GRAPHENE OXIDE-CHITOSAN

COMPOSITE HYDROGELS AS BROAD-

SPECTRUM ADSORBENT FOR WATER

PURIFICATION

Submitted by:

Anilov V. Saludez

9-Napier

Submitted to:

Ms. Cecile Santiago

 Table of Contents

Title………………………………………………………………………………………………..i

Acknowledgement………………………………………………………………………………ii

Table of Contents………………….………..……………………………….………………….iii

Abstract…………………………………………………………………………………………..1

Introduction ……………………………………………………………………………………...2

Background of the Study……………………………..………………………………...2

Statement of the Problem…………………………………………………………..….4

Significance of the Study…...…………………………………………………………..4

Statement of Hypothesis…………………………..…………………………………...4

Scope and Limitation……………………………………………………………………5

Review of Related Literature and Studies……………………………………………………6

Review of Related Literature…………………………………………………………..6

Review of Related Studies……………………………………………………………..8

Methodology

Collection of Materials…………………………………………………………………11

Preparation of Graphene Oxide……………………………………………………...11

Preparation of Graphene Oxide-Chitosan…………………………………………..12

 Batch and Filtration Adsoption Experiment…………………………………………12

Characterization……………………………………………………………………….13

Bibliography…………………………………………………………………………………….14

Plagiarism Checker Form……………………………………………………………………..15

 ACKNOWLEDGEMENT

I would like to extend my deepest gratitude to following people for their

unwavering support:

I would like to give thanks to our Research Adviser, Ms. Ma. Cecilia Santiago

because of her guidance to correct this Research Paper and also to this opportunity to

give us an experience in making research paper.

I would like to express my deepest gratitude to my Mother, Jocelyn Vina and to

my Aunt, Evelyn Gonzales because of their unwavering support in Financial for printing

research papers.

I also want to give thanks to my classmates and friends for cheering me up to do

this and their advices in making this research paper.

I would like to extend my deepest sincerest gratitude to Dion Douglas Fortes, for

accompanying me in making this research paper even though he is also busy in making

his research study too.

Lastly, my deepest gratitude to Almighty God because of his guidance to me, on

giving me wisdom and understanding for this research study.

 ABSTRACT

Water pollution is one of the most pervasive problems afflicting people throughout the world,

while adsorption is the most widely used method to remove the contaminants from water.

Here, in this paper, we report an eco-friendly graphene oxide–chitosan (GO–CS) hydrogel

as a new type of adsorbent for water purification. The GO–CS hydrogels were

prepared viaself-assembly of GO sheets and CS chains. A three-dimensional network

composed of GO sheets crosslinked by CS was found in GO–CS hydrogels. The GO–CS

composite hydrogels showed high adsorption capacity towards different contaminants,

including cationic and anionic dyes, as well as heavy metal ions. The mechanism of

the dye adsorption was investigated with a spectral method, and an electrostatic interaction

was found to be the major interaction between ionic dyes and the hydrogel. The influence of

the hydrogel composition on the adsorption capacity towards different adsorbates was also

studied. Finally, it was demonstrated that the GO–CS hydrogel can be used as column

packing, to fabricate a column for water purification by filtration.

 INTRODUCTION

BACKGROUND OF THE STUDY

Among the Natural Resources water is the most vital element, and is critical for the survival of

all living organisms including human, food production, and economic development. Today there

are many cities worldwide facing an acute shortage of water and nearly 40 percent of the

world’s food supply is grown under irrigation and a wide variety of industrial processes depends

on water. The Development and growth are all higly influenced by water-its regional and

seasonal availability and the quality of surface and groundwater. (Halder, 2015) Water

Contamination is global environmental concern. Wastewater from different industries produces

many kinds of toxic dyes and heavy metal ions. The contaminants can cause mass mortality of

aquatic lives and distinction of species. Many people suffer due to the lack of potable water.

(Chen et al., 2012)

One of the most rapidly developing fields in the world is Water Purification. In some countries in

the world convert sea water into fresh water for human consumption and irrigation processes by

desalination technologies. Likewise, water purification is one of the rapidly developing fields in

the field of science and technology followed by the set of laboratory scale researches and the

process scaling up by engineering techniques. In Sri Lanka, chemical engineer’s role in water

purification is to find the most scenario, the role of the chemical engineer in water purification is

to find the most fitting and economical method by modifying the process of water purification

(Samarasiri, 2015)

In terms of most abundant basic biopolymer and is structurally similar to cellulose which is

composed of only one monomer of glucose. Chitosan solubility, biodegradability, reactivity, and

adsorption of many substrates depend on the amount of protonated amino groups in the
polymeric chain, therefore on the proportion of acetylated and non-acetylated D-glucosamine

units. Chitosan is insoluble in water, organic solvents and aqueous bases and it is soluble after

stirring in acids such as acetic, nitric, hydrochloric, perchloric and phosphoric (Guibal, 2004;

Kluget al., 1998; Kubota et al., 2000; Kurita, 2006; Anthonsen & Smidsroed, 1995; Rinaudo,

2006; Sankararamakrishnan & Sanghi, 2006).

Here, in order to solve the, we prepared GO–Chitosan (GO–CS) composite hydrogels as new

broad-spectrum adsorbents for water purification. GO composite hydrogels can be prepared by

three-dimensional (3D) self-assembly of GO sheets promoted by different types of crosslinking

agents. In these hydrogels GO sheets remain less aggregated, showing large surface area, and

the interconnected pores in the hydrogels allow adsorbate molecules to diffuse easily into the

absorbent. In the present work, we chose CS as the crosslinking agent, which has a strong

electrostatic interaction with GO sheets. Combining excellent biocompatibility, biodegradability

and antibacterial property, CS, a lowcost natural biomaterial, has been considered as a green

adsorbent for the removal of metal ions because it contains various chelating groups such as

amino and hydroxyl groups. Moreover, CS was reported to be able to remove anionic dyes via

electrostatic interactions. Therefore, the incorporation of CS can provide GO–CS composite

hydrogels with the ability of adsorbing anionic dyes. In fact, our results demonstrate that GO–

CS composite hydrogels have large adsorption capacity towards both cationic and anionic dyes,

as well as metal ions. The adsorption capacities of the hydrogel towards different adsorbates

can be adjusted by changing the composition of the hydrogel, and the adsorption process the

GO–CS hydrogel can be easily collected from the water by filtration or decantation. Moreover,

we will further show that the GO–CS hydrogel can be used as column packing, to fabricate a

column for water purification by filtration (Mater, 2013)

STATEMENT OF THE PROBLEM

This study aims to make a Graphene Oxide-Chitosan Composite Hydrogels that

can use as an adsorbent to remove contaminants.

 Does the Graphene Oxide is good adsorbent for many types of

contamination?

 Can Chitosan is able to remove anionic dyes via Electrostatic

Interactions?

SIGNIFICANCE OF THE STUDY

This study signifies that the Chitosan has an ability to remove anionic dyes so

therefore the incorporate hydrogel can provide Graphene Oxide-Chitosan Composite

Hydrogels with the ability of adsorbing anionic dyes.

STATEMENT OF HYPOTHESIS

This study hypothesizes the following:

 Graphene Oxide is becoming a potential candidate as a high performance

adsorbent therefore the capacity of graphene can be significantly

increased by decorating it with functional groups or other material.

 An electrostatic interaction was found to be the major interaction between

ionic dyes and hydrogel so, it is effective to use Chitosan to remove

anionic dyes.
SCOPE AND LIMITATION

`This study will conduct for a month or less. Graphene Oxide-Chitosan are the

variables that will use because they show a high-adsorption capacity towards different

contaminants. The first procedure wil do is the preparation of Graphene Oxide, this

procedure will do using the modified hummers method. Next,the preparation of

Graphene-Oxide Chitosan hydrogels where the Chitosan Stock Solution with a

concentration of 25% was prepared by dissolving one gram of Chitosan in One Hundred

mL to be followed by Batch and Filtration Adsorption Experiments then the

Characaterization. This study wants to make an Eco-friendly Graphene Oxide-Chitosan

Composite Hydrogels that can use for Column Packing.

 REVIEW of RELATED LITERATURE & STUDIES

Review of Related Literature

Graphene Oxide- Graphene is an exciting material. It has a large theoretical specific

surface area, high intrinsic mobility and thermal conductivity, and its optical

transmittance and good electrical conductivity merit attention for applications such as for

transparent conductive electrodes, among many other potential applications. Graphene

has been experimentally studied for over 40 years, and measurements of transport

properties in micromechanically exfoliated layers, of graphene grown on Silicate

Calcium large area graphene grown on copper (Cu) substrates, as well as a variety of

studies involving the use of chemically modifi ed graphene (CMG) to make new

materials, have in part led to a surge in the number of publications. (Zhu et al., 2010)

Chitosan- The most abundant basic biopolymer is Chitosan. It composed one monomer

of glucose. Its solubilty and adsorption of many substrates depend on the amount of

protonated amino groups in the polymeric chain, therefore on the proportion of

acetylated and non-acetylated D-glucosamine units. The amino groups (pKa from 6.2 to

7.0) are completely protonated in acids with pKa smaller than 6.2 making chitosan

soluble. Chitosan is insoluble in water, organic solvents and aqueous bases and it is

soluble after stirring in acids such as acetic, nitric, hydrochloric, perchloric and

phosphoric (Guibal, 2004; Kluget al., 1998; Kubota et al., 2000; Kurita, 2006; Anthonsen

& Smidsroed, 1995; Rinaudo, 2006; Sankararamakrishnan & Sanghi, 2006).

Adsorbent- absorption is a physical or chemical phenomenon or a processin

which atoms, molecules or ions enter some bulk phase – gas, liquid or solid material.

This is a different process from adsorption, since molecules undergoing absorption are

taken up by the volume, not by the surface (as in the case for adsorption). A more

general term is sorption, which covers absorption, adsorption, and ion exchange.

Absorption is a condition in which something takes in another substance. (Kotelainen,

2017)

Water Purification- process by which undesired chemical compounds, organic and

inorganic materials, and biological contaminants are removed from water. That process

also includes distillation (the conversion of a liquid into vapour to condense it back to

liquid form) and deionization (ion removal through the extraction of dissolved salts). One

major purpose of water purification is to provide clean drinking water. Water purification

also meets the needs of medical, pharmacological, chemical, and industrial applications

for clean and potable water. The purification procedure reduces the concentration of

contaminants such as suspended particles, parasites, bacteria, algae, viruses,

and fungi. Water purification takes place on scales from the large (e.g., for an entire

city) to the small (e.g., for individual households). (Lanfair, 2018)

Hydrogel- Hydrogels are water-swollen polymeric materials that maintain a distinct

three-dimensional structure. They were the first biomaterials designed for use in the

human body. Traditional methods of biomaterials synthesis include crosslinking

copolymerization, crosslinking of reactive polymer precursors, and crosslinking via

polymer-polymer reaction. These methods of hydrogel synthesis were limited in the

control of their detailed structure. Due to side reactions the networks contain cycles,

unreacted pendant groups, and entanglements. Other inadequacies of traditional

hydrogels have been poor mechanical properties and slow or delayed response times to

external stimuli. (Kopecek, 2007)

Review of Related Studies

Recent advances in the use of graphene-family nanoadsorbents for removal of

toxic pollutants from wastewater

ShamikChowdhury RajasekharBalasubramanian

Abstract

The most promising and robust methgod of purifying water is Adsorption, it is a low cost

and with high-efficiency. Carbon-based materials have been extensively explored for

adsorption applications because of their good chemical stability, structural diversity, low

density, and suitability for large scale production.. In this review article, we present a

synthesis of the current knowledge available on this broad and versatile family of

graphene nanomaterials for removal of dyes, potentially toxic elements, phenolic

compounds and other organic chemicals from aquatic systems. The challenges involved

in the development of these novel nanoadsorbents for decontamination of wastewaters

have also been examined to help identify future directions for this emerging field to

continue to grow.
Carbon-based nanomaterials for removal of chemical and biological

contaminants from water: A review of mechanisms and applications

Sean C.Smith Debora F.Rodrigues

Abstract

In recent years, significant discoveries related to antimicrobial and adsorption properties

of carbon-based nanomaterials have led to new avenues for removal of various

biological and organic/inorganic contaminants in drinking water. Furthermore, progress

in the synthesis of multifunctional nanocomposites paves the way for their application in

advanced water treatment system design. This review article describes and compares

the adsorptive and antimicrobial properties of four common classes of carbon

nanomaterials: single- and multi-walled carbon nanotubes, graphene, and graphene

oxide, as well as some of their most important polymeric and metallic nanocomposites.

Barriers for application of these nanomaterials in sustainable water treatment are also

addressed.

Bio-inspired surface-functionalization of graphene oxide for the adsorption of

organic dyes and heavy metal ions with a superhigh capacity

Zhihui Dong,abc  Dong Wang,*a  Xia Liu,a  Xianfeng Pei,a  Liwei Chena  and  Jian

Jin*a 

Abstract

By utilizing the synergistic effect of poly-dopamine (PD) with functional groups and

graphene oxide (GO) with a high surface area, a series of sub-nano thick PD layer

coated GO (PD/GO) composites were fabricated by a well-controlled self-polymerization

of dopamine via catechol chemistry and used for effectively decontaminating

wastewater. It was concluded that the adsorption process was based on the

Eschenmoser salt assisted 1,4-Michael addition reaction between the ortho position of

the catechol phenolic hydroxyl group of PD and Eschenmoser groups in the dyes. The

adsorption isotherms were explored according to the Langmuir and Freundlich models

respectively, and matched well with the Langmuir model. The thermodynamic

parameters were also calculated, which suggested an exothermic and spontaneous

adsorption process. In addition, PD/GO exhibited an improved adsorption capacity for

heavy metal than pure PD and GO. The result indicates the effect of individual

components on designing new functional composites with high performance.

 METHODOLOGY

Collection of Materials

Natural graphite powders will buy from DKL Laboratory Supplies(Espana,Manila) . CS,

methylene blue (MB, 98.5%), Eosin ,copper nitrate, lead nitrate, acetic acid, and

concentrated nitric acid was purchase from DKL Laboratory Supplies. All the chemicals

will use as receive without further purification.

Preparation of Graphene Oxide

GO will prepare from natural graphite powder by a modified Hummers method.38,39

Graphite (3.0 g) will add to concentrated sulfuric acid (70 mL) under stirring at room

temperature, then sodium nitrate (1.5 g) will add, and the mixture will cool to 0 C. Under

vigorous agitation, potassium permanganate (9.0 g) will add slowly to keep the

temperature of the suspension lower than 20 C. Successively, the reaction system will

transfer to a 35–40 C water bath for about 0.5 h, forming a thick paste. Then, 140 mL of

water will add, and the solution will stir for another 15 min. An additional 500 mL of

water will add, followed by a slow addition of 20 mL of H2O2 (30%), turning the color of

the solution from brown to yellow. The mixture will filter and wash with 1 : 10 HCl

aqueous solution (250 mL) to remove metal ions followed by repeated washing with

water and centrifugation to remove the acid. The resulting solid will disperse in water by

stirring overnight to make a GO aqueous dispersion. The obtained brown dispersion will
purify by dialysis for 2 weeks to remove the remaining acid and salt impurities. Finally, it

will subject to centrifugation at 4000 rpm for 30 min to remove aggregates. The

concentration of the suspension will determine by drying the GO dispersion with a

certain volume and weighing the residual GO.

Preparation Of Go–Cs Hydrogels

A CS stock solution with a concentration of 2.5% will prepare by dissolving 1 g of CS in

100 mL of 2.5% aqueous acetic acid, and stirring overnight. The formation of the gel will

confirm by a tube inversion method. To make the gelation process complete, the

hydrogels will Scheme Chemical structures of GO, CS, MB and Eosin. hydrogels

contain 5 mg mL GO and various amounts of CS. Method II will use to prepare the GO–

CS hydrogel in situ in a column. In Method II, 0.6 mL NaOH (0.5 mol L1 ) will add to the

GO suspension, then 0.25 mL CS solution (5 mg L1 ) will mix with the above

suspension by violent shaking, yielding a viscous blend solution. This GO–CS mixture

will pour into a 10 mL syringe (diameter 1.5 cm). Excessive HCl (0.1 mol L1 ) will add

carefully onto the mixture without disturbing the interface of the mixture and allowed to

pass through the mixture, while the pH of the outlet effluent from the syringe will

monitor. When the effluent became acidic, HCl will replace by water to wash the formed

hydrogel in the syringe, to remove the residual HCl and the formed salt, until the effluent

became neutral. The hydrogel-led syringe will then use as a column to purify water by

filtration.

Batch And Filtration Adsorption Experiments

MB, Eosin Y , copper nitrate, and lead nitrate will choose as the model compounds for

cationic dyes, anionic dyes and metal ions, respectively. The store solutions will prepare

by directly dissolving the model compounds with known weight in deionized water. For

Eosin Y solution, the concentration will determine by the absorbance at 516 nm in the

ultraviolet-visible spectrum. To measure the adsorption capacities of GO–CS hydrogels,

12.5 mg hydrogel will be added into 100 mL pollutant solution containing dyes or metal

ions. At predetermined time intervals, concentrations of pollutant solutions were

measured with an UV-Vis spectrometer or atomic absorption spectrometer. The time

required to achieve the equilibrium adsorption state was determined by the adsorption

kinetic curve. The isotherm measurement was conducted by changing the initial

concentration of the pollutant solutions, and the adsorption time was set longer than ten.

All the adsorption experiments were carried out at room temperature, which was

measured to be 21.1 C. The filtration adsorption experiment will conduct with a syringe

(the volume capacity is 10 mL and the diameter is 1.5 cm) as the column. The GO–CS

hydrogel will prepare in the syringe in situ with Method II. MB and Eosin Y solutions will

allow to penetrate through the column. The effluent will collect every 5 mL and its

concentration was measured. The adsorption of the hydrogel column will calculate

according to the effluent concentration.

Characterization

Scanning electron micrographs (SEMs) will be recorded on a 1530 scanning electron

microscope (LEO) operated at 20 kV. X-ray diffraction measurements will be conducted

using an Advance X-ray diffractometer with Cu Ka radiation. The measurement of metal

concentrations will be conducted using an MOLAAR M6 atomic absorption

spectrophotometer. Rheological studies will be performed on an ARES rheometer using

a 25 mm diameter parallel plate with a 1 mm plate–plate gap, and the strain will mixed

at 0.2%.
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Nanoparticles towards Methylene Blue." MDPI (2018).

Akpomie, Kovo G. "Mechanism on the sorption of heavy metals from binary-solution by

a low cost montmorillonite and its desorption potential" Elsevier (2015).

Wei MD, Wang. "Preparation and Characterization of self-assembly hydrogels with

exfoliated montmorillonite nanosheets and chitosan" PUBFACTS (2017).

Charlesworth, Susanne. "A new strategy for heavy metal polluted environments: a

review of Microbial Biosorbents" PMC (2017).

Pareek, Shreya. "A simple teachnology that can solve India's water problem for just Rs

3,000" HUFFPOST (2015)

Yadav, Anuj K. "Removal of heavy metals from emerging cellulosic low-cost

adsorbents: a review" Springer Link (2017)

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