Universidade de São Paulo

Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto

Departamento de Química .

“Synthesis of nanoparticles in
colloidal systems”

Profª . Drª. Ana Paula Ramos

Camila Bussola Tovani

Ribeirão Preto
September, 2015
 Content
1. Nanomaterials

2. Synthesis of nanoparticles

3. Steps involved in nanomaterials synthesis

4. Methods of nanoparticle synthesis

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

• SEC VI TO XV D.C: STAINED VIBRANT IN EUROPEAN CATHEDRALS.

Ceramic Iraq - British

Museum Notredame Cathedral. SEC IV a.d.: o Lycurgus Cup
(Rome) - British Museum

4
• 1857 – Michel Faraday
Reported the synthesis and
colors of colloidal systems of gold
nanoparticles

Pioneering work that encouraged the further

publications of thousands of article related to
synthesis , modification and properties of
metallic nanoparticles

Understanding of the physicochemical

characteristics of these systems 5
Some applications of inorganic 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

*Brussels, 18 de October 2011 – European scientific

commission. 7
( a) spherical ( b ) road
and (c) prism gold
nanoparticles.
... and how to synthesize nanomaterials???

In a general way, the methods to obtain nanostructured materials are

classified in two big groups:

“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.

9
“top-down” Technique:
(Physical)

“bottom-up” Technique:
(Chemical)

10
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

(Rivera-Gil et al. Accounts of chemical research , 2013, vol. 46, no. 3)

Nanoparticles synthesis
Mechanism is not fully understood yet. Originally developed
for aqueous colloidal
suspensions based on
Modelo de La Mer - 1950 sulfur

2 different steps -Nucleation

Current theory
- Growth

(Xiaomin Li, Zhang F. Chem. Soc. Rev., 2015,44, 1346-1378)

Nanoparticles with different size and shapes ....

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 Formation of nanoparticles in colloidal systems

xAy+ (aq) + yBx- (aq) ⇌ AxBy

The equilibrium relationship between the product
and its reactants is expressed as the solubility
product constant:

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

(http://2011.igem.org/Team:KULeuven/Thermodynamics acessed in 02-09-2015)

Growth
1) The amount of mateial avaliables
2) The viscosity of the medium – Diiffusion
3) The ease with which the material is correctly oriented and
incorporated into crystal lattice of the particle
4) Adsorption of impurities on the particles surface
5) Particle-Particle aggregation

•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.

Time-lapse sequence (extracted from a video) illustrating Ostwald ripening.

Bubble ( MEZZENGA1 R. et al nature materials | VOL 4 | OCTOBER 2005)
Secondary processes, such as Ostwald ripening and aggregation, will dramatically
affect the size, morphology, and properties of the products
Controlling each step of crystallization
process

1) Concentration

2) Temperature

3) Stirring velocity
Controlling each step of crystallization process
1) Fast nucleation – smaller nanoparticles

V nucleção > V geração das espécies precursoras

[precursores] < Cmin cessando a nucleação

2) Slow nucleation – bigger nanoparticles

Ao mesmo tempo que os centros de nucleação são formados
ocorre o cresimento das partículas

Growth – controlled by diffusion

Medium viscosity
Concentration
 Concentration effect

 All the systems were

submited to the same time
reaction

 The number of nucleous

formed is proportional to
the medium concentration

 After the same time of

growth , at the higher
concentration the
contribution of smaller
particles increases.

a) Particle size ditribution curves of gold sol prepared at different

concentrations b) Nucleation rate curves for gold sols prepared
at different concentrations. [T. Turkevich, Gold Bull 18, 86 (1985)]
 24 h reaction
Changing the precursor concentration Sol-gel process

Ti(OC3H7)4: isopropanol: acac: water Ti(OC3H7)4: isopropanol: acac: water

0,5: 20: 2: 2 2,0: 20: 2: 2
C1 C2 [4xC1]

TiO2 nanoparticles obtained at different reactantes concentration and high time reaction
 Temperature

Higher termperatures : the size of the

nanoparticles increses? ??

TEM images of iron oxide nanoparticles grown at (a) T1(1

◦C); (b) T2 (22 ◦C); (c) T3(53 ◦C); (d) T4 (74 ◦C) and (e) T5(95
◦C), respectively

(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)

 While in the growth process the temperature has been changed.

At higher temperatures, the solubility is larger and more nuclei are
dissolved for growth

 Therefore, the size of the particles increases with the growth

temperature for individual samples, as observed in the TEM size
analyses.
Stirring velocity

 Rapid reactants mixing in a

timescale of milliseconds during co-
precipitation .

 Because the rapid mixing, the

super-saturation state is reached
rapidly and a large amount of initial
nuclei were formed in a short time

 The nucleation can be separated

from the growth stage and lead to
particles with nanosize and narrow TEM micrograph and respective particle size distribution
diagrams for iron oxide nanoparticles prepared by
size distribution
continuous FIS (top panels A and B) and batch methods
(bottom panels C and) D .

( Salazar-Alvarez G, Muhammed M and Zagorodi A. 2006 Chem. Eng. Sci. 61 4625)

 Limitations of La Mer model
Considers the step of nucleation short and quick.
Maximum
supersaturation
Nucleation
Concentration

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.

Sugimoto very slow nucleation step resulting in the formation of

polydisperse nucleus and the growth occurs through the Ostwald process.
Stability of colloidal systems
Diferences between a regular and a colloidal precipitation: adicional satbilization
step avoiding the agregation
Methods to synthesize nanoparticles...

Coprecipitation

Stöber
Sol-Gel
Modified Stöber - Pechini Method

Methods Hidro and solvothermal

Microwave assisted reactions

Use of templates

Reverse microemulsions as nanoreactors

Coprecipitation
 Formation of low solubility species in supersaturation medium

 Commonly amorphous materials are obtained

Reactions at ambient temperature Theraml treatment

Low cost equipments and reagents
Calcium carbonate films
 Sol-Gel Method

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)

Acidic Catalysis Electrophilic

center

Nucleophile
Stöber method
Pechini Method – 1967 Polimeric precursor method
 Modification of the sol-gel process for metals that do not have sufficiently
stable alkoxides

Technic developed aiming the production of films based on metallic

nanoparticles

 Widely used to obtain nanostructured solid

Homogeneous distribution of (Scheme of Pechini method reactions. H. Lee et al * J.

ions throughout a polymeric Mater. Chem., 2003, 13, 2626–2632)
network
Figure 5. TEM image of nanocrystalline BiFeO3 calcined at 800 ºC. Inset: normal distribution of particle sizes. (Ferri
E. J. et al. Braz et a J. Braz. Chem. Soc Vol. 19, No. 6, 200)
 Hidro and solvothermal methods
Autogenous pressure
Description has originated in
geochemical description of mineral
formation processes

water as solvent
Hidrothermal High temperatures – min 100°C
vapor pressure- 1 atm

Redissolution and recrystallization

Formation of materials with high degree of

crystallinity
Solvothermal: solvents diffrent of water
TiO2 nanoparticles
Síntese 1.0

Before After TiO2 após tratamento solvotermal

TiO2 antes do tratamento solvotermal

Intensidade
20 30 40 50 60 70
2
Solvothermal synthesis X Under ambient conditions

50
Ambient conditions
Solvothermal synthesis
40

30
Intensity

20

10

0
20 30 40 50 60 70
 Microwave assisted reactions

Microwave Regular
heating heating

 Synthesis in minutes, instead

of hours or even days

 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

Calcium carbonate nanotubes

 Reverse microemulsions as nanoreactors

Water

Oil
Water

(de Sousa Filho, P. C, Serra, O. A. Quim. Nova, Vol. 38, No. 5, 679-
696, 2015)

(Gd-BHC NP BHC is benzenehexacarboxylate)

(M. L Kathryn et al . Chem. Commun., 2010, 46, 5832–5849 |

5833)
 Final Remarks
 The present lecture related the mainly concepts involved in the colloidal
synthesis of nanoparticles comprising traditionally consolidated technical and the
more recently developed aspects preparations.

 In general, all methods discussed consis, in essence, the application of physical

and chemical principles basic governing the phenomena of nucleation, growth
and aggregation.

Based on these principle, is possible to develop different methodologies to

synthesize inorganic nanoparticles in liquid phase with the features according to
the immense range applications.
References
Thank you for your attention!!!
Mechanism

The hydrolysis reactions occour via nucleophilic bimolecular substitution (SN2)

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

Interação com a radiação provoca a

EXCITAÇÃO COLETIVA DOS ELÉTRONS
DIMINUIÇÃO DA ENTROPIA DO
SISTEMA -> FORÇA RESTAURADORA
Oscilação eletrônica na região do visível

POLARIZAÇÃO DA PARTÍCULA

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