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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,9/19/16
India

Outline
Introduction
Literature review
Methods
Objectives of the study
Result and discussion
Synthesis of AgBr nanoparticles
Synthesis Silica nanoparticles
Core/shell nanoparticles

Conclusions & Future 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, solgel, 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.

The hollow nanoparticles can be prepared by removing core materials.


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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.
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Continue..
Methods

Product

Finding

W/O/W
emulsion

Gold/silver
Nanospheres

Degradation of Basic
dye

Bardr et al.
2007

Sol-gel

Au/Au

Au is catalyst

Basic

R,emulsion

Gold/silica

biocompatible

Basic

Shimizu et al
2003
Kumar et al.
2006

R. emulsion
R. emulsion

Fe/Silica

Photo catalyst

Basic

TiO2/SiO2

Photo catalyst

Basic

Xu et al. 2006
Park et al 2005

Micelle

Ag/SiO2

Hollow Silica

basic

kim et al 2009

Complex
solution

Ni/SiO2

Flower, star
like structure

Basic

Libor et al.
2009

Liz-Marzan

Au/SiO2

Thermally
stable

Basic

Zhang et al.
2009

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Medium of reference
solution

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.

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Problems
Control

of particle size

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
To

the growth kinetics of core nanoparticles

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 stober method

Aqueous solution: The reactants are taken in aqueous


solution and nanoparticles are formed by
precipitation reaction in the solution.
Stober 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 hollow nanoparticles.
Core

particle (AgBr) synthesis

Surface

modification of core particle

Coating

with shell material

Core-shell

composite particles synthesis

shell

+
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core

10

Synthesis of AgBr nanoparticles


The

silver bromide nanoparticles were prepared by


simple precipitation methods.

The

AgBr 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

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

Absorbance (a.u.)

0.6

0.4

0.2

0.0

0.1 mmol/L
0.05 mmol/L
0.01 mmol/L
0

50
100
Time (min)

150

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.
It is 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
constant

effect

on

coarsening

The coarsening rate constant increases almost linearly with the


increase in reactant concentration.

350

400

200

0
0.00

Aqueous Sol.
TX-100

0.02 0.04 0.06 0.08 0.10


Reactant Concentration(mmol/L)

3 3 -3
Radius(nm ) r x10

Coarsening Constant(kc)

600

300

0.1 mmol/L
0.05 mmol/L
0.01 mmol/L

250
200
150
100
50
0
0

20

40
60
Time (min)

80

100

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

3
0

3
av and

Where r
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

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

0.9

Absorbance

Absorbance (a.u.)

1.0

0.8
0.7
0.6

1.0
0.1 mmol/L
0.8
0.05 mmol/L
120min
60min
0.6
0.01
mmol/L
30min
5min
0.4
0.2
0.1 mmol/L
0.0 250 300 350 400 450 500
W
avelength(nm)

0.5
0.4

50

100
Time (min)

150

200

Particle size (nm)

140
120

Aqueous
TX-100

100
80
60
40
0.00
0.03
0.06
0.09
Concentration of reactant (mmol/L)

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

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

In ten sity (a .u .)

1500
200
220

1000

TX-100 222

500
Aqueous

0
20

30

40
2 (Degrees)

50

60

Powder X-ray diffraction pattern of AgBr NP in pure aqueous and TX-100


media
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SEM images of AgBr NP

SEM images of AgBr nanoparticles (A) using 0.01 mmol AgNO3, (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
nanoparticles

of

Silica

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

Size (nm)

550
500
450
400
350

The lowest size is


266 nm at 0.1
mmol concentration
of TEOS and large
size is 557 nm at 50
mmol of TEOS

300
250

10

20

30

40

50

Concentration (mmol)

The particles size of silica nanoparticles against concentration of TEOS.

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SEM images of SiO2


(a)

(b)

The SEM images of silica nanoparticles at 0.1 mmol concentration


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Effect of Time
180
160
140
120

S1
TEOS
S2

100
Absorbance
80
60
40
20
0
300

800 1300 1800 2300 2800 3300 3800 4300


Wave number (cm-1)

The FTIR spectra of silica nanoparticles at 0.1 mmol concentration of TEOS


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Effect of Surfactant
P artic le
S ize (nm )

700
600
Aq
CTAB
SDBS
TX-100

500
400
300
200
0

Concentration (mmol)

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)

The SEM images of silica nanoparticles in CTAB (a), TX-100 (b), aqueous
solution (c) and SDBS solution (d) at 0.1 mmol concentration
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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

Intensity

1.5
5 min
20 min
30 min
60 min
120 min

1.0
0.5
0.0

The

240

270
300
330
Wavelength (nm)

uv-visible spectra of AgBr in CTAB solution.


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SEM images of AgBr prepared in CTAB


solution

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Particle Size (nm )

Effect of Concentration
400
300
200
100
0

0.1
0.2
0.3
0.4
0.5
TEOS Concentration (mmol)

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 5-40 nm.
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Study of
spectra
4

core/shell

15
Intensity

Intensity (a.u)

fluorescence

20

AgBr@SiO2
AgBr + SiO2

by

AgBr

10
5

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

0
400

450
500
550
Wavelength (nm)

600

Flouroscence spectra of core-shell particles (L) and AgBr NP


(R)
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TEM images of AgBr/SiO2 core/shell NP

The

size of core/shell NP is 98

nm.
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SEM images of core/shell nanoparticles

The

core/shell nanoparticle images


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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.
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Conclusion and Future work


In

the same way other materials can be coated on

AgBr nanoparticles.
The

AgBr nanoparticles may dissolved in ammonium

hydroaxide.
The

hollow silica can be prepared by removing the

core AgBe NP.


The

application of core/shell and hollow silica nano

particle can be studied.


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Thank you

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References
Kumar

A, Pushparaj VL, Murugesan S, et al., Synthesis Of silica-gold nanocomposites


and their porous nanoparticles by an in-situ Approach. Langmuir, 22, 2006, 8631-8634.
Husein, M. M., Rodil, E. and Vera, J. H., A novel method for the preparation of silver
chloride nanoparticles starting from their solid powder using microemulsions. J.
Colloid Interface Sci. 288, 2005, 457467.
Husein, M. M., Rodil, E. and Vera, J. H., Formation of silver chloride nanoparticles in
microemulsions by direct precipitation with the surfactant counterion. Langmuir 19,
2003, 8467-8474.
Husein, M. M., Rodil, E. and Vera, J. H., Formation of silver bromide precipitate of
nanoparticles in a single microemulsion utilizing the surfactant counterion. J. Colloid
Interface Sci. 273, 2004, 426434.
Husein, M. M., Rodil, E. and Vera, J. H., A novel approach for the preparation of AgBr
nanoparticles from their bulk solid precursor using CTAB microemulsions. Langmuir
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