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Seminario-Crescimento de Macromoleculas
Seminario-Crescimento de Macromoleculas
“Synthesis of nanoparticles in
colloidal systems”
Ribeirão Preto
September, 2015
Content
1. Nanomaterials
2. Synthesis of nanoparticles
6. Final remarks
7. References
Association of osteogenic proteins in biominerals and
metallic oxides doped with rare-earth: interaction with
membrane models systems.
Nanomaterials...
• THE FIRST APPLICATIONS OF METALLIC NANOPARTICLES IN COLLOIDAL
SYSTEMS DATE OF TIMES PRIOR TO MODERN SCIENCE
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• 1857 – Michel Faraday
Reported the synthesis and
colors of colloidal systems of gold
nanoparticles
Microelectronic devices
Catalysis
Biological probes
Optical devices
Special glasses
Sensors
Lenses
High
Performance
Ceramics
Osteinductor materials
Cosmetics
But after all, what is a nanomaterial ?
Some definitions...
1 nm = 10-9 m
Nanomaterials*:
Structured compounds with dimensions
between 1 and 100 nm
“top-down” technique
The materials are synthesized at regualr grades and after are modeled (have their
dimensions reduced ) to nano scale trhough physical mthods .
“bottom-up” technique
Consists in modeling the atoms or molecules arrangement to obtain the
nanostructures.
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“top-down” Technique:
(Physical)
“bottom-up” Technique:
(Chemical)
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Which provides special properties to these systems???
High surface area ( the surface phenomena are the most important)
High ratio área/ volume
(A. Manuel ; T. Trindade - Quím. Nova vol.35 no.7 São Paulo 2012)
The size of the particles changes the number of atoms on its surface
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Importance of controlling the properties of nanomaterials .
The simple controlled variation of certain reaction parameters can lead to the formation of
products with completely different properties….
The need to meet different methods of synthesis and as each parameter may be
varied in order to obtain the product with the desired properties
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Formation of nanoparticles in colloidal systems
Ksp = (aA)x(aB)
ᴦ = (aA.)y+(aB)x
Ksp
Grau de supersaturação
ᴦ= Csat Solutes concentration (Yugang Sun, Chem. Soc. Rev., 2013, 42, 2497)
S Concentration at the equilibrium
The degree of supersaturation can be regarded as the driving force to the nucleation
process, and as much as the difference between Csat and S more easier will be the
solid formation.
Thermodynamics of homogeneous nucleation
P and T cte
DG = γ dA
The critical size
(Nguyen T. K. Thanh, N. Maclean, and S. Mahiddine, Chem. Rev. 2014, 114, 7610−7630)
Small nucleous are instable due to the high surface energy, and the high pressure
Nucleation
•Is critical to determine the properties of the final
nanoparticles
o Homogeneous
o Heterogeneous Ex: nanoparticles in the reaction medium
•At very high concentrations the viscosity of the medium slows down the
rate of crystal growth
Ostwald ripening - 1900
Is the phenomenon by which smaller particles are essentially consumed by larger
particles during the growth process.
1) Concentration
2) Temperature
3) Stirring velocity
Controlling each step of crystallization process
1) Fast nucleation – smaller nanoparticles
Medium viscosity
Concentration
Concentration effect
TiO2 nanoparticles obtained at different reactantes concentration and high time reaction
Temperature
(F. Mei, S. Valter, O. Richard, B. Lyubov and R. KV. Nanotechnology 23 (2012) 145601)
It can be explained by Ostwald ripening effect
Te nucleation process is almost the same for these samples (fast)
At higher temperatures, the solubility is larger and more nuclei are
dissolved for growth
Growth
Time
(de Sousa Filho, P. C, Serra, O. A. Quim. Nova, Vol. 38, No. 5, 679-696, 2015)
Ocaña quick nucleation, although the final particles wil be formed by
aggregation of smaller and initial nucleus.
Coprecipitation
Stöber
Sol-Gel
Modified Stöber - Pechini Method
Use of templates
Precursor Alkoxides
Hydrolysis
Salts
Condensation
Sol
Sol-Gel Some examples of alkoxides precursors
Tetraethy orthosilicate
TEOS Titanium isopropoxide
Zirconium isopropoxide
Tetrabutyl titanate
Tetrabutyl zirconate
Cerium t-butoxide
Some reactions related to the sol gel process
1)Hydrolysis
Sais
Alcóxidos
2)Condensation
3.1 The hydrolysis reaction
Mechanism
The hydrolysis reactions occour via nucleophilic bimolecular substitution (SN2)
Acid Catalysis
Electrophilic
center
Nucleophile
3.2 A reação de Condensação
Mechanism
The condensations reactions occour via nucleophilic bimolecular substitution
(SN2)
Nucleophile
Stöber method
Pechini Method – 1967 Polimeric precursor method
Modification of the sol-gel process for metals that do not have sufficiently
stable alkoxides
water as solvent
Hidrothermal High temperatures – min 100°C
vapor pressure- 1 atm
Intensidade
20 30 40 50 60 70
2
Solvothermal synthesis X Under ambient conditions
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Ambient conditions
Solvothermal synthesis
40
30
Intensity
20
10
0
20 30 40 50 60 70
Microwave assisted reactions
Microwave Regular
heating heating
Homogenous heating
avoiding the formation of
intermediate products
TEM micrograph of Ag nanoparticles prepared in an aqueous system using AgNO3 as the silver source, L-lysine as a reducing agent, via
microwave irradiation at 150 °C for only 10 s ( Zhu I. J. Chen F. Chem. Rev. 2014, 114, 6462−6555)
Use of templates
Water
Oil
Water
(de Sousa Filho, P. C, Serra, O. A. Quim. Nova, Vol. 38, No. 5, 679-
696, 2015)
Basic Catalysis
Electrophilic
center
Nucleophile
Mechanism
The condensations reactions occour via nucleophilic bimolecular substitution
(SN2)
Basic Catalysis
Ressonância plasmônica
Oscilações dos elétrons de condução em ressonância com a luz incidente
Elétrons possuem maior mobilidade
POLARIZAÇÃO DA PARTÍCULA
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