CHAPTER ONE

1.0 INTRODUCTION

1.1 Background to the Study

Carbon, which is a necessary component in both living and nonliving systems, carries a

tremendous amount of weight due to the fact that it is so abundant. However, because its cycle

plays such an important part in promoting sustainable growth within human civilization, there

has been an increased emphasis placed on the process of capturing carbon for use in energy

conversion systems. Among many natural carbon fuels, C1 liquid fuels such as methanol have

been largely utilized and employed in direct alcohol fuel cells (Wang et al., 2019). Because of its

high energy density, ease of handling, and availability, methanol is a fuel that is often employed.

Direct methanol fuel cells (DMFCs) offer a potential solution for energy conversion and hold

promise as they circumvent safety concerns associated with hydrogen fuel. These fuel cells,

which utilize liquid methanol as their energy source, possess several advantages such as compact

size, high theoretical energy efficiency, and environmentally-friendly operation, making them a

compelling option for portable power generation (Munjewar et al., 2017). Furthermore, the

utilization of methanol fuel in DMFCs enables the realization of a sustainable carbon cycle by

combining the reduction of CO2 and other carbon-containing molecules to produce methanol,

which can be directly utilized in the fuel cells (Abdelkareem et al., 2021). However, attention has

been given to the green cycle of methanol production and consummation.

The electrode material is unquestionably a crucial factor in the electro-chemical oxidation of

methanol, where a highly effective electrocatalyst is required. Methanol may be oxidized in an

acid and alkaline electrolyte, simulating the fuel cell processes that take place in a fuel cell
configuration employing an acid and alkaline membrane (Fang and Feng, 2020). To comprehend

the transfer processes, cell functions, and suitable design geometries for the best fuel cell

performance, a theoretical simulation model has been created (Ahmadi et al., 2016). The

sluggish methanol oxidation reaction (MOR) kinetics and high production costs of DMFCs make

it difficult for them to be successfully commercialized. These issues are anticipated to be greatly

addressed by the selection of an appropriate anode catalyst (Huang and Wang, 2014). Platinum

(Pt) is utilized as the anode catalyst in DMFC devices because of its superior catalytic

capabilities, but because it is easily harmed by carbon monoxide (CO) and other carbonaceous

species produced during the electro-oxidation of methanol, its activity is reduced (Chung et al.,

2015). Approximately 38.56 percent of the entire cost of making fuel cells is incurred by the

platinum catalyst alone (James et al., 2009). These limitations prevent Pt from being used as an

electrocatalyst in DMFCs to its full potential. The development of active, reliable, and affordable

electrocatalysts for MOR is therefore one of the key issues facing fuel cell technology (Debe,

2012).

In recent years, graphene, a two-dimensional carbon allotrope that stands out for having a single

sheet of carbon atoms arranged in a hexagonal lattice, has attracted a lot of interest from the

scientific community. This one-of-a-kind form of carbon boasts extraordinary physical and

chemical characteristics, which make it a very attractive candidate for a wide range of

applications in a variety of technical fields (Geim and Novoselov, 2007). Some of these fields

include nanoelectronics, sensors, nanocomposites, batteries, supercapacitors, and hydrogen

storage. Notably, graphene has the ability to act as a catalyst in direct methanol fuel cells. This

presents benefits over carbon nanotubes, which are widely known for their remarkable electrical,

mechanical, and structural capabilities (Yoo et al., 2009). According to Dikin et al. (2009),
graphene has physically stable features that are equivalent to those of carbon nanotubes while

adding a greater surface area. In this study, the potential of grapheme oxide will be investigated

and evaluated for sustainable purpose.

1.2 Statement of the Problem

In direct methanol fuel cells (DMFCs), the electrooxidation of methanol is a critical step in

converting methanol into electrical energy. However, the widespread adoption of DMFCs is

hindered by the high cost and susceptibility to poisoning of catalysts like platinum. Therefore,

there is an urgent need to explore new catalysts for methanol electrooxidation that are affordable,

stable, and exhibit high activity. The use of reduced graphene oxide (rGO) derived from cerium-

oxide and lanthanum as an electrode material shows promise in addressing this challenge.

However, comprehensive research is required to evaluate the performance and electrocatalytic

activity of rGO for methanol electrooxidation, determining its suitability for efficient utilization.

1.3 Aim and Objectives

1.3.1 Aim

The aim of the study is investigate the electrochemical properties and performance of reduced

grapheme oxide derived from cerium-oxide/lanthanum as catalyst for the electro-oxidation of

methanol

1.3.2 Objectives

The specific objectives of this research are to;

i. synthesize and characterize a reduced graphene oxide from cerium-oxide/lanthanum

ii. evaluate the catalytic activity of the reduced grapheme oxide on the electro-oxidation of

methanol;

iii. compare and validate the effectiveness of reduced grapheme oxide

1.4 Motivation for the Study

The necessity to overcome significant obstacles and realize methanol's promise as a clean and

effective energy source served as the impetus for this investigation. To tackle climate change and

lessen reliance on fossil fuels, the globe is putting more and more effort into making the switch

to cleaner, more sustainable energy sources. In order to improve the electro-oxidation of

methanol and facilitate its conversion, effective and long-lasting catalysts are needed. The

practical application meets problems connected to the oxidation of methanol. This study looks

into reduced grapheme oxide, a catalyst made of cerium oxide and lanthanum, with the goal of

improving catalytic performance, overcoming obstacles, and developing methanol fuel cell

technology.

1.5 Significance of the Study

The study on the electro-oxidation of methanol by reduced graphene oxide from

cerium-oxide/lanthanum holds significant importance for several reasons; Methanol fuel cells

have the potential to be a clean and efficient energy source, but the development of efficient

methanol oxidation catalysts is crucial for their practical implementation. This study contributes

to the advancement of methanol fuel cell technology by investigating the catalytic properties of

reduced graphene oxide derived from cerium-oxide/lanthanum, potentially leading to the

development of highly efficient and durable catalyst materials. Reduced graphene oxide is a

promising catalyst material due to its high conductivity, large surface area, and chemical
stability. By exploring reduced graphene oxide derived from cerium-oxide/lanthanum, the study

expands the range of catalyst materials available for methanol electro-oxidation.

This research may provide insights into the unique properties and advantages of this specific

catalyst material, potentially leading to the development of improved catalysts for other

electrochemical applications as well. Investigating the electro-oxidation of methanol on reduced

graphene oxide from cerium-oxide/lanthanum allows for a deeper understanding of the

underlying catalytic mechanisms involved in this reaction. By studying the reaction kinetics,

reaction intermediates, and surface interactions, researchers can gain valuable insights into the

active sites and reaction path ways, which can be applied to design and optimize future catalysts

for methanol oxidation.

1.6 Definition of Terms

Electro-oxidation: Electro-oxidation refers to the process of oxidizing a substance at an

electrode surface in the presence of an electric current. It involves the transfer of electrons from

the substance being oxidized (the fuel) to the electrode, leading to the generation of an oxidation

reaction.

Reduced: In the context of chemical reactions and processes, the term "reduced" refers to a

chemical species or compound that has gained electrons or undergone a reduction reaction.

Reduction involves the addition of electrons to a chemical species, resulting in a decrease in its

oxidation state or an increase in its negative charge. When a compound or species is reduced, it

typically becomes more stable or less reactive.

 CHAPTER TWO

2.0 LITERATURE REVIEW

2.1 Methanol

Methanol is a chemical substance that is also known as methyl alcohol or wood alcohol. It is a

volatile liquid that is colorless and has the chemical formula CH 3OH. It is the most basic kind of

alcohol and consists of a methyl group (-CH3) and a hydroxyl group (-OH) connected to each

other. The vast majority of methanol that is manufactured is put to use in the synthesis of other

chemicals by the chemical industry, either as a starting material or as a solvent. The remaining

portion is put to use in the fuel and energy industries, where its application is growing (Ott et al.,

2000). Methanol has a long history of application in the manufacturing of a variety of products,

including adhesives, paints, LCD screens, silicones, and medications. Today, the manufacturing

of wood products and automobiles also make significant use of methanol.

Methanol's ability to act as a solvent has made it an important component in the production of

paints and adhesives (Stoye and Freitag, 2008). It is an essential component in the production of

adhesives, which are used in a wide variety of sectors, including construction and packaging,

among others. Methanol has been shown to be beneficial in a wide variety of industrial

processes, in addition to the uses that were just described. According to Verhelst et al., (2019,

methanol appears to be one of the most commonly traded chemicals in the world. Since a few

years ago, it has been extensively employed for energy applications. According to Landalv

(2017), around 20 million to 120 tons of methanol are produced each year as fuel or a fuel mix

component, and this amount is growing every year.

2.1.1 History of Methanol

Methanol has a rich and extensive history due to its diverse range of applications. In 1661, Sir

Robert Boyle first produced methanol by purifying crude wood vinegar using milk of lime,

giving it the name "adiaphorus spiritus lignorum." Later, in the 19th century, both Dumas and

Justus Von Liebig independently identified the composition of methanol. These discoveries led

to the introduction of the term "methyl" in chemistry in 1835. Between 1830 and 1923,

methanol, commonly known as "wood alcohol," was primarily derived from the dry distillation

of wood. However, in 1913, A. Mittasch and colleagues at BASF developed an efficient method

for synthesizing organic molecules, including methanol, from carbon monoxide and hydrogen

using iron oxide catalysts. Subsequently, in the early 1920s, M. PIER and colleagues achieved a

crucial breakthrough by creating a sulfur-resistant zinc oxide-chromium oxide catalyst (ZnO-

Cr2O3), paving the way for large-scale industrial production of methanol.

High pressures (25–35 MPa) and high temperatures (320–450 °C) were utilized throughout the

process, which was put into full-scale production at the BASF Leuna Works by the time the year

1923 came to a close. This marked the transition from the procedure's development stage into

full-scale production. On the other hand, in the 1960s, ICI (Imperial Chemical Industries) found

an alternate process for the manufacturing of methanol. This approach called for the utilization

of highly selective copper oxide catalysts during the reaction of sulfur-free synthesis gas with a

significant quantity of carbon dioxide. The reaction conditions in this and other related low-

pressure processes were very modest, falling between 5 and 10 megapascals and 200 and 300

degrees Celsius. These technological advances and conceptualizations continue to be the

cornerstone upon which modern industrial methanol production is built.

2.1.2 Physical Properties

Methanol is a liquid at normal room temperature and atmospheric pressure, characterized by its

moderate vapor pressure and high polarity (Shirazi et al., 2019). It is a transparent and colorless

compound that possesses solvent properties, making it suitable for a wide range of applications

as a typical organic solvent. Methanol exhibits the ability to dissolve substances with both high

and medium polarity, effectively facilitating the dissolution of a diverse range of compounds.

One of the notable features of methanol is its miscibility with various solvents. It can readily mix

with water, alcohols, and numerous organic solvents, forming homogeneous solutions (Zhang et

al., 2017). This property of miscibility enhances its versatility as a solvent, as it enables the

blending of different substances and the creation of tailored solvent systems. While methanol

displays good miscibility with polar solvents, its compatibility with nonpolar solvents such as

oils and fats is limited. Methanol exhibits a reduced ability to dissolve or mix with these

nonpolar substances due to the disparity in their polarities. However, certain degrees of

compatibility may be achieved depending on the specific nonpolar solvents, though it may not be

as efficient as with polar solvents.

The boiling point of methanol is 64.96°C (148.93°F), while its solidification point is -93.9°C (-

137°F). It burns with a flame that does not produce light and has the ability to combine with air

to create explosive mixes. Methanol is a dangerous toxin even though it smells a lot like ethyl

alcohol, the intoxicant present in alcoholic beverages. According to the Center for Disease

Control and Prevention (2009) drinking methanol-containing combinations has caused blindness

and even death in multiple occasions. Because methanol vapor is a little denser than air, it can

scatter and catch fire. Using dry chemicals, carbon dioxide, water spray, or alcohol-resistant
foam, you can put out a methanol fire. It is important to note that methanol fires do not create

visible flames under normal lighting conditions.

Figure 2.1: Molecular Structure of Methanol

2.1.3 Chemical Properties

Methanol, being the simplest aliphatic alcohol, possesses certain chemical characteristics. As a

representative example of this class of compounds, its reactivity primarily stems from the

functional hydroxyl group. Methanol undergoes reactions by breaking either the carbon-oxygen

(CO) or the oxygen-hydrogen (OH) bond, resulting in substitution of the hydrogen (H) or

hydroxyl (OH) group (Alcohols, Aliphatic). However, unlike higher aliphatic alcohols, methanol

does not undergo b-elimination reactions leading to the formation of multiple bonds.
Various significant chemical reactions involving methanol include:

 Dehydrogenation

It is possible for methanol to go through dehydrogenation reactions, which remove hydrogen

atoms from its molecular structure (Okamoto et al., 2003). Methanol may change during

dehydrogenation, resulting in the production of intermediate species such formaldehyde (CH 2O)

and others. Methanol dehydrogenation is frequently used in industrial settings as a critical step in

the creation of several compounds. Typically, the employment of specialist catalysts, such as

copper-zinc oxide or silver-based catalysts, which increase reaction efficiency, facilitates this

process. Formaldehyde, a crucial chemical intermediate with several uses, is one notable

byproduct of the dehydrogenation of methanol (Tavibian and Sharifzadeh, 2023). For the

production of several compounds, such as resins, polymers, solvents, and medicines,

formaldehyde is used as a building block. It is frequently used in sectors including healthcare,

textile, automotive, and woodworking.

 Carbonylation

Through catalytic reactions, methanol may combine with carbon monoxide to produce carbonyl

compounds. Various carbonyl compounds, which are organic molecules with a carbon-oxygen

double bond (C=O), are created when methanol and carbon monoxide are combined under

particular circumstances (Wang et al., 2022). Usually, transition metal catalysts like rhodium,

iridium, or cobalt complexes are used to catalyze this process. With the aid of these catalysts,

carbon monoxide and methanol can be converted into carbonyl compounds like acetic acid,

acetaldehyde, or methyl acetate.

  Combustion

Methanol (CH3OH) is a flammable liquid that can undergo combustion in the presence of oxygen

(O2) to produce carbon dioxide (CO2) and water (H2O). The balanced chemical equation for this

reaction is:

2CH3OH + 3O2 → 2CO2 + 4H2O

In this reaction, two molecules of methanol react with three molecules of oxygen gas. The

oxygen is typically supplied from the air. The reaction is exothermic, meaning it releases heat

energy. During the combustion of methanol, the carbon atoms in methanol are oxidized from the

+1 oxidation state in CH3OH to the +4 oxidation state in CO 2. The hydrogen atoms are also

oxidized from the -2 oxidation state in CH3OH to the +1 oxidation state in H2O.

 Reaction with Acid (Esterification)

Methanol (CH3OH) can react with carboxylic acids, such as acetic acid (CH3COOH), to form

esters through an esterification reaction (Mandake et al., 2013). One common example is the

reaction between methanol and acetic acid to produce methyl acetate (CH3COOCH3), as shown

in the balanced equation:

CH3OH + CH3COOH ⇌ CH3COOCH3 + H2O

A methanol molecule and an acetic acid molecule interact in this process. An ester bond (-COO-)

is created when the hydroxyl group (-OH) of methanol interacts with the carboxyl group (-

COOH) of acetic acid. Because esterification processes can reach an equilibrium state, the two

arrows show that the reaction is reversible. Acids like sulfuric acid (H 2SO4) or hydrochloric acid

(HCl), which protonate the carboxylic acid to make it more reactive, are commonly used to
catalyze the process. The carboxyl group receives a proton (H+) donation from the acid catalyst,

boosting its electrophilicity and enabling it to interact with the methanol's nucleophilic hydroxyl

group. Methyl acetate and water are the products of the esterification process. The ester product

is methyl acetate, and water is emitted as a byproduct. A water molecule is eliminated during the

esterification process by the condensation of the hydroxyl and carboxyl groups.

 Reaction with Halogens

Methanol (CH3OH) can undergo substitution reactions with halogens, such as chlorine (Cl 2) or

bromine (Br2), to form haloalkanes (McMurry, 2010). One specific example is the reaction

between methanol and chlorine to produce chloromethane (CH3Cl), as shown in the balanced

equation:

CH3OH + Cl2 → CH3Cl + H2O

In this reaction, methanol reacts with chlorine gas. The chlorine molecule (Cl 2) is highly reactive

and can undergo homolytic cleavage upon exposure to heat, light, or a radical initiator to form

chlorine radicals (Cl•). One chlorine radical reacts with a molecule of methanol, leading to the

substitution of a hydrogen atom in methanol with a chlorine atom.

The reaction takes place through a free radical mechanism. Initially, a chlorine radical abstracts a

hydrogen atom from methanol, generating a hydroxyl radical (•OH) and a methyl radical (•CH3).

The methyl radical then reacts with another chlorine molecule to form chloromethane (CH 3Cl)

and regenerate chlorine radical. The overall reaction can be summarized as:

CH3OH + Cl• → •OH + •CH3 •CH3 + Cl2 → CH3Cl + Cl•

The reaction is typically conducted under UV light or in the presence of a radical initiator to

initiate the formation of chlorine radicals. In this process, one molecule of methanol reacts with

one chlorine radical at a time, allowing for the substitution of a hydrogen atom with a chlorine

atom. As a result of the substitution reaction, chloromethane and water are formed.

Chloromethane, also known as methyl chloride, is a colorless gas at room temperature. It is used

as a solvent, as a precursor in the production of silicone polymers, and in the synthesis of other

organic compounds.

The diverse chemical reactions exhibited by methanol find widespread applications across

various fields. Methanol, as an active member of the alcohol group in organic compounds, plays

a vital role in numerous industrial and scientific contexts. It is worth emphasizing that the

reactions mention above are few of its capabilities and these reactions necessitate specific

conditions and frequently rely on suitable catalysts to enable the desired chemical conversions

(Ott et al., 2012).

2.2 Industrial Application of Methanol

1. Fuel and Energy: Methanol is widely used as a fuel and fuel additive. It can be utilized

as a clean-burning alternative to gasoline or diesel in internal combustion engines, reducing

emissions of pollutants such as sulfur oxides and particulate matter (Zhen and Wang, 2015).

Methanol is also used in fuel cells as a hydrogen carrier for generating electricity (Hardem et al.,

2019). Electronic gadgets that require external power sources for charging, such laptops, mp3

players, and mobile devices, have seen a substantial increase in popularity recently. Researchers

are currently looking at practical alternatives to conventional rechargeable battery systems, such

as those based on lithium (Li) and nickel (Ni), to meet this expanding requirement. Their efforts
are concentrated on creating energy-efficient techniques and removing the dependency on

outside power sources for fuel cell charging. Proton exchange membrane (PEM) fuel cells are a

popular choice among these electrochemical devices because they are effective at converting

chemical energy into electrical energy. In particular, the direct methanol fuel cell (DMFC), a

form of PEM fuel cell, runs at room temperature and uses methanol or methanol solutions as the

fuel. (Li and Faghri, 2013).

2. Chemical Manufacturing: Methanol serves as a vital building block in the production of

various chemicals. It is a precursor in the synthesis of formaldehyde, acetic acid, methyl tert-

butyl ether (MTBE), dimethyl ether (DME), and other important chemicals. These chemicals, in

turn, are used in the production of resins, plastics, solvents, adhesives, and coatings.

3. Biodiesel Production: Methanol plays a crucial role in the production of biodiesel. It

reacts with vegetable oils or animal fats in a process called transesterification, resulting in the

conversion of these feedstocks into methyl esters, which form the basis of biodiesel fuel (Fadhil

et al., 2017).

4. Solvents: Methanol's excellent solvent properties make it a preferred choice in various

industries. It is used as a solvent for paints, inks, dyes, and coatings. Methanol's ability to

dissolve a wide range of substances with different polarities makes it valuable in extraction

processes, such as herbal extractions and pharmaceutical manufacturing.

5. Formaldehyde Production: Methanol is a primary feedstock for the production of

formaldehyde, which is utilized in the manufacturing of plastics, resins, adhesives, textiles, and

other industrial applications. Formaldehyde is a key component in the production of urea-

formaldehyde resins, which find use in the construction and furniture industries (Tabibian et al.,

2023).

6. Intermediate in Petrochemical Refining: Methanol is used as an intermediate in the

refining of petroleum. It helps convert crude oil into valuable products like gasoline and olefins

through processes like methanol-to-gasoline (MTG) and methanol-to-olefins (MTO) (Yang et al.,

2020).

7. Pharmaceuticals: Methanol is used in the manufacturing of pharmaceuticals, including

medications, antibiotics, and antiseptics. It serves as a solvent and reactant in various synthesis

processes within the pharmaceutical industry.

2.3 Electro-oxidation

Electrooxidation is a vital process in electrochemistry, involving the oxidation of species at an

electrode surface (Bard & Faulkner, 2001). It plays a crucial role in numerous applications,

including energy conversion, environmental remediation, and chemical synthesis. The principles

of electrooxidation are governed by various factors, such as the electrode-electrolyte interface

and charge transfer mechanisms (Trasatti, 1991). Theoretical models, such as the Butler-Volmer

equation, are commonly used to describe the kinetics of electrooxidation reactions (Newman,

2004). The choice of electrode material significantly impacts electrooxidation performance.

Noble metals, such as platinum and gold, are renowned for their high electrocatalytic activity in

electrooxidation processes (Gasteiger et al., 2005). In addition, transition metal oxides, such as

ruthenium oxide (RuO2) and iridium oxide (IrO2), have shown promising potential as electrode

materials for electrooxidation reactions (Fabbri et al., 2019).

Catalysts are often employed to enhance the efficiency of electrooxidation reactions. Platinum-

based catalysts, like Pt/C, are widely recognized for their exceptional electrocatalytic properties

(Chen & Zhang, 2017). Furthermore, non-noble metal catalysts, including transition metal

sulfides and nitrides, have emerged as viable alternatives due to their earth-abundant nature

(Chen et al., 2012). Electrooxidation finds broad applications in various fields. For instance, in

fuel cells, electrooxidation facilitates the efficient conversion of fuels, such as methanol and

ethanol, into electrical energy (Antolini, 2007). It is also employed in the electrochemical

treatment of organic pollutants, enabling their degradation and removal from wastewater (Pérez

et al., 2011). Additionally, electrooxidation reactions play a crucial role in the electrosynthesis of

valuable chemicals by selectively oxidizing organic compounds (Bae et al., 2020).

2.3.1 Electrode Materials for Electrooxidaation

1. Noble Metals

Noble metals, such as platinum (Pt) and gold (Au), have long been recognized for their

exceptional electrocatalytic properties in electrooxidation processes. Pt electrodes, in particular,

exhibit high catalytic activity, stability, and tolerance to poisoning effects (Gasteiger et al.,

2005). The unique electronic structure and surface properties of noble metals contribute to their

effectiveness as electrocatalysts for a wide range of reactions.

2. Transition Metal Oxides and Chalcogenides

Transition metal oxides and chalcogenides have garnered significant attention as alternative

electrode materials for electrooxidation reactions. Materials like ruthenium oxide (RuO2),

iridium oxide (IrO2), and manganese oxides (MnOx) have shown promising electrocatalytic

activity and stability (Fabbri et al., 2019). These materials offer advantages such as earth-
abundance, low cost, and tunable properties, making them attractive for various electrochemical

applications.

3. Carbon-based Materials

Carbon-based materials, including graphene, carbon nanotubes (CNTs), and carbon nanofibers

(CNFs), have emerged as versatile electrode materials for electrooxidation. Their high surface

area, excellent electrical conductivity, and good chemical stability make them suitable candidates

for enhancing electrocatalytic activity (Chen & Zhang, 2017). Functionalization and doping of

carbon materials further improve their electrochemical performance and selectivity.

4. Metal Alloys and Composites

Metal alloys and composites offer an opportunity to optimize electrocatalytic activity and

enhance the stability of electrode materials. Bimetallic alloys, such as platinum-nickel (Pt-Ni)

and platinum-ruthenium (Pt-Ru), exhibit synergistic effects and improved catalytic properties

compared to pure metals (Chen et al., 2012). Composite materials, such as metal nanoparticles

supported on conductive substrates, provide increased surface area and enhanced mass transport

properties, leading to improved electrooxidation performance.

2.3.2 Applications of Electrooxidation

1. Energy Conversion

Electrooxidation plays a vital role in energy conversion processes, particularly in fuel cells. Fuel

cells are electrochemical devices that convert the chemical energy of fuels directly into electrical

energy. Electrooxidation is responsible for the efficient oxidation of fuel species, such as

hydrogen, methanol, ethanol, and formic acid, at the anode of fuel cells (Antolini, 2007). This
process generates a flow of electrons, which can be harnessed to produce electrical power. The

high efficiency and low environmental impact of fuel cells make them attractive for various

applications, including transportation, portable electronics, and stationary power generation.

2. Environmental Remediation

Electrooxidation offers effective solutions for environmental remediation and wastewater

treatment. Electrochemical oxidation processes are utilized to degrade and remove organic

pollutants, including pesticides, pharmaceuticals, and industrial wastewater contaminants (Pérez

et al., 2011). By applying an electric potential to the electrode, electrooxidation promotes the

breakdown of organic compounds through oxidation reactions. This method provides a

sustainable and efficient approach to mitigate water pollution and address environmental

concerns.

3. Organic Synthesis

Electrooxidation plays a significant role in organic synthesis, enabling the selective oxidation of

organic compounds. By harnessing the power of electrooxidation, various functional groups can

be selectively oxidized to generate valuable chemicals. For example, alcohols can be oxidized to

aldehydes, ketones, or carboxylic acids using electrochemical methods (Bae et al., 2020). This

approach offers advantages over traditional chemical oxidation methods, as it provides milder

reaction conditions, increased selectivity, and reduced environmental impact.

4. Water Purification

Electrooxidation processes have been employed for water purification and disinfection.

Electrochemical methods, such as electrochlorination and electrogenerated oxidants, utilize

electrooxidation to produce reactive species that can effectively kill bacteria, viruses, and other

microorganisms in water (Rajeshwar et al., 2008). These electrochemical approaches offer

advantages such as on-site generation, high efficiency, and the absence of harmful disinfection

byproducts.

5. Electroorganic Synthesis

Electrooxidation has gained attention in the field of electroorganic synthesis, which involves the

use of electricity to drive organic reactions. This approach offers a sustainable and selective

method for the synthesis of complex organic molecules. Electrooxidation allows the

functionalization of organic compounds, such as the introduction of functional groups, formation

of carbon-carbon bonds, and oxidative coupling reactions. The use of electrode materials and

appropriate reaction conditions enables precise control over reaction outcomes (Pletcher et al.,

2018).

6. Electroanlytical Techniques

Electrooxidation is an essential component of a number of different electroanalytical methods,

including voltammetry and amperometry, amongst others. The oxidation of analytes at electrodes

is utilized in these methods in order to gain information on the chemical composition and

concentration of compounds found in solution. Analytical methods based on electrooxidation

find uses in a wide variety of professions and businesses, including quality control in a variety of

different sectors, pharmaceutical research, and environmental monitoring.

2.4 Graphene Oxide and Reduced Graphene Oxide

Graphite oxide exhibits a layered structure that is similar to that of graphite, a well-known form

of carbon. However, in graphite oxide, the carbon atom plane is extensively decorated with

oxygen-containing functional groups. These groups introduce significant changes to the structure

and properties of the material. The presence of these oxygen moieties not only increases the

interlayer spacing between the graphene-like layers but also imparts hydrophilicity to the

atomically thin layers. Due to the hydrophilic nature of graphite oxide, when subjected to

ultrasonication in water, the oxidized layers have the potential to separate or exfoliate from the

bulk material. This process involves the dispersion of graphite oxide in water followed by the

application of ultrasonic energy, which induces vibrations and creates cavitation bubbles. These

cavitation bubbles generate shear forces and mechanical stresses, leading to the exfoliation of the

graphite oxide layers. The resulting sheets that have been successfully exfoliated or peeled off,

retaining one or a few layers of carbon atoms, are referred to as graphene oxide (GO) (Ray,

2015).

Graphene oxide, like graphene, consists of a two-dimensional arrangement of carbon atoms.

However, unlike graphene, which is a single layer of carbon atoms, graphene oxide typically

comprises multiple layers. The presence of oxygen-containing groups in graphene oxide imparts

unique properties and functionalities, making it distinct from pristine graphene. These oxygen

moieties introduce hydrophilicity, improve dispersibility in water, and enable further chemical

modifications and functionalization. The exfoliation of graphite oxide into graphene oxide

nanosheets has attracted significant interest due to the unique properties and potential

applications of graphene-based materials. Graphene oxide exhibits exceptional mechanical

strength, high surface area, and good electrical conductivity, along with the ability to undergo

chemical modifications to tailor its properties for specific applications.

Reduced graphene oxide (rGO) is derived from the chemical or thermal treatment of graphene

oxide. The typical process involves reducing the oxidized graphene oxide located between

graphite sheets. Several reducing agents, such as hydrazine, hydrazine hydrate, l-ascorbic acid,

and sodium borohydride, are commonly used to convert graphene oxide into rGO. Researchers

have explored the use of plant extracts for rGO preparation, as they are environmentally friendly

and easy to obtain. Plant extracts provide reducing and capping agents required for nanoparticle

synthesis. The functional groups present in rGO enable interactions with biomolecules like DNA,

proteins, peptides, and enzymes, facilitating easy chemical modifications. The utilization of

biomolecules for rGO synthesis is favored due to their cost-effectiveness, reduced labor and time

requirements for the reduction process, non-toxic and biocompatible nature, and potential

therapeutic applications. Moreover, the larger surface area of rGO contributes to its enhanced

effectiveness.

2.6 Lanthanum

Lanthanum, a rare earth element, is widely used in various industries due to its unique properties

and applications (Döbereiner & Gschneidner Jr., 2008). Its soft and malleable nature, combined

with its good electrical conductivity, makes it suitable for use in certain electronic applications

(Gupta & Krishnamurthy, 2004). Symbolized by the letter La and assigned the atomic number

57, lanthanum is one of the chemical elements. When it is exposed to air, the metal gradually

becomes a silvery-white color and becomes softer and more ductile. Lanthanum is the first and

the prototype element in the lanthanide series, which consists of 15 elements that are chemically
related to one another and are located between lanthanum and lutetium in the periodic table. This

element is the namesake of the lanthanide series. Historically, lanthanum has been categorized

among the other rare earth elements. Although compounds with an oxidation state of +2 are

known to exist, the typical oxidation state of rare earth elements is +3, which is the same as for

the vast majority of other rare earth elements. Lanthanum is necessary for the survival of some

bacteria but serves no biological purpose in humans. Although it does not pose a significant

threat to human health, it does possess antibacterial action.

In nature, lanthanum is almost always found in close proximity to cerium and the other rare earth

elements. The element lanthanum was discovered for the first time in 1839 by the Swedish

scientist Carl Gustaf Mosander as an impurity in cerium nitrate. The name lanthanum comes

from the Ancient Greek word v (lanthanein), which means "to lie hidden." Lanthanum is

approximately three times as plentiful as lead despite the fact that it is considered to be a rare

earth element. It ranks 28th on the list of most prevalent elements found in the crust of the planet.

About a quarter of the total lanthanide content that may be found in minerals like monazite and

bastnasite is made up of lanthanum. Because of the difficulty of the method required to separate

it from those minerals, pure lanthanum metal was not isolated for the first time until 1923.

Lanthanum oxide (La2O3) is utilized in the production of high-quality optical glasses and

ceramic materials, enhancing their refractive index and mechanical strength (Jiang & Yang,

2014). Lanthanum-based catalysts play a crucial role in petroleum refining processes, improving

fuel production efficiency (Kumar & Kumar, 2017). Additionally, lanthanum is employed in the

manufacturing of NiMH batteries, contributing to their enhanced capacity and power output

(Zhang & Zhou, 2014). In the lighting industry, lanthanum is utilized in the production of carbon

arc lamps, which are essential for applications such as stage lighting and high-intensity discharge
lighting (Döbereiner & Gschneidner Jr., 2008). Lanthanum-based phosphors are key components

in CRTs and fluorescent lighting, enabling the generation of colored displays and energy-

efficient lighting (Jiang & Yang, 2014). Furthermore, lanthanum, in combination with other rare

earth elements, is used in the production of permanent magnets for applications in electric

motors, generators, and MRI systems (Kumar & Kumar, 2017). The significance of lanthanum in

these diverse applications underscores its importance in various industries and ongoing research

and development efforts in lanthanum-based materials (Gupta & Krishnamurthy, 2004). The

abundance and desirable characteristics of lanthanum make it a valuable element for

advancements in energy, electronics, and materials science (Zhang & Zhou, 2014).