SORAN UNIVERSITY

FACULTY OF ENGINEERING
CHEMICAL ENGINEERING DEPARTMENT

Process optimization and catalytic efficacy of a new green catalyst

synthesized by one-pot microwave-assisted technique
A dissertation submitted for partial fulfillment of the requirement for the award of the degree of
Bachelor in Chemical Engineering

By
Mustafa Ismail
Abdulqadir Luqman
Natalie Ninos
Amin Muayad

Supervisor
Prof.Dr. Ibtisam Kamal

May 2020
Contents
CHAPTER ONE........................................................................................................................................2
INTRODUCTION.....................................................................................................................................2
1.1 Genaral Introduction..........................................................................................................................2
1.2 Uses of catalyst.....................................................................................................................................3
1.3 Methology.............................................................................................................................................4
1.4 Objective..............................................................................................................................................5
CHAPTER TWO.......................................................................................................................................6
INTRODUCTION.....................................................................................................................................6
2. INTRODUCTION.................................................................................................................................6
2.1Green chemistry and catalysis.............................................................................................................6
2.2 Catalyst Systems and types.................................................................................................................6
2.2.1 catalyst types.....................................................................................................................................7
2.2.2 Heterogeneous Catalyst Systems.....................................................................................................9
2.3 Nano catalyst production technique.................................................................................................10
2.3.1Background:.....................................................................................................................................10
2.3.2 Synthetic approaches for NPs as nano catalysts...........................................................................10
2.3.3 Application of nano catalyst:.........................................................................................................12
2.4 Microwave assisted technique for catalyst preparation..................................................................14
2.4.1 Microwaves and its application.....................................................................................................14
2.4.2 Microwave assisted technique for catalyst preparation...............................................................15
2.4.3 Synthesis of green nano catalyst using microwave.......................................................................16
CHAPTER THREE........................................................................................................................................20
3.1 Process selection...........................................................................................................................20
3.2 Flow sheet and process description............................................................................................22
3.3 Material Balance...........................................................................................................................24
REFERENCES........................................................................................................................................27

1
 CHAPTER ONE
INTRODUCTION
1.1 Genaral Introduction
Catalysis provides sustainable and cost-effective methods to transform raw materials into
valuable chemicals. Thus, catalytic processes have long become essential to solving the energy
and environmental challenges that we currently face around the globe. Catalysis can be broadly
divided into homogeneous and heterogeneous catalysis. Homogeneous catalysis involves
catalysts and reactants in the same phase [1]. As homogeneous catalysts are generally soluble
molecular or ionic compounds, they have more easily accessible active catalytic sites, and thus
often exhibit good catalytic activity. Moreover, their structures and functional groups can easily
be changed to result in chemo-, regio-, and enantioselectivity. However, despite their many
advantages and being widely used in industry, homogeneous catalysts do have some
disadvantages, which is mainly to do with the fact that they are difficult to separate from the final
products or reaction mixtures. Furthermore, even with the use of numerous techniques, such as
chromatography, distillation, or extraction, the removal of trace amounts of residual catalytic
species from the reaction mixture is always challenging in the case of homogeneous catalysis.
This is an important issue that requires attention, given the fact that the presence of trace
amounts of catalytic moieties, especially metallic ones, is strictly regulated in the commodity
chemicals and pharmaceutical products, which are often produced using catalysts. All of these
issues together, therefore, pose major hurdles for homogeneous catalysts, making many of them
to have only limited applications. Some of these drawbacks of homogeneous catalysts can be
overcome by supporting the homogeneous catalytic species on solid support materials and
producing their corresponding solid catalysts, known as heterogeneous catalysts [2]. The general
approach behind the synthesis of heterogeneous catalysts involves either the entrapment
(immobilization) or the attachment of an active catalytic moiety on the solid support material.
The former can be accomplished by letting the catalytic species to adsorb on the solid support
materials, whereas the latter can be realized by tethering the catalytic groups on the support
materials with covalent bonds, preferably with strong covalent bonds that can tolerate severe
reaction conditions. Because of the physical attachment of the catalytic groups onto the solid
support materials, heterogeneous catalysts often possess numerous advantages, such as their ease
of handling, efficient recovery, enhanced stabilityand shelf-life, and reusability. However,

2
because the reactants and the catalysts in heterogeneous catalysis must necessarily be in two
different phases, the interaction between the reactant and the catalyst is reduced [3]. This, in turn,
can result in reduced overall catalytic activity in heterogeneous catalysts compared with their
homogeneous counterparts. Possible leaching of active catalytic sites from the solid support
materials, either from the cleavage of the covalent bonds between the catalytic groups and the
solid support material or from the possible desorption of the catalytic groups off the solid support
material, can also be an issue for some heterogeneous catalytic systems. Although the
concentration of trace metals can often be much smaller in heterogeneous catalytic systems
compared with that in the corresponding homogeneous catalytic systems, such possible leached
trace metals in heterogeneous catalytic systems might still require separation from final
products[4]. To overcome some of the limitations associated with catalysts, new catalytic
systems were needed that could have the advantages of catalytic systems, allow all catalytic
active sites to be accessible and effective (i.e., give good catalytic activity, selectivity, and yield),
and make catalyst separation easily possible (i.e., stable catalyst, catalyst recovery, and catalyst
reuse)[5]. Nanocatalysts and nanocatalysis could meet the need of such new catalyst

1.2 Uses of catalyst

Nanocatalysis has since quite a while ago become a significant piece of nanoscience.[7]
Nanoparticles can substitute customary materials and fill in as dynamic and stable heterogeneous
catalysts[6] or as help materials for different synergist groups.[7] Due to their little sizes,
synergist dynamic nanoparticles have higher surface territory and expanded uncovered dynamic
destinations, and along these lines improved contact regions with reactants, likened to those of
homogeneous reactant frameworks. Simultaneously, nanostructured impetuses can act as
heterogeneous impetuses ; in this manner, they can likewise be effectively isolated from the
response blends. Notwithstanding their tunable synergist action and selectivity, frequently with
exercises near homogeneous reactant frameworks, the solidness of nanocatalysts can be
improved by fitting the concoction and physical properties of the nanomaterials by different
engineered strategies. For example, nanocatalysts with better activity, stability, and selectivity
can be designed and synthesized merely by controlling the sizes, shapes, and morphologies of
nanomaterials. [7–9]

3
1.3 Methology
There are several methods to prepare a variety of supported catalysts, namely
1. impregnation of a preformed support with a solution of metal salt followed by

Drying and reduction,[10]

2. ion exchange with the support by cationic organometallic complex followed by

Drying and reduction,[11]

3. coprecipitation of hydroxides of both support and metal followed by drying,

Calcinations, and reduction,[12]

4. deposition–precipitation of metal hydroxide to a suspension of the support followed by drying,

calcinations, and reduction,[13]

5. chemical vapor deposition of a volatile compound of metal to a high-area support through an

inert gas,[14] and

6. chemical reduction of a metal salt in solution and subsequent dispersion on a support.[15]

Those method mensioned can be enhanced by diffrent technology such as the microwave.
Microwave-helped natural amalgamation (MAOS) has been perceived as one of the most
dominant and economical apparatuses in manufactured science and has pulled in a lot of
consideration because of its particular highlights including productive nuclear use, improved
temperature guideline, response homogeneity, and potential changes of actuation parameters.
Certainly, numerous reports have shown that a wide scope of metal-catalyzed responses and
cross-coupling responses advantage enormously from MW warming, displaying quicker
response energy .The discussion on 'explicit MW impacts' and 'non-warm MW impacts' proceeds
while they are being explored for explicit compound responses .Kappe and colleagues have
reconsidered Dudley's work on Friedel-Crafts benzylation of [D10] p-xylene utilizing the 2-
benzyloxy-1-methylpyridinium salt and closed the MW impact doesn't happen [16] .

4
1.4 Objective
1. Prepration of nano catalyst using sustainable material green synthesis route.
2. Studying the use of microwave-assisted technique as new method for the prepration of
the nanocatalyst
3. Studying the effect of the operating variables on the catalyst yield and performance.
4. Studing the properties of the prepared catalyst.

5
 CHAPTER TWO
INTRODUCTION
2. INTRODUCTION
Chemistry has played, and continues to play, a fundamental role on almost every aspect of
modern society. The range of chemical products in nowadays society is huge, and those products
make precious offerings to the quality of our lives. However, the manufactures of chemicals have
given rise to global problems, which cause damage to both humans and the environment. Green
Chemistry is a chemical philosophy that encourages the design of products and processes that
reduce or eliminate the use and generation of hazardous substances. One of the keys to the
success of this approach lies in the development of catalysts. Especially, heterogeneous catalysts
have attracted much attention due to their potentials for realizing the concept of green chemistry.
[17]

2.1Green chemistry and catalysis

Green chemistry is basically the study that holds the philosophy of designing and producing
material that causes no harm to the environment. its an application of environmentally friendly
materials to be used in our life.[18] The act of green chemistry had been exist since 40s aa an act
of pollution prevention , one of the first efforts for developing green chemistry which there was
no name for was in early 1990 when the United kingdom and Italy have launched major
creativitys in green chemistry and, more recently, the Green and Sustainable Chemistry Network
was initiated in Japan. [19] but one of the major progressing in green chemistry was in also
1990s when Paul Anastas and John Warner coined the two letter word “green chemistry” and
developed the twelve principles of green chemistry. Roji noyori identified three keys of
development in green chemistry in 2005 use of supercritical carbon dioxide as green solvent,
aqueous hydrogen peroxide for clean oxidations and the use of hydrogen in asymmetric
synthesis.[20]

2.2 Catalyst Systems and types

Catalysts are traditionally divided into two major groups based on the type of phase of the
catalyst is in relative to the catalytic reaction mixtures, that is, homogeneous or heterogeneous
catalysts. Homogeneous catalysts are those that exist in the same phase as the reactants. They are
generally soluble organic or organometallic complexes and often give chemo-, regio-, and
stereoselective products. However, they are relatively difficult to separate from reaction mixtures

6
for reuse at the end of reactions. On the other hand, there are solid or insoluble catalysts, also
called heterogeneous catalysts.[21]

2.2.1 catalyst types

There are a number of different classes of heterogeneous catalyst materials, each of which will
have different microwave absorption processes. We mention three significant ones here, noting,
however, that this breakdown is far from exhaustive

1. Acid catalysts
The traditional catalyst hydrogen fluoride, an extremely corrosive, hazardous and toxic chemical
used in the production of linear alkylbenzenes (LAB's), has been successfully replaced by a solid
acid catalyst, viz. fluorided silica-alumina catalyst, which does not require special material of
construction (of the container), involves lower operating costs and obviates the need for an acid
scrubbing system and waste disposal of calcium fluoride.
2. Oxidation catalyst
A large number of supported reagents have been used in the liquid phase partial oxidation of
organic substrates. There has been considerable success in the use of molecular sieves (titanium
and vanadium) in commercial unitsY The most important application of titanium silicates (TS-I)
is the hydroxylation of phenol, giving mixtures of hydroquinone and catechol. The process is
clean, giving excellent conversion to product with very little waste. [22]

1. Basic catalysts
In contrast to the areas of heterogeneous oxidation catalysis and solid acid catalysis, the use of
solid base catalysis in liquid phase reactions has not met the same level of breakthrough.
The industrial applications of basic catalysts are in the alkylation of phenol, side chain alkylation
and isomerisation reactions. [23]
In addition to what has been stated above, the following catalysts/catalytic processes find wide
applications in industry.
2. Biocatalysis: The most important conversions in the context of green chemistry is with the
help of enzymes or biocatalysts
3. Phase transfer catalysis and crown ethers: These find numerous applications in organic
synthesis in industry and in the laboratories
4. Photocatalysis: A large number of conversions/syntheses have been
Carried out photolytically. [24]

7
 3. Polymer supported catalyst
The conventional catalyst which is normally used in the homogenous phase, is linked to a
polymer backbone and is used in this form to catalyze different reactions. Following are some of
the polymer supported catalysts and their applications.
I. Polystyrene-aluminium Chloride
It is used to prepare ethers from alcohols. Thus, dicyclopropyl carbinol on treatment with
[25]
Polystyrene-Alel3 is a useful catalyst for synthetic reactions, which require both a dehydrating
agent and a Lewis acid. Thus, acetals are obtained in good yield by the reaction of aldehyde,
alcohol and polymeric AICl3 in an organic inert solvent.
II. Polymeric Super Acid Catalysts
A polymeric super acid catalyst is obtained by binding aluminum chloride to sulfonated
polystyrene. This polymeric super acid catalyst is used for the cracking and isomerisation of
alkanes (e.g. n-hexane) at 357°C at atmospheric pressure. Normally the above cracking and
isomerisation is carried out in the presence of Lewis acid at high temperature and high pressure.
[26]
III. Polystyrene-metaUoporphyrins
These catalysts are useful for the oxidation of thiols to disulphide (a very facile reaction) in
presence of base and are rapid even at room temperature. [27]
IV. Polymer Supported Photosensitizers
The photosensitizers supply molecular oxygen in a photochemical reaction. Examples of usual
photo sensitizers are Rose-Bengal, eosin-y, fluorescein. The photo sensitizers are bound to
Merifield type resin via ester bond A polymer-bound rose-bengal photosensitizer is
commercially available. The efficiency of SEN SIT OX is about 65% of that of Rose-Bengal, but
the high yields of the products and the ease of isolation more than compensate the slightly longer
reaction periods .[28]
V. Polymer Supported Phase Transfer Catalysts
The use of phase transfer catalysts. When the organophi1ic orium salts and crown ethers are
immobilized. On a polymer matrix, they retain most of their catalytic activity. However, the
reaction rates are slower because of the difficulty in bringing the reacting species in contact with
the catalytic site. This drawback is overcome by using a long chain to bind the catalyst to the

8
 polymer matrix. The advantage of using these polymers supported catalysts is that the product
formed is separated from the reaction mixture by simple filtration and that the recycling of the
Catalyst is possible. [29]
VI. Miscellaneous Illustrations
Following are some typical illustrations using catalysts in green chemistry.
 TiD 2 Photocatalyst in Green Chemistry
 Solid Support Reagents
 Synthesis of Bromoorganics: Development of Newer and Ecofriendly Bromination
Protocols and Brominating Agents
 Synthesis ofPyridinium Fluorochromate (PFC)
 Synthesis of Iso octane

2.2.2 Heterogeneous Catalyst Systems

 Solid oxide catalysis: This includes any bulk oxide used to catalyze a reaction
at its surface. Typical examples are the simple binary oxides such as SiO2,

Al2O3, TiO2, and ZrO2, and ternary oxides such as spinels and perovskites.

Porous silicate and alumino silicate materials such as zeolites and templated

mesoporous sieves also fall into this category.

 Metals: Metals: Metal surfaces, particularly late metals such as Ni, Cu, and Ag, catalyze
many commercial processes.

 Support catalysis: Support catalysts: The supported catalyst is primarily the category
defined by

an oxide support with an active site deposited on the surface that performs all

or part of the catalytic function. The active site can be an isolated transition

metal ion or complex or a metal particle All of these systems will exhibit different microwave
absorption processes that originate from different loss processes.[30]

9
2.3 Nano catalyst production technique
2.3.1Background:
Catalysis plays a central role in chemical transformations and lies at the heart of countless
chemical protocols, from academic research at laboratories level to the chemical industry level.
By using catalytic reagents, one can reduce the temperature of a transformation, reduce reagent-
based waste and enhance the selectivity of a reaction that potentially avoids the unwanted side
reactions leading to a green technology. In 1998, Anastas and Warner suggested a set of twelve
principles which is the main philosophy of Green chemistry to reduce or eliminate chemicals and
chemical processes that have negative environmental impacts. Designing and developing ideal
catalysts is one of the very important concepts of green chemistry. According to these principles
catalytic reagents (as selective as possible) are superior to stoichiometric reagents.
Stoichiometric reagents are used in excess and work only once while catalytic reagents used in
small amounts and can carry out a single reaction many times. To work more like nature is the
base of all the twelve principles of green chemistry. Nature clearly provided hints to us to carry
out environmentally benign reactions by using micro-organisms and/or enzymes. In the absence
of catalyst, variety of products i.e. medicines, fine chemicals, polymers, fibres, fuels, paints,
lubricants, and a myriad of other value added products essential to humans, would not be
feasible. Catalysis contributes the mechanism by which chemical transformations take place thus
enabling the commercially viable creation of desired materials. Thus, by using catalysts
manufacturing protocols can be made more economic, green and sustainable. Apart from heavy
metal catalysts which are mostly not recoverable from system, softer catalysts like zeolites,
phase transfer catalysts, e.g., crown ethers, are found more industrial applications.[31]
2.3.2 Synthetic approaches for NPs as nano catalysts
Are catalysts mostly heterogenous catalysts converted to metal nanoparticels using them for
speeding the process of catalyzing? At the same time catalytic reaction can occur. . Nanoparticle
catalysts can also be easily separated and recycleMetal nanoparticles have a higher surface area
so there is increased catalytic activity because more cad with more retention of catalytic activity
than their bulk counterparts. Catalyst play two different roles in process , they can act as a
support for catalytic process They are typically used under mild conditions to prevent
decomposition of the nanoparticles at extreme conditions.[32]

10
the way of nano technique:

Figure 1 describes the synthesis of nano catalyst [33]

As restriction arises in its definition about its size, the chemistry of nanoparticles mainly depends
on two things i.e. (i) synthesis of NPs well controlled in size and shape and (ii) molecular
approach to find more selective applications of NPs especially in nanocatalysis. Synthesis of NPs
in well controlled size is mainly made by using different stabilizing agents or capping agents i.e.
ligands (thiols, phosphines, amines), surfactants (ammonium salts), polymers (polyvinyl
alcohols, polyvinyl pyrrolidone, blockcopolymers), dendrimers (polyamidoamine), ions,
polyoxoanions, etc. Appropriate choice of the protecting/stabilizing agents is also a very
important factor because these can alter the surface properties of the NPs, as it can modify the
nature of active sites (morphology) and the surface chemical environment (steric and/or
electronic effect). Selectivity and reactivity of the NPs has a critical importance as it can
influence the course of a reaction which mainly depends on surface state of NPs. Thus,
selectivity and reactivity of NPs depends on mainly two concerns e.g. (i) control of crystal
structure and morphology and (ii) control of surface composition. Activity of NPs is concern of
(i) surface structure, (ii) exposure of different crystallographic facets and increased no. of edges,
corners & faces. Therefore, efficient control of morphology of the nanoparticles is becoming an
interesting task all over the world in recent years.[34]

11
2.3.3 Application of nano catalyst:
Catalysis is one of the pioneer applications of nanoparticles. Various elements and materials like
aluminium, iron, titanium dioxide, clays, and silica all have been used as catalysts in nanoscale
for many years. But appropriate explanation of its tremendous catalytic behaviour showing by
NPs still has not been fully understood. Large surface area of nanoparticles has a straight forward
positive effect on reaction rate and may also be a reasonable explanation of its catalytic activity.
Structure and shape-based properties of any materials at its nanoscale size can also effect the
catalytic activity of a material. The fine tuning of nanocatalysts, in terms of composition
(bimetallic, core-shell type or use of supports), shape and size has accomplished greater
selectivity. Thus the question here is how the physical properties of nanoparticles affect their
catalytic properties, and how fabrication parameters can in turn affect those physical properties.
By better understanding of these, a scientist can design nanocatalysts which are highly active,
highly selective, and highly resilient. All these advantages will enable industrial chemical
reactions to become more resource efficient, consume less energy, and produce less waste which
help to counter the environmental impact caused by our reliance on chemical process [32-36].
Nanoparticles are recognized as the most important industrial catalyst and have wider application
ranging from chemical manufacturing to energy conversion and storage. Variable and particle-
specific catalytic activity of nanoparticles is due to its heterogeneity and their individual
differences in size and shape. Scheme 2 represents basic difference in bulk catalysis and catalysis
shown by nanoscale materials.[35]

Figure 2 compares the efficiency of homogenous, heterogenous and nano catalyst. [36]
12
By precisely controlling the size, shape, spatial distribution, surface composition and electronic
structure, and thermal and chemical stability of the individual nano components, it can be widely
used in catalysis with newer properties and activity. Nanostructured catalysts have been the
subject of considerable academic and industrial research attention in recent times due to the
numerous potential benefits that can accrue through their use[37].

Figure 3 is the advantages of nano catalyst. [38]

Figure 4 contains some of the applications of nano catalyst. [38]

13
2.4 Microwave assisted technique for catalyst preparation
2.4.1 Microwaves and its application
Microwave radiations are electromagnetic radiations crossing the frequency range 30 GHz–300
MHz (i.e., from a wavelength of 1 m to 1 cm). they are used widely in communications and in
heating processes The energy released from the combustion process cannot be sustained for very
long, so that further development of energy sources has relied heavily on the energy of the atom
through nuclear reactions that have been shown to have serious consequences. For the long term,
for sustaining life and further development, mankind will have to rely on the energy from
electromagnetic waves (radio waves and light) Microwave radiation has now been used for more
than 20 years as a heat source for materials synthesis and sintering. For this reason, the energy
embodied in the microwaves can be absorbed by substances directly; energy saving is one of the
advantages. [39]

Applications of microwaves:

14
 figure 5,6 show some of the many micro wave applicatins. [40]

and In addition to the unique ability to promote reactions, microwave technology can offer
reduced processing time, costs, and energy consumption over conventional heating methods.

2.4.2 Microwave assisted technique for catalyst preparation

Many industrial processes using heterogeneous catalysts are high-temperature processes wherein
both components of the reaction (i.e., catalyst and medium) are heated to the temperature
required for the reaction to occur. Microwave heating can, under suitably designed conditions,
selectively heat the catalyst to the temperature required for substrate activation, allowing the
medium for remaining at a substantially lower temperature. A potential advantage is that quick
activation of the substrate occurs on the hot surface of the catalysts, which also imparts kinetic
energy that rapidly ejects the product from the hot surface into the cooler medium, thereby
impeding further reaction, it has also been reported that if thisset of conditions is optimized (i.e.,
very hot catalyst and cool surroundings), then product selectivity can favor the kinetic product
over the thermodynamic one This latter observation is especially right with a gas solid
reactionheat transfer ways in a microwave-driven heterogeneously catalyzed system. The
microwaves heat the catalyst through direct absorption of the radiation, the magnitude of which
is dictated by the radiation intensity (I) and the absorption cross section of the catalyst material

15
(𝛼cat) In a gas–solid reaction, however, the opposite is true, and Tcat ≫ Tmed. as can be no
heating of the gaseous medium (𝛼med =0), and convective heat flow from the catalyst to the
surroundings (hc) will be significantly less than in a condensed phase reaction. This means the
gas solid reactions will exhibit a high degree of selective heating under microwave irradiation
and are more possible to provide the energy savings when compared to convective heating. [41].

2.4.3 Synthesis of green nano catalyst using microwave

There is a growing interest in applying green chemistry for nanocatalysis applications. Catalysis
provides sustainable and cost-effective methods to transform raw materials into valuable
chemicals. Thus, catalytic processes have long become essential to solving the energy and
environmental challenges that we currently face around the globe On the basis of a Scifinder
Scholar search, the field of applying green chemistry to catalysis with nanoparticles has
undergone an explosive growth. The preparation, characterization, and catalytic performance of
bimetallic nanoparticles for solvent-free hydrogenation reactions have been reviewed
Heterogeneous gold, silver, and copper nanoparticles using hydrotalcite as the support material
have been used for environmentally benign organic transformations such as aerobic oxidation of
alcohols, lactonization of diols, and deoxygenation of epoxides and nitro aromatic compounds
One review article focuses on nanocatalysis for green chemistry development such as using
microwave heating with nanocatalysis in benign aqueous reaction media A variety of new
nanocatalysts that have high relevance to green chemistry are discussed such as molecular sieve
catalysts for regioselective oxyfunctionalization of alkanes, Fischer–Tropsch catalysts for the
production of fuel, enantioselective catalysts, etc, Synthesis of silver nanoparticles using the
green photo catalyst here is as an example for synthesizing green nano catalyst using microwave
Silver nanoparticles have been synthesized using several green methods such as the seed-
mediated growth method, doing the synthesis in the presence of ionic liquids, and other reduction
methods such as hydrazine reduction method, and sodium borohydride reduction method. Silver
nanoparticles have been synthesized by a green photocatalytic method in which the synthesis is
conducted in water, , the figure below shows silver nanoparticles that are synthesized using a
photocatalytic process , Calcium-alginate stabilized silver nanoparticles are prepared using a
photochemical green synthetic method These nanoparticles are used as catalysts for the 4-
nitrophenol reduction reaction [42]. Microwave chemistry is based on two main principles, the
dipolar mechanism and the electrical conductor mechanism. The dipolar mechanism occurs

16
when, under a very high frequency electric field, a polar molecule attempts to follow the field in
the same alignment. When this happens, the molecules release enough heat to drive the reaction
forward. In the second mechanism, the irradiated sample is an electrical conductor and the
charge carriers, ions and electrons, move through the material under the influence of the electric
field and lead to polarization within the sample. These induced currents and any electrical
resistance will heat the sample. microwave (MW)-assisted synthetic approach for producing
silver nanostructures. MW heating has received considerable attention as a promising new
method for the one-pot synthesis of metallic nanostructures in solutions. Researchers have
successfully demonstrated the application of this method in the preparation of silver (Ag), gold
(Au), platinum (Pt), and gold–palladium (Au–Pd) nanostructures. MW heating conditions allow
not only for the preparation of spherical nanoparticles within a few minutes but also for the
formation of single crystalline polygonal plates, sheets, rods, wires, tubes, and dendrites.[43]

The morphologies and sizes of the nanostructures can be controlled by changing various
experimental parameters, such as the concentration of metallic salt precursors, the surfactant
polymers, the chain length of the surfactant polymers, the solvents, and the operation reaction
temperature. In general, nanostructures with smaller sizes, narrower size distributions, and a

17
higher degree of crystallization have been obtained more consistently via MW heating than by
heating with a conventional oil-bath. The use of microwaves to heat samples is a viable avenue
for the greener synthesis of nanomaterials and provides several desirable features such as shorter
reaction times, reduced energy consumption, and better product yields.[44]
Microwave assisted green catalyst
The phytochemicals located in plant extracts are being reported to cause reduction of metal ions
to nanoparticles (NPs) and, ultimately eliminate the use of toxic chemicals, high pressure
temperature, energy and preservation of microbial cultures.Thus, green synthesis of NPs using
phytocompounds as bio-reductants is attaining a greater impetus. A variety of plant materials,
such as leaf extracts, fruit, bark, fruit peels, root and callus have been explored for the synthesis
of NPs in different sizes and shapes. Synthesis of metal NPs is a developing research area owing
to distinctive catalytic, optical, magnetic and electrical properties of NPs and their potential
applications.[45]
Here the synthesis of silver nano particles as mentioned above is an example. the methods for
synthesis of silver (nanoparticlesAgNPs) has been increased followed due to their antimicrobial
prophylaxis in wound treatment, sterilization of medical devices, oral health protection, and food
sanitation. the stability and protracted antibacterial action of AgNPs depends on their tendency to
combine and release of silver ions. Surface modification of AgNPs with citrate,
polyvinylpyrrolidone, and amino acids has been reported to get functional stability. AgNPs
coated with Agrimoniae herba extract as reducing agent and stabilizer confer better stability and
pharmacological activity as compare to bare AgNPs Various techniques for AgNPs synthesis
such as surface adsorption and deposition, arc discharge, laser chemical vapor deposition, plasma
and emulsion polymerization have been reported [46].
Recently, silver and iron NPs of various sizes and morphologies have been synthesized by using
coffee and green tea extract, n. Indeed, the synthesis of NPs using plant extract is potentially
advantageous over microorganisms due to the ease of biohazards and the culture of the
microorganisms. the synthesis of AgNPs, using aqueous leaf extract of Eucalyptus globulus, an
aromatic tree, belonging to a large genus of the Myrtaceae family, It has been widely refined in
many countries, including India [47].

18
Fig 7 and 8 shows the kinetics of AgNPs synthesis without and with microwave treatment.[48]

19
CHAPTER THREE

Chapter 3

20
The experimental part includes the preparation of plant extract and Ag NPs and characterization
of the NPs by UV-visible analysis.

3.1 Introduction
Basic microwave heating, Microwave are electromagnetic waves in the range of 300 MHz (0.3
GHz) to 300 GHz, with a typical frequency of 2.450 MHz for both domestic microwave ovens
and laboratory equipment (1).

Figure: The spectrum of electromagnetic waves (1)

There are basically three different ways how materials can interact with microwaves:
Reflection: Conducting materials (like metals) do not absorb, but reflect microwaves. Heating
does not occur.

 Absorption: Dielectric materials (i.e. which can be polarized by an electric field) absorb
microwaves, and therefore become hot. Typical examples are water, acids or polar
organic solvents.
 Transmission: Insulating materials (like polymers, quartz or ceramics) are transparent to
microwaves. Heating does not occur.

21
 Fig. Microwave heating mechanisim
3.2 Microwave versus conventional heating
During classical oil bath heating the reaction mixture is heated in a conductive way: the hotplate
heats the oil bath, the oil bath heats the vessel container (flask) and the hot vessel container heats
the reaction mixture (heating from the outside to the inside). In contrast, microwave irradiation
results in energy efficient internal heating by direct coupling of microwave energy with dipoles
and/or ions that are present in the reaction mixture. Microwaves pass through the (almost)
microwave-transparent vessel wall and heat the reaction mixture on a molecular basis – by direct
interaction with the molecules. Due to this direct “in-core” heating (no initial heating of the
vessel surface), microwave irradiation results in inverted temperature gradients as compared to a
conventionally heated system. The conversion of electromagnetic energy into heat energy works
highly efficiently and results in extremely fast heating rates – not reproducible with conventional
heating. Additionally, no direct contact to a heating core is necessary, enabling the heating of
different vessel sizes, shapes and amounts with the same microwave.

22
Fig. Simplified schemes of the heat distribution in a conventionally heated reaction mixture (a),
and in a microwave heated reaction mixture (b). While conventionally the heat comes from the
outside and goes into the reaction mixture by convection currents (resulting in a very hot vessel
wall), microwaves go through the almost microwave-transparent vessel wall and directly heat the
reaction mixture on a molecular basis (2).

3.3 preparation and characterization of silver NPs

3.3.1. Preparation of plant extract
 Fresh leaves of cactus were collected from local farm of Soran city. The pins were removed and
the leaves were washed thoroughly with distilled water. About 200 gm of leaves were cut into
small pieces. Finely cut leaves were dipped into a beaker containing 400 ml distilled water. After
that the mixture was boiled for 3 hr. The extract was filtered using Whatmann filter paper and
filtrate was collected.

3.3.2. Microwave irradiation mediated synthesis of silver nanoparticles

Rapid and friendly synthesis of Ag Nps can be conducted using Microwave technology (4). The
extract of cactus leaves was mixed with aqueous solution of 1 mM Silver nitrate in 1:4 ratio in
conical flask under aseptic conditions. The pH was adjusted to 8.0. The solution was subjected to
microwave irradiation and color change was observed.

23
The Operating variables
1. The effect of the microwave radiation (MW) power (GHz) in the synthesis of Silver NPs in
aqueous media by biosynthesis, leading to the formation of silver colloids.

2. The effect of time of formation NPs

 Fig. (a): Silver nitrate solution, (b): Cactus extract, (c ): Siver NPs colloid

3.3.3. UV-visible spectrophotometer analysis

 The bio reduction of silver ions in aqueous solution is monitored by UV-Vis spectra of the
solution between 300~600 nm using UV-visible spectrophotometer (5, 6). Distilled water is
taken to adjust the baseline.
Typical spectra of Ag NPs are presented below.

Typical UV-visible spectrophotometer analysis of silver nanoparticles synthesized by

biosynthesis route (6)

24
3.4 flow sheet diagram

25
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