KWAME NKRUMAH UNIVERSITY OF SCIENCE AND

TECHNOLOGY

FACULTY OF PHYSICAL AND COMPUTATIONAL

SCIENCES DEPARTMENT
OF CHEMISTRY

SYNTHESIS OF IRON SULFIDE NANOPARTICLES FROM

THIOUREA USING THE MELT METHOD

THESIS SUBMITTED TO THE DEPARTMENT OF CHEMISTRY

BY

ADU MATTHEW

AND

CHINYERE SACKEY KORKOI

SUPERVISOR

PROFFESOR NATHANIEL OWUSU BOADI

SEPTEMBER 2022

Table of contents
 1.Chapter one
1.1 introduction…………………………………. 1

1.2 Problem statement……………………………. 3

1.3 Aims and objectives………………………. 4

1.4 Justification………………………………… 5

2.Chapter two
2.0 literature review………………………………… 7

3. chapter three
3.0Experimental method…………………………. 21

4. chapter four
4.0 results and discussion………………………. 23

5. conclusion.............................................................................
References......................................................................................

CHAPTER ONE
1.0 Introduction

The development of semiconductor nanoparticles has gained considerable attention in recent

years due to the fact that their properties strongly depend on the size of the particle. By

varying the size of the nanoparticles (NP’s) it is possible to tune the band gap of the material

which makes it unique with characteristics intermediate between those of molecules and bulk

semiconductors. The binary chalcogenide semiconductor Nanoparticles of CuS, ZnS, CdSe,

SnS, PbS, PbSe, FeS2, etc. have been investigated for its industrial application because of

their wide range of semiconducting properties and unique structural properties . iron sulfide

has a special place among these chalcogenide semicondutors because of its nontoxicity and

the earth abundance. Among the actually existing earth abundant inorganic photovoltaic

materials the cost of extraction of iron sulfide is among the lowest. As well as its excellent

optical property such as suitable band gap (Morales-Gallardo et al., 2016). Nanoparticles

(NPs), because of their size, unusual crystal shapes, and lattice orders, have received great

scientific and technological interest in environmental remediation. FeS based minerals are a

particularly important, viable reactive medium, which displays higher reactivity than zero-

valent iron in the reductive dechlorination of chlorinated hydrocarbons Nano-sized FeS

particles are expected to exhibit much higher reactivity because of their larger surface area

than bulk particles. Various methods have been employed to produce FeS NPs, including

high-energy mechanical milling combined with mechanochemical processing , sulfate-

reducing bacteria-assisted production , carbon dioxide laser pyrolysis of iron complexes , and

reverse micelle or polymer-stabilized wet-chemical synthesis . However, the preparation of

functionalized FeS NPs using different methods still remains a great challenge. One of the

unique approaches used to prepare inorganic NPs is through the use of poly(amidoamine)

(PAMAM) dendrimers as templates or stabilizers. Dendrimers are a novel class of polymers

with a close to spherical shape and a narrow size distribution that can be used as templates or
stabilizers to form relatively monodispersed organic/inorganic hybrid NPs. It has been

demonstrated that copper sulfide and cadmium sulfide can be formed using PAMAM

dendrimers as templates or stabilizers. The crucial role played by dendrimers to synthesize

dendrimer-stabilized NPs is that metal ions are usually complexed with dendrimer ligands

(e.g. interior tertiary amines, terminal functional groups) through coordination, electrostatic

interaction, etc, followed by reduction or other reactions to form inorganic NPs stabilized by

dendrimers. To our knowledge, there is no reported literature describing the use of PAMAM

dendrimers as stabilizers to synthesize FeS NPs. It is known that functionalized dendrimer

derivatives can be used as templates or stabilizers to synthesize metal NPs with desired

functionalities . For instance, Au NPs prepared using hydrophobically modified PAMAM

dendrimers as templates can be dissolved into various organic solvents(Shi et al., 2006).

Recently, synthesis and application of the nano-crystalline semiconductor materials have

attracted a huge interest due to their unique optical and electrical properties, higher surface to

volume ratios and an increased percentage of atoms at the grain boundaries. When the

diameter of these semiconductor nanoparticles (NPs) is less than a certain value, known as

the exciton Bohr radius, are often specified as quantum dots (QDs) . In this case, their

spectral properties become size-dependent, and can turn into potential wells that confine and

stabilize electrons in discrete energy levels (Raouf Hosseini and Nasiri Sarvi, 2015).

Iron sulfides refer to several types of compounds containing iron and sulfur . The crystal

shapes and physical properties of iron sulfides change significantly depending on the

variation of iron content. Recently, iron sulfides are recognized as a valuable inorganic

material in many areas, especially environmental remediation because of its chalcophilic

nature and reducing capability. For example, iron sulfides exhibit a high affinity for heavy

metals and chlorinated pollutants. It is expected that the improved catalytic properties can be

achieved by a combination of iron sulfides and zerovalent metals. Although several studies
have addressed the effect of sulfur compounds on iron-mediated dechlorination, the exact

mechanism of the process has not been elucidated yet(Kim et al., 2011).

1.1 problem statement

Solar cells are made of semiconductor materials. In a semiconductor all valence electrons

reside in the valence band and the lowest lying unoccupied band is called the conduction

band.

The region in between, where there are no energy states, is called the band gap.

Most of the solar cells on the market today are based on silicon crystals. Silicon has 14

electrons (electronic configuration: 1s2 2s2 2p6 3s2 3p2) with 4 electrons in the outermost shell.

If silicon is doped with pentavalent arsenic atoms (5 electrons in the valence shell) from

group 15, the 1 extra electron from each arsenic atom does not chemically bond with the

silicon atom and becomes a free electron. These free electrons that cannot chemically bond to

the neighbouring atoms, move around freely in the conduction band. This type of

semiconductor is called an n-type semiconductor, or in other words, a semiconductor rich in

electrons. Likewise, if silicon is doped with trivalent boron atoms (3 electrons in the valence

shell) from group 13, each dopant atom shares only 3 electrons with the neighbouring silicon

atom as they have 1 less electron in the valence shell when compared to silicon(Altermatt,

2005).
Silicon solar cells are very expensive due to the cost in processing it .although the primary

source of silicon is Quartz, which is found abundantly in sand, is the most common form of

silica. Silica is used to produce metallurgical grade silicon, which then undergoes several

stages of purification and refining steps to produce silicon of high purity for applications in

the photovoltaic (PV) industry. with such limitations there is the need to find an alternative

source of getting a semiconductor to silicon . this paper therefore focuses on synthesing iron

sulfides nanoparticles which can be an alternative to silicon to be used in solar panels(Kumar

et al., 2017). iron sulfide , is an important functional materials and have attracted

considerable experimental and theoretical interests in the past decades. The unique physical

properties of the nonmagnetic semiconductor FeS2 (pyrite) have made it a potential

photovoltaic (PV) absorber with high-efficiency and low cost (Allan, Labib and Holeil,

2016).

1.2 aims and objectives

1.2.1 main objectives

 Synthesis and characterisation of iron sulphide nanoparticles

 Application of the iron sulphide as a semiconductor in solar panels

1.2.2 specific objectives

 Ftir analysis

 Uv visible analysis
  Proton NMR analysis
 TGA analysis

1.3 justification

There is an abundant sunlight globally but there are a few solar energy systems .this is

because the cost is installing solar energy systems or buying their products is very high as

compared to the hydroelectric power. This is due to the fact that ,silicon which is the primary

semiconductor usually used in solar panels is very expensive although it is naturally abundant

but there is a high cost in processing silicon in order to be used in solar cells to absorb

sunlight to converted into usable form of energy(Liu and Chi, 2016).

Global electricity demand could be met with available solar energy potential due to its

abundant, inexhaustible nature . The Global Horizontal Irradiation and Direct Normal

Irradiation maps of Ghana in figure 4 shows the overall solar potential for thermal and

photovoltaic applications. Ghana receives some of the highest amounts of radiation, globally,

which makes it suitable for various solar energy applications particularly towards the northern

part of the country . Daily solar insolation levels range from 4 kWh/m 2 to 6 kWh/m2 with an

annual sunshine duration range between 1800 and 3000 h per annum which offers a high

potential for solar electricity generation . This data is further confirmed in the Solar Wind

Energy Resource Assessment (SWERA) report on Ghana(Lopez-varo et al., 2016).

Fig. 4. GHI solar map of Ghana

Despite this potential, challenges such as political will, technical expertise, availability of

components, financing, availability of land, and others have hindered the growth of the sector

over the years . Recent advances in research have, however, reduced the cost of electricity

from solar energy(Mensah et al., 2021). In Ghana, solar energy installations contribute 90%

of all renewable energy installations according to a study by Gyamfi et al. Energy policy is at

the heart of the issues affecting the implementation of solar energy in Ghana. Others include

solar energy usage in power generation as well as heating and cooling purposes, technical

feasibility, equipment supply, and manufacture, as well as financing(Esmaili, Sheibani and

Rashchi, 2017).
 CHAPTER TWO(2)

Literature review

Nanoparticles 1 to 100 nm

A nanoparticle is a small particle that ranges between 1 to 100 nanometres in size.

Undetectable by the human eye, nanoparticles can exhibit significantly different physical and

chemical properties to their larger material counterparts. The definition given by the

European Commission states that the particle size of at least half of the particles in the

number size distribution must measure 100 nm or below. Most nanoparticles are made up of

only a few hundred atoms(Sonai Muthu, Samikannu and Gopalan, 2019).

The table below shows the size of nanoparticles compared to other structures:

Particle Type Diameter Size Range

Atoms and small mole- 0.1 nm cules

Particle Type Diameter Size Range

Fine particles (also 100 to 2,500 nm called

particulate matter - PM2.5)

Thickness of paper 100,000 nm

Coarse particles (PM10, 2500 to 10,000 nm

or dust)
 For example, copper is considered a soft material, with bulk copper bending when its

atoms cluster at the 50nm scale. Consequently, copper nanoparticles smaller then 50nm are

considered a very hard material, with drastically different malleability and ductility

performance when compared to bulk copper. The change in size can also affect the melting

characteristics; gold nanoparticles melt at much lower temperatures (300 °C for 2.5 nm size)
than bulk gold (1064 °C)(Hu and Zhang, 2006). Moreover, absorption of solar radiation is

much higher in materials composed of nanoparticles than in thin films of continuous sheets of

material. Nanomaterials can occur naturally, be created as the by-products of combustion

reactions, or be produced purposefully through engineering to perform a specialized

function..Due to the ability to generate the materials in a particular way to play a specific role,

the use of nanomaterials spans across a wide variety of industries, from healthcare and

cosmetics to environmental preservation and air purification(Yuan, Wang and Gao, 2020).

The healthcare field, for example, utilises nanomaterials in a variety of ways, with one major

use being drug delivery. One example of this process is whereby nanoparticles are being

developed to assist the transportation of chemotherapy drugs directly to cancerous growths, as

well as to deliver drugs to areas of arteries that are damaged in order to fight cardiovascular

disease. Carbon nanotubes are also being developed in order to be used in processes such as

the addition of antibodies to the nanotubes to create bacteria sensors.In aerospace, carbon

nanotubes can be used in the morphing of aircraft wings(Bhunia et al., 2018). The nanotubes

are used in a composite form to bend in response to the application of an electric voltage.

Elsewhere, environmental preservation processes make use of nanomaterials too . In this case,

nanowires. Applications are being developed to use the nanowires - zinc oxide nanowires - in

flexible solar cells as well as to play a role in the treatment of polluted water.In the cosmetics

industry, mineral nanoparticles – such as titanium oxide – are used in sunscreen, due to the

poor stability that conventional chemical UV protection offers in the long-term. Just as the

bulk material would, titanium oxide nanoparticles are able to provide improved UV

protection while also having the added advantage of removing the cosmetically unappealing

whitening associated with sunscreen in their nano-form(Bera, Busupalli and Prasad, 2018).

The sports industry has been producing baseball bats that have been made with carbon

nanotubes, making the bats lighter and therefore improving their performance. Further use of
nanomaterials in this industry can be identified in the use of antimicrobial nanotechnology in

items such as the towels and mats used by sportspeople, in order to prevent illnesses caused

by bacteria Nanomaterials have also been developed for use in the military. One example is

the use of mobile pigment nanoparticles being used to produce a better form of camouflage,

through injection of the particles into the material of soldiers’ uniforms. Additionally, the

military have developed sensor systems using nanomaterials, such as titanium dioxide, that

can detect biological agents.The use of nano-titanium dioxide also extends to use in coatings

to form self-cleaning surfaces, such as those of plastic garden chairs. A sealed film of water is

created on the coating, and any dirt dissolves in the film, after which the next shower will

remove the dirt and essentially clean the chairs.Controlling the size, shape and material of the

nanoparticle enables engineers to design photovoltaics (PV) and solar thermal products with

tailored solar absorption rates. Absorption of solar radiation is much higher in materials

composed of nanoparticles than in thin films of continuous sheets of material.The Sol-Gel

process is a method for producing solid material from nanoparticles(Sathiyaraj and

Thirumaran, 2019). Whilst it is generally viewed as a relatively new industrial technology, it

is used extensively in a number of industries, such as abrasive powder manufacture, coatings

production and optical fibres.

Nanotechnology is a known field of research since last century. Since ‘‘nanotechnology” was

presented by Nobel laureate Richard P. Feyn man during his well famous 1959 lecture

‘‘There’s Plenty of Room at the Bottom” (Feynman, 1960), there have been made various

revolutionary developments in the field of nanotechnology. Nanotechnology produced

materials of various types at nanoscale level. Nanoparticles(NPs) are wide class of materials

that include particulate substances,which have one dimension less than 100 nm at least

Depending on the overall shape these materials can be 0D,1D, 2D or 3D . The importance of

these materialized when researchers found that size can influence the physiochemical
properties of a substance e.g. the optical properties. A 20-nm gold (Au), platinum (Pt), silver

(Ag), and palladium (Pd) NPs have characteristic wine red color, yellowish gray, black and

dark black col-ors, respectively. Au NPs synthesized with different sizes. These NPs showed

characteristic colors and properties with the variation of size and shape(Mohapatra et al.,

2019).

Synthetically produced nanoparticles play an important role in nanotechnology. They are a

wide class of materials whose extension in all three dimensions lies between 1 and 100

nanometers. Nanoparticles are now being used for instance in the manufacture of

scratchproof eyeglasses, crack-resistant paints, anti-graffiti coatings for walls, transparent

sunscreens, stainrepellent fabrics, self-cleaning windows and ceramic coatings for solar cells.

Nanoparticles can contribute to stronger, lighter, cleaner and 'smarter' surfaces and systems.

Synthetically produced nanoparticles play an important role in nanotechnology and find use

in many applications. This includes dispersions in gases (e.g. as aerosols), as ultrafine

powder, for thin-films, distributed in fluids (dispersed, for example ferrofluids) or embedded

in a solid body (nanocomposites)(Zhang et al., 2020). One striking example of what these

novel coatings can do is LiquiGlide, which is about to end consumers' infamous battle with

the ketchup bottle: There are numerous ways of nanoparticle classifications: Natural or man-

made? Synthetically produced or by-products? Organic or inorganic? By size; shape; surface

properties; or functionalization.

The diversity of synthetic nanoparticles is considerable. They are distinct in their properties

and applications. In addition to their size, synthetic nanoparticles vary in chemical

composition, shape, surface characteristics and mode of production.

In addition to commercially produced nanomaterials . many nanoparticles are not solely a

product of modern technology, but are also created by natural processes such as volcano
eruptions or forest fires. Naturally occurring nanoparticles also include ultrafine sand grains

of mineral origin (e.g. oxides, carbonates). Large quantities of nanoparticles are

unintentionally created by the combustion of diesel fuel (ultrafine particles) or during

barbecuing(Mensah et al., 2018).

Nanoscale Dimensions

Scientists classify nanomaterials based on the number of dimensions of a material, which are

outside the nanoscale (<100 nm) range.

Accordingly, in zero-dimensional (0D) nanomaterials all the dimensions are measured within

the nanoscale (no dimensions are larger than 100 nm). Most commonly, 0D nanomaterials are

nanoparticles.

In one-dimensional nanomaterials (1D), one dimension is outside the nanoscale. This class

includes nanotubes, nanorods, and nanowires.In two-dimensional nanomaterials (2D), two

dimensions are outside the nanoscale. This class exhibits plate-like shapes and includes

graphene, nanofilms, nanolayers, and nanocoatings.

Three-dimensional nanomaterials (3D) are materials that are not confined to the nanoscale in

any dimension. This class can contain bulk powders, dispersions of nanoparticles, bundles of

nanowires, and nanotubes as well as multi-nanolayers.

Two principal factors cause the properties of materials in nanoparticle size to differ

significantly from their bulk form: increased relative surface area, and quantum size

effects. These factors can change or enhance properties such as reactivity, strength and

electrical characteris-

tics
Surface Area
As a particle decreases in size, a greater proportion of atoms are found at the surface

compared to those inside. At a particle diameter of 10 nm, 20 % of the approximately 30 000

atoms of the entire particle are positioned on its surface; at a particle diameter of 5 nm, the

value increases to 40 %, and at 1 nm diameter, almost all of the atoms are on the surface. The

surface atoms, as opposed to those inside the material, have fewer direct neighbors and

therefore contain so-called unsaturated bonds. These are responsible for the higher reactivity

of the particle surface.

Thus nanoparticles have a much greater surface area per unit mass compared with larger

particles. As growth and catalytic chemical reactions occur at surfaces, this means that a

given mass of material in nanoparticulate form will be much more reactive than the same

mass of material made up of larger particles. To understand the effect of particle size on

surface area, consider an American Silver Eagle coin. This silver dollar contains 31 grams of

coin silver and has a total surface area of approximately 3000 square millimeters. If the same

amount of coin silver were divided into tiny particles – say 10 nanometer in diameter – the

total surface area of those particles would be 7000 square meters (which is equal to the size of

a soccer field – or larger than the floor space of the White House, which is 5100 square

meters). In other words: when the amount of coin silver contained in a silver dollar is

rendered into 10 nm particles, the surface area of those particles is over 2 million times

greater than the surface area of the silver dollar!

Increased reactivity is the basis for numerous applications. Precisely controlling particle

diameter yields a new generation of catalysts with high selectivity; such catalysts accelerate

chemical processes.
This high reactivity also reduces the melting point, so that using nanoparticular raw materials

would reduce the firing temperature in the case of ceramics. More importantly, the

composites (solids composed of various materials) would shrink less during the hardening

process, a particularly important feature in dental prosthetics for example.

Quantum Size Effect

The so-called quantum size effect describes the physics of electron properties in solids with

great reductions in particle size. This effect does not come into play by going from macro to

micro dimensions. However, it becomes dominant when the nanometer size range is reached.

Quantum effects can begin to dominate the behavior of matter at the nanoscale – particularly

at the lower end (single digit and low tens of nanometers) – affecting the optical, electrical

and magnetic behavior of materials.

The causes of these drastic changes stem from the weird world of quantum physics. The bulk

properties of any material are merely the average of all the quantum forces affecting all the

atoms that make up the material. As you make things smaller and smaller, you eventually

reach a point where the averaging no longer works and you have to deal with the specific

behavior of individual atoms or molecules – behavior that can be very different to when these

atoms are aggregated into a bulk material.

Materials reduced to the nanoscale can suddenly show very different properties compared to

what they show on a macroscale. For instance, opaque substances become transparent

(copper); inert materials become catalysts (platinum); stable materials turn combustible

(aluminum); solids turn into liquids at room temperature (gold); insulators become

conductors (silicon).
Varying nanoparticle size not only modifies reactivity but can also alter the optical characteristics such as

transparency, absorption, luminescence and scattering. Although particles measuring only a few

nanometers in diameter lie far below the wavelength range of visible light (380 to 780 nm), they can

absorb light of specific wavelengths.

These effects can only be understood on a quantum mechanics level. In the case of quantum

dots, which are composed of semiconductor materials, particle size can be used to adjust the

wavelength of the fluorescence, for example. These optical features make nanoparticles

especially interesting for applications in optoelectronics, cosmetics and medical diagnostics.

Different Types Of Nanoparticles

Nanoparticles can be classified into different types according to the size, morphology,

physical and chemical properties. Some of them are carbon-based nanoparticles, ceramic

nanoparticles, metal nanoparticles, semiconductor nanoparticles, polymeric nanoparticles and

lipid-based nanoparticles.

Nanoparticles types are commonly divided in two main groups: organic and inorganic. The

first group includes micelles, dendrimers, liposomes, hybrid and compact polymeric

nanoparticles. The second group includes fullerenes, quantum dots, silica and metal

nanoparticles.

Another way of classifying nanoparticles is based on their morphology, size and chemical

properties. Based on physical and chemical characteristics, some of the important classes of

nanoparticles are:

Carbon-based – (fullerenes, carbon nanotubes, graphene, carbon dots). These materials are of

great interest due to their electrical conductivity, high strength, structure, electron affinity,

and versatility.
Metal – They are purely made of the metals precursors. Due to well-known localized surface

plasmon resonance (LSPR) characteristics, these these possess unique optoelectrical proper-

ties.

Ceramic – These inorganic nonmetallic solids are getting great attention of researchers due to

their use in applications such as catalysis, photocatalysis, photodegradation of dyes, and

imaging applications.

Semiconductor – Semiconductor materials possess properties between metals and non-metals

and have wide bandgaps. Bandgap tuning results in significant alteration in their properties.

Therefore, they are very important materials in photocatalysis, photo optics and electronic

devices.

Polymers – Scientists have developed many techniques to synthesize polymeric nanoparticles

for a wide range of applications including surface coating, sensor technology, catalysis, and

nanomedicine.

Liquid-phase eutectic gallium–indium (EGaIn) alloy nanoparticles.

Lipids – These NPs contain lipid moieties and are used in many biomedical applications as

drug carriers (the mRNA Covid-19 vaccines are using lipid nanotechnology). Lipid

nanoparticles are also regarded as highly promising systems for delivering nucleic acids in

gene therapy.

Synthesis of Nanoparticles
Specific synthesis processes are employed to produce the various nanoparticles, coatings,

dispersions or composites. Defined production and reaction conditions are crucial in

obtaining such size-dependent particle features. Particle size, chemical composition,

crystallinity and shape can be controlled by temperature, pH-value, concentration, chemical

composition, surface modifications and process control.

Two basic strategies are used to produce nanoparticles: top-down and bottom-up. Read all

about it in our detailed article on how nanoparticles are made.

In general, the term top-down refers here to the mechanical crushing of source material using

a milling process. In the bottom-up strategy, structures are built up by chemical and self-

assembly processes. The selection of the respective process depends on the chemical

composition and the desired features specified for the nanoparticles.

Typical synthetic methods for nanoparticles for the (a) top-down and (b) bottom-up approaches. (©

Arabian Journal of Chemistry)

Characteristics of Nanoparticles
Researchers are still challenged by the task of determining the physicochemical properties of

nanoparticles and exploring their structure-function relationships. A key limitation is their

ability to fully investigate the nanoscale realm: Different characterization techniques are

based on different physical properties, therefore only providing a partial picture of the

nanoparticle characteristics. Making matters more challenging yet, the characterization

methods themselves can directly affect the measured quantities of nanoparticles.

Nanoparticles exist in various chemical compositions ranging from micelles to metal(oxide)s,

from synthetic polymers to large biomolecules. Each of these materials features a completely

different chemistry, which can be analyzed by a variety of methods including optical

spectroscopy, X-ray fluorescence and absorbance, Raman spectroscopy, and solid-state

NMR. However, often the behavior of nanoparticles is largely governed by their nanometer

dimensions. As such, throughout nanoparticle characterization, the investigation of size,

shape, surface charge and porosity is a fundamental step for fully understanding and

predicting their behavior.

Application of nanoparticles
The fields of application for nanoparticles are wide ranging , They play a major role in

materials development. The great expectations we place on today's nanoparticle-containing

materials is based on the hope that the different material properties such as conductivity,

weight, stability, flexibility, heat resistance etc. can be specified independently from one

another.Nanoparticle applications also have been introduced on the market in paints,

polymer nanocomposites and nanopigments. Numerous nanotechnology products have been

on the market for some time now. In the chemical sector this includes Carbon Black (soot

particles), for printing black; in the automobile sector this includes scratch-resistant paints,
filler in tires and anti-reflective layers. Nanoparticles exist for highly efficient hydrogen

storage systems, self-healing materials, and coatings that switch their color using sensor

technology.

In the life sciences, nanoparticles are used for biochips as well as for so-called markers. They

are also used in sunscreens and cosmetic products. In medical diagnostics, nanoparticles are

increasingly being used as contrast media; they are also a tool in cancer therapy as drug

delivery agents. Nanoparticles are promising in regenerative medicine, for example in tissue

cultures.

Thiourea

Thiourea is an organo-sulfur compound with formula SC(NH 2)2. It is structurally similar to

urea except that oxygen atom is replaced by a sulfur atom. The properties of urea and

thiourea differ significantly. Thiourea has a wide range of applications. In plants, low

concentration of thiourea was first used as a dormancy breaking agent (Tukey and Carlson,

1945). The effect was correlated with catalase inhibition which facilitates H 2O2 mediated

oxidation of NADPH that acts as oxidant in pentose pathway to produce glucose (Hendricks

and Taylorson, 1975). Later, it was adopted as a plant growth regulator (Gul and Weber,

1998). During recent years, thiourea has been widely used for enhancing plant growth, stress

tolerance and crop yield (Sahu et al., 2006; Mathur et al., 2006; Shahba et al., 2008; Mani et

al., 2012; Amin et al., 2013;

Pandey et al., 2013; for details refer Table 1). At the physiological level, these effects are due

to coordinated regulation of plant source-to-sink relationship (Pandey et al., 2013) and

enhanced translocation of metabolites from source (leaves) to sink (pods) (Srivastava et al.,

2008). At molecular level, thiourea effects are related with its ability to scavenge broad range

of reactive oxygen species, such as H 2O2 and superoxide radical, produced under biological

system (Kelner et al., 1990; Gao et al., 2008). Since, ROS mediated signaling, also termed as

“Redox signaling” is well established as one of the central regulators of stress signaling in

plants (Steinhorst and Kudla, 2013; Gilroy et al., 2014); thiourea application was utilized as a

strategy to delineate redox regulated components associated with calcium and ABA signaling

in germinating seeds of Brassica juncea (Srivastava et al., 2010a). The molecular level

changes induced by thiourea were also positively reflected in terms of improved energetics

(Srivastava et al., 2009), antioxidant defense (Srivastava et al., 2011), plant-water

homeostasis (Srivastava et al., 2010b), and sulfur metabolism (Srivastava et al., 2014) in

plants against different environmental stresses. Apart from indirect effects of thiourea which

are associated with its ROS scavenging action, the direct effects have also been demonstrated

at higher thiourea concentration (in mM range; for indirect effects thiourea was provided in

μM). These include irreversible inhibition of catalase (Hendricks and Taylorson, 1975),

antinitrification (Grant and Wu, 2008), and antiweeding (Kannan and Zwanenburg, 2014)

properties of thiourea(Chen et al., 2005)

Chapter 3
Experimental method

Synthesis of iron (III) thiourea complex

 2.4g of thiourea was dissolved in 15ml distilled water

 the mixture was stirred until a homogenous clear solution was formed
  2.0 g iron (III) chloride was dissolved in 15ml disstiled water and stirred forming a

yellow uniform solution

 The two solutions were mixed together forming a yellowish brown solution

 The solution was then heated to boiling and allow to cool down to room temperature

 The cooled solution was then stirred and green crystals started forming, this was

allowed to stand for about 30minutes and more crysatls were formed

 The mixture was then filtered and the residue(crystals) on the filter paper was tried

forming pure crystals

 Further characterization was performed on the complex synthesized .these includes

FT

–IR analysis ,NMR ,TGA, UV-VIS to determine the various functional

groups ,structural elucidation ,decomposition pathway and to find out whether our

complex absorbs in the uv-vis region and also confirm the various chromophores

present in the complex respectively

Preparation of iron sulphide nanoparticles

 Part of the the complex formed was put on an aluminium foil ,folded nicely and was

inserted in the tubular furnance .the furnance was set at a temperature of 300℃ and

timed of one hour.this is done to decompose the organic portions of the complex

formed leaving behind the inorganic portions (Fe and S).

 After the due time , the sample was taken out of the furnance and uv-vis analysis

was performed on it. this was done in order to calculate the band by using talc plot.
 Chapter 4

Results and discussion

FTIR spectra of pure thiourea and iron(III) thiourea complex

FTIR spectroscopy was used to study the interactions between the pure thiourea and the iron

chloride and also the functional groups present in the pure thiourea and that of the iron

chloride . FTIR spectra of the pure thiourea and iron sulphide nanoparticles are presented in

the Figure below. The pure thiourea spectrum shows a characteristic bands at 3360-3262,

1570-1395, , and 1000-1250cm-1 assigned to the v(N–H), v(C=S), and v(C-N), stretching

vibrations. The iron sulphide nanoparticles show similar bands at the same frequencies but

with lower intensities, which confirms the interactions of the thiourea and the iron chloride.
 Figure.1Ftir spectra of pure thiourea

figure.2 ftir spectra of iron thiourea complex

The proton NMR spectra of the complex showed two signals on the spectrum with the first

signal around 2.4ppm which corresponds to the solvent ( DMSO) peak. The next peak was

found around 3.5 pmm with an integration of 12 with corresponds to the twelve equivalent

protons in the proposed structure of the complex.

 figure.3 1H NMR of thiourea complex

Nmr analysis was used to confirm the structure of the proposed structure of the complex Two

major peaks were shown on the nmr spectrum ,both peaks were singlet . the first peak around

2.3 ppm corresponds to the solvent (DMSO) peak and the other is for the twelve equivalent

protons in the complex with an integration of 12.

276.6nm, 0.7549A
 Fig .4 Uv –vis spectrum of complex

The uv-vis spectrum of the complex showed two absorbances which is as a results of the

transition metal (Fe) present in the complex and the other chromosphores present as well.

Uv-vis spectrum of iron sufide nanoparticle

The uv –vis spectrum of the nanoparticle showed a single absorbance in the uv region ,

indicating that the nanoparticle can absorb light in the uv region . the calculated band gap was

around 4.46eV.
 Fig .5 TGA spectra of complex

The TGA spectra shows three decomposition pathways for the complex . the first

decomposition has to do with the lost of moisture and in the second decomposition 88.528%

of the total weight of the cvomplex was lost with 8.385% remaining as the residue .the %

decomposition of the residue was found to bew closer the molecular weight of iron in the

complex synthesized.

Conclusion

tri –chloro tris-thiourea iron (III) complex was used as a single source precursor for the

synthesis of iron sulfide nanoparticles with a % yield of 54% and a melting point

temperature range of 114-118 ℃. Ftir analysis shows the existence of metal sulfide in the

synthesized complex whiles the uv-vis spectra of the complex confirm the possibility of the

complex absorbing radiations from the sun as well as the synthesized nanoparticle . the band
of 4.46eV of the nanoparticle indicates that the nanoparticle can absorbs light in the uv

region making it a useful material in solar panels.

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