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MICROWAVE ASSISTED
SYNTHESIS METALLIC
NANOSTRUCTURES
P R E S E N T E D B Y :
J O Y C E J O S E P H ( N T 1 4 0 0 1 )
I S T M S C . N A N O S C I E N C E & T E C H N O L O G Y
A GREEN CHEMISTRY APPROACH
Green chemistry is the utilization of a set of principles that
reduces or eliminates the use or generation of hazardous
substances in the design, manufacture and application of
chemical products.
A variety of metallic nanostructures, including spherical particles,
sheets, plates, rods, wires, tubes, and dendrites can be
achieved by microwave irradiation.
Out of the 12 principles of green chemistry, the following are
taken care through MW synthesis
 Prevention of waste
 Less hazardous chemical synthesis
 Design for energy efficiency
 Inherently safer chemistry for accident prevention
2
3
Microwave
radiation
Dipolar
polarization
Ionic
conduction
Electric
component
MICROWAVE IRRADIATION(0.3-300 GHZ)
POSSIBLE EFFECTS OF MW HEATING
There are two kinds of effects of MW dielectric heating: thermal
and non-thermal
Thermal effects
k =A*e
Loss tangent factor
Superheating effects of solvents at atmospheric pressure
Selective heating of microwave absorbing reagents and catalysts
Elimination of wall effects
4
5
Non thermal
effects
Polar reaction
mechanism
Interaction of
electric field with
reaction medium
molecules
Orientation of
molecules
Increase in
polarity from
ground state to
transition state
Lowering of
activation energy
Increase in
reactivity
Preparation of Au spherical nanoparticles:
 Au nanoparticles have been synthesized by reduction of Au salts in
various solvents under oil-bath heating for many hours. When HAuCl4
was reduced in methanol or ethanol,[for 0.5–5 min in the presence of PVP
under MW heating (480– 1100 W), mono dispersed, small spherical
nanoparticles, with diameters below 11 nm, were synthesized within a
few minutes.
 Spherical Au particles by using a closed chamber of an MW system with
precise temperature control function.
 When HAuCl4 was reduced in an aqueous solution containing citrate as a
stabilizer for 15– 30 min, Au particles sizes could be reduced from 85 to
13 nm with increasing reaction temperature, heating time, and rate of
temperature increase.
6
 A commercial MW oven is modified by installing a condenser and thermocouple
through holes in the top and a magnetic stirrer plate coated with Teflon in the
bottom of the oven.
 A thermocouple made of an optical fiber, which is not damaged under MW
irradiation, is used.
 A glass flask is placed in the MW oven with a power of 300– 1100 W and
connected to a condenser, into which a mixture of metallic salt, surfactant,
and, if necessary, a small amount of nucleation reagent is added.
 A surfactant such as polyvinyl pyrrolidone (PVP) acts as a stabilizer for the
product nanostructures. The reagent solution is irradiated by MW in a
continuous wave (CW) mode or a pulse mode.
 The pulse mode is more useful for the temperature control of the heating
media. Products particles are generally characterized by using transmission
electron microscopy (TEM), scanning electron microscopy (SEM), selected area
electron diffraction (SAED) pattern, X-ray diffraction (XRD), and UV visible
absorption spectroscopy.
 Before measuring the TEM photographs, surfactants were often separated from
nanostructures by centrifugation.
7
8
9
ADVANTAGES
 faster reactions
 less byproducts
 pure compounds
 absolute control over reaction parameters
 selective heating / activation of catalysts
 low energy input (max=300w, typical reaction ~20w)
 green solvents (H2O, EtOH, acetone) used
 less solvent usage ( 0.5-5mL per reaction)
 software-supported experiment documentation
10
APPLICATIONS
 Heck reaction
 Suzuki reaction
 Negishi and Kumada reaction
 Multicomponent reactions
 Solid phase synthesis
 Reactions in the absence of solvents
11
CONCLUSION
 Uniform heating of the solution
 Homogeneous nucleation
 Shorter crystallization time
 Short thermal induction period, which can lead to energy savings
 Selective formation of specific morphology
 Absence of convection processes, easy control, and low cost.
DISADVANTAGE:
 MW heating is a promising heating method, a further wide application to
preparation and control of various kinds of metallic nanostructures, which
are key materials in nanotechnology, is expected.
 Unfortunately, detailed mechanism for the preparation of metallic
nanostructures under MW irradiation has not been clarified.
12
13
REFERNCE:
 Microwave-Assisted Synthesis of Metallic Nanostructures in
Solution
Masaharu Tsuji,*[a] Masayuki Hashimoto,[b] Yuki Nishizawa,[b]
Masatoshi Kubokawa,[b] and Takeshi Tsuji
 Solid State Ionics
F. Fievet, J. P. Lagier, B. Blin, B. Beaudoin, M. Fiflarz

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Microwave Assisted Synthesis of Metallic Nanostructures

  • 1. MICROWAVE ASSISTED SYNTHESIS METALLIC NANOSTRUCTURES P R E S E N T E D B Y : J O Y C E J O S E P H ( N T 1 4 0 0 1 ) I S T M S C . N A N O S C I E N C E & T E C H N O L O G Y
  • 2. A GREEN CHEMISTRY APPROACH Green chemistry is the utilization of a set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products. A variety of metallic nanostructures, including spherical particles, sheets, plates, rods, wires, tubes, and dendrites can be achieved by microwave irradiation. Out of the 12 principles of green chemistry, the following are taken care through MW synthesis  Prevention of waste  Less hazardous chemical synthesis  Design for energy efficiency  Inherently safer chemistry for accident prevention 2
  • 4. POSSIBLE EFFECTS OF MW HEATING There are two kinds of effects of MW dielectric heating: thermal and non-thermal Thermal effects k =A*e Loss tangent factor Superheating effects of solvents at atmospheric pressure Selective heating of microwave absorbing reagents and catalysts Elimination of wall effects 4
  • 5. 5 Non thermal effects Polar reaction mechanism Interaction of electric field with reaction medium molecules Orientation of molecules Increase in polarity from ground state to transition state Lowering of activation energy Increase in reactivity
  • 6. Preparation of Au spherical nanoparticles:  Au nanoparticles have been synthesized by reduction of Au salts in various solvents under oil-bath heating for many hours. When HAuCl4 was reduced in methanol or ethanol,[for 0.5–5 min in the presence of PVP under MW heating (480– 1100 W), mono dispersed, small spherical nanoparticles, with diameters below 11 nm, were synthesized within a few minutes.  Spherical Au particles by using a closed chamber of an MW system with precise temperature control function.  When HAuCl4 was reduced in an aqueous solution containing citrate as a stabilizer for 15– 30 min, Au particles sizes could be reduced from 85 to 13 nm with increasing reaction temperature, heating time, and rate of temperature increase. 6
  • 7.  A commercial MW oven is modified by installing a condenser and thermocouple through holes in the top and a magnetic stirrer plate coated with Teflon in the bottom of the oven.  A thermocouple made of an optical fiber, which is not damaged under MW irradiation, is used.  A glass flask is placed in the MW oven with a power of 300– 1100 W and connected to a condenser, into which a mixture of metallic salt, surfactant, and, if necessary, a small amount of nucleation reagent is added.  A surfactant such as polyvinyl pyrrolidone (PVP) acts as a stabilizer for the product nanostructures. The reagent solution is irradiated by MW in a continuous wave (CW) mode or a pulse mode.  The pulse mode is more useful for the temperature control of the heating media. Products particles are generally characterized by using transmission electron microscopy (TEM), scanning electron microscopy (SEM), selected area electron diffraction (SAED) pattern, X-ray diffraction (XRD), and UV visible absorption spectroscopy.  Before measuring the TEM photographs, surfactants were often separated from nanostructures by centrifugation. 7
  • 8. 8
  • 9. 9
  • 10. ADVANTAGES  faster reactions  less byproducts  pure compounds  absolute control over reaction parameters  selective heating / activation of catalysts  low energy input (max=300w, typical reaction ~20w)  green solvents (H2O, EtOH, acetone) used  less solvent usage ( 0.5-5mL per reaction)  software-supported experiment documentation 10
  • 11. APPLICATIONS  Heck reaction  Suzuki reaction  Negishi and Kumada reaction  Multicomponent reactions  Solid phase synthesis  Reactions in the absence of solvents 11
  • 12. CONCLUSION  Uniform heating of the solution  Homogeneous nucleation  Shorter crystallization time  Short thermal induction period, which can lead to energy savings  Selective formation of specific morphology  Absence of convection processes, easy control, and low cost. DISADVANTAGE:  MW heating is a promising heating method, a further wide application to preparation and control of various kinds of metallic nanostructures, which are key materials in nanotechnology, is expected.  Unfortunately, detailed mechanism for the preparation of metallic nanostructures under MW irradiation has not been clarified. 12
  • 13. 13 REFERNCE:  Microwave-Assisted Synthesis of Metallic Nanostructures in Solution Masaharu Tsuji,*[a] Masayuki Hashimoto,[b] Yuki Nishizawa,[b] Masatoshi Kubokawa,[b] and Takeshi Tsuji  Solid State Ionics F. Fievet, J. P. Lagier, B. Blin, B. Beaudoin, M. Fiflarz