Preparation of PEG8K-Pd Nanoparticles and Their Characterization by DLS Technique
Preparation of PEG8K-Pd Nanoparticles and Their Characterization by DLS Technique
By
Miss Ritu Kumari
Acknowledgements
First and foremost, I would like to extend my sincere gratitude to my
supervisor, Dr. Rupesh Kumar for allowing me to work on this project. His
enthusiasm and integral view on research and mission for providing high
quality work has made a deep inspiration on me and at the same time enriched
my growth as a researcher. I greatly acknowledge his, guidance, effort and for
being a backbone of my training and this thesis.
I am highly thankful to the Principle, Kirori Mal College, for allowing me to
do my training. Apart from my efforts, the success of any project largely
depends largely on the encouragement and guidelines of many others. I am also
thankful to Miss Umisha Singh and Miss Priyanka Dutta for their continuous
support and knowledge throughout my internship at KMC. I also convey my
thanks to staff members of the laboratories of the college for allowing me to
avail the facilities available there.
I would also like to thank my internal coordinator Dr. Joydeep Dutta, for
being supportive and encouraging my research work. His valuable inputs,
wisdom, knowledge and commitments always inspired and motivated me.
Ritu Kumari
M.Sc Applied Chemistry
Bonafide Certificate
I approve the project of Miss Ritu Kumari, entitled To Study PEG8K- Pd
nanoparticles by DLS Technique is worthy of consideration for the award of
degree of Master of Science and is the record of original and bonafide research
work carried out by her under my supervision. The results contain in it have not
been submitted in part or full to any other university or institute for award of any
degree/diploma.
Ritu Kumari
(Candidate)
Internal Co-ordinator
Abstract
This work presents the result of preparation of Pd nanoparticles by
chemical reduction method. In this work a systematic study of preparation
of PEG8K-Pd nanoparticles and characterization of Pd nanoparticles
using DLS technique is reported. The samples have been synthesized using
PEG8K and palladium acetate solution using 1,4-dioxane with methanol as
reducing agent.
Pd(OAc)2 + PEG8000
R.T.,5hr
Methanol
PEG8K-Pd
Table of Contents
Introduction
Chapter 1 Instrumentation
1.1 Dynamic Light Scattering studies
10
13
13
14
15
16
19
20
21
23
3.2 Solvents
23
3.3 Instrumentations
23
24
26
3.6 Results
27
3.7 Conclusion
30
6
Abbreviations
DLS
TEM
HPLC
1000
Mw
MN
Np
Nanoparticles
Pd
Palladium
Pd(OAc)2
Palladium Diacetate
PEG
PEG8K
PEG8K-Pd
PEO
Polyethylene Oxide
POE
Polyoxyethylene
QELS
SEM
TGA
XRD
X-Ray Diffraction
Introduction
Chapter 1:
Instrumentation
1. Characterization of Nanoparticles
1.1.
11
14
15
Chapter 2:
Literature Survey
18
configuration
of
palladium
metal
is
1s2,2s2,2p6,3s2,3p6,4s2,3d10,4p6,5s0, 4d10.
Atomic radius of palladium metal is 137 pm. Standard reduction potential
palladium metal is 0.938V.
Palladium is a chemical element with the chemical symbol Pd and an atomic
number of 46. It is a rare and lustrous silvery white metal discovered in 1803
by William Hyde Wollaston. He named it after the asteroid Pallas which itself
named after the epithet of the Greek goddess Athena, acquired by her when she
slew Pallas. Palladium, platinum, rhodium, ruthenium, iridium and osmium
form a group of elements referred to as platinum group metals (PGMS). These
have similar chemical properties, but palladium has the lowest melting point
and is the least dense of them.
Palladium plays a key role in the technology used for fuel cells which combine
hydrogen and oxygen to produce water, heat and electricity. Palladium belongs
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to group 10 in the periodic table. Palladium is a soft silver white metal that
resembles platinum. It is soft and ductile when annealed and greatly increases
its strength and hardness when cold-worked. Palladium dissolves slowly in
hydrochloric sulfuric and nitric acid. This metal also does not react with
oxygen at normal temperature (and does not tarnish in air). Palladium
heated to 8000C will produce a layer of palladium(II) oxide(PdO). It lightly
tarnishes in moist atmosphere containing sulfur. Common oxidation states of
palladium are 0, +1, +2, +3 and +4. Although originally +3 was thought of as
one of the fundamental oxidation states of palladium, there is no evidence for
palladium occurring in the +3 oxidation states, this has been investigated via Xray diffraction for a number of compounds, indicator a dimer of palladium (II)
and palladium(IV).
Chapter 3
Preparation
of
PEG8K-Pd
Characterization
3.1 Materials
22
Nanoparticles
and
Their
Purity of the chemicals have a great influence on the properties and stability of
the nanoparticles. Therefore it is equally important to discuss about the purity
of the chemicals and materials used in the experiments. In the following
experiments, a chemical reduction method was used which consisted of
polyethylene glycol having molecular weight 8000, palladium acetate, HPLC
grade methanol, HPLC grade deionized water and HPLC grade 1,4-dioxane.
3.2 Solvents
(a) HPLC grade methanol and 1,4-dioxane was purchased from Sigma-Aldrich
of HPLC grade.
(b) HPLC grade deionized water was used to prepare all the solutions.
3.3 Instrumentation
The PEG8K-Pd nanoparticle catalysts were characterized by QELS, TEM,
EDX, SEM, XRD, IR, TGA, and UV-Visible techniques.
QELS measurements for determining the size of nanoparticles were performed
using Photo Core-FC instrument with open modular architecture goniometer.
Air cooled He/Ne was operated at 633nm and 20mw as light source. The time
dependence of the intensity autocorrelation function of the scattered intensity
was derived by using a 288-channel digital correlator.
3.4 Experimental
The goal is to obtain nanoparticle narrow sized distribution and well
stabilized palladium PEG capped nanoparticles.
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R.T.,5hr
Methanol
PEG8K-Pd
3.6 Results
Characterization of prepared PEG8K-Pd nanoparticles by DLS
26
a.
b.
c.
d.
e.
f.
27
g.
h.
i.
Sample Name
PEG8K (ml)
Pd(OAc)2 (ml)
Polydispersity
(s.d./mean2)
RI-1
0.9
0.1
NA
36.79
RI-2
0.8
0.2
54.86
0.341
RI-3
0.7
0.3
59.70
0.042
RI-4
0.6
0.4
67.43
0.600
RI-5
0.5
0.5
45.48
0.052
RI-6
0.4
0.6
36.35
0.427
RI-7
0.3
0.7
30.83
0.205
RI-8
0.2
0.8
32.88
0.342
RI-9
0.1
0.9
NA
480.8
We selected samples Fig.(b) (sample name: RI-2) and (h) (sample name: RI-8) as the
best results from above table . The samples that were collected are reprepared in a
set of 3 to check the reproducibility of the procedure so that the procedure can be
standardized.
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29
Sample Name
PEG8K (ml)
Pd(OAc)2 (ml)
Polydispersity
(s.d./mean2)
RI-2a
0.8
0.2
52.32
0.445
RI-2b
0.8
0.2
51.50
0.643
RI-2c
0.8
0.2
55.61
0.417
RI-8a
0.2
0.8
43.48
0.082
RI-8b
0.2
0.8
60.19
1.250
RI-8c
0.2
0.8
75.78
0.274
DLS evaluation of the nanoparticles indicates that the size distributions of the particles are very
narrow. We begin the studies with some preliminary investigations of the particle core size by
using QELS. The palladium nanoparticles are capped by PEG8K molecules that provided
sufficient hydrophobicity to the nanoparticles. These particles are stable upto several months at
room temperature. Using DLS data we found that sample RI-2b with size 51.50nm and
polydispersity 0.643 and RI-8a with mean size 43.48nm and polydispersity 0.082 are the best
prepared nanoparticles among the reported samples.
3.7 Conclusion
The utilization of nanodimensional materials offer significant benefits in a range of
different applications. In order to maximize their usefulness, reliable synthesis are
required that can generate well-defined nanoparticles with a high degree of
polydispersity. This aim is being achieved in the synthesis of PEG8K-Palladium
nanoparticles by using polyethylene glycol 8,000 sterically bulky molecules to control the
synthesis. This enables the properties such as the size, shape, solubility and surface
functionality of the resulting nanoparticles to be carefully tuned. Such materials are being
explored for many different applications, especially in catalysis, where palladium can
effectively catalyze a range of different transformations.
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From the DLS data we found that sample RI-2b with size 51.50nm and
polydispersity 0.643 and RI-8a with mean size 43.48nm and polydispersity 0.082 are
the best prepared nanoparticles among the reported samples. Thus we achieved our
goal of preparing smallest size nanoparticles with highest polydispersity using
chemical reduction method.
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