degradation rate of most phenolic compound
is described as first-order kinetics. The pseudo first-order kinetics is determined by
plotting a graph of ln (C0/Ct) as a function of time.
The slope line is the apparent first-order constant rate (Kapp). The relationship
of Langmuir-Hinshelwood model can be determined by plotting 1/ Kapp as function of

25
Co. Finally, the reaction rate constant and the adsorption equilibrium constant were
calculated.

3.8 Analytical Procedures

The analytical procedures of photo catalytic degradation activity will included

of determination of phenol concentration and the measurement of biological oxygen
demand (BOD), chemical oxygen demand (COD), and total organic carbon (TOC).
The elemental analyses of the metal ions in solution during an experiment during an
experiment were determined by AAS (Sapawe et al., 2013).

3.8.1 Phenol concentration determination

The vital measurement of the phenol concentration is by UV-Vis of the

phenolic compounds. Next, the degradation percentage is calculated as follows:

, % = (
) 100 (3.2)

Where Co represents the initial concentration (mg/L) and Ct denotes a variable

concentration (mg/L).

In addition, the calibration curve for phenolic compounds concentration

measurement was established in order to determine the exact amount of phenol that
will be removed. A range of 10 mg/L to 150 mg/L of phenol concentration was
conducted for the pH of 3, 5, 7, 9 and 11.The linear regression with R2 > 0.99 was
achieved, therefore, the actual value of phenol concentration that degrade was highly
detected with a good agreement.

3.8.2 Biological oxygen demand

In order to calculate the biological oxygen demand (BOD), the solution need
to be measure and the BOD bottles is then incubated at 293 K for five days. The
difference in dissolved oxygen is used to calculate BOD. The samples of bottles were

26
wrapped with aluminium foil to prevent from the light source in order to quench the
hydroxyl radicals (Sapawe, 2012).

3.8.3 Chemical Oxygen demand

According to APHA standard methods 1995 Chemical oxygen demand is a

measurement of the oxygen equivalent of the organic matter content of a sample that
is susceptible to oxidation by strong chemical oxidant. The equipment used is The
HACH DR4000 spectrometer is used for chemical oxygen demand (COD)
measurement. The test was performed by added the sample into cuvette and heat for
2 h at 423 K. At the end of this period, the colour intensity in the solution was
measure.

27
 CHAPTER 4

RESULT AND DISCCUSION

4.0 Preface

This chapter will discuss about the characterization of silver oxide deposited
onto the coconut shell and experimental result that been obtained. Three primary
parts will be clarified in this area which is the principal part is the characteristic of
photocatalyst, the second part is action test of photocatalytic and last part is
examination of biodegradability. The photocatalyst had undergo four tests which is
effect of pH water, effect of metal loading (wt %), effect of catalyst dosage (g/L) and
effect of initial phenol concentration (mg/L). Meanwhile, for the last part phenol
concentration was tested using BOD5 and COD method in order to determine the
level of phenol that been degraded by the photocatalyst.

4.2 Characterizations

The characterization photocatalyst by FTIR such as functional group and the

new peak that was observed in FTIR spectra was discussed in 4.2.1. Besides that,
the morphology and structural feature before and after the adsorption process has
been described in 4.2.2.

4.2.1 Characterization of photocatalyst by Fourier Transform Infra-Red (FT-IR)

FT-IR is a method of measuring infrared absorption and emission spectra.

The objective studying the absorption using FT-IR is to know how well a sample
absorbs light at each wavelength. Furthermore, the objective is to study the
functional group that is obtainable on surface of absorbent give high impact toward
adsorption capacity (Ricordel et al., 2001). Hence, in order to theorize the synergy

28
between CNS and AgO/CNS with different metal loading (wt %), the functional group
those are obtainable on surface of CNS and AgO/CNS need to be determined.

Figure 4.1 FT-IR analysis of CNS and AgO-CNS with different metal loading.

The FTIR spectra of CNS and AgO-CNS( 1wt%, 3wt%, 5wt%, 7wt% and
10wt%) which are before adsorption that have been determined by using FT-IR
spectroscopy. According to the figure 4.1 above, CNS and 1wt% consist the broad
and intense absorption peaks at around 3335 cm1 correspond to the OH stretching
vibrations due to intra-molecular hydrogen bonding of polymeric compounds
(macromolecular associations) such as alcohols, phenols and carboxylic acids as in
pectin, cellulose and lignin (Moradi, 2012). Thus it showed the presence of free-
hydroxyl groups on the adsorbent surface. In fact, Carboxyl (COOH) and hydroxyl
(OH) groups are binding site available on the surface of CNS and AgO-CNS as well
has other distinct binding sites (Pehlivan et al., 2013).

29
Figure 4.2 Analysis result comparison FTIR for AgO-CNS before and AgO-CNS after

From Figure 4.2, it can be seen broad O-H stretch of AgO-CNS is changed
after degradation. In fact, by adding AgO-CNs in the phenol solution increase the
intensity between the bands. Hence, there are large broad band at range 2500 to
3500 cm-1. The strong and broad wavelength refers to functional group of O-H. The
O-H groups and C=O bands shows the relation of phenol on the surface of AgO-CNS
which means, the adsorption of phenol onto the AgO-CNS surface was proven by
this results obtained (Sapawe, 2013).

4.3 Photocatalytic activity testing

The photocatalyst had undergo four tests which is effect of pH water, Effect of
metal loading (wt %), Effect of catalyst dosage (g/L) and Effect of initial phenol
concentration (mg/L).

4.3.1 Performance test

The performance test was studied in order to compare the

performance between CNS and AgO-CNS. The degradation percentage of phenol by

30
CNS and AgO-CNS has been analyzed as shows in the Figure 4.3 below. The
percentage degradation of phenol for CNS and AgO-CNS are about 40% and 80%
respectively. In this performance test, AGO-CNS shows highest value in degradation
percentage of phenol rather than CNS. After the electrosynthesis of AgO, the
porosity of adsorbent increased where give great number of internal pore of
adsorbent that was contributed on higher degradation of phenol. Besides that, the
enhancement of adsorbent surface area by AgO resulted on higher degradation of
phenol because of the active or binding site for adsorption of phenol onto AgO-CNS
surface was increased.

Figure 4.3 Performances between CNS and AgO-CNS

4.3.2 Effect of pH

Determination of pH was examined because it is one of the most important

factors that can affect photocatalyst activity since level pH of wastewater influence
the rate surface charge properties of photocatalyst. Hence, the rate of photocatalyst
is depending to the pH level of wastewater. Moreover, not only industrial but also

31
household water typically released at different pH qualities, indeed it is importance to
study the effect of pH on the percentage degradation of phenol.

Figure 4.4 Effect of pH water in degradation of phenol

The role of pH on the efficiency of photocatalytic degradation in solutions of

phenol was studied in range of 3 11; the result is plotted in Figure 4.4. From the
result obtained, for 2 h of irradiation, 63% and 73% of phenol was removed for pH 3
and pH 5 respectively. Meanwhile, for pH 9 and pH 11, 52% and 44% of phenol was
removed respectively. It could be seen that the degradation of phenol is generally
more enhanced in acidic solution compare to alkaline solutions. The best results in
case of solutions of phenol were obtained at pH 7 and 90% of phenol was removed
occurring at the end of 2 h. At pH of 7, the electrostatic attraction force between
phenol molecules and positively charged Ago resulted in maximum oxidation activity,
and thus led to high degradation efficiency of phenol (Alamn & Tawfeq., 2014).
Under that circumstance, it can be prove that degradation of phenol is favorable for
acidic and neutral solution.

32
4.3.3 Effect of metal loading (wt %)

Metal loading is weight of Ago that has been electrosynthesis deposited on

coconut shell that on figure 4.5, 1 wt% give the highest percentage of degradation of
phenol which is 90% while 10 wt% give the lowest percentage of phenol removal
which is 50%. Whereas, 3 wt%, 5 wt% and 7 wt% give 78%, 70%, and 58% of phenol
removal respectively. The increasing of metal loading will increase the total surface
area which can lead higher removal of phenol and increased in rate of phenol
degradation. However, as can be seen at figure 4.5 higher metal loading, wt% lower
the percentage of degradation. Consequently, further increases of metal loading will
result in decreasing of phenol degradation as the higher particle concentration will
increase the turbidity of the suspension thus reduced the light penetration and inhibit
photodegradation (Sapawe et al., 2013).

Figure 4.5 Effect of metal loading on degradation of phenol

4.3.4 Effect of catalyst dosage (g/L)

The effect of photocatalyst dosages on the degradation of phenol in aqueous

solution was studied. The results were illustrated in Figure 4.6. The degradation
efficiency decreased with increasing the amounts from 0.10 g/L up to 0.50 g/L. In this
analysis, the capability of photocatalyst is measure by the percentage of phenol
degradation.

33
 Figure 4.6 Effect of catalyst dosage on degradation of phenol

As can be seen, 0.50 g/L of Ago/CNS deposited onto coconut shell

only can degrade 55% of phenol. Meanwhile, 0.20 g/L, 0.30 g/L and 0.40 g/L
degrade 80%, 70% and 60% respectively rather than 0.10g/L, which its capable to
degrade 91%% of phenol. Theoretically, increased in degradation of percentage was
most likely the result of a decreasing in number of active sites with higher amount of
catalyst loading, which contribute to an increase in the number of photons and
phenol molecules absorbed. However, when Ago is overdosed, the number of active
sites on the photocatalyst surface may become almost constant because of the
decreased light penetration, the increased light scattering and the loss in surface
area occasioned by interactions of particle to particles at high solid concentration.
Therefore, 0.10g/L was selected as the optimal amounts of photocatalyst for the
sequential experiment.

4.3.5 Effect of initial phenol concentration (mg/ L)

Figure 4.7 below, shows the photocatalytic degradation rates of phenol

solutions with different initial concentrations which are 10 mg/L, 20 mg/L, 30 mg/L, 50
mg/L, 70 mg/L and 100 mg/L following the same condition of treatment process. The

34
results showed that the photocatalytic degradation rate decreased with increasing
initial concentration of phenol solution.

Figure 4.7 Effect of initial concentration to degradation of phenol

The effect of initial concentration on the removal of phenol is shown in Figure

4.7 that the percentage removal of phenol decreases as the initial concentration of
phenol increases. It is observed that the percentage removals of phenol at 120 min
become 87%, 80%, 75%, 68%, 58% and 52% at 10 mg/L, 20 mg/L, 30 mg/L, 50 m/ L
70 mg/L and 100 mg/L respectively. The result shows that the concentration of 10
mg/L gives higher percentage of degradation. In fact, increasing degradation of
phenol possibly happened due to the decrease formation of hydroxyl radicals on the
catalyst surface corresponded to the increasing in phenol concentration (Sapawe et
al,.2013). Moreover, higher concentration showed lower efficiency because of the
formation of layers of phenol on the catalyst surface.
In addition, large amount of adsorbed phenol were found to inhibit the
reaction with the phenol molecules, since there was no direct contact of the catalyst
with photogenerated holes or hydroxyl radical (Sapawe et al., 2013). The reason for
this can be explained by considering the formation of hydroxyl radicals in water by
the irradiation. For a given irradiation sample and time, it can be expected that the
production of OH radicals remains constant. Under such conditions the extent of
reaction between hydroxyl radicals and phenol molecules increases.

35
4.4 Kinetic Study

The last objective of this study is investigation of kinetic. The kinetic

degradation of phenol is study by using various reactions at pH 7 with different of
initial concentration ranging from 10 mg/L to 100 mg/L. As a result, initial
concentration 10 mg/L gave almost completes (87 %) degradation after 2 h of
irradiation. Generally, the influence of initial concentration of the solution on the
photocatalytic degradation rate of most described by pseudo first-order kinetics,
which rationalized in terms of Langmuir-Hinshelwood model modified to
accommodate reaction occurring solid-liquid interface (Sapawe et al., 2013). Higher
concentration showed lower efficiency of ln Ct = -Kt + ln C0. Where k is the pseudo
first order rate Co and Ct is the concentration of phenol initial time t, respectively. The
Eq. () yields Eq. ().

Table 4.1 Kinetic Study in degradation of phenol

Initial ReactionRate R2 Initial 1/ro 1/C0
Concentration, , kapp (min-1) Reaction
C0(mg/L) Rate,ro
(mg/L/min)
10 1.1295 0.9502 11.295 0.0885 0.1
20 0.9093 0.9306 18.186 0.0549 0.05
30 0.7842 0.9367 23.526 0.04251 0.0333
50 0.6426 0.9418 32.13 0.03112 0.02
70 0.5017 0.9164 35.119 0.02848 0.0142
100 0.4241 0.9177 42.41 0.02358 0.01

The straight line resulting from a plot of ln (C0/Ct) as function shown in Figure
4.8 proved that phenol degradation catalyzed by AgO/CNS follows first-order
kinetics. The slope of the line is the apparent first-order rate constants (Kapp). The
value of k obtained from this experiment, is listed in Table 4.1 and show a significant
effect of AgO/CNS on the degradation of phenol. A lower concentration of phenol
results in higher first-order rate constant. Hence it shows that, the suitability of the
system for low phenol concentration (Sapawe et al., 2013)

36
 FIGURE 4.8 Pseudo first-order kinetics model

Theoretically, the photodegradation of phenol using AgO/CNS is an interface

process which may follow the Langmuir-Hinshelwood model. From Figure 4.8 a linear
plot was obtained by plotting 1/Kapp as a function of C0 indicating that the
photodegradation of phenol AgO/CNS is consistent with Langmuir-Hinshelwood
model. The reaction constant and the adsorption equilibrium constant were
calculated to be KR =60.606 L-1 h-1 and KLH = 0.02172 L mg1. Since the value of KR
larger than KLH, it indicated that a surface reaction when the phenol is adsorbed was
controlling the step of the process (Rahman et al., 2015).

4.5 Investigation on biodegradability

The purpose of this study is to determine biodegradability of phenol. The

amount of oxygen required by aerobic microorganisms to decompose the organic
matter with in five days was measured through BOD5 method. Meanwhile, the COD
test also has been evaluated for both before and after degradation of phenol.

37
4.5.1 BOD5 and COD

Figure 4.9 COD and BOD5 before and after reaction (condition: pH 7, 3wt%, 0.3 g/L,
and 10mg/L)

The chemical oxygen demand (COD) and biochemical oxygen demand

(BOD) for phenol solution were measured and the results are shown in Figure 4.9. In
the present case, COD indirectly determines the amount of organic compounds
present in the aqueous solution (Sapawe et al., 2013). The initial COD values of
phenol solutions of concentration16 mg/L were measured. After irradiation with
fluorescent light for 2 h, it only shows 63% of COD was removed. In fact, the
percentage of COD removal is less than the percent of degradation of (87%). From
the result obtained, it can be concluded that the elimination of the chromophoric
group of the phenol molecules is only responsible for degradation. The elimination
occurs when phenol is adsorbed onto the catalyst surface to form sulfoxide
compound via electronic reorganization. Then, the sulfoxide form was dissociated
into most probable benzene ring compounds, resulting in only partial mineralization
of the phenol molecule (Sapawe et al., 2013). Besides that, the five days biochemical
oxygen demand (BOD5) was determined in order to study the amount of oxygen,
which is consumed by the microorganism to degrade the organic matter during a five
days period. The changes in value of BOD5 can refer in Figure 4.9. it shows that
BOD5 value is decreasing from 7.56 mg/L to 2.23 mg/L. Theoretically, BOD5/COD
ratio can be used as a biodegradability index for the aqueous phenol solution

38
(Sapawe et al., 2013).Hence the ratio before is 0.47 meanwhile the ratio after is 0.37.
As result, the ratio after is decrease and it shows that phenol is not biodegradable
after being adsorbed by AgO/CNs. Although this may be true it is recommended to
increase the irradiation time until 6 h. According to Sapawe non-biodegradable can
be turn to biodegradable after 6 h of irradiation.

39
 CHAPTER 5

CONCLUSION

5.0 Preface

This is the last part of the thesis. It consist of section 5.1 and 5.2. 5.1
generally conclude all the study and analysis from the result obtained at chapter 4
meanwhile 5.2 is recommendation for that might be use for the next study in order to
improve the efficiency of the photocatalyst.

5.1 Summary

In this study, four objective studies were achieved. The first objective is to
create a new photocatalyst. AgO was deposited on CNS by using the one-pot
electrosynthesis method in order to create photocatalyst. The method used in this
study was simple, has low cost because it used recycle coconut shell and does not
require high temperature or pressure. The second objective is achieved when the
obtained photocatalyst were characterized by Fourier Transmitter Infrared
Spectrometer to analyze the hydrocarbon exist in the photocatalyst. Phenol in
aqueous solution was selected to be the model organic pollutant in waste water in
order to study potential of the photocatalyst.

The potential of the photo catalyst (AgO/CNS) in degradation phenolic

compound from aqueous solution using batch system under visible light radiation at
room temperature was measured under various parameters such as effect of light
radiation at room temperature will be measured under various parameters such as
effect of light source, effect of pH (3, 5, 7, 9, 11) effect of catalyst dosage (0.10, 0.20,
0.30, 0.40, 0.50 g/L) and effect of initial concentration (10, 20, 30, 50, 70, 100 mg/L).
The degradation of phenolic compounds is then will evaluated by UV-Vis. As a result,
the excellent photoresponse of 1 wt% of AgO/CNS was achieved using amount of

40
0.10 g/L of the catalyst, resulting in phenol degradation after 2 hours of degradation
at pH 7 under room temperature and 10 mg/L of phenol initial concentration. When
the pH of the phenol solution was decreased, the photodegradation rate was found to
be improved, due to a higher formation of hydroxyl radicals for decomposition of the
dye. For different initial phenol concentrations, it can be deduced that the
photodegradation rate is reduced when the phenol concentration becomes higher.
The kinetic photocatalytic degradation was studied in order to achieve the last
objective. The kinetic photocatalytic degradation phenol was studied using the
Langmuir-Hinshelwood model and were found to be KR =60.606 L-1 h-1 and KLH =
0.02172 L mg-1.

5.2 Recommendations

In this study, one pot electrosynthesis silver oxide deposited on Cocos

Nucifera (coconut) shell for photocatalytic degradation of phenol is successful. In
future study it is recommended to apply photocatalytic degradation of other chemical
compound.In addition, coconut shell was used as absorbent. According to previous
study there is numerous kind of absorbance that can be used. it is recommended to
use waste as catalyst supporting because it help us to contribute individually to
recycle campaign. Furthermore, its help to reduce solid and organic waste and save
the environment in the future. As an example coconut husk, egg shell, Sugarcane
bagasse, shrimp shell and waste green tea can be used for the next study.

41
References

Ahmed, S., Rasul, M. G., Martens, W. N., Brown R. and Hashib, M. A. (2010).
Heterogeneous Photocatalytic Degradation Of Phenols In Wastewater: A
Review On Current Status and Developments, Desalination, 261(1-2),pp.
318.

Annadurai, G., Juang, R. S. and Lee, D. J. (2002). Use of Cellulose-Based Wastes.

For Adsorption of Dyes From Aqueous Solution. Journal of Hazardous
Materials, B92, 263 274.

Bamuza, P. (2014) Photocatalytic Degradation of Phenolic Compounds and Algal

Metabolites in Water. Engineering and Information, 77 123.

Basha, K, Rajendran, V, and Thangavelu V. (2010). Recent Advances In The

Biodegradation of Phenol: A Review. Faculty of Engineering and Technology,
218 219.

Cicek, F.,Ozer, D. and Ozer, A. (2006). Low Cost Removal Of Reactive Dyes Using
Wheat Bran. Journal of Hazardous Materials, 146, 408 416.

Chanathaworn, J, Bunyakan, C, Wiyaratn, W. and Chungsiriporn, J. (2012).

Photocatalytic Decolorization Of Basic Dye By Tio2 Nanoparticle In Ph
Photoreactor: Songklanakarin, J. Sci. Technol., 34, 203 210.

Dogan, M., Abak, H., and Alkan, M. (2009). Adsorption Of Methylene Blue Onto
Hazelnut Shell Kinetics, Mechanism and Activation Parameter. Journal of
Hazardous Materials, 164, 172 181.

Giwa, A., Nkeonyen, P. O., Bello, K. A. and Kolawole, K. A. (2010). Photocatalytic

Decolourization and Degradation of C. I. Basic Blue 41 Using TiO2
Nanoparticles. Jpurnal of Environmental Protection, 3, 1063 1069.

42
Gupta, V. K. and Suhas (2009). "Application Of Low-Cost Adsorbents For Dye
Removal. A review." Journal of Environmental Management, 90(8), 2313
2342 .

Jadhav, D and Vanjara A, (2003). Removal Of Phenol From Wastewater Using

Sawdust Polymerized Sawdust and Sawdust Carbon. Indian Journal
Technology, 35 40.

Kifferstein, D. K. A. B. "WATER POLLUTION AND SOCIETY." From

http://www.umich.edu/~gs265/society/waterpollution.html.

Hameed, B.H.., Mahmoud D.K, and Ahmad A.L (2008). Equilibrium Modeling and
Kinetic Studies on the Adsorption of Basic Dye by A Low-cost Adsorbent:
Coconut (Cocos nucifera ) Bunch Waste. Journal of hazardous Materials,
158, 65 72.

Kulkarni S. J. and Kaware P. J. (2013). Review on Research For Removal of Phenol

From Wastewater, 2 5.

Lee and Wan, I. (1993). Study of Photocatalytic Property of Titanium (IV) University
Microfilms International, 16 72.

Manahan S. E. (2010). Environmental Chemistry, U.S: CRC Press, 317 318.

Metcalf and Eddy (2003). Wastewater Engineering: Treatment and Reuse. New York:
Mc. Graw Hill International Edition.

Molva, M. (2004) Removal of Phenol from Industrial Wastewaters Using Lignitic

Coals. Institute of Technology, 1 60.

Nagda, G.K., Diwan A. M., and Ghole V.S. (2007). Potential of Endue Leaf Refuse
For Phenol Removal in Aqueous Systems. Journal of Applied Ecology and
Environmental Research, 5(2), 1 9.

Rahmani, A.R., Zarrabi, M., Samarghandi, M. R., Afkhami, A. and Ghaffari,H.R.

(2010). Degradation of Azo Dye Reactive Black 5 and Acid Orange 7 by
Fenton-Like Mechanism, Iranian Journal of Chemical Engineering, 7.

43
Rajabi, H. and Farsi, M. (2015). Quantum Dot Based Photocatalytic Decolorization
As An Efficient And Green Strategy For The Removal Of Anionic Dye.
Materials Science in Semiconductor Processing, 31, 478 486.
Ricordel, S., Taha, S., Cisse, I. and Dorange, G. (2001). Heavy Metal Removal by
Adsorption onto Peanut Husks Carbon; Characterization, Kinetic Study and
Modeling. Separation and Purification Technology, 24, 389 440.

Sachin, B. and Rahul, V. (2014) Review on Research Removal of Phenol from

Wastewater by Using Different Methods. International Journal of Scientific
and Research Publications, 4(5), 1 3.

Saiful Azhar, S. A., Abdul Ghaniey and Liew (2005). Dye Removal from Aqueous
Solution by Using Adsorption on Treated Sugarcane Bagasse. American
Journal of Applied Sciences, 2(9), 1 5.

Sapawe, N., Jaafar, N. F., Hairom, N. H. H., Satar, M. A. H., Ariffin, M. N.,
Triwahyono , S. and Jalil, A. A., (2011). A Facile Preparation Of Nanosized
ZnO And Its Use In Photocatalytic Decolorization Of Methyl Orange. Journal
of Fundamental Sciences, 7, 19 23.

Sapawe, N., Jalil, A.A., and Triwahyono, S., (2011). Photodecomposition Of

Methylene Blue Over Egzro2/HY In Aqueous Alkaline Solution. Journal of
Fundamental Sciences, 7(2), 137 139.

Sapawe, N., Jalil, A.A., and Triwahyono, S., (2013). One-Pot Electro-Synthesis Of
ZrO2 ZnO/HY Nanocomposite For Photocatalytic Decolorization Of Various
Dye Contaminants. Chemical Engineering Journal, 225, 254 265.

Sapawe, N., Jalil, A.A., and Triwahyono, S., (2013). Photodecolorization Of

Methylene Blue Over EgZrO2/EgZnO/EgFe2o3/HY Photocatalyst: Effect Of
Radical Scavenger. Malaysian Journal of Fundamental and Applied Sciences,
9(2), 67 73.

Solis, R. R., Rivas F. J. Perez-bote J.L. and Gimeno.(2015). Photocatalytic

Ozonation Of 4 Chloro-2-Methylphenoxyacetic Acid and Its Reaction

44
 Intermediate 4 Chloro-2 Methyl Phenol. Journal of the Taiwan Institute Of
Chemicals Engineers, 126 230.

Sunil, S. A., Ming, Y. C., Duu-Jong, L. and Nan-Qi, R. (2007). Degradation of Phenol
by AerobicGranules and Isolated Yeast. Candida Tropicalis. Biotechnol.
Bioeng, 96, 844 852.

Udom, I., Myers, D. P., Ram K. M. and Hepp, F.A. (2014). Optimization of
Photocatalytic Degradation of Phenol Using Simple Photocatalytic Reactor.
Scientific Research, 744 750.

Wang, H. and Wang. J. (2007), Electrochemical Degradation of 4-chlorophenol Using

A Novel Pd/C Gas-Diffusion Electrode. Applied Catalysis B; Environmental,
77, 58 65.

Yang, L. Chu, D. and Wang, L. (2015). Porous Hexapod Cuo Nanostructure:

Precursor Mediated Fabrication, Characterization, and Visible-Light Induced
Photocatalytic Degradation Of Phenol. Materials Letters. 247 249.

45