Sonochemical synthesis

What is Ultrasound?

Higher the frequency of ultrasound, the shorter the wavelength

A sinusoidal wave in a nonuniform medium, with loss. As the
wave slows down, the wavelength gets shorter and the
amplitude increases; after a place of maximum response, the
short wavelength is associated with a high loss and the wave
dies out.
Ultrasound is a sound wave with a high pitch that can not be heard by the human ear (i.e.
frequencies above 18 kHz).
Above that frequency, the use of ultrasound in chemistry is divided into two main distinct
categories:
 High frequency or diagnostic ultrasound (2-10 MHz) used mainly for
medical applications (e.g. for prenatal image scanning) and as a diagnostic
tool
 Low frequency or power ultrasound (20 kHz – 2 MHz) where
cavitation phenomenon occurs.
What is Sonochemical Synthesis?
When a fluid is subjected to power ultrasound or commonly
termed ‘sonicated’, tiny bubbles or cavitation bubbles are
produced.
These cavitation bubbles undergo very short and violent collapse
within the fluid generating local ‘hotspots’ of high energy
(temperatures of up to 5000oC and pressures of up to 2000
atms), leading to (i) radical formation and (ii) jets of liquid of high
velocity (up to 50 m.s-1) within the fluid. Heating and cooling
rates above 1010 K/s

Glass Beaker with water

Acoustic Cavitation
Bubbles
Mesoporous TiO2

Hot Spot
Ultrasound waves are produced by a transducer. A
transducer is a device that takes power from one
Ultrasonic pressure source, converts the energy into another form, and
wave delivers the power to another target. The transducer
converts electrical signals to ultrasound waves.
Ultrasonic Transducer
Acoustic Cavitation:
Characteristics of the Ultrasonic Wave:
Ultrasound travels through a liquid as a longitudinal wave, i.e., the molecules of the liquid
oscillate about their equilibrium positions in the direction of the motion of the wave.
The effective pressure in any given region of liquid is determined by the equation, Pt = Ph +
Pa, where Pt = the total pressure in a specific region in the liquid, Ph = the hydrostatic
pressure and Pa = the acoustic pressure in a particular region and time.

Relatively low pressure regions

Direction of the
ultrasonic wave:

Relatively high pressure regions

Pressure effects in the liquid due to an ultrasonic wave

Nucleation, Growth and Collapse of Microbubbles:
• Intramolecular bond breaking, pockets of gas entrapment on microscopic impurities (e.g., dust
particles), inherently present in any liquid, or in imperfections on the wall of the vessel.
• The gas nuclei expand under the influence of the ultrasonic wave and detach to form free
microbubbles in the liquid. The microbubbles continue to adsorb energy from the wave and grow
isothermally.
• When the microbubbles reach a critical size, they implode violently.
Assuming adiabatic collapse, the temperature of the hot spot can be
estimated using the equation below. This equation demonstrates the
importance of g in determining the collapse temperature (note, the
collapse is not completely adiabatic, so the thermal conductivity will
effect Tf in a real system).

An adiabatic process is a process in which no heat is Rmax 3(g-1)

transferred. This can happen if the process happens so Tf = T i
quickly that there is no time to transfer heat, or if the Rmin
system is very well insulated from its surroundings.

Where, Tf is the temperature of the core, Ti is ambient temperature,

Rmax and Rmin are the maximum and minimum bubble radius and g is The Sonochemical Hot Spot
the ratio of specific heats (Cp/Cv) of the gas inside the bubble. g = 1.67
for monoatomic gases and 1.40 for diatomic gases.

The collapse of bubbles is accompanied by the simultaneous emission

of light (Sonoluminescence)
Sonochemical reactions can occur in three different regions

Region 1: interior of collapsing gas bubbles (i.e., the core) in which very
high temperatures and pressures exist.

solvent vapor inside the bubble undergoes pyrolysis reactions.

Region 2: interface between the collapsing bubble and the bulk solvent,
where high temperature and pressure gradients exist.

the relative efficiency of non-volatile solutes to decompose

thermally or to scavenge radicals formed in the
hot spot depends on their ability to accumulate at the
gas/solution interface of the growing microbubble.

Region 3: bulk solution at ambient temperature. Free radicals formed in

the hot regions may diffuse to the bulk solution and react to yield
products similar to those found in aqueous radiation chemistry.

Thus, sonochemistry can partly be understood in terms of a

combination of combustion chemistry and radiation chemistry
What we can Synthesis through Sonochemical Method?
The sonochemical method is advantageous as it is nonhazardous, rapid in reaction rate, and
produces nanoparticles.

a) Deposition of nanoparticles on ceramic and polymeric surfaces

b) Insertion of nanomaterials into mesoporous materials
c) Formation of protein-micro- and nanospheres
d) Preparation of hollow metal nanoparticles

Sonochemical Synthesis of Nanosized Hollow Hematite

J. Bang, K. S. Suslick, J American Chemical Society, 2007, 129, 2242-2243

Carbon nanoparticles (0.1g) and Iron pentacarbonyl (0.5mL) in 40mL of hexadecane

High-intensity ultrasound horn
(1cm2 Ti horn at 20 kHz and 50 W/cm2 at 20°C for 3h under Ar flow)

Fe/carbon composite
Quickly washed with pentane and filtered under
air to remove hexadecane and unreacted Fe(CO)5
Dried and Oxidized

Washed again with pentane

Red Hematite (a – Fe2O3)

Results
Biomimetic Synthesis
 Biomimetic Synthesis
Nature is a school for material science and its associated discipline such as chemistry,
biology, physics or engineering
Nature fascinates scientists and engineers with numerous examples of exceptionally
building materials
These materials often show complex hierarchical organization from the nanometer to the
macroscopic scale
Learning from nature and imitating the growth and assembly processes found in nature
enable new strategies for the design of nanoarchitectures
Biomimetic or bio-inspired processes generally occur under mild conditions such as room
temperature, aqueous environment, and neutral pH, and thus are benign in comparison to
traditional chemical reactions
Biologically inspired synthesis, hierarchical structuring, and stimuli-responsive materials
chemistry may enable nanostructured materials systems with unprecedented functions
Many exciting bioinspired materials concepts are currently under development, such as
composite materials with nacre-like flaw tolerance, gecko-inspired reversible adhesives, and
advanced photonic structures that mimic butterfly wings
 Type of Biological Ingredients
There are large number of techniques available to synthesize different types
of nano materials in the form of colloids, clusters, powders.

Synthesis of nano materials using biological ingredients can be roughly

divided into following three types.

Use of microorganisms

Microorganisms are the organisms which are detectable under microscope

such as bacteria, fungi, yeasts etc
Some bacteria are quite useful and are used in the processing of cheese,
curds, bread, alcohol, vaccines etc
Some are harmful and are responsible for spoiling food or causing diseases
Microorganisms are capable of interacting with metals coming in
contact with them through their cell and form nanoparticles.

Use of plant extracts or enzymes

Use of templates like DNA, membranes, viruses and diatoms

Synthesis of nanoparticles by different Bacteria
Microorganisms Type of nanoparticle
Bacillus subtilis Gold
Shewanella algae Gold
Pseudomonas stutzeri Silver
Lactobacillus Gold, silver, Au–Ag alloy
Clostridium
Thermoaceticum Cadmium sulfide
Klebsiella aerogenes Cadmium sulfide
Escherichia coli Cadmium sulfide
Desulfobacteriaceae Zinc sulfide
Thermoanaerobacter
Ethanolicus Magnetite
Magnetospirillium
Magnetotacticum Magnetite
Thermomonospora sp Gold
Rhodococcus Gold
Chlorella vulgaris Gold
Phaeodactylum
Tricornutum Cadmium sulfide
Synthesis of nanoparticles by different fungus and yeast
Microorganisms Type of nanoparticle

Yeast

Candida glabrata Cadmium sulfide

Torulopsis sp. Lead sulfide
Schizosaccharomyces Pombe Cadmium sulfide
MKY3 Silver

Fungi

Verticillium Gold, silver

Fusarium oxysporum Gold, silver, Au–Ag alloy, CdS, ZrO2
Colletotrichum sp. Gold
 Structure of Bacteria
Bacteria are a large group of unicellular,prokaryote, microorganisms
Few micrometers in length, bacteria have a wide range of shapes,
ranging from spheres to rods and spirals.
 Synthesis of nanoparticles using Bactetria
• Synthesis of metallic nanostructures of noble metals such as silver (Ag),
by using a combination of culture supernatanant of Bacillus subtilis and
microwave (MW) irradiation in water and nanoparticles were in the
range of 5-60 nm in dimension.
• In the presence of Shewanella algae and hydrogen gas, the Au ions are
completely reduced, which results in the formation of 10 to 20 nm gold
nanoparticles.
• In addition to gold and silver nanoparticles, there is much attention in the
development of protocols for the synthesis of semiconductors (the so-
called quantum dots) such as CdS, ZnS, and PbS.
• When Klebsiella aerogenes is exposed to Cd2+ ions in the growth
medium, 20 to 200nm CdS formed on the cell surface.
• Spherical aggregates of 2 to 5nm diameter sphalerite (ZnS) particles are
formed within natural biofilms dominated by sulfate-reducing bacteria of
the family Desulfobacteriaceae.
1).The SEM micrograph recorded from the silver 2).TEM micrograph of silver nanoparticles Bacillus
nanoparticle synthesized by K. pneumoniae subtilis culture supernatant and reacted with 1 mM Ag+
ions for 120 h at 40oC.

(A) TEM image of the gold nanoparticles produced by

the reaction of 10−3 M aqueous HAuCl4 solution
with bacteria R. capsulata biomass at pH 7.

(B) TEM image of the gold nanoparticles produced by

the reaction of 10−3 M aqueous HAuCl4 solution
with bacteria R. capsulata biomass at pH 4.
 Preparation of cell free microbial extract Biosynthesis of silver nanoparticles

Culture medium were prepared Silver nitrate at concentration of 10-3 M was

separately added supernatent(1% V/V)

Sterilized and inoculated with

The reaction between supernatants and
fresh culture of E. coli
Ag+ ions was carried out in the dark or
bright condition.

The cultured flasks were

incubated at 37oC for 24h
The silver nanoparticles were
characterized by scanning electron
microscopy.
After incubation, the cultures were
centrifuged at 12000 rpm and their
supernatants were used for synthesis
of nanoparticles.
 Mechanism of formation silver nanoparticles
•Silver ions form a silver salt

•Salt trapped on the surface of the fungal cells due to

interaction between the positivelly charged silver ions and
negatively charged carboxylic groups in the enzymes in cell
walls of mycelia

•The ions after nucleation can grow by further accumulation

of silver ions to form nanoparticles

• Similarly, gold nanoparticles can be produced using

Verticillium sp.

•The mechanism is briefly explained below,

 Biosynthesis of silver nanoparticles
Using Fusarium oxysporum was grown by 7 days

The biomass was filtrated and resuspended in sterile water

The biomass was filtrated and AgNO3 (10 mM) was added in the
fungal liquid

The F. oxysporum biomass were a pale yellow color before the

addition of Ag+ ions and this changed to a brownish color on
completion of the reaction with Ag+ ions for 28 h.
 Absorptions were measured in UV-Vis

SEM micrograph from F. oxysporum 07 SD

strain at ×11000 magnification.

UV-Vis spectra recorded as a function of time of reaction of an aqueous solution

of 10-3 M AgNO3 with the fungal biomass (07SD). The inset shows the UV-Vis
absorption in the low wavelength region.
 Conclusion:
• The synthesis of nanoparticles using microbes is
rapid and very easiest method.
• Compared to by other methods like chemical or
physical methods, the synthesis of nanoparticles
using microbes is the best method .