Synthesis and characterization of AgBr/SiO 2

core/shell nanoparticles
Presented by
Minaketan Ray
(608CH601)
Under the guidance of
Dr. Santanu Paria

Department of Chemical Engineering

National institute of Technology, Rourkela
Orissa,02/08/17
India 1
Outline
Introduction
Literature review
Methods
Objectives of the study
Result and dicussion
Synthesis of AgBr nanoparticles
Synthesis Silica nanoparticles
Core/shell nanoparticles
Conclusions & Further Work

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 Introduction
The core/shell nanoparticles mean one material is coated over another
material.
Many researcher has been prepared core/shell by micro emulsion, sol-
gel, CVD and other methods.
Among them micro emulsion is used by many due to small size particle
formation. But the separation of particles is difficult.
Similarly in sol-gel methods particle size control is difficult than
separation.
The CVD method is required inert atmosphere, high temperature,
carrier gas for synthesis of core/shell particles.
Because of draw back of different methods, its a challenge to synthesis
core/shell nanoparticles in easy way.

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Literature review
There are many studies available on the preparation of
silver halide nanoparticles (Husein et al. 2005, 2003,
2007; Oleshko et al. 2008; Bai et al. 2008; Liu et al.
2007) but there are limited studies on kinetics of
particle formation (Spirin et al. 2008; Hasse et al.
2006).
Husein et al. (2003, 2004 and 2007) have prepared
silver chloride and bromide nanoparticles in the
microemulsion method.
For first time, in 1968, Stober et al. reported a
pioneering method for the synthesis of spherical and
monodisperse silica.
02/08/17 4
 Continue..
Methods Product Finding Medium of reference
solution
W/O/W Gold/silver Degradation of Basic Bardr et al.
emulsion Nanospheres dye 2007
Sol-gel Au/SiO2 Au is catalyst Basic Shimizu et al
2003
R. emulsion Gold/SiO2 biocompatible Basic Kumar et al.
2006
R. emulsion Fe/SiO2 Photo catalyst Basic Xu et al. 2006
R. emulsion TiO2/SiO2 Photo catalyst Basic Park et al 2005
Micelle Ag/SiO2 Hollow Silica basic kim et al 2009
Complex Ni/SiO2 Flower, star Basic Libor et al.
solution like structure 2009
Liz-Marzan Au/SiO2 Thermally Basic Zhang et al.
stable 2009
02/08/17 5
 Methodology
To prepare a efficient and commercial root for synthesis
core/shell nanoparticles is a challenge.
There are various method available like- sol-gel method,
microemulsion, CVD method, spray precipitation methods
etc.
The aqueous solution has more advantages to synthesis
AgBr nanoparticles.
The core/shell NP is prepared using modified stober
methods.
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Problems
Control of particle size
Uniform coating of shell materials on core particle
Shape of the core/shell nanoparticles
Separation and Isolation of core/shell nanospheres
from solution
Preparation of hollow by removing core materials

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Objective of the study
To synthesis and characterize a suitable core
nanomaterials
To study the growth kinetics of core nanoparticles
To modify the surface of the core nanomaterials and
study the different parameters that affect particle
size and shape
To synthesis and study the property of the Core-
Shell nanoparticles

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 Chemical Synthetic Roots
Two synthetic roots follows for preparation of
nanoparticles.
Aqueous solution
Modified stber method
Aqueous solution: The reactants are taken in aqueous
solution and nanoparticles are formed by
precipitation reaction in the solution.
Stber methods: Scientist stober prepared silica
monosphere nanoparticles in alcohol medium
instead emulsion method. The core-shell
nanoparticles are prepared by modifying the
method.

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Preparation of core/shell nanoparticles.

The steps for synthesis of core/shell nanoparticles.

Core particle (AgBr) synthesis
Surface modification of core particle
Coating with shell material
Core/shell composite particles synthesis

shell
+
02/08/17 core 10
 Synthesis of AgBr nanoparticles
The AgBr nanoparticles were prepared by simple
precipitation methods.
TheAgBr has studied in both aqueous and surfactant
medium.
The particle size (diameter) was analyzed by dynamic
light scattering (DLS) technique
The kinetics of particle formation was also studied
spectrophotometrically using a UV-vis-NIR
spectrometer.
The particle shape and size was observed under a SEM .

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Effect of reactant concentration on
particle size and time

Figure 1. (a) The growth kinetics of AgBr nanoparticles using different

reactant concentrations in aqueous media and (b) The distribution of AgBr
nanoparticles.

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Kinetic study by Uv-visible spectroscopy

0.6

Absorbance (a.u.)
0.4

0.2 0.1 mmol/L

0.05 mmol/L
0.01 mmol/L
0.0
0 50 100 150
Time (min)

Figure 2. The growth kinetics of AgBr nanoparticles in

aqueous media using different reactant concentrations by
UV-vis spectrophotometry at 270 nm wavelength.

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The equllibrium Time

The equilibrium particle sizes are 1371, 902, and

832 nm for 0.01, 0.05 and 0.1 mmol concentrations
of reactant respectively obtained from the DLS data.
Itis observed that the saturation time for 0.01, 0.05,
and 0.1 mmol AgNO3 are ~ 30, ~ 55, and ~ 60 min
respectively.
Moreover, 6070 % of the equilibrium size is
achieved within 10 min and after that there is a slow
increase in size for all three concentrations.

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Concentration effect on coarsening
constant
The coarsening rate constant increases almost linearly
with the increase in reactant concentration.
600 350

3 3 -3
300
Coarsening Constant(kc)

Radius(nm ) r x10
0.1 mmol/L
250
400 0.05 mmol/L
200 0.01 mmol/L
150
200 Aqueous Sol. 100
TX-100
50
0
0
0.00 0.02 0.04 0.06 0.08 0.10 0 20 40 60 80 100
Reactant Concentration(mmol/L) Time (min)

Figure 3. The plot of cube of the radius of AgBr particles vs. time prepared in
aqueous media.(R). The plot of coarsening constant with the increasing reactant
concentration in the pure aqueous and TX-100 media (L)
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,

Coarsening rate Constant

From the LSW model (Lifshitz, Slyozov, and
Wagner) coarsening kinetics can be written as

r r kct
3
av 0
3

3
Where r av and r03 are the average and initial particle
radius respectively, kc is diffusion limited coarsening rate
constant, and t is time.

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Kinetics of AgBr NP in surfactant
solution

Figure 4: The growth kinetics of AgBr particles in TX-100 media using

different reactant concentrations. (b) The distribution of AgBr nanoparticles

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 Growth kinetics of AgBr NP in surfactant
solution
140
1.0 1.0 Aqueous
0.1 mmol/L
0.8 120 TX-100

Particle size (nm)

0.9 120min
Absorbance (a.u.)

0.05 mmol/L
0.6 60min
Absorbance
30min 0.01 mmol/L
0.8 0.4 5min 100
0.2 0.1 mmol/L
0.7 0.0 250 300 350 400 450 500 80
0.6
W avelength(nm)
60
0.5
40
0.4 0.00 0.03 0.06 0.09
0 50 100 150 200
Concentration of reactant (mmol/L)
Time (min)

Figure 5: The growth kinetics of AgBr nanoparticles in TX-100 media

using different reactant concentrations at 238 nm.(L) The change in
equilibrium particle size of AgBr nanoparticles with the reactant
concentration in pure aqueous and TX-100 media (R)

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Effect of temperature

Figure 6. The growth of AgBr nanoparticles at different temperatures

from 0.1 mmol/L AgNO3 concentration. (a) Aqueous media (b) TX-100
media.
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 X-ray diffraction of AgBr Nanoparticle

1500
In ten sity (a .u .)
200
220
1000 TX-100 222

500

Aqueous
0
20 30 40 50 60
2 (Degrees)

Figure 7. Powder X-ray diffraction pattern of AgBr NP in pure

aqueous and TX-100 media
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 SEM images of AgBr NP

Figure 8. SEM images of AgBr nanoparticles (A) using 0.01 mmol AgNO 3,
(B) 0.1 mmol AgNO3 (C) 0.01 mmol AgNO3 in the presence of TX-100.
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 Conclusion
Lower size particles can be obtained in pure aqueous
media by increasing the reactant concentration.
The coarsening rate constant for the particle formation
increases linearly with the increase in reactant
concentration.
The presence of nonionic surfactant generates smaller
size of particles than the pure aqueous media.
The temperature effect shows that in pure aqueous
media there is an increase in particle size with the
increase in temperature from 20-30 C after that the
change is not significant till 40 C.

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 Synthesis of Silica nanoparticles
The silica particles are synthesized by modified stober
methods.
The molar concentration of precursor mixture TEOS:
NH4OH:C2H5OH was 0.003: 1: 1. The concentration of silica
was varied from 0.1 mmol to 50 mmol.
The water to TEOS ratios (R) was varied from 4 to 20.
The concentration of surfactant was three cmc of the total
solution.

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Mechanism of Silica
nanoparticles
Formation of silica nanoparticles are proceeds via two
reactions: (i) Silanol groups are formed by hydrolysis
reaction
Si-(OR) 4 + H2O Si- (OH)4 + 4 R-OH
(ii)Siloxane bridges are formed by a condensation
polymerization reaction
2 Si-(OH)4 2 (Si-O-Si) + 4 H2O
The two reactions, hydrolysis and condensation reaction
depends on the various parameters that take part in the
reaction.

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The effect of Concentration on particle
sizes

650

600 The lowest size is

550 266 nm at 0.1
500 mmol concentration
Size (nm)

450 of TEOS and large

400 size is 557 nm at 50
350 mmol of TEOS
300

250

0 10 20 30 40 50
Concentration (mmol)

Figure 9. The particles size of silica nanoparticles against concentration

of TEOS.

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 SEM images of SiO2

(a) (b)

Figure 10. The SEM images of silica nanoparticles at 0.1 mmol concentration

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 Effect of Time

Figure 11. The FTIR spectra of silica nanoparticles at 0.1 mmol concentration
of TEOS

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 Effect of Surfactant
700

S ize (nm )
600

Aq
500
CTAB
SDBS
P artic le

400 TX-100

300

200
0 1 2 3 4 5

Concentration (mmol)

Figure 12. The particles are linearly increased along with concentration
of precursors solution. The smallest particle size is 3288 nm and
bigger size is 7407.

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Effect of sonication and pH
The size of the silica nanoparticles was 4335
nm in without sonication, but due to sonication
the particle size become 2596 nm.
We found that pH 11 is very good condition for
the reaction.

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SEM images of silica nanoparticles
(a) (b)

(d) (c)

Figure 13. The SEM images of silica nanoparticles in CTAB (a), TX-100 (b),
aqueous solution (c) and SDBS solution (d) at 0.1 mmol concentration
02/08/17 30
Conclusion

The silica nano and micro sphere has successfully

prepared by modified stober methods.
The interesting result of particles size was given by
TX-100 solution. Even high concentration (5 mmol)
of precursors solution, it did not allow to grow big
particles. So we got smaller size of particle
compared to other surfactant.

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Core/shell nanoparticles
The AgBr/silica core/shell particles are synthesized by
modified stober methods.
The AgBr nanoparticle was prepared in aqueous solution
and then equimolar concentration of CTAB was mixed to it
under cyclomixer. In a single reaction vessels all the reactant
were mixed under continuous stirring condition.
The reagent were used as 3.94 ml of absolute ethanol, 0.8 ml
of ammonium hydroxide, 0.06 ml of 0.1 mmol of
Tetraethylorthosilicate 0.3 ml of AgBr and 0.3 ml of double
distilled water.
The mixture was kept for 1 hour in stirring condition stirring
and then particles were separated by centrifuge and followed
by washing in ethanol.

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 Uv-visible spectra of AgBr

2.0

1.5
5 min
Intensity

1.0 20 min
30 min
60 min
0.5 120 min

0.0
240 270 300 330
Wavelength (nm)

Figure 14. The uv-visible spectra of AgBr in CTAB solution.

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SEM images of AgBr NP prepared in
CTAB solution

Figure 15. The SEM images of AgBr NP of 0.1 mmol concentration of

AgNO3 solution
02/08/17 34
Effect of Concentration
400

Particle Size (nm )

300

200

100

0
0.1 0.2 0.3 0.4 0.5
TEOS Concentration (mmol)

Figure 16. The core-shell particle sizes varied from 95 nm to 430 nm. It is
found that the bigger particle size found on higher concentration of TEOS.

All these cases the core materials are same size, only shell thickness changes.
Hence on increasing the concentration of TEOS, the shell thickness increases.
The shell thickness was varied from 5-240 nm.

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 Study of core/shell by fluorescence
spectra
AgBr@SiO2 20
4
AgBr + SiO2

3 15 AgBr
Intensity (a.u)

Intensity
2 10

1
5
0
0
250 300 350 400 450 500 550 600 400 450 500 550 600
wavelength (nm) Wavelength (nm)

Figure 17. Fluorescence spectra of core-shell particles (L) and

AgBr NP (R)

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 TEM images of AgBr/SiO2 core/shell NP

Figure 18. The size of core/shell NP is 98 nm.

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 SEM images of AgBr/SiO2 core/shell
nanoparticles

Figure 19. The AgBr/silica core/shell nanoparticle images

02/08/17 38
 Conclusion
The surface properties of silver bromide nanoparticle are
successfully modified using surfactant solution.
The AgBr@SiO2 core-shell nanoparticles have been prepared
within 100 nm by modified stober methods. The spherical
composite materials are formed.
The shell thickness can be controlled on varying the
concentration of precursors solution. Silica can be coated on
other material by modifying the surface of the core shell
materials.

02/08/17 39
Conclusion and Future work
In the same way other materials can be coated on
AgBr nanoparticles.
The AgBr nanoparticles may dissolved in
ammonium hydroxide.
The hollow silica can be prepared by removing the
core AgBr NP.
The application of core/shell and hollow silica nano
particle can be studied.

02/08/17 40
 Publication
Ray Minaketan and Santanu Paria, Growth kinetics of
silver bromide nanoparticles in aqueous surfactant
solutions. J Ind. Eng. Chem. Res., 2011, 50 (20), pp
1160111607.
Ray Minaketan and Santanu Paria, Preparation of Silver
Bromide Nanoparticles in Aqueous TX-100 and CTAB
Solutions. CHEMFERENCE ' 09, IIT Madras, 2009, p 23.

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Thank
you

02/08/17 42
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