CHAPTER I

THE PROBLEM AND ITS BACKGROUND

INTRODUCTION

The amount of freshwater accessible to humans remains the same. Humans

simply recycle them to be able to reuse them. Despite the constant amount of

freshwater, the demands for it are increasing over time. Population is rising and all living

organisms require water to survive, and freshwater is not only used for drinking. In fact,

according to the World Water Assessment Programm, about 70% of the freshwater is

used for irrigation, 22% for industry and 8% for domestic use.

As for human consumption, there are communities with no access to potable

water. These people are left with no option but to consume what is available to them,

unsafe and health-risking water. Instead of helping them to refuel themselves, drinking

this kind of water would even make them experience discomfort. This is an alarming

issue because this can lead to even bigger health issues.

Contaminated water is a current world issue. Contamination can come from

different pollutants and some of these could be heavy metals. Due to the industrial

processes of modernization, the threat of heavy metals as contaminants in the

environment is one of the concerns worldwide. Heavy metals being present in our water

resources pose a significant threat that must be addressed. These heavy metals if

consumed in great amounts can make the person sick and cause health issue. Thus, in

order to prevent more people to experience discomfort due to drinking unsafe and

polluted water, the removal of heavy metals from the drinking water can be a huge help

for the people.

cadmium, chromium, copper, nickel, lead and mercury. These heavy metals when taken

in huge amounts, accumulated due to often consumption of contaminated water, can

cause serious problems and can lead to death.

There are many ways that heavy metals reach the waterways. According to

Lenntech, the most common way is from the mining industries, specifically from their

drainage systems but other ways are because of the volcanic eruptions, weathering of

rocks and from a variety of human activities that involves these metal pollutants.

Another pollution that poses threat on our environment is the textile factory

wastewater. These textile wastewater factories consume enormous quantities of water

which results to huge volume of wastewater due to the different steps in the textile

industry. Printing and dyeing often produce wastewater that is full in colour, residues of

chemicals and synthetic dyes, complex components, and even heavy metal ions.

(Zongping Wang, et. al., 2011)

Coloured wastewater is toxic to human and marine life if discharged into the

bodies of water without proper wastewater treatment. These wastes are high in

concentration of Chemical Oxygen Demand (COD) and Biological Oxygen Demand

(BOD) and ample amounts of heavy metals, suspended solids and other toxic

contaminants. Many sophisticated methods of purification and treatment is introduced

such as nano-filtration, coagulation, flocculation, reverse osmosis and ultra-filtration but

these are all expensive and complex which may not also be available in some

developing countries. (Rahman FBA, et. al., 2016)

Based on the data gathered by the researchers, adsorption has garnered great

amounts of potentiality in protecting the environment. That is why, adsorption, in this

wastewater before it is discharged in our bodies of water. Nowadays, some adsorbents

are efficient in the removal of synthetic dyes and contaminants but some are not. With

this, researchers must constantly seek for new adsorbent materials which are effective in

these kinds of treatments but also cost-effective and accessible. (Rahman FBA, et. al.,

2016)

Due to this, a cheap solution for the water pollution must be constantly studied

and be refined for efficiency and optimization This is the reason why the researchers are

eager to conduct a study on creating an adsorption material that can potentially be used

in adsorbing heavy metals and dyes in wastewater from the industry simultaneously

thus, broad-spectrum adsorbent.

In this study, sodium alginate will be used and it will be the one responsible for

the hydrogel form of the composite. According to Modernist Pantry, sodium alginate is

derived from brown seaweeds. It is commonly used in the food industry for many uses

such as thickener and suspender. This is present in ice creams, yogurt and jams to

name a few. With the properties of sodium alginate, when it is combined with the

graphene oxide, it will be a convenient product for the adsorption of heavy metals in

water. It doesnt mix with water, therefore, after the adsorption process; the composite

can be easily removed from the water.

Graphene oxide alone has unique properties that adsorbs heavy metals and ionic

dyes, however there is a need to recover the adsorbent from the wastewater and it will

be hard if there will still be several processes utilized since it will only be complex and

costly. With this, the researchers thought of cross-linking the sodium alginate and

graphene oxide to maximize it potentials and capabilities. Sodium alginate is immiscible

wastewater for recovery along with the graphene oxide. Sodium alginate also has

potentials as an adsorbent for ionic dyes which is a great attribute for the hydrogel to be

formed since it would be another contribution to its adsorption capacity.

The researchers will be simulating the wastewater in this study by putting heavy

metals and ionic dyes in the water. With this, the created material will adsorb the heavy

metals (Cd (II)) and ionic dyes (methylene blue) simultaneously. The success of this

study would open avenue for new research and for the improvement of the wastewater

treatment especially in the textile industry.

STATEMENT OF THE PROBLEM

The aim of this study is to be able to create a new adsorbent material that can be

used in water filtration using Graphene Oxide and Sodium Alginate. This study is not

only beneficial because of its application, but its development and study will be an

addition to the currently limited research on graphene science. Specifically, this seeks

answers to the following questions:

1. What are the parameters considered in the formation of Graphene

Oxide/Alginate Hydrogel Composite in terms of:

1.1 Physical;

1.2 Chemical;

1.3 Mechanical properties?

2. How effective is the hydrogel composite when it comes to the heavy metal

adsorbing capacity on contaminated water in terms of the following parameters?

2.1 Adsorbing time

2.2 Amount of contaminants adsorbed

and hydrogel form?

4. What are the methods in disposing the hydrogel composite after the adsorption

process?

NULL HYPOTHESIS

This study tested the null hypothesis that there is no significant difference in the

adsorption capacity between the aerogel and hydrogel form of graphene oxide-sodium

alginate composite.

SIGNIFICANCE OF THE STUDY

This study entitled Graphene Oxide/Alginate Composite Hydrogel as a Broad-

Spectrum Adsorbent for Water Purification and its Physicochemical-Mechanical

Properties introduces a new and innovative method of heavy metal and dye adsorption

accentuating on the capacity of graphene oxide in the form of a sodium alginate-based

hydrogel. The paper would be beneficial to the following:

To the people who have limited access to clean and safe drinking water due to

the presence of heavy metals, the hydrogel composite can help them have an easier

and more convenient way on accessing safe drinking water. This will also promote better

health for the people and better water quality.

To the development of graphene science and its propagators, the results of this

research will be an addition to its overall study. Since there are still few researches

about the applications of graphene with its superlative properties, this study will be an

important gateway for more discoveries.

To the present researchers, the research will help them hone their individual

skills and group identities in the intellectual and social aspects.

supporting research on their studies. This can also help in impelling curiosity in starting a

related study.

SCOPE AND DELIMITATION OF THE STUDY

This study revolves around the formation of Graphene Oxide/Alginate hydrogen

composite and the analysis of its physicochemical properties and adsorbing capacity.

The hydrogel composites reactivity on the presence of certain heavy metals will be the

basis on its adsorbing capacity.

The water simulation or testing, where the hydrogel composite is to be subjected,

is limited on the quality of water with the specific heavy metal and dye content. Another

limitation of this study revolves on the quality of graphite to be used. The graphite that

will be used is to be obtained from a specific industry to ensure the consistency and

control for this variable in the research.

For the hydrogel composites properties, the limitations of the composite will be

based on its components. The raw materials and reagents are limited to specific and

consistent characteristics. The raw materials must be of constant quality and the

reagents must be of good purity.

However, since the researchers are only focused adsorption capacity of the

hydrogel composite for heavy metals and dyes, the study will not be able to analyze and

examine the reaction of the composite to other compounds present in the water.

CONCEPTUAL FRAMEWORK

For the primary step, the essential materials for this study, Graphite and Sodium

Alginate, and the other components are gathered and are under the input section. This is

followed by the synthesizing of graphene oxide using modified Hummers method. After

the formation of the graphene oxide, the graphene oxide is introduced to the sodium
alginate hydrogel. This hydrogel is a cross-link of GO nanosheets and sodium alginate

via self-assembly. This formed material will then be subjected to simulation on

contaminated water to observe its adsorption capacity. The specific metal to be

simulated is Cd (II), and for ionic dyes is methylene blue. The properties of the hydrogel

composite are to be noted and characterized using several laboratory analyses such as

FTIR and Scanning Electron Microscopy. Its adsorption capacity observed from the

simulation should also be analysed. The testing shall be a simultaneous adsorption of

heavy metals and ionic dyes. The graphical representation of the procedure for this

study is shown in Figure 1.

INPUT PROCESS OUTPUT

Synthesis of
Graphite Powder Graphene Oxide
Graphene
using modified Oxide/Alginate
Sodium Alginate Hummers method Hydrogel
Composite
(isasama pa ba
to:Potassium
Permanganate Introduction of the
Sodium Alginate Adsorption
Phosphoric Acid Hydrogel via self Capacity Results
assembly
Sulfuric Acid
Characterization
Hydrochloric Acid
on the
Simulation of the physicochemical
Hydrogen
Hydrogel and mechanical
Peroxide
Composite on properties of the
Deionized water) contaminated hydrogel
water composite

Figure 1. Conceptual Framework

To have better understanding of the study, the following terms are defined

conceptually.

Aerogel. According to Oxford Dictionaries, the term aerogel is a solid material derived

from a convention gel and has a very low density. In this study,

Adsorption. According to Chemistry Learning, the term adsorption is a phenomenon

wherein large number of molecular species accumulate at a liquid or solid surface in

which they are in contact. In this study, adsorption is the process involved in order to

remove the heavy metals and dyes in the water for its purification.

Centrifuge. According to Merriam-Webster Dictionary, the term centrifuge is an

equipment which uses centrifugal force used for separating substances of different

densities, for removing moisture, or for simulating gravitational effects. In this study, in

order to synthesize graphene oxide, graphite undergoes series of processes and one

process involves centrifugation in drying.

Composite. According to Oxford Dictionaries, the term composite is a thing made up of

various parts or elements. In this study, this refers to the hydrogel composite which is

the combination of graphene oxide and sodium alginate.

Contaminant. According to Cambrige Dictionary, the term contaminant is any potentially

undesirable substance that make something less pure or toxic. In this study, this refers

to the heavy metal and dye pollutants that are to be removed by the hydrogel composite.

Graphene. According to Graphenea, the term graphene is a thin layer carbon based

material and are bonded together in repeating hexagonal patterns. In this study, this

refers to the single layer that comprises graphite.

form of graphene, laced with oxygen-containing groups. In this study, this refers to the

main component of the adsorbing hydrogel composite.

Graphite. According to Merriam-Webster Dictionary, the term graphite is a soft black

lustrous form of carbon that conducts electricity and is used in lead pencils and

electrolytic anodes, as a lubricant, and as a moderator in nuclear reactors. In this study,

this refers to the raw material where graphene oxide is to be synthesized from.

Heavy metals. According to Lenntech, the term heavy metals refer to any relatively

dense metallic element and is toxic or poisonous at low concentrations. In this study,

these are pollutants to be removed by the hydrogel composite.

Hydrogel. According to Merriam-Webster Dictionary, the term hydrogel is a gel made up

of network of polymer chains dispersed in water. In this study, this is the output from the

combination of the graphene oxide and sodium alginate. The hydrogels adsorption

capacity and properties are to be observed and studied.

Hummers Method. This is introduced by Dr. William Hummer and Dr. Richard

Offeman, where graphene oxide is synthesized from graphite using potassium

permanganate, sulphuric acid and sodium nitrate. In this study, this refers to the original

method where the procedure of this research is based.

Modified Hummers Method. This is introduced by Dr. James Tour and Dr. Ayrat

Dimiev of Rice University, where, compared with the classical method, this process used

more potassium permanganate and used phosphoric acid along with the sulfuric acid in

the reactions and has a greater graphene oxide yield. In this study, this refers to the

method that the researchers will use in order to synthesize graphene oxide.
Methylene blue. According to Merriam-Webster Dictionary, the term methylene blue is a

basic thiazine dye C16H18ClN3S3H2O used especially as a biological stain, an antidote in

cyanide poisoning, and an oxidation-reduction indicator. In this study, this refers to one

of the dye pollutants that is to be removed in the adsorption.

Porosity. According to Corrosionpedia, the term porosity is the presence of tiny

openings or spaces within a material. In this study, this refers to the property of the

hydrogel composite that the researchers are to improve in comparison with the aerogel

form.

Sodium Alginate. According to National Institutes of Health, the term sodium alginate is

the sodium salt form of alginic acid and gum mainly extracted from the cell walls of

brown algae, with chelating activity. In this study, this is the material to be used in order

to make the composite in hydrogel form.

Synthesis. According to Merriam-Webster Dictionary, the term synthesis is the

production of a substance by the union of chemical elements, groups, or simpler

compounds or by the degradation of a complex compound. In the study, this refers to the

formation of graphene oxide from graphite using a modified version of the Hummers

method.

Water purification. According to Science Daily, the term water purification is the

process of eliminating undesirable chemicals or natural contaminants from raw water to

produce safe drinking water for mankinds consumption. In this study, this refers to the

removal of the heavy metal and dye pollutants in the water.

All About Water. (2011). [ebook] Available at:

https://www.iaea.org/sites/default/files/publications/magazines/bulletin/bull53-

1/53105911720.pdf

Modernistpantry.com. (2017). Sodium Alginate. [online] Available at:

https://www.modernistpantry.com/sodium-alginate.html

Chemistrylearning.com. (2017). Adsorption and its Types | Chemistry Learning.

[online] Available at: http://www.chemistrylearning.com/adsorption/

Fuente, J. (2017). Graphene Oxide - What Is It?. [online] Graphenea. Available

at: https://www.graphenea.com/pages/graphene-oxide#.WfiUn9CWaUk

Lenntech.com. (2017). Heavy Metals - Lenntech. [online] Available at:

https://www.lenntech.com/processes/heavy/heavy-metals/heavy-

metals.htm#ixzz4x56gxMJR

Corrosionpedia. (2017). What is Porosity? - Definition from Corrosionpedia.

[online] Available at: https://www.corrosionpedia.com/definition/906/porosity

ScienceDaily. (2017). Water purification. [online] Available at:

https://www.sciencedaily.com/terms/water_purification.htm

Pubchem.ncbi.nlm.nih.gov. (2017). Sodium alginate. [online] Available at:

https://pubchem.ncbi.nlm.nih.gov/compound/5102882#section=Top

Rahman FBA, Akter M (2016) Removal of Dyes Form Textile Wastewater by

Adsorption using Shrimp Shell. Int J Waste Resour 6:244. doi:10.4172/2252-

5211.1000244

Miaomiao Xue, Kai Huang and Zizheng Liu (2011). Textile Dyeing Wastewater

Treatment. [ebook] Available at: http://cdn.intechweb.org/pdfs/22395.pdf