CHAPTER 1

INTRODUCTION

1.1 Introduction

The word "nanotechnology" comes from the prefix "nano" in the International

System of Unit (SI), which stands for one billionth of a meter, or lO9 m (Taylor et al., 2001).

Nano is derived from the Greek term “dwarf “and is associated with the Spanish word

“Nino” Professor N. Taniguchi coined the term nanotechnology in 1974. In general,

nanotechnology can be understood as a technology of design, fabrication, and applications

of nanostructures and nanomaterials and a fundamental understanding of physical properties

and phenomena of nanomaterials and nanostructures (Sandhu et al., 2006). Nanotechnology

is a multidisciplinary field that includes chemistry, engineering, biology, and medicine, with

many promising applications, such as cancer early detection, accurate diagnosis, and

individualized treatment (Cai et al., 2007). A particle that exhibits one or more dimensions

on the nanoscale (< 100 nm) is considered a nanoparticles (NPs) (Faraji et al., 2009). When

a material is reduced to the nanoscale, its physicochemical properties change dramatically,

including melting point, fluorescence, electrical conductivity, magnetic permeability, and

chemical reactivity (Murray et al., 2000, Pankhurst et al., 2003, Park et al., 2003).

Nanoparticles are used in a variety of fields, including material science and biomedicine.

The creation of novel nanodevices and nanostructures for catalysis, sensors, data storage,

bio authentication investigations, optical filters, and electrical devices has sparked research

in this sector (Aiken et al., 1999, Cheng et al., 2003, Weiping et al., 1997, Maxwell et al.,

2002, Leroux et al., 2009, and Gittins et al., 2000).

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1.2 Titanium dioxide (TiO2)

The Titanium dioxide (TiO2) seems to be an n-type semiconductor of the transition

metal oxide family. The three most common polymorphs are Anatase, Rutile, and Brookite.

Brookite is orthorhombic, while Anatase and Rutile are tetragonal crystal structures.

Brookite is more challenging to obtain than the other two polymorphic crystals. In

photocatalysis, titanium dioxide nanoparticles are commonly used in the rutile and anatase

phases (Hanini et al., 2013). Anatase has a high activity level, reduced recombination rates,

and absorbs water and hydroxyl groups (Hurum et al., 2003). Rutile and Anatase have an

orthorhombic crystal structure that can be classified based on the TiO6 octahedral chains

(Gupta et al., 2007). The deformation of each octahedron and the arrangement of the

octahedral chains differ between the two crystal formations (Asl et al., 2012, Brayner et al.,

2013, Senić et al., 2011, Shi et al., 2007). An octahedron of six O2- ions surrounds each Ti4+

ions. The rutile phase of the octahedron is irregular, with minor orthorhombic distortion. In

the rutile structure, each octahedron is in contact with 10 neighbor octahedrons (two sharing

edge oxygen pairs and eight sharing corner oxygen atoms), while in the anatase structure,

each octahedron is in contact with eight neighbors (four sharing an edge and four sharing a

corner). These differences in lattice structures cause different mass densities and electronic

band structures between the two forms of TiO2. Titanium dioxide nanoparticles are highly

stable, high adsorption ability, non-toxic, and inexpensive (Hamad et al., 2016, Pavasupree

et al., 2015, Liu et al., 2011, Farbod et al., 2013).

The semiconductor TiO2 is widely used in air and water purification, photovoltaic

cells, self-cleaning coatings, sensors, sterilization, antibacterial activity, and hydrogen

evolution (Chen et al., 2006, Akurati et al., 2006, Mital et al., 2011). Much innovative

heterogeneous photocatalysis based on TiO2 for environmental cleaning applications has

been actively explored for these reasons. The disadvantage of titanium dioxide nanoparticles

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is that they do not absorb visible light and have a greater recombination rate (Verma et al.,

2019). The results of mixing noble metal (Ag) with TiO2 to improve photocatalytic

properties and bandgap are described in this thesis.

Figure 1.1 Three different phases of titanium dioxide

1.2.1 Importance of Titanium dioxide nanoparticles

 It is used in paints, cosmetics, sunscreens, plastic and rubber manufacturing,

electronics and pharmaceuticals.

 Strong antibacterial agent.

 Drug carrier.

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  Titanium dioxide nanoparticles are used in industrial sectors including

environmental applications, synthetic textiles, food, packaging, and medical care.

1.3 Silver nanoparticles (Ag)

Noble metal nanoparticles such as gold and silver have attracted more scientific

attention than any other metal nanoparticle because of their remarkable magnetic, optical,

antimicrobial, and electrical characteristics. Ag-NPs are used in catalysis, optoelectronics,

photonics, pharmaceuticals, antimicrobial goods, electronics, sensing, and therapies in the

research field due to their unique properties (Habibullah et al., 2021). Because of their

antifungal and antibacterial properties and their inexpensive production costs, Ag-NPs are

used in consumer goods. For example, silver nanoparticles are used as deodorizers and

disinfectants in food packaging, coatings, clothing, and packaging. The polyol method,

acrylate/citrate reduction, light reduction, microwave irradiation, and green synthesis are

standard methods for generating Ag-NPs (Babu Maddinedi et al., 2017).

On the other hand, toxic chemicals must be used for these costly synthesis techniques

and require more energy. As a result, the growing demand for novel biosynthesis methods

for the preparation of NPs is safe, environmentally nature for large-scale production and

cost-effectiveness (Jia et al., 2006). Green synthesis methods are more valuable than the

other chemical reduction process that are often used.

1.3.1 Importance of silver nanoparticles

 Silver nanoparticles are used for the purification and quality management of air,

biosensing, imaging, and drug delivery system.

 Biologically integrated silver nanoparticles have many applications, such as coatings

for solar energy absorption and intercalation material for electrical batteries, optical

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 receptors, catalysts in chemical reactions, bio labeling, and antimicrobials

(Premasudha et al., 2015).

 Silver nanoparticles are cytotoxic, but they have enormous applications in the field

of high sensitivity bimolecular detection and diagnostics, antimicrobials and

therapeutics, catalysis and micro-electronics.

 Silver nanoparticles have some potential applications like diagnostic biomedical

optical imaging, biological implants (like heart valves) and medical application like

wound dressings, contraceptive devices, surgical instruments and bone prosthesis

(Ashe et al., 2011).

1.4 Activated carbon

Activated carbon is a type of microcrystalline carbon with a large surface area and

high porosity. It can be found as foam solid with a high surface area contained within a stiff

granule or particle structure with a limited volume (Yağşi et al., 2004). Its chemical

composition enables it to adsorb organic and nonpolar molecules preferentially from gaseous

or liquid streams. Because of its strong adsorption capacity, activated carbon has become

one of the most technically essential and frequently used adsorbents. Current technology

requires the massive output of activated carbon (Rashed et al., 2013).

Dehydration, carbonization, and oxidation of organic compounds produce activated

carbon obtained by a well-regulated procedure. Peat, coal, lignite, wood, and agricultural

by-products such as coconut shell, almond shell, rice husks, and other agricultural by-

products are often used commercially (Mdoe et al., 2014). Activated carbon is synthesized

via a chemical activation process. The most widely used activation agents are Phosphoric

acid, Zinc chloride, Sodium Hydroxide, and Magnesium salts. Chemical agents dehydrate

the environment and inhibit tar production during carbonization (Artmann et al., 2018).

Chemical activation is usually done at lower temperatures than pyrolysis and steam or carbon

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dioxide activation processes. Because base crystallites with smaller diameters are formed at

lower temperatures, it helps to create a microscopic structure. Most of the activated carbon-

accessible surface area is nonpolar (Liao et al., 2019).

1.4.1 Importance of Activated carbon

 Activated carbon is used in methane hydrogen storage, air purification, solvent

recovery, gold purifications, and water purifications, etc.

 Activated carbon is used to treat poisonings.

 Activated carbon helps to extract direct oral anticoagulants such as dabigatran,

apixaban, rivaroxaban, and edoxaban from blood plasma samples.

 Carbon absorption has numerous applications in removing pollutants from air or

water streams (Pierobon et al., 2018).

1.5 Nanocomposites

Nanocomposites are multiphase solid materials of one, two, or three dimensions of

less than 100 nanometers (nm) and have nanoscale repetitive distances between the various

stages of material formation. The concept behind nanocomposite is to create and construct

new materials with exceptional flexibility and improved physical properties using nanometer

sized building blocks (Sharif et al., 2018). The mechanical, electrical, thermal, optical,

electrochemical, and catalytic properties vary considerably from composite materials. For

these consequences, size limitations have been proposed:

• <5 nm for catalytic activity

• <20 nm for making a hard magnetic material soft

• <50 nm for refractive index changes

• <100 nm for achieving superparamagnetic, mechanical strengthening or

restricting matrix dislocation movement (Bagheri et al., 2016).

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1.5.1 Ceramic-matrix nanocomposites

Ceramic matrix composites (CMC’s) consist of ceramic fibers embedded in the

ceramic matrix. The matrix and fibers can contain any ceramic material, including carbon

and carbon fibers. Ceramic is often occupied by a group of oxides, such as nitrides, borides,

and silicide, while the second component is usually a metal (Chawla et al., 2013). The two

components are finely dispersed from each other to express specific optical, electrical,

magnetic, biological, and corrosion resistance properties. An excellent example of ceramic-

metal composite is TiO2 and Cu. The mixtures were found immiscible over large areas in

the Gibb’s triangle of Cu-O-Ti (Yaqoob et al., 2020).

1.5.2 Metal-matrix nanocomposites

Metal matrix nanocomposites (MMC’s) can also be defined as reinforced metal

matrix composites. These composites can be classified as continuous and non-continuous

reinforced materials (Camargo et al., 2009). One of the more critical nanocomposites is

carbon doped metal matrix composites, new emerging material being developed to utilize

carbon nanotube materials with high tensile strength and electrical conductivity. CNT-MMC

with optimal properties in these areas is essential for the perception of

(a) Development of economically manufactured synthesis.

(b) Providing a uniform dispersion of nanotubes in the metallic matrix.

(c) Strong interfacial adhesion between the metallic matrix and the carbon nanotubes

(Mekuria et al., 2020).

In addition to carbon nanotubes doped metal matrix composites, boron nitride reinforced

metal matrix composites, and carbon nitride doped metal matrix composites are new research

areas on metal matrix nanocomposites.

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1.5.3 Importance of nanocomposites

 Thin film-based nanocomposites are used in computer chips.

 Solid polymer electrolyte for batteries.

 Composites are used as automotive engine parts and fuel tanks.

 Nanocomposites dramatically improve the mechanical properties, including

strength, modulus and dimensional stability (Hassan et al., 2012).

1.6 Synthesis of nanoparticles

Nanotechnology is the key to synthesis and manipulate nanoparticles and nanostructured

materials. It allows researchers to explore unique physical properties and phenomena to

realize potential applications of nanostructures and nanomaterials. As illustrated in Fig.1.2,

the most prevalent nanomaterials synthesis techniques.

1.6.1 Top down synthesis

Planar, lithography, etching, and deposition processes are commonly used in top-

down procedures to transfer a predesigned pattern to a substrate, creating complex high

density structures in well-defined places on substrates and their integrated systems. The top-

down method shows that it is highly effective in various applications, the most recent

example being microelectronics. They can create nanostructures with highly stable shapes

and electrical properties. As improvements continue to push the clarity limits of top-down

approaches, the increases in this resolution are accompanied by a rapid increase in cost with

each successive production level.

1.6.2 Bottom up synthesis

Bottom-up approaches are a powerful alternative to traditional top-down methods, in

which functional structures are assembled from well-defined chemically and physically

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synthesized nanoscale building blocks. The bottom-up approach is similar to how nature

uses proteins and other macromolecules to construct complex biological systems. By

defining vital nanometer scale metrics through synthesis and subsequent assembly, the

bottom-up approach has the potential to go far beyond the limits and functionality of top-

down technology. Furthermore, the bottom-up method is likely to allow new device ideas

and functional systems, resulting in technologies we have not yet envisaged. For example,

in an integrated Nano system, it is feasible to mix chemically different nanoscale building

components that could not be merged in top-down processing, resulting in unique functions

or combination of functions. Because these qualities influence their corresponding physical

attributes, the bottom-up method demands nanostructured building pieces with precisely

regulated and adjustable chemical composition, structure, size, and shape. The confinement

of chemical reactions, nucleation, and growth processes may also create nanoparticles of

different oxides. Thermodynamic synthesis and kinetic synthesis are the two types of

synthesis techniques available. The synthesis process under the thermodynamic method

includes of hyper saturation generation and nucleation.

The formation of nanoparticles is done by controlling the concentration of precursors

accessible for growth by an operating system or controlling the process over a small area.

Bottom-up synthesis includes methods such as hydrothermal, co-precipitation, sol-gel, and

solution mixing. The chemical synthesis is effectively covered, and the reaction is

adequately controlled to prevent the formation of new particles. Integrating nanoparticles

with optimum control over particle size distribution, morphology, purity, and efficiency

using environmentally friendly economic processes has always been challenging for

researchers (Mandal et al., 2006). A few bottom-up techniques for synthesizing titanium

dioxides include hydrothermal, combustion synthesis, gas phase techniques, microwave

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synthesis, and sol-gel processing. In this work, the research materials were created utilizing

the co-precipitation and hydrothermal processing approach.

Figure 1.2 Overview of the Top-down and Bottom-up approaches

1.6.3 Green synthesis

The green synthesis technique has attracted a lot of interest among the various

approaches for nanoparticle synthesis. Green synthesis overcomes chemical and physical

methods in terms of less toxicity, cost, and environmental friendliness. It can be readily

scaled up for large scale synthesis and does not need the use of high pressure, energy,

temperature, and hazardous chemicals. Plants may also be scaled up for large-scale synthesis

of nanoparticles regulated in size, shape, and disparity. Green synthesis is a type of bottom-

up method in which the predominant reaction is reduction/oxidation. Chemical synthesis

methods frequently result in hazardous chemicals absorbed on the surface, which might

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negatively impact medical applications. The green production of metal nanoparticles

utilizing microorganisms and plant extracts has received much attention (Gardea-Torresdey

et al., 1999).

Furthermore, because nanoparticles are formed extracellularly, using plant extracts

in nanoparticle creation is more advantageous than other methods. Plant extracts are

generally responsible for reducing metal compounds into their respective nanoparticles due

to their antioxidant or reducing capabilities. Gardea-Torresdey was the first to describe the

production of Au-NPs by alfalfa plants based on the accumulation of Nano sized gold

particles in a live plant (Gardea-Torresdey et al. 2002). The produced Au-NPs were

discovered to have icosahedron and twinned geometric morphologies in size ranges of 4 nm

and 6-10 nm, respectively. Gardea-Torresdey described the production of Ag-NPs in alfalfa

seedlings in a live plant system. These nanoparticles had an icosahedral shape and were 2-4

nm in size. Although the reduction of silver nitrate using plant extract was generally

sluggish, it benefited from creating stable and homogenous nanoparticles without any

additional chemical stabilizers. The development of clean, nontoxic, and ecologically

acceptable “green chemistry” techniques utilizing species ranging from bacteria to fungus

and even plants will help synthesize and assemble nanoparticles (Mohammadinejad et al.,

2016). As a result, inorganic compounds are produced by both unicellular and multicellular

organisms, either intracellularly or extracellularly. The green synthesis of nanoparticles

involves three main processes that must be examined from the stand point of green

chemistry, including

(1) Choosing a solvent media.

(2) Environmentally friendly reduction agent selection.

(3) Nanoparticle stability necessitates the use of environmentally friendly chemicals.

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 They maintained product integrity such as structure, shape and size disparity,

functionality, purity, and stability. While utilizing greener techniques, wherever feasible

poses linked problems in manufacturing metal nanoparticles in a green environment.

Biological synthesis is a green chemistry technique that bridges the gap between

nanotechnology and biotechnology. Bacteria, fungi, yeasts, viruses, phototrophic eukaryotes

such as plants, algae, and human cell lines used as reducing and capping agents, produced

metal nanoparticles (Sachin et al., 2021). Metal nanoparticles were created using

biomolecules from these extracts, such as enzymes/proteins, amino acids, polysaccharides,

and vitamins. The use of plant extract in the production of metal nanoparticles has proven

advantageous over other biological methods because it eliminates the time-consuming

procedure of maintaining cell cultures (Singh et al., 2018). The potential of plants and

microorganisms as natural materials for nanoparticles synthesis has yet to be fully explored

due to their diverse biodiversity.

An essential area of metal and metal oxide nanoparticle synthesis is the utilization of

plants in the green synthesis process. Plants and plant products are more sustainable and

renewable resources for nanoparticle synthesis than microorganisms, requiring expensive

microbial culture maintenance and downstream processing (Parveen et al., 2016). Different

secondary metabolites, enzymes, proteins, and other reducing agents with electron shuttling

substances are generally involved in producing metal nanoparticles by plant components.

1.6.4 Chemical synthesis

The co-precipitation technique involves carrying down a precipitate of substances

normally soluble under the conditions employed. The controlled release of anions and

cations assist in regulating the nucleation and particle growth kinetics, which helps to

synthesis mono dispersive nanoparticles (Iravani et al., 2014). However, the control of

chemical homogeneity and particle size is difficult in mixed oxide precipitation.

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Furthermore, the appropriate control of experimental parameters, such as pH, the

concentration of the reactants and ions, and temperature, are essential as these determine the

precipitation process (Patra et al., 2014, Nyamukamba et al., 2018). It has been found that

chemical methods are effective, convenient and straight forward to handle. Three steps are

often followed in chemical synthesis: (1) Metal-based precursors, (2) Capping oxidants, and

(3) Reducing agents (Villaverde-Cantizano et al., 2021).

The synthesis of metal nanoparticles in the co-precipitation system includes

converting salts into stable and colloidal monodispersed nanoparticles utilizing an organic

or inorganic reducing agent in a suitable organic solvent and the presence of a suitable

stabilizing agent. As a result, chemical techniques are versatile in producing a wide range of

metal, metal oxide NPs (Mourdikoudis et al., 2021, Adegoke et al., 2015).

1.6.5 Hydrothermal synthesis

Hydrothermal processing can be defined as any heterogeneous reaction in an aqueous

solvent (or non-aqueous solvent for solvothermal processing) under high pressure and

temperature conditions, which induces the dissolution and recrystallization of materials

relatively insoluble under ordinary conditions. In comparative terms, the hydrothermal

processing of materials is considered environmentally benign. Further, the hydrothermal

technique offers the highly controlled diffusivity of strong solvent media in a closed system.

In the context of nanotechnology, the hydrothermal process provides an ideal method for

producing ‘designer particulates, i.e., mono dispersed particles with high purity, high

crystallinity, and controlled physicochemical characteristics. Such particles are in great

demand by industry. The hydrothermal apparatus, commonly known as an autoclave,

reactor, pressure vessel, or high pressure bomb, must meet various objectives, processing

conditions, and tolerances. A generic hydrothermal autoclave should be:

1) Leak proof under high pressure/temperature conditions.

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 2) Easily assembled/disassembled.

3) Inert to acids, bases, and oxidizing agents.

4) Resilient to high pressure and temperature experiments so that no machining or

treatment is needed after each experimental run.

1.7 Photocatalytic degradation

1.7.1 Waste water treatment

Textile industry wastewater has a significant environmental threat since many

chemically different dyes are released into the atmosphere. About 10-15 % of the dyes

remain in the wastewater during synthesis and processing, and it isn't easy to separate

because of its complex chemical structure. Moreover, most of the dyes used in the textile

industries are stable to light and non-biodegradable. Hence, treatment of wastewater before

discharge to the environment is essential to reduce the problems faced by humans and other

living organisms in the water.

1.7.2 Various industrial treatments of textile dyes

Water and land pollution caused by the dumping of untreated toxic dye waste is

associated with global environmental problems due to the textile industry (Devi et al., 2008).

Several techniques are currently used in the textile industry to handle this effluent do not

quickly extract the dyes from the effluents, but all these conventional techniques (Khan et

al., 2017). It is expensive to build, and its management and maintenance are reasonably

costly and complicated (Anpo et al., 2010). Physical approaches have been used to eliminate

dye contaminants, such as adsorption on activated carbon, ultrafiltration, reverse osmosis,

coagulation by chemical agents, ion exchange on synthetic adsorbent resins (Saien et al.,

2007, Youssef et al., 2016). The main drawback of these approaches is that instead of

destroying them, they move the contaminant from one point to another and cause secondary

contamination. These create other environmental problems, which require more care

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(Trulove et al., 2010, Wang et al., 2006). Conventional biological methods are also

ineffective in removing textile dyes due to the many aromatics present in dye molecules

(Wang et al., 2004). Chlorination and ozonation are also used for clothing effluent

applications. Although the color and organics are removed from these methods, the process

is not economically viable (Tijani et al., 2014, Mouele et al., 2015). Hence, it is imperative

to find an alternative solution to effectively removing hazardous dyes and organics from

industrial effluents.

Advanced oxidation technology is one of the most environmentally friendly methods

used because of its chemical durability to eliminate recalcitrant organic compounds that are

not easily treated by current conventional processes. In the presence of highly reactive

species such as ozone, hydrogen peroxide, and hydroxyl radicals at ambient temperature and

pressure, degradation of biologically persistent pollutants occurs (Borgarello et al., 1986).

These hydroxyl radicals are unstable, nonselective, and powerful oxidants compared

to other known oxidizing agents like potassium permanganate. The hydroxyl radical reacts

efficiently to fragment organic pollutants into harmless end products, CO2 and H2O. Due to

the high standard reduction potential of OH• radicals have been described as the most potent

oxidants in decomposing organic compounds into CO2 (Kharisov et al., 2016). The

advanced oxidation process is broadly classified into homogeneous photocatalysis and

heterogeneous photocatalysis (Aparicio et al., 2012). Homogeneous photocatalysis is a

single-phase system. Its applications to treat contaminated water involve using an oxidant to

generate radicals, which attack the organic pollutants to initiate oxidation (Linsebigler et al.,

1995).

Heterogeneous photocatalytic techniques have shown tremendous potential towards

addressing challenges related to water and land contamination caused due to effluents. This

process involves an interaction of UV light with a semiconductor catalyst, capable of

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degrading organic pollutants by oxidative and reductive pathways. In heterogeneous

photocatalysis, photo-induced molecular transformation occurs at the surface of the catalyst.

Based on initial photoexcitation, photocatalysis can be divided into two types: catalyzed

photoreaction and sensitized photoreaction. Initial photoexcitation occurs in the catalyst in

catalyzed photoreaction, and electron transfer occurs from the catalyst to the adsorbate

molecule. In sensitized photoreaction, initial photoexcitation occurs in the adsorbate

molecule, which transfers the electron to the catalyst (Ibhadon et al., 2013).

1.7.3 Mechanism of photocatalytic degradation

Heterogeneous photocatalysis has proven to be a promising approach for degrading

organic molecules among the several recognized Advanced Oxidation Processes. This

technique is more effective than other AOP’s because they are inexpensive and can easily

mineralize various organic compounds (Pera-Titus et al., 2004). The basic steps for

heterogeneous photocatalysis consist of transferring the reactants in the liquid phase

followed by adsorption of the reactant on the catalyst surface, the reaction in the adsorbed

phase, desorption of the product, and finally, removing the byproducts in the liquid phase

(Pawar et al., 2018). The photocatalytic degradation of an organic compound such as dye is

believed to take place according to the following mechanism: When a catalyst is exposed to

light radiation, electrons are promoted from the valence band to the conduction band, which

produces an electron-hole pair

Catalyst + hυ → ecb- + hvb+

Where ecb-electrons in the conduction band, hvb+ are the holes in the valence band

(Collin et al., 2019). Both these entities can migrate to the catalyst surface to enter a redox

reaction with other species present on the surface. In most cases hvb+ can react quickly with

surface bound H2O to produce OH. radicals, whereas ecb- can react with O2 to produce

superoxide radical anion of oxygen.

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 H2O + hvb+ → .OH + H+

O2 + ecb - → O2-

This reaction prevents the recombination of electrons and holes, which are produced in

the first step. The OH and O2- radicals produced in the above manner react with the dye,

mineralizing the dye into other harmless species responsible for the decoloration of the dye

(Cuerda-Correa et al., 2020). It is noted that all reactions in photocatalysis are possible due

to the presence of both dissolved oxygen and water molecules. The recombination rates and

degradation efficiency depend on the catalyst, crystallinity, surface morphology, surface

area, bandgap, pH, light intensity, irradiation time, and the concentration of dye (Bustillo-

Lecompte et al., 2020).

1.8 Antibacterial activity

The global growth of bacterial resistance to conventional medical practices is a

serious threat to human health. Microorganisms have been developing resistance to many

antibiotics due to the indiscriminate use of antimicrobial drugs, increasing clinical problems

in treating infections (Abouelkheir et al., 2016). Physicians have little choice to treat such

conditions because of the increasing incidences of diseases with emerging multidrug

resistance. Therefore, there is an immediate need to develop new approaches to handle this

problem. One of the promising approaches for overcoming bacterial resistance is the use of

metallic nanoparticles. Owing to their small size and higher surface-to-volume ratio,

nanoparticles have an enlarged contact area with microorganisms. This feature enhances the

biological and chemical activity of the nanoparticles with high antibacterial efficacy.

Another essential property of metallic nanoparticles is their ability to target different

bacterial structures. Ag-NPs and Au-NPs have various applications in nanoscale devices and

technologies among the various metallic nanoparticles. The antimicrobial activity of silver

ions was known since ancient times, and silver ions are widely used in catheters, bum

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wounds, and dental work. Silver is non-toxic and is capable of killing about 650 types of

diseases causing microorganisms. It has been used as a bactericide for water purification and

preventing bacteria and algae buildup in water filters for more than a decade. Silver products

have long been known to have strong inhibitory and bactericidal effects, as well as a broad

spectrum of antimicrobial activities, which have been used for centuries to prevent and treat

various diseases (Durán et al., 2011). It has a significant potential for preventing infections,

healing wounds, and anti-inflammatory. Silver based compounds, being biocompatible at

effective concentrations, are mainly investigated as antibacterial agents against

microorganisms. when in the form of non-agglomerated and well-dispersed nanoparticles.

Besides inherent chemical, physical, and optical properties arising from petite sizes, Ag-NPs

have shown promising potential as antibacterial or antimicrobial agents. Hence, Ag-NPs had

been incorporated in textile fabrics, polymers, dental material, medical devices, and burn

dressing to eliminate microorganisms. (Duran et al., 2011) showed that silver nanoparticles,

like their bulk counterpart, are an effective antimicrobial agent against various pathogenic

organisms.

1.8.1 Mechanism of antibacterial activity

Still, there is no possible mechanism to prove the antibacterial activity of

nanoparticles. Few works of literature report some interesting finds to explore the plausible

mechanism of antibacterial action of nanoparticles. According to that, two findings are

predominantly reported,

(i) Destruction of membrane permeability by the electrostatic interaction and

(ii) Creation of reactive oxygen species (ROS) (Ahmad et al., 2020).

The discharge of ions from the nanoparticles may actively bind with the negatively

charged gram-negative and gram-positive bacteria cell membranes through electrostatic

interaction. The changes in membrane permeability resulted in the improper regulation of

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the transport mechanism in the plasma membrane leads to cell death. Besides, the ions may

destruct the intracellular enzyme activity, biomolecules like DNA and proteins, which leads

to cell death.

Interestingly, Sondhi and Sondhi have reported that the negatively charged silver

nanoparticles may spoil the cell membrane by generating a small hollow-like structure called

pits on the membrane. Still, the query is not cleared on how the negatively charged silver

ions bind and destruct the negatively charged cell membrane. The report of their study

demonstrated the development of pits in the membrane resulted in the demolition of the cell

membrane. The generation of ROS by the silver ions could inhibit the function of respiratory

enzymes and subsequently cause oxidative stress and resulted in cell death (Dakal et al.,

2016).

1.9 Literature review

The proteins present in Capsicum annum L. extract were responsible for the

reduction and stabilization of Ag ions to silver nanoparticles. Nanoparticles were spherical

in shape ranging between 30-70 nm in size reported by (Li et al., 2007). (Daizy Philip et al.,

2009) reported the extracellular synthesis method for the preparation of Au, Ag and Au-Ag

nanoparticles, using the extract of Volvariella volvacea as reducing agents. Au-NPs of 24

different sizes (20-150 nm) and shapes from triangular Nano prisms to nearly spherical and

hexagonal are obtained by this green method. (Daizy Philip et al., 2011) also reported that

the water soluble compounds such as flavonoids and terpenoids present in the tulsi leaf are

also responsible for the preparation of Ag-NPs.

The biosynthesis of Ag-NPs by a novel, simple green chemistry procedure using

citrus sinensis peel extract as a reducing and a capping agent has been reported by (Kaviya

et al., 2011). The effect of temperature on the synthesis of Ag-NPs was carried out at room

temperature 25°C and 60°C. The successful formation of silver nanoparticles has been

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confirmed by UV-vis, FTIR, XRD, EDX, FESEM, and TEM analysis and their antibacterial

activity has been studied. Green synthesis and characterizations of Ag-NPs using leaf extract

of Rosa rugosa reported by (Shashi Prabha Dubey et al., 2010). The influences of different

concentrations of Rosa rugosa leaf extract and different metal ion concentrations on the

above cases on the synthesis of Ag-NPs were evaluated. They characterize the synthesized

Ag-NPs by UV-vis, TEM, XRD, FTIR, Zeta sizer, and EDX. The prepared Ag-NPs were

mostly spherical with some triangular and hexagonal in 25 shapes with the average particle

size of 12 nm and showed an SPR peak at 451 nm.

(Daizy Philip et al., 2013) have presented an environmentally benign method for the

synthesis of stable and crystalline Ag-NPs and Au-NPs using edible oil at 373 K. Fine

control over the size of the nanoparticles and shape from triangular to nearly spherical is

achieved by varying the quantity of coconut oil. The nanoparticles have been characterized

by UV-Vis, TEM, FTIR, and XRD. A facile and eco-friendly method has been developed

by (Aruna Jyothi Koraa et al., 2010) for the synthesis of Ag-NPs using gum kondagogu

(Cochlospermum gossypium), a natural biopolymer. The effect of reaction conditions such

as the gum particle size, concentration of gum, metal ion concentration, and reaction time

was also studied. Monodispersed Ag-NPs of size 3 nm were synthesized. They have reported

nearly monodispersed and size controlled spherical nanoparticles of around 3 nm by

optimizing the reaction conditions using UV-vis, TEM, and XRD analysis. They have been

investigated the synthesized Ag-NPs had significant antibacterial action on both the Gram

classes of bacteria using FTIR and Raman spectroscopy. As the Ag-NPs are encapsulated

with functional group rich gum, they can be easily integrated for various applications.

The synthesis and characterization of Ag-NPs using aqueous seed extract of Jatropha

curcas have been reported by (Harekrishna Bar et al., 2009). They have been shown that the

particles are crystalline with face-centered cubic geometry and mostly spherical particles

20
with a diameter ranging from 15 to 50 nm. Bio-inspired Ag-NPs were synthesized with the

aid of a novel, non-toxic, eco-friendly biological material, namely, banana peel extract

(BPE) has been reported by (Ashok Bankara et at., 2010). Ag-NPs were formed when the

reaction conditions were altered concerning pH, BPE content, the concentration of silver

nitrate, and incubation temperature. The EDS and XRD analysis confirmed the presence of

Ag-NPs. FTIR indicated different functional groups such as carboxyl, amine, and hydroxyl

in the synthetic process. These Ag-NPs displayed antimicrobial activity against fungal as

well as bacterial cultures.

(Behravan et al., 2019) reported the synthesis of silver nanoparticles using Berberis

vulgaris leaf and root extract by the green synthesis method. The synthesized silver

nanomaterials are for application in biomedical due to their lesser particle size and spherical

shape of nanomaterials. (Rani et al., 2020) prepared high stable silver nanoparticles via a

novel green synthesis process and investigated their biological and photocatalytic properties.

Compared with other metallic nanoparticles, the silver nanoparticles significantly improved

the photocatalytic degradation efficiency of reactive red-141 (RR-141) dye by 97 % because

of its larger specific surface area, spherically arranged nanoparticles, and lower optical

nanoparticles reflectance. (Chand et al., 2020) prepared silver nano powder with various

plant extracts and analyzed photocatalytic activity to reduce Congo red, methyl red, and

methyl orange dye solutions. The results show that synthesized materials have better

photocatalytic reactivity than the reference material employed. (Rajkumar et al., 2020)

prepared a nanosilver using Chlorella Vulgaris by a green approach method. Positive

photocatalytic activities for methylene blue removal under UV-Visible irradiation technique

were reported and resulted in maximum degradation efficiency of 97 % at the end of 2.5

hours.

21
 (Parvathiraja et al., 2020) synthesized silver nanoparticles successfully through a

biosynthesis method. Effects of the particle size value of the nanoparticles, optical property,

and recycled silver on the photocatalytic degradation of methyl blue (MB) in Ag suspensions

under ultraviolet (UV) illumination. The results indicate that a low pH value, the proper

amount of H2O2, and pure silver will facilitate the photocatalytic oxidation of the MB

solution.

(Kolya et al., 2015) synthesized pure silver nanoparticles via the green synthesis

method and reported that the adsorption ability of the nanoparticles for Congo red dye (Azo

dye) is higher. Fabricated silver nanoparticles using Amaranthusgangetics Linn leaf extract

and exhibited good antibacterial activity and photocatalytic performance in the

photochemical degradation of Congo red under visible-light irradiation. (Sivaramakrishnan

et al., 2019) Synthesized silver nanoparticles using Leucasaspera leaf extract via the green

synthesis method, and its photocatalytic properties showed higher photocatalytic activity

than the Lanasyn Blue dye. Biological activities were tested against Bacillus subtilis (26.3

mm) and E-Coli (23 mm) bacteria. (Ravichandran et al., 2019) synthesized silver

nanoparticles with a high specific surface area prepared by green synthesis process using

Parkiaspeciosa leaves extract and removing methylene blue (MB) pollutant by UV-

irradiation process. The antibacterial and antioxidant activity of silver nanoparticles has been

examined.

(Saha et al., 2017) reported the synthesis and characterization of stable silver

nanoparticles and their photocatalytic activities by the degradation of Methylene blue dye.

(Ndikau et al., 2017) synthesized silver nanoparticles using Citrulluslanatus fruit rind extract

via green synthesis. Its photocatalytic properties were tested against 4-Nitro Phenol,

Methylene blue, Methyl orange, and PR, using NaBH4 reducing agent. (Parvathiraja et al.,

2019) prepared silver nanoparticles through a facile green chemistry route and the

22
nanoparticles exhibited degradation of 72% methylene blue dye within 2 hrs. under visible-

light illumination.

(Muniandy et al. 2017) prepared mesoporous anatase TiO2 nanoparticles via green

synthesis and exhibited the photodegradation of Methylene blue. (Ngoepe et al., 2020)

synthesized titanium dioxide nanoparticles by a green synthesis method. The photocatalytic

activity was evaluated by degradation of Methylene blue dye in an aqueous solution under

visible light and UV irradiation. (Sankar et al., 2015) synthesized colloidal titanium dioxide

nanoparticles by a modified sol-gel method, and the photocatalytic activity was evaluated

by degradation of methyl red dye. (Rajkumari et al., 2019) synthesized titanium dioxide

nanoparticles using the Aloe barbadensis mill and evaluate its anti-biofilm potent against

Pseudomonas aeruginosa. (Santhoshkumar et al., 2014) synthesized titanium dioxide

nanoparticles using Psidium guajava extract as a stabilizer to test its antibacterial and

antioxidant properties. (Diantoro et al., 2018) studied the photocatalytic activity of pH

modified Titania. They showed its higher photocatalytic activity than commercial TiO2 to

decompose Methylene Blue dye in UV and visible light. (Sun et al., 2019) biosynthesis TiO2

nanoparticles and their applications to treat brain injury an in vitro toxicity study towards

the central nervous system.

(Sathiyan et al., 2020) prepared size-controlled TiO2 nanoparticles by sol-gel

method, and their photocatalytic activities were studied by photodegradation of methylene

blue (MB) and Congo red (CR) in water under UV and simulant solar light irradiation,

respectively. (Gautam et al., 2016) synthesized Anatase and rutile phase TiO2 nanoparticles.

The prepared samples show enhanced ultraviolet light photocatalytic performances of

Methylene Blue, Methyl Orange, Rhodamine B, indigo carmine, and Eriochrome Black.

(Amini et al., 2016) reported high photocatalytic activity of TiO2 and ZnO nanoparticles

23
prepared by chemical methods and their photocatalytic decomposition of methylene blue

(MB), Rhodamine B (RhB), Acridine Orange (AO) under visible light.

(Guarin et al., 2018) synthesized activated carbon using Algae D. Antarctica and

reported suitable photocatalytic activity under sun-light excitation to degrade methylene blue

(MB). (Alene et al., 2020) synthesized economical alternative bio adsorbent Nano powders

by pyrolysis method, and the prepared samples exhibited higher photocatalytic activity for

basic blue dye from aqueous solution. (Ani et al., 2020) reported activated carbon made from

biomass materials to extract dyes, heavy metals, and crude oil components from aqueous

environments. Biomass sources promote biomass in removing industrial waste from water

solutions, such as oil spills, dyes, and other harmful substances. (Basaleh et al., 2018)

prepared activated carbon from municipal waste in Saudi Arabia and reported its

photocatalytic activity to degrade Methylene Blue. (Cui et al., 2020) synthesized

mesoporous bio char-based photocatalyst and reported its photocatalytic activity to degrade

Brilliant green and 4-Nitrophenol.

(Taha et al., 2020) prepared activated carbon decorated Ag/ZnO-based

nanocomposite (Ag-ZnO) with different Ag/ZnO ratios by a facile one-pot hydrothermal

method, and 4-nitrophenol evaluates their adsorption capacity and photocatalytic activity.

Biological properties were tested against 16 various microbial pathogens. (Devi et al., 2019)

synthesized AC doped silver nanoparticles using a sol-gel process and reported its

antibacterial activity and photocatalytic activity for the degradation of Malachite green

oxalate. (Karthik et al., 2016) synthesized silver doped activated carbon by the sol-gel

synthetic route, and both cationic and anionic dyes investigate the photocatalytic

performance. The result revealed that the AC doped Ag has higher activity than the undoped

AC. (Louis et al., 2019) demonstrated a simple one-step synthesis methodology for a silver-

loaded porous carbon composite for the photocatalytic degradation of organic pollutants in

24
water. Methyl orange dye was the model pollutant used to evaluate the photocatalytic

performance of the photoelectrodes in which Ag-doped carbon exhibited good catalytic

activity than undoped Ag.

(Nguyen et al., 2020) prepared Gd3+ doped mesoporous TiO2 (m-TiO2) nanoparticles

using CTAB as directing agent and pore-forming agent via a hydrothermal process, and its

photocatalytic activity towards RhB dye were reported. (Mendez-Medrano et al., 2016)

synthesized Ag-doped Titania nanoparticles and CuO nanocluster, and the photocatalytic

activity was evaluated by degradation of dyes (Reactive Brilliant Red X-3B and RhB) in

aqueous solution under visible light and UV irradiation. (Angkaew et al., 2012) reported

that silver titanium dioxide core-shell (Ag@TiO2) nanoparticles with change in Ag and TiO2

at different ratios of metal oxide nanoparticles for optical applications.

1.10 Importance of the work

Removal of environmental pollutants through semiconductor photocatalyst has received

importance in recent years. In the present work, metal (Ag), metal oxides TiO2 and activated

carbon are selected as study materials because of their chemical stability, non-toxic and

sensitive to light irradiation. Hydrothermal method is chosen for the preparation of

monodispersed and homogeneous nanocomposites relatively at low temperatures with a

control over size and morphology. The band gap of anatase TiO2 nanoparticles (wide band

gap) lies in the UV region, hence it is aimed to shift its band gap from UV to visible region

by the addition of low band gap semiconducting material activated carbon and also by the

inclusion of silver due its surface plasmon resonance effect. All the samples are evaluated

by their biological and photocatalytic degradation activity for the removal of MB and their

results are compared.

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1.11 Objectives of the present work

 To synthesize phase pure anatase TiO2, Ag, Activated carbon and AC/Ag/TiO2

nanocomposites by hydrothermal method.

 To extend the absorption edge of TiO2 from UV to visible region by forming

nanocomposites with AC as well as with the incorporation of Ag.

 To study the influence of Ag inclusion in TiO2 and AC/Ag/TiO2 nanocomposites.

 To study the photocatalytic performance of these materials for the degradation of

MB dye and to analyze their biological activities.

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