University of Engineering & Technology, Lahore

Anam Nazir
2016-Mphil-App-Phy-18
Nanomaterials-Synthesis, Properties and Applications
Assignment Topic: Synthesis of Nanoparticles
Synthesis of Nanoparticles
Reduction of metal complexes in dilute solutions is the general method in the synthesis of
1
metal colloidal dispersion s , and a variety of methods have been developed to initiate and
control the reduction reactions.
The formation of monosized metallic nanoparticles is achieved in most cases by a
combination of
a low concentration of solute
polymeric monolayer adhered onto the growth surfaces.
Both a low concentration and a polymeric monolayer would hinder the diffusion of growth
species from the surrounding solution to the growth surfaces, so that the diffusion process is
likely to be the rate limiting step of subsequent growth of initial nuclei, resulting in the formation
of uniformly sized nanoparticles.
Use of precursors, reduction reagents, polymer stabilizers
In the synthesis of metallic nanoparticles, or more specifically speaking, metallic colloidal
2 3 4
dispersion, various types of precurso rs , reduction reagent s , polymer stabilizer s ,
other chemicals, and methods were used to promote or control
The reduction reactions
The initial nucleation
The subsequent growth of initial nuclei.
The precursors include: elemental metals, inorganic salts and metal complexes, such as, Ni, Co,
, HAuCl 4 , , RhCl3 , H 2 PtCl 6 and PdCl2 .

Reduction reagents includes: sodium citrate, hydrogen peroxide, hydroxylamine hydrochloride,

citric acid, carbon monoxide, phosphorus, hydrogen, formaldehyde, aqueous methanol, sodium
carbon- ate and sodium hydroxide.
Examples of polymeric stabilizers include polyvinyl alcohol (PVA) and sodium polyacrylate

Synthesis of some nanoparticles

Synthesis of Au nanoparticles
Synthesis of Rh nanoparticles
Synthesis of Pt nanoparticles
Synthesis of Pd nanoparticles
Synthesis of Ag nanoparticles
Synthesis of Metallic nanoparticles(Co, Ni,Pd)
 Synthesis of Au nanoparticles
In 1857 Faraday published a comprehensive study on the preparation and properties of
colloidal gold.
A variety of methods have been developed for the synthesis of gold nanoparticles, and
among them, sodium citrate reduction of chlorauric acid at 100C was developed more than 50
years ago and remains the most commonly used method.
The classical (or standard) experimental conditions are as follows.
a. Chlorauric acid dissolves into water to make 20 ml very dilute solution of -2.5 X 104M.
b. Then 1 ml 0.5% sodium citrate is added into the boiling solution.
c. The mixture is kept at 100C till color changes, while maintaining the overall volume of
the solution by adding water.
Such prepared colloidal sol has
Excellent stability
Uniform particle size of 20nm in diameter.
Some Important Results
It has been demonstrated that a large number of initial nuclei formed in the nucleation stage
would result in a larger number of nanoparticles with smaller size and narrower size
distribution.

Synthesis of Rh nanoparticles
Hirai and coworker prepared a colloidal dispersion of rhodium.
Colloidal dispersion of rhodium by
Refluxing a solution of rhodium chloride and PVA in a mixture of methanol and water at
79C.
The volume ratio of methanol to water was 1: 1.
Refluxing was carried out in argon or air for 0.2 to 16 hours.
In this process, methanol was used as a reduction reagent and the reduction reaction was
straightforward.
PVA was used as a polymer stabilizer and also served as a diffusion barrier.
Rh nanoparticles prepared were found to have mean diameters ranging from 0.8 to 4 nm.
Some Important Results
 A bimodal size distribution was found, with large particles of 4 nm and small ones of 0.8
nm.
5
Increasing refluxing tim e was found to result in a decrease of small particles and an
6
increase of large particles, which was attributed to Ostwald ripenin g .

Synthesis of Pt nanoparticles

Henglein et al. studied and compared three different methods for the preparation of Pt
nanoparticles:

Radiolysis
Hydrogen reduction
Citrate reduction.
Radiolysis
The y-rays of Co (60) was used to generate hydrated electrons, hydrogen atoms and 1
-hydroxyl methyl radicals. These radicals would subsequently reduce Pt 2 in K 2 Pt
Cl 4 to the zero-valence state, which formed Pt particles with a mean diameter of 1.8 nm.

Hydrogen reduction

Hydrogen reduction of K 2 Pt Cl 4 was developed by Rampino and Nord19 and PVA was

used to stabilize both Pt particles in the experiments.

In this method, precursors in dilute aqueous solution were first hydrolyzed to form
hydroxides prior to hydrogen reduction. For Pt, sodium hydroxide was required to ensure the
hydrolysis reaction.
When no catalyst was used, during aging prior to the introduction of hydrogen gas, the Pt
precursor complexes could be converted to a large extent into aquated complexes within a
few hours at ambient temperature.
The aquated complexes were then reduced by hydrogen.
Such prepared Pt particles have a mean diameter of 7.0 nm.
Some important Results
It was found that
the polymeric stabilizer, either sodium polyacrylate or polyphosphate, had a
strong influence on the rate of the reduction reaction.
 This indicates that the polymeric stabilizer may exert catalytic influences on
reduction, in addition to their stabilization and diffusion barrier roles.
Citrate reduction
Citrate reduction of PtC1 is also known as Turkevich method, which was initially
developed for the synthesis of uniformly sized gold nanoparticles. In this method,
H 2 PtCl 6 was mixed with sodium citrate and boiled for 1 hr., yielded Pt particles of 2.5 nm

in diameter.

Synthesis of Pd nanoparticles

Hydrogen reduction of PdCl2 was developed by Rampino and Nord19 and PVA was used to

stabilize Pd particles in the experiments.

Hydrogen reduction
In this method, precursors in dilute aqueous solution were first hydrolyzed to form
hydroxides prior to hydrogen reduction. For Pd, sodium carbonate was used as a catalyst to
promote the hydrolysis reaction.

Synthesis of Ag nanoparticles
Synthesis of monosize Ag nanoparticles
Synthesis of Ag nanoparticles can be achieved by
the illumination of aqueous solutions containing AgC104, acetone, 2-propanol
and various polymer stabilizer.
UV illumination generates ketyl radicals via excitation of acetone and subsequent
hydrogen atom abstraction from 2-propanol:
The ketyl radical may hrther undergo protolytic dissociation reaction:
Both the ketyl radical and radical anions react with and reduce silver ions to
silver atoms:
With the presence of polyethyl- eneimine as polymer stabilizer ,silver nanoparticles formed using
the above photochemical reduction process have a mean size of 7nm with a narrow size
distribution
Some Important Results
Both reactions have a rather low reaction rate, and thus favor the production of
monosized silver nanoparticles.
Synthesis of Amorphous Ag nanoparticles
Amorphous silver nanoparticles of -20nm were prepared by sono- chemical reduction of
an aqueous silver nitrate solution at a temperature of 10C, in an atmosphere of argon and
hydrogen.
The reaction was explained as follows.
The ultrasound resulted in decomposition of water into hydrogen and hydroxyl radicals.
Hydrogen radicals would reduce silver ions into silver atoms, which subsequently
nucleate and grow to silver nanoclusters.
Some hydroxyl radicals would combine to form an oxidant, hydrogen peroxide, which
may oxidize silver nanoclusters to silver oxide.
The addition of hydrogen gas was to remove the hydrogen peroxides from the solution so
as prevent the oxidation of silver nanoparticles.
Amorphous silver nanoparticles of 20nm are prepared by this method.

Synthesis of Metallic nanoparticles(Co,Ni)

Metallic nanoparticles can also be prepared by an electrochemical deposition method.
This synthesis employs

a simple electrochemical cell containing only a metal anode and a metal or glassy carbon
cathode.
The electrolyte consists of organic solutions of tetraalkylammonium halogenides, which
also serve as stabilizers for the produced metal nanoparticles.
Upon application of an electric field, the anode undergoes oxidative dissolution forming
metal ions, which would migrate toward the cathode.
The reduction of metal ions by ammonium ions leads to the nucleation and subsequent
growth of metallic nanoparticles in the solution.
With this method, nanoparticles of Pd, Ni and Co with diameters ranging from 1.4 to 4.8 nm
were produced.
Some Important Results
It was found that the current density has an appreciable influence on the size of metallic
particles; increasing the current density results in a reduced particle size.
______________________________________________________________________________

1.Metal colloidal dispersions are dispersed state of metal particles ranging from 1um to 1nm.

2.Precursors are compounds which participate in reaction to form another compound.

3.Reducing Agents are material which donate ion or compound which oxidize itself.

4.Polymer stabilizer are used directly/ by combining to prevent the various effect such as oxidation, chain scission and
uncontrolled recombinants and cross-linking reactions that are caused by the photo-oxidation of polymers.

5.Refluxing time is time involving the condensation of vapors and the return of this condensate to the system from which it
originated.

6.Ostward Ripening :-small crystals or sol particles dissolve, and redeposit onto larger crystals or sol particles.