Synthesis and Fabrication of

Nanomaterials
Nanotechnology in future everyday life
 Nanomaterials
 Nanomaterial is the material with at least one of the dimensions
less than 100 nm
 Conventional materials have grain size anywhere from 100 µm to
1 mm and more
 The average size of an atom is in the order of 1-2 Angstrom in
radius
 1 nm = 10 Angstroms
 1 nm there may be 3-5 atoms
 Approximate length of 1 nm = 10 hydrogen atoms (or) 5 silicon
atoms alligned in line
 What happens as particle size becomes very small?
1) Large surface to volume ratio of atoms
2) Electrons are confined (metal to non-metal transition). Quantum
effects
3) More disordered dipoles (electric and magnetic) on surface than
in bulk
These can led to dramatic changes or enhancement of fundamental
properties such as material strength, electrical or thermal
characteristics and heightened (bio) chemical reactivity
 Nanomaterials
Surface Effects:
 As a particle decreases in size, a greater proportion of atoms
are found at the surface compared to those inside.
Ex: A particle of
 Size – 30 nm  5% of its atoms on its surface
 Size – 10 nm 20% of its atoms on its surface
 Size – 3 nm  50% of its atoms on its surface

 Due to vast surface area, all nanostructured materials possess

a huge surface energy and thus are thermodynamically
unstable or metastable
Palladium cluster
 Nanomaterials
Quantum Effects:
 Quantum confinement effect is observed when the size of
the particle is too small to be comparable to the
wavelength of the electron.
 Confinement confine the motion of randomly moving
electrons to restrict its motion in specific energy levels
(discreetness)
 Quantum  the atomic realm of particles

 As the size of a particle decreases, the decrease in

confining dimension makes the energy levels discrete
and this increases or widens up the band gap.
Disordered dipoles:

Ferromagnetic/ferroelectric Paramagnetic/paraelectric
 No change Physical laws and effects differ
mm-----------------------µm------------------------------------nm

Electronic Physical Chemical

properties properties properties

Quantum size Microstructure, Structure,

effect melting point, catalysis,
hardness, etc reactivity

Interfaces and
surfaces become very
important
 History of Nanoscience and Naotechnology
 Colloidal gold has been used since Ancient Roman time
(4th century AD) to color glass depending on the
concentration of gold

2400 years ago

 The Lycurgus cup, when illuminated from outside,

appears green. However, when illuminated from within,
it glows red. The glass contains silver (66.2%), gold
(31.2%), and copper (2.6%), up to 100 nm in size.
 (a) Michael Faraday’s colloidal solution of gold in the
Royal Institution of Great Britain, (b) High resolution
transmission electron microscopic image of individual
colloidal gold particles (at a magnification of 107 x)
prepared according to the Faraday’s recipe
 Richard Feynman: There’s plenty of room
at the bottom, 1959
 The first time the idea of
nanotechnology was introduced was in
1959, when Richard Feynman, a
Physicist at Caltech, gave a talk called
“There’s plenty room at the bottom”.

 Though he never explicitly mentioned

“nanotechnology”, Feynman
suggested that it will eventually be
possible to precisely manipulate atoms
and molecules.
 First, the scanning Tunnelling Microscope
(STM) was invented by Binning and Rohrer
in 1981

With this technology, individual atoms could be clearly

identified for the first time
Limitations in scanning tunnelling microscopy
were eliminated through the 1986 invention
of the Atomic Force Microscope

Using contact to create an

image, this microscope
could image non-
conducting materials such
as organic molecules.
1989-First atomic manipulation at IBM by Don
Eigler

Xenon atoms on Nickel surface

 1987 First single-electron transistor created

 1991 Carbon Nanotubes discovered

 2000 US Launches National Nanotechnology

 Classification of nanomaterials
1) Zero dimensional (0-D)
2) One dimensional (1-D)
3) Two-dimensional (2-D)
4) Three-dimensional (3-D)
1) Zero dimensional:
These are the materials having all the dimensions within the
nanoscale (no dimensions are larger than 100 nm)
Ex: nanopsheres, nanoclusters

2) One dimensional:
These are the materials having one dimension is outside the
nanoscale (one dimension is larger than 100 nm)
Ex: nanowires, nanorods, nanotubes, nanopillars,
carbon nanotubes (CNT)
 Classification of nanomaterials
3) Two dimensional:
These are the materials having two dimensions are outside the
nanoscale. (Two dimensions are larger than 100 nm). This class
exhibits plate-like shapes and includes graphene, nanofilms,
nanolayers, and nanocoatings

4) Three dimensional:
These are the materials that are not confined to the nanoscale in any
dimension (All three dimensions are larger than 100 nm)
Ex: Graphite, diamond, bulk powders, dispersions of nanoparticles,
bundles of nanowires.
 Approach to nanomaterials

 More wastage  Less wastage

 Surface Energy

 The bond distance between surface atoms and sub-surface atoms becomes smaller

 P.E of surface atoms > P.E of interior atoms

𝑤𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 𝑑𝐺
 Surface energy (γ)= =
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑎𝑟𝑒𝑎 𝑑𝐴

 Energy required to create a unit area of new surface

𝑁𝑏ερ𝑎 N b = No. of broken bonds
γ= ε = bond strength
2
ρa =Surface atomic density
 Surface energy reduction
 Different known mechanism to reduce the surface energy
for a given surface with a fixed surface are :

1) Surface relaxation
2) Surface reconstruction
3) Surface adsorption through chemical or physical
adsorption of chemical species
4) Composition segregation
Reduction of surface energy for nanoparticle
 One is to reduce the total surface area. That is, surface tends to
become spherical.
 For crystalline particles, facets forms because they have smaller
surface energy than a spherical surface does.
 Facets with a lower miller
index have a lower surface
energy than that with a
higher miller index.
 Therefore, crystal is often
surrounded by low index
surfaces
 Wulff plot is used to
determine the shape or
surfaces of an equilibrium
crystal
 Crystal growth with Nonfacets
 At certain high temperature, the equilibrium crystal surfaces may
not be smooth, and difference in surface energy of various crystal
facets may disappear. Such a transition is called surface roughening
(or) roughening transition.

 Most nanoparticles grown at elevated temperatures are spherical in

shape (not facets)

 Kinetic factors (processing or crystal growth conditions) may also

prevent formation of facets.
 Mechanism for reduction of overall
surface energy
 Combining individual nanostructures together to form large
structures so as to reduce the overall surface area, which includes:
1) Sintering: individual structures merge together which occurs at
70% of Tm.

2) Ostwald ripening: a large one grows at the expense of the smaller

one until the latter disappears completely, and becomes a single
crystal. It occurs at relatively low temperature.

3) Agglomeration: agglomeration of individual nanostructures

through chemical bonds and physical attraction forces at interfaces
without altering the individual nanostructures.
 Ostwald ripening process

 Results in
1) Abnormal grain growth which leads to inhomogeneous
microstructure and inferior mechanical properties of the products
2) Eliminate smaller particles and the size distribution becomes
narrower during growth of nanoparticles
 Triggering and stopping of Ostwald
Ripening process
 Ostwald ripening process can be triggered after initial nucleation
and subsequent growth by raising the temperature.
 The concentration of solid in solvent falls below the equilibrium
solubility of small nanoparticles, and the small ones dissolve into
the solvent.
 Once a nanoparticle starts to dissolve into the solvent, the
dissolution process never stops until the nanoparticle is dissolved
completely.
 The large particles will grow until the concentration of solid in the
solvent equals the equilibrium solubility of these large
nanoparticles.
 Stabilization of nanoparticles

Electrostatic stabilization: kinetically stable

Steric stabilization: thermodynamically stable

 Electrostatic stabilization – surface charge
density
 When a solid emerges in a polar solvent or an electrolyte solution, a
surface charge will be developed due to:

1) Preferential adsorption of ions due to dissolution

2) Dissociation of surface charged species

3) Isomorphic substitution of ions

4) Accumulation or depletion of electrons at the surface

5) Physical adsorption of charges species onto the surface

 Surface charge density

 Therefore, a electrode potential is established as Nernst equation

𝑅𝑇
𝐸 = 𝐸𝑜 − ln[𝑎𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑜𝑓 𝑖𝑜𝑛𝑠]
𝑛𝐹
Where
Eo = standard electrode potential when the concentration of the ions is
unity
Ni = valence state of ions
R g = gas constant
F = Faradays constant
 The surface potential of a solid varies with the concentration of the
ions in the surrounding solution and can be either positive or
negative
 For surface charge in oxides
 The surface charge in oxides is from preferential dissolution or
deposition of ions
 The ions adsorbed on the solid surface determine the surface
charge, and are referred to as charge determining ions.
 In the oxide system, typical charge determining ions are protons and
hydroxyl groups and their concentration are described by pH
 The concentration of charge determining ions corresponding to a
neutral or zero-charged surface is called point of zero charge (PZC)
 When pH < PZC (corresponds to a neutral surface), H+ is the charge
determining ions and the surface is positively charged
 When pH > PZC (neutral), OH- is the charge determining ions and
the surface is negatively charged
 Electric potential at the proximity of solid surface
 The distribution of both ions are mainly controlled by combination
of following forces
 Coulombic force or electrostatic force
 Entropic force or dispersionSurface charge
 Brownian motion determining
ions
Counter
 The combined result is the ions
concentration of counter ions
is the highest near the solid
surface and decreases as the
distance from the surface
increases

 The inhomogeneous distribution of ions in the proximity of solid

surface lead to the formation of double layer
 Interaction between two particles

 Same charge  Same charge brought together

 Opposite charge  Opposite charge & electrolyte added
 Limitations of electrostatic stabilization
 It is only applicable to dilute systems

 It is almost not possible to redisperse the agglomerated particles

 It is difficult to apply to multiple phase systems, since in a given

condition, different solids develop different surface charge and
electric potential
 Steric stabilization (or) polymer stabilization
 It is thermodynamic stabilization method, so that particles are
always redispersible

 A very high concentration can be accommodated, and the dispersion

medium can be completely depleted

 It is not electrolyte sensitive

 It is suitable to multiple phase systems

 Polymeric stabilization leads to monosized
nanoparticles
 Polymeric stabilization leads to narrow size distribution.

 Polymer layer adsorbed on the surface of nanoparticles serves as a

diffusion barrier to the growth species, resulting in a diffusion
limited growth.

 Diffusion limited growth would reduce the size distribution of the

initial nuclei, leading to monosized nanoparticle.
 Good or poor solvent

 When polymer dissolved in a solvent tends to expand to reduce the

overall Gibbs free energy of the system, such a solvent is called
good solvent.

 When polymer in solvent tends to coil up or collapse to reduce the

Gibbs free energy, such a solvent is called poor solvent
Different kinds of polymer interacting with
solid wall
 Interaction between polymer layers
 Coverage of polymer on the solid surface less than 50%
 Interpenetration of polymer layer
 Freedom reduction of polymer
 Reduction of entropy
 Increase of Gibbs free energy
 Interaction between polymer layers
 Coverage of polymer on the solid surface approaching 100%
 Compressed of two polymer layers
 Coil up of polymer in both layers
 Reduction of entropy
 Increase of Gibbs free energy

Poor solvent and

low coverage,
interpenetration
leads to further
coil up of polymer,
decrease in gibbs
free enegy
Mixed steric and electric interactions
 Synthesis methods – bottom up approach
 Various synthesis methods or techniques can be grouped
into two categories
1. Thermodynamic equilibrium approach:
a) Generation of supersaturation,
b) Nucleation
c) Subsequent growth
2. Kinetic approach (reactant concentration, diffusion,
solubility, reaction rate):
a) Limiting the amount of precursors available for the
growth
b) Confining the process in a limited space
 Requirements of nanoparticles
1. Identical size of all particles (monosized or with
uniform size distribution)
2. Identical shape or morphology
3. Identical chemical composition and crystal structure
among different particles and within individual
particles, such as core and surface composition must be
the same
4. Individually dispersed or redispersible (no
agglomeration)
Nanoparticles through homogeneous nucleation
 Homogeneous nucleation refers to the formation of
nuclei of new phase uniformly through out the parent
phase
 Here, we refer phase transformation from liquid state to
solid phase
 Phase transformation depends on an important
thermodynamic property – change in free energy (ΔG)
 Transformation occurs when there is a reduction in free
energy, i.e., when ΔG < 0
 When concentration of solute exceeds its equilibrium
solubility or temperature decreases below the phase
transformation point, a new phase appears
Nanoparticles through homogeneous nucleation
Nanoparticles through homogeneous nucleation
 Assume that the nuclei of solid phase form within the
interior of the liquid
 Assume that the nucleus is spherical with a radius r
 Two contributions to free energy change
Free energy difference between solid
and liquid phases – volume free
energy (ΔGv)
Contribution from solid-liquid phase
boundary during the transformation or
surface energy (γ)
 Total free energy change = volume free energy + surface
energy
4
ΔG= 𝜋𝑟 3 ΔGv + 4𝜋𝑟 2 γ
3
Nanoparticles through homogeneous nucleation

r* = critical radius
ΔG* = activation free energy
Nanoparticles through homogeneous nucleation
 The total free energy increases, passes through a maximum and
then decreases
 The trend of ΔG physically implies that the free energy increases
as a solid particle starts to form through the clustering of the
atoms in the liquid
 If the cluster size reaches a critical radius r*, it will continue to
grow as the free energy starts decreasing thereafter.
 If the cluster radius is less than the critical radius r*, it will
shrink or dissolve
 The subcritical particle with radius less than r* is called an
embryo and the particle with radius greater than r* is called
nucleus
 The free energy change, at the critical radius r*is called critical
free energy change ΔG*, called activation free energy
Nanoparticles through homogeneous nucleation

The free energy required for the formation of a

stable nucleus is the activation free energy

𝑑(Δ𝐺) 𝑑 4 3
= ( πr ΔGv + 4πr2γ) = 4πr2ΔGv + 8πrγ = 0
𝑑𝑟 𝑑𝑟 3

∗ 2γ 16πγ
𝑟 = − ΔG* =
Δ𝐺𝑣 3Δ𝐺𝑣 2
Nanoparticles through homogeneous nucleation

r* = critical radius
ΔG* = activation free energy
If the temperature is father from TE, then nucleation happens easily.
Nanoparticles through homogeneous nucleation

r* = critical radius
ΔG* = activation free energy
Nanoparticles through homogeneous nucleation
 Growth of an embryo
The growth begins when an embryo reaches a
critical radius (r*)
 Nucleation continues elsewhere in the liquid phase
 The growth process of the nuclei involves
Generation of growth species Diffusion
Diffusion of growth species from bulk to the growth surface
Adsorption of the growth species onto the growth surface
Surface growth through irreversible incorporation of growth
species onto the solid surface (Growth)
 A diffusion limited growth would result in a different size
distribution of nanoparticles as compared with growth-
limited process
 Growth controlled by diffusion
 When the concentration of the growth species reduces
below the minimum concentration for nucleation, nucleation
stops and growth continues
Growth controlled by surface process
Desired – diffusion limited growth
 Gas phase synthesis
 Gas – phase processes were the first applied to synthesize
nanoparticles
 In gas-phase processes, a vapour of the material condenses to form
small particles.
 It produces equiaxed crystallites and the crystal size of the powder is
few nanometres and the size distribution is narrow
 The crystal size is dependent on the inert gas pressure and temperature
 The process of particle formation may be divided into four major
steps:
1) Nucleation
2) Condensation
3) Coagulation
4) Agglomeration
Gas phase synthesis of nanomaterials- thermal
evaporation inert gas condensation
 Thermal evaporation is the most popular technique due to its easy
handling and good yield.
 Pure nanocrystalline metals like Cu, Au, Pd, Ni, Fe etc can be
synthesized with a narrow particle size distribution between 5-20 nm.
 The simplest method to produce nanoparticles is by heating the
desired materials in a heat resistant crucible containing the desired
material.
 Gas pressure and temperature can be varied to vary the particle size in
thermal evaporation technique
 This method is appropriate only for materials that have a high vapour
pressure at the heated temperatures
 Alloys with different vapor pressures are difficult to make by thermal
evaporation
 Gas phase synthesis of single phase
nanomaterials
 Energy is normally introduced into the precursor by arc heating, or
electron bean heating or joule heating
 The atoms are evaporated into an atmosphere, which is either inert
(He) or reactive (to form a compound)
 The hot atoms of the evaporated matter loose energy by collision with
the atoms of the cold gas and undergo condensation into small clusters
via homogeneous nucleation
 The clusters would continue to
grow if they remain in the
supersaturated region
 To control their size, they need
to be rapidly removed from the
supersaturated environment by
a carrier gas
Flame assisted spray pyrolysis
 Laser ablation process
 This technique consists of ablation of a material by means of laser
irradiation
 The ablated atoms condense into clusters or nanoparticles, which are
continuously collected in liquid
 A wide range of nanopowders of metals, metallic alloys,
semiconductors and metal oxides can be synthesized by this method
Controlling the shape of the metal nanocrystal in
gaseous environment
 In heterogenous catalysis, it has been reported that the gas molecules
can chemisorb onto the surface of a nanocrystal via covalent bonding
and thus effectively reduce the specific surface free energy
 Due to the involvement of covalent bonding, the adsorbate can
preferentially bind only to a specific type of facet on the surface and
alters the surface free energy of different facets, leading to the
formation of nanocrystals with profiles deviated from the Wulff shape
 Ex: Pt nanocrystals on SiO2 substrate were found to change shape
when the sample was annealed at 600 ºC in the presence of different
gas molecules
 N2
 H2
 Truncated
 Cubes
cuboctahedrons
 Ex: Pt nanocrystals on Al2O3 powder when the sample was annealed
under different gas environment.
 If the interaction between the gas molecules and Pt surface is
relatively weak, as in the case of air where only physisorption was
involved, the relative surface energies for different facets of a
nanocrystal will be almost equivalent to the case in vacuum resulting
in spherical shape predicted by wulff construction.
 In other case the sulfur has preferential binding to Pt(100) resulting in
lowering its free energy
 Therefore, Pt nanocrystals were transformed into a cubic shape
enclosed by six {100} facets as long as there is adequate amount of
H2S in the gas
 H2 containing trace
 Air at 700 ̊C for 1 h amount of H2S at 500 ̊C
 Spherical shape for 16 h
 Cubic shape
Factors limiting the potential application of gas-phase method
are

 High temperature

 Limited choices of gases

 Switching to solution-phase method can overcome this

limitations due to the availability of different capping agents
for each type of facets
 Shape of nanocrystal in a solution in the
presence of capping agent
 Capping agents are ionic species, small molecules, or macromolecules
that can selectively bind to different types of facets on a nanocrystal to
alter their surface free energies

 When a capping agent is introduced into a solution, the type of facet

stabilized by the capping agent will exhibit a lower surface free
energy, leading to the formation of nanocrystals with a shape that
maximizes the expression of that type of facets.

 Since the capping agent chemisorbed in a facet will hinder or prevent

the deposition of atoms onto this facet, surface capping will eventually
lead to the formation of a shape with that particular facet
The facets covered by the capping agent will take a slower
growth rate and thus a greater proportion on the surface

Truncated
octahedral seed

 With introduction of capping agent for {100} facets, then γ{100} <
γ{111}, and the growth will be faster along the <111> directions
 Due to difference in the growth rate, the ratio between the areas of
{100} and {111} facets on the surface will gradually increase, and the
nanocrystal will evolve from truncated octahedron to cuboctahedron,
truncated cube, and eventually a cube enclosed by {100} facets only.
 Since we have wide variety of chemicals that can acts as capping
agents for different types of surfaces, solution-phase synthesis
provides a powerful route for the preparation of metal nanocrystals
with a myriad shapes

 The preferential binding of a capping agent to a specific metal surface

may be attributed to many factors, including the crystal structure and
the function group of a capping agent, as well as the electronic and
surface structure of the metal

 The binding energy of a chemical species to a metal surface can be

calculated through computational approach based on DFT and ab
initio calculations
 Ex: Binding of PVP to Ag surface were studied using DFT
 PVP repeating unit: ethane and 2-pyrrolidone (2P)
 Since ethane is inert and nonpolar species, its interaction with Ag
surface should only involve van der Waals attraction
 In contrast, the oxygen and nitrogen atoms in the 2P ring can form
much stronger bonds with Ag surface
 The study suggests that both interactions, including van der Waal
attraction and covalent bonding, need to be taken into consideration to
calculate the total binding energies
 The calculation results indicate that binding of PVP to Ag(100) is
stronger than to Ag(111)
Ag cubes Ag octahedrons
 Surface coverage density of the capping agent
 For Synthesis of Pd nanocrystals
 Precursor: Soduim tetrachloropalladate (Na2PdCl4)
 Reducing agent: ascorbic acid
 Capping agent: Br-
Coverage density of capping agent
 Larger physical dimensions of a polymer based capping
agent may compromise its role when nanocrystal with very
small sizes are involved

 Ex: PVP is no longer effective in capping the {100} facets

to generate Ag cubes with edge lengths shorter than 30 nm

 In contrast, the much smaller size of Br- ions make them

well-suited for capping the {100} facets of Ag cubes with
dimensions smaller than 30 nm
 Thermodynamic control in solution phase is a simple and yet effective
strategy that can be easily implemented during experiments

 A thermodynamically controlled synthesis can be implemented in two

slightly different ways
i. Introducing different type of capping agents to selectively chemisorb
onto different types of metal surfaces and thus lower the surface free
energy of the facets
ii. Controlling the covering density of a capping agent by adjusting its
concentration
Limitations:
 No capping agent capable of preferentially stabilizing high index
facets of metal nanocrystal
 Impossible to synthesize nanocrystals with asymmetric shapes or
structures
Kinetic control
 Synthesis of Metallic Nanoparticles
 General method for metal colloid: Reduction of metal complexes in
dilute solution

 Various methods have been developed to initiate and control the

reduction reactions

 In most cases, monosized metallic nanoparticles is achieved by a

combination of low concentration of solute and polymeric
monolayer adhered onto the growth surface (diffusion limited
growth)

 For synthesis of metallic nanoparticles, various types of precursors,

reduction reagents, other chemicals and methods were used to
promote or control the reduction reactions, initial nucleation and
subsequent growth of the initial nuclei
 Gold Nanoparticles

 Colloidal gold has been studied extensively for a long time.

 A variety of methods have been developed for the synthesis

of gold nanoparticles, and among them, sodium citrate
reduction of chloroauric acid at 100 ⁰C remains the most
commonly used method.
 Preparation of 2.5x10-4M Au colloids (sodium citrate
reduction method or Turkevich method)
1) Make a solution of ~5.0 x 10-3M HAuCl4 in water. (0.1699 g
HAuCl4 in 100 ml deionized water)
2) Take 1 mL of that solution and add it to another 18 mL of H2O (now
~ 2.5 x 10-4M)
3) Make a solution of 0.5% sodium citrate (0.25 g in 50 ml of H2O)
4) Heat the 19 mL solution of HAuCl4 until it begins to boil
5) Add 1 mL of 0.5% sodium citrate solution, as soon as boiling
commences
6) Continue heating until a color change is evident (pale purple)
7) Remove the solution from the heating element and continue to stir
until it has cooled to room temperature
This method yields fairly uniform size colloids with a diameter of 15-20
nm
 Influence of reduction reagents
 The size and size distribution of metallic colloids vary significantly
with the types of reduction reagents used in the synthesis
 In general, a strong reduction reaction promotes a fast reaction rate
and favours the formation of smaller nanoparticles
 A weak reduction reagent induces a slow reaction rate and favours
relatively larger particles
 However, a slow reaction may results in either wider or narrower size
distribution
 If the slow reaction leads to continuous formation of new nuclei or
secondary nuclei, a wider size distribution would be obtained.
 On the other hand, if no further nucleation or secondary nucleation
occurs, a slow reduction reaction would lead to diffusion-limited
growth leading to narrow size distribution
 Using the same reduction reagent, nanoparticle size can be varied by
changing the synthesis conditions
 It was also found that the reduction reagents have noticeable
influences on the morphology of the gold colloidal particles
 Reduction reagent Shape
Sodium citrate Spherical
Hydrogen peroxide Spherical
Hydroxylamine Cubical {100} facets
hydrochloride
Citric acid Trigons or very thin platelets of
trigonal symmetry {111} facets

Concentration of the reduction reagent and pH of the

reagent have noticeable effect on the shape of
nanoparticles. Ex: lowering the pH value caused the {111}
facets to develop at the expense of the {100} facets
 Stronger reduction
reagent

 The stronger reduction reagents would generate an abrupt surge of the concentration
of the growth species, resulting in a very high super saturation. Consequently, a
large number of initial nuclei would form
 For a given concentration of metal precursor, the formation of large number of initial
nuclei would result in a smaller size of the grown nanoparticles
 A decreased reduction rate can also be achieved using a low
concentration of reactant
 Ex: Silver nanoparticles were synthesized by reduction of silver
nitrate using formaldehyde in aqueous solution
 Effects of polymer
 A strong absorption of polymer would occupy the growth sites and
reduce the growth rate of nanoparticles
 A full coverage of polymer can hinder the diffusion of growth species
from the surrounding solution to the surface of the particles
 In addition, polymer may interact with solute, catalyst, or solvent and
affect reaction
 Ex: Ahmadi et al. studied the influence of polymer stabilizer (sodium
polyacrylate) on the shape of the colloidal platinum nanoparticles
 Under same experimental condition and using the same polymer
stabilizer but changing the ratio of stabilizer to that of Pt ions from 1:1
to 5:1 produced different shapes of Pt nanoparticles
 1:1  cubic particles
 5:1  tetrahedral particles
Effects of polymer/pt ion concentration
5:1
 Without using polymer

 Silver nanoparticles through tollens

process (20-30 nm)
 Tollen's process: reduction of Ag+ ions
is done by introducing saccharides in
the presence of ammonia
 Electrostatic stabilization
 Particle size is sensitive to temperature
 Silver Nanoparticles
 Chemical synthesis of silver nanoparticles of different size and shapes
(nanorod, nanospindle, nanocube, nanosphere, nanoellipsoid and some
plate like structures)
 Precursor: Silver nitrate (AgNO3)
 Reducing agent: Benzoic acid
 Stabilizer: polyvinyl pyrolidone (PVP)
 Temp: 60 – 120 ºC at 10 ºC interval
 It has been found that by taking the higher value of the ratio between
AgNO3 and PVP but with the same amount of benzoic acid, different
shapes of silver nanoparticles such as spherical, triangular,
pentagonal, hexagonal and some elongated shapes are produced
 Two cases:
1) AgNO3:0.0025 mol, PVP = 1 g, benzoic acid =0.5 g, Temp= 60-120 ºC, Interval =
10 ºC
2) AgNO3=0.025 mol, PVP = 1 g, benzoic acid =0.5 g, Temp= 60-120 ºC, Interval = 10
ºC
Case-I
Nanorods Nanorods
Aspect ratio ~7 Aspect ratio ~6

Spindle shape Cube with sharp

494 x 281 nm corners
Aspect ratio ~1.7 360 nm

Spherical and
Cube particles Plate like
340 nm structure
Case-II
 Silver Nanoparticles
 Monodisperse samples of silver nanocubes were
synthesized in large quantities by reducing silver nitrate
(AgNO3) with ethylene glycol in the presence of
poly(vinylpyrrolidone) at 160 ºC.
 These cubes are single crystals and were characterized by a
slightly truncated shape bounded by {100}, {110}, and
{111} facets
 The presence of PVP and its molar ratio (in terms of
repeating unit) relative to silver nitrate both played
important roles in determining the geometric shape and size
of the product.
 Along with that the temperature and the concentration of
AgNO3 also played an important role in morphology and
dimensions
 Preparation of 1.0x10-3M Ag colloids (sodium citrate
reduction method or Turkevich method)
1) Make a solution of ~5.0 x 10-3M AgNO3 in water. (0.0425 g in 50 ml
deionized water)
2) Take 25 mL of that solution and add it to another 100 mL of H2O
(now ~ 1.0 x 10-3M)
3) Make a solution of 1% sodium citrate (0.5 g in 50 ml of H2O)
4) Heat the 125 mL solution of AgNO3 until it begins to boil
5) Add 5 mL of 1% sodium citrate solution, as soon as boiling
commences
6) Continue heating until a color change is evident (pale yellow)
7) Remove the solution from the heating element and continue to stir
until it has cooled o room temperature
This method yields relatively large size nanocrystallites with a diameter
of 60-80 nm