Materials Synthesis Lab

CY-575
Nanomaterial Synthesis
 Solid State Reaction

➢ Common synthesis method to obtain polycrystalline material from solid reagents

➢ Advantage of solid state reaction method includes the simplicity and large scale production

➢ Widely used method includes the preparation of solids from mixture of starting material

➢ Reaction Condition

➢ Structural properties of the reactants

➢ Surface area of the solids

➢ Thermodymic free energy change associated with the reaction

 Different Synthesis Method

1.Solid state Reaction(ZnO,SiO2 )

2.Co-precipitaion Method(CoFe2O4, NiFe2O4)
3.Reduction Route(CuS,CdS)
4.Sol-Gel Method(Silica nanoparticle, GO)
Solid state reaction is based the three principles:

(i) area of contact between reacting solids,

(ii) the rate of diffusion and
(iii) the rate of nucleation of the product phase.

Limitations

➢ reagents are more difficult to work with,

➢ hard to control exact stoichiometry in certain cases
➢ sometimes it is not possible to find compatible reagents for the reaction.
Synthesis of ZnO
Chemical Required
zinc sulphate heptahydrate, deionized water, ethanol, methanol and sodium hydroxide
Procedure
Weigh 2.87 g of zinc sulphate heptahydrate and transfer it into a clean and dry mortar pestle. Grind it for about 5
min. To this add 0.8 g of sodium hydroxide with 4-5 drops of methanol and continue grinding for 40 min, till a
superfine powder is obtained. Using a mixture of water and ethanol (3:1) transfer the powder to centrifuge tubes.
Then centrifuge the zinc oxide at 4000 rpm. Wash the particles twice using the water-ethanol mixture. Then dry the
particles in oven at 60oC for overnight.

Centrifuge
dry

Mortor
OBSERVATION:

Colour of the product:

Texture of the product:
Weight of the product:
Percentage yield:
Characterization
XRD FTIR

DLS:
Zeta potential:
FESEM and TEM image of ZnO
EDAX
Application

Zinc oxide has a broad range of applications such as in pigments,

rubber additives, gas sensors, catalytic reactions, electronic
devices and components for the pharmaceutical and cosmetic
industries
 Synthesis of SiO2

Chemical Required
sodium silicate nonahydrate, deionized water, ethanol, methanol, dil. nitric acid and ammonium chloride.

Procedure
Weigh 5.68 g of sodium silicate nonahydrate and transfer it into a clean and dry mortar pestle. Grind it for
about 5 min. To this add 2.14 g of ammonium chloride with 4-5 drops of methanol and continue grinding for
40 min, till a superfine powder is obtained. Using a mixture of water and ethanol (3:1) transfer the powder
to centrifuge tubes. Then centrifuge the silicon dioxide at 4000 rpm. Wash the particles twice using the
water-ethanol-2 drops dilute nitric acid mixture. Then dry the particles in oven at 60oC for overnight.

Centrifuge dry
Characterization
SiO2
It is usually used to manufacture glass, ceramics and abrasives.
 Coprecipitation Method

The coprecipitation technique involves the precipitation of metal in the form

of hydroxide from a salt precursor with the help of a base in a solvent.

The controlled release of anions and cations assists to regulate

the nucleation and particle growth kinetics, which helps to synthesize
monodispersed nanoparticles.

Coprecipitation reactions involve the simultaneous occurrence of nucleation,

growth, coarsening, and/or agglomeration processes.
➢ There are three main mechanisms of coprecipitation: inclusion, occlusion,
and adsorption.

➢ An inclusion (incorporation in the crystal lattice) occurs when the impurity

occupies a lattice site in the crystal structure of the carrier, resulting in
a crystallographic defect; this can happen when the ionic radius and charge
of the impurity are similar to those of the carrier.

➢ An adsorbate is an impurity that is weakly, or strongly, bound (adsorbed) to

the surface of the precipitate. An occlusion occurs when an adsorbed
impurity gets physically trapped inside the crystal as it grows.
The advantages of the coprecipitation method are the high yield, high
product purity, the lack of necessity to use organic solvents, easily
reproducible, and low cost .
Synthesis of Cobalt Ferrite
 Charcaterization
FTIR Study
XRD Study
Cobalt ferrite (CoFe2O4) has an inverse spinel structure in which, in the
ideal state, all Co2+ ions are in B sites, and Fe3+ ions are equally distributed
between A and B sites.
Applications
Nickel Ferrite
➢ NiFe2O4 is a cubic ferromagnetic oxide with a typical inverse spinel structure where Ni2+ ions
occupy octahedric B-sites and Fe3+ ions equally distributed between tetrahedric A-sites and
octahedric B-sites.
➢ Nickel ferrite has an inverse spinel structure showing ferrimagnetism that originates from the
magnetic moment of anti parallel spins between Fe3+ ions at tetrahedral sites and Ni2+ ions at
octahedral sites of the cubic structure
Synthesis of Nickel Ferrite
Characterization
FTIR

➢ The bands at 552 cm-1 and 464 cm-1 represented

tetrahedral and octahedral modes of NiFe2O4,
respectively.
➢ The band located at 3389 cm-1 could be attributed to
the symmetric vibration of -OH groups.
➢ The bands with peaks observed at 1038 cm-1 could be
assigned to O-H bending vibration.
➢ The peak at 2333 cm-1 was ascribed to H-O-H bending
vibration of the free or absorbed water.
SEM
TEM
DLS and Zeta
Applications

Nickel ferrite is an important magnetic material with a variety of applications, such

as fabrication of ferrofluids, catalysis, and magnetic refrigeration and is one
of the most important soft ferrites with high electromagnetic performance, low
coercivity, good mechanical hardness, and chemical stability.
Sol-Gel Method

The sol–gel process is a wet-chemical technique used for the fabrication of both glassy and ceramic
materials. In this process, the sol (or solution) evolves gradually towards the formation of a gel-like network
containing both a liquid phase and a solid phase.

The sol–gel process is a wet chemical technique also known as chemical solution deposition, and involves
several steps, in the following chronological order: hydrolysis and polycondensation, gelation, aging,
drying, densification, and crystallization.

The process handles the transformation of monomers into a colloidal solution (the Sol) that acts as the
forerunner for an integrated network (the Gel) of either discrete particles or network polymers.

The synthesis is generally carried out in an organic cosolvent (alkoxysilanes are not water-soluble), through
simultaneous or sequential reactions of hydrolysis (eq 3.1) and polycondensation, releasing water or alcohol
Synthesis of silica particles by using sol-gel method
Preparation
Characterization

XRD
FESEM study
TEM
FTIR
Applications
Synthesis of Graphene oxide By Hummer’s Method

➢ Graphene is simply one atomic layer of graphite

- a layer of sp2 bonded carbon atoms arranged
in a hexagonal or honeycomb lattice.

➢ Graphite is a commonly found mineral and is

composed of many layers of graphene.

➢ Graphene is an allotrope of carbon consisting of a

single layer of atoms arranged in a two-
dimensional honeycomb lattice nanostructure.
➢ The name is derived from "graphite" and the suffix -
ene, reflecting the fact that the graphite allotrope of
carbon contains numerous double bonds.
 ➢ Graphene oxide contains flakes of monolayer and
few layer graphene, interspersed with
water (depending on the base media, the platelet to
platelet interactions can be weakened by surface
functionality, leading to improved hydrophilicity).

➢ Graphene oxide is achieved by the strong exfoliation of

graphite layers in acidic conditions.

➢ Graphene has a large theoretical specific surface area,

high intrinsic mobility, high Young’s modulus and
thermal conductivity, and its optical transmittance and
good electrical conductivity exhibits it be an exciting
material among many other materials.

Structure of GO(graphene oxide)

Hummers' method was developed in 1958 as a safer, faster and
more efficient method of producing graphite oxide. Before the
method was developed, the production of graphite oxide was slow
and hazardous to make because of the use of concentrated sulfuric
and nitric acid.
➢ Permanganate is a commonly used oxidant (e.g. dihydroxylations), the active species is, in fact,
dimanganese heptoxide (Mn2O7). The bimetallic heptoxide is far more reactive than its monometallic
tetraoxide counterpart. H2O2 has been used to reduce the excess KMnO4, not as an oxidizing agent.

Significance

➢ The method has been taken up by many researchers and chemists who are interested in the use of
graphite oxide for other purposes, because it is the fastest conventional method of producing graphite
oxide while maintaining a relatively high C/O ratio.

Definition

Hummers' method is a chemical process that can be used to generate graphite oxide through the addition
of potassium permanganate to a solution of graphite, sodium nitrate, and sulfuric acid. It is commonly used by
engineering and lab technicians as a reliable method of producing quantities of graphite oxide. It is also able to be
revised in the creation of a one-molecule-thick version of the substance known as graphene oxide.
 Why Hummer method?

Before the method was developed, the production of graphite oxide was slow and
hazardous to make because of the use of concentrated sulfuric and nitric acid.
The Staudenmeier–Hoffman–Hamdi method introduced the addition of potassium
chlorate. However, this method had more hazards and produced one gram of graphite
oxide to ten grams of potassium chlorate.

A comparison of Hummers method to the Staudenmeier method

Carbon-to-
Method % Carbon % Oxygen % Water % Ash oxygen atomic
ratio
Hummers 47.06 27.97 22.99 1.98 2.25
Staudenmeier 52.112 23.99 22.2 1.90 2.89
XRD
FESEM TEM
DLS Zeta
Applications
 Reduction route method

✓ Chemical reduction is one of the most prevalent methods to synthesize colloidal metal particles,
because of its convenient operation and simple equipment needed. One approach is a two-step process
where a strong reductant, mostly NaBH4, is used to initiate the reaction, forming small particles.
✓ A chemical reduction technique typically includes the reduction in metal salts in various solvents and
reducing agent
✓ Reduction is a chemical reaction that involves the gaining of electrons by one of the atoms
involved in the reaction between two chemicals. The term refers to the element that accepts electrons,
as the oxidation state of the element that gains electrons is lowered. ... This is called redox.
 Cds synthesis

The preparation of CdS nanoparticles was first published by Henglein et al. in 1982 by the reaction of Cd(ClO4)2 with
Na2S on the surface of silica particles which showed absorption at 515 nm.Bulk CdS is a direct bandgap material
(2.42 eV).
 Cds Synthesis

In a typical procedure, 10 mg of sulphur powder and 15 mg of cadmium chloride was taken in a beaker containing 50 mL
of THF:water (1:4) mixture.
This stock solution was stirred at room temperature for 5 min. Then, 4 drops of hydrazine hydrate was added to this
solution under vigorous stirring.
The reaction was stirred for 24 h and the formed particles were collected by centrifugation at 4000 rpm. Collected CdS
particles were washed with carbon disulphide (5 mL, twice), ethanol (10 mL, twice) and deionized water (10 mL, thrice).
Then sample was dried at room temperature for 24 h.
XRD
 Application

➢ CdS nanoparticles have applications as an excellent photographic developer for

detection of cancers and other diseases and in treatment of cancer cells

➢ The antibacterial and antifungal biological activity on various food borne bacteria and
fungi can be studied with the use of CdS nanoparticles
CuS synthesis

10 mg of sulphur powder and 12 mg of cupric chloride was taken in a beaker containing 50 mL of

THF:water (1:4) mixture.
This stock solution was stirred at room temperature for 5 min. Then, 4 drops of hydrazine hydrate
was added to this solution under vigorous stirring.
The reaction was stirred for 24 h and the formed particles were collected by centrifugation at
4000 rpm. Collected CdS particles were washed with carbon disulphide (5 mL, twice), ethanol (10
mL, twice) and deionized water (10 mL, thrice). Then sample was dried at room temperature for
24 h.
CuS
SEM
TEM
 Application

CuS has important applications in the fields of photocatalysis, solar cells, sensors, semiconducting
materials, and high capacity cathode materials in lithium secondary batteries due to its nonlinear optical
properties, increased conductivity at high temperatures, and excellent solar radiation absorbing properties
Synthesis of porous silica by cetyl trimethyl ammonium bromide (CTAB) as surfactant

➢ Surfactants can be used as soft templates for the synthesis of porous materials. The nano assemblies of various types
of surfactants support in controlling the morphology of particles synthesized under different conditions.

➢ Mainly there are three types of surfactants, cationic, anionic and non-ionic.

➢ CTAB is a cationic surfactant which is commonly used to synthesize spherical porous silica material.

➢ In this method, first the formation of micellar assemblies takes place followed by deposition of hydrolysed silica
precursor. The removal of surfactant is performed by calcination.
Classification of Pores in materials

Pores in materials can be classified according to their size.

Porous materials can be subdivided into 3 categories, according to IUPAC:

1. Microporous materials: 0.2–2 nm
2. Mesoporous materials: 2–50 nm
3. Macroporous materials: 50–1000 nm
Porous materials can be classified according to their periodicity.

1. Highly ordered materials.

Ex: Zeolites, MOFs, COCs (PMS).

2. Semi ordered materials.

Ex: COFs,

3. Random porous materials.

Ex: Porous organic polymers (POP).
 Porous silica

➢ Take 50 mL of deionized water in a beaker and add 10 mL of ethanol under continuous stirring for 10
minutes. 0.5 mg of cetyl trimethyl ammonium bromide was added and stirred till the CTAB gets completely
dissolved.
➢ The temperature of the mixture was maintained at 50oC. To this mixture, dropwise 1 mL of Tetraethyl
orthosilicate was added under vigorous stirring (avoid bubbles).
➢ Continue stirring for 90 min and then collect the precipitate using centrifuge. Wash the particles using a
mixture of water and ethanol (3:1).
➢ Then centrifuge the silica particles at 4000 rpm. Wash the particles twice using the water-ethanol mixture.
Then dry the particles in oven at 60C for overnight. Remove the CTAB by calcination at 550oC for 4h.
DLS