Preparation of PEG8K-Pd Nanoparticles and Their

Characterization by DLS Technique

Project Work Submitted to the Department of Applied

Sciences for the partial fulfillment of the degree of
Masters of Science
in
Applied Chemistry

By
Miss Ritu Kumari

Under the supervision of

Dr Rupesh Kumar
Kirori Mal College, University of Delhi

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

Dr. Joydeep Dutta

(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

Scheme 1: Synthesis of PEG8K-Pd nanoparticles

Table of Contents
Introduction

Chapter 1 Instrumentation
1.1 Dynamic Light Scattering studies

10

1.2 Transmission Electron Microscope

13

1.3 Scanning Electron Microscope

13

1.4 X-Ray Diffraction

14

1.5 Thermogravimetric Analysis

15

Chapter 2 Literature survey on the role of PEG, Palladium

Nanoparticles
2.1 PEG Chemistry

16

2.2 Palladium Chemistry

19

2.3 Applications of Pd nanoparticles

20

2.4 Transition Metal Nanoparticles Palladium

21

Chapter 3 Preparation of PEG8K-Pd Nanoparticles and Their

Characterization
3.1 Material

23

3.2 Solvents

23

3.3 Instrumentations

23

3.4 Experimental Discussion

24

3.5 Experimental Procedure

26

3.6 Results

27

3.7 Conclusion

30
6

Abbreviations

DLS

Dynamic Light Scattering

TEM

Transmission Electron Microscopy

HPLC

High Performance Liquid Chromatography

1000

Mw

Average Molecular Weight

MN

Number Average Molecular Weight

Np

Nanoparticles

Pd

Palladium

Pd(OAc)2

Palladium Diacetate

PEG

Poly Ethylene Glycol

PEG8K

Polyethylene Glycol 8,000

PEG8K-Pd

Polyethylene Glycol 8,000-Palladium

PEO

Polyethylene Oxide

POE

Polyoxyethylene

QELS

Quasi-Electric Light Scattering

SEM

Scanning Electron Microscope

TGA

Thermo Gravimetric Analysis

XRD

X-Ray Diffraction

Introduction

Nanotechnology represents on the major breakthroughs modern science,

enabling materials of distinctive size and composition to be formed. Such
nanodimensional materials (in the 1-100nm size domain) are seen as a bridge
between atomic and bulk material and have been shown to exhibit a variety of
unique chemical, physical and electronic properties. The studies of these
properties has become an increasingly important area in chemistry, physics,
biology and medicine and material sciences. However reliable preparation of
nanomaterials are required for their exploitation and this remains an area of
active research. Whilst much research has focused on nanomaterials of coinage
metal (especially gold), interest in the properties of transition metal
nanoparticles is also considerable and growing. The high surface area-tovolume ratio makes nanomaterials highly desirable for use as potential
catalysts. Given that palladium is one of the most efficient metal in catalysis,
the study of palladium based nanomaterials is hugely important and valuable.
As a consequence of, nanoparticles of palladium have been extensively studied
in the wide range of catalytic applications including hydrogenation, oxidation,
carbon-carbon bond formation and electrochemical reactions in fuel cells.
However it should be noted that the applications of palladium go beyond
catalysis. In the present report the synthesis of the palladium nanoparticles
with well controlled particle sizes and shapes of high monodispersity is a key
technology in producing materials that are more effective and efficient than the
current state of art. For example, particle size can play a critical role in
catalytic process and monodispersed particle with an optimal size enables the
most efficient use of the valuable metal and the highest selectivity in the
subsequent reaction.

Chapter 1:

Instrumentation
1. Characterization of Nanoparticles
1.1.

Dynamic light scattering (DLS)

DLS , sometimes referred to as Quasi Electric Light Scattering (QELS), is a

non invasive, well-establishing technique for measuring the shape and size
distribution of molecules and particles typically in the submicron region , and
with latest technology lower than 1nm.

Figure 1 Dynamic Light Scattering

Instrument

Here a solution containing particles is placed in the path of monochromatic

beam of light and the temporal fluctuations of the scattering light due to the
Brownian motion of the particles are determined.
Let us assume that a detector of light is fixed at some angle with respect to the
direction of the incident beam and at some fixed distance from the scattering
volume, which contains a large number of particles. Here the small particles
will be undergoing a diffusive Brownian motion. Hence the distance that
scattered wave travels to the detector varies a function of time. The scattered
10

waves then can interfere constructively or destructively depending on the

differences in the distance travelled to the detector and the result is an average
intensity with superimposed fluctuations. Smaller particles will move rapidly
and can cause high frequency of fluctuations, whereas larger particles will
move slowly and can cause low frequency of fluctuations. With the help of a
spectrum analyzer, all these frequencies can be measured. But the most
efficient concept, which is used to analyze these fluctuating signals, is
correlation. When two variable or two signals are highly correlated then a
change in one can be used to predict the change in the other. Thus correlation
can be defined as the average of the product of the two quantities,
mathematically. Auto-correlation is just the average of the product of a variable
with a delayed version of itself.
In DLS, one of the important terms is sample time. When the total time over
which a measurement is made, is divided into small intervals of time then this
small interval of time is called sample time. In each of these intervals the
scattered light intensity, as represented by the number of electrical pulses
registered during sample time, fluctuates about a mean value. The intensity of
auto-correlation function is formed by averaging the product of intensity is of
these small time intervals as the function of time between the intervals. Auto
correlation function, C(t), is defined as a function of the time between intervals.
As t increases, correlation is lost and the function approaches a constant
background term B. for shorter time, correlation is high. In between these two
limits, the function decays exponentially for a monodisperse suspension of
rigid, globular particles and is given by
C(t)=Ae-2t + B
Where, A is an optical constant which is determined. is related to the
relaxation of fluctuations and is expressed as
= D q2

11

The value of q is calculated from the scattering angle , the wavelength of

laser 0, and the refractive index, n, of the suspending liquid:
q = (4n/0) sin/2
the translational diffusion coefficient, D, is the main quantity measured by
DLS. Now the translational diffusion coefficient, D, is related to the particle
size of different shapes like sphere, ellipsoid cylinder size etc. The most useful
assumption of the particle size is the spherical assumption. For a sphere, D is
given by the Strokes-Einstein equation:
D = kT / 3d
Where k is the Boltzmanns constant (1.38054x10 -23joules/kelvin), T is the
temperature in kelvin, is the viscosity of the liquid in which the particle is
suspended, d is the particle diameter. Thus by substituting the value of T, D and
, the size of the particle can be determined. This equation assumes that
particles are moving independently, so the measurements must be made in
dilute suspensions. The molecular weight of the polymers in the solution can be
calculated from the translational diffusion coefficient:
Typical applications of dynamic light scattering are the characterization of
particles emulsions or molecules, which have been dispersed or dissolved in a
liquid. The Brownian motion of particles or molecules in suspension causes
laser light to be scattered at different intensities. Analysis of these intensity
fluctuations yields velocity of the Brownian motion and hence the particle size
using the Strokes-Einstein relationship.
In our experiments, 2ml sonicated aqueous/methalonic dispersion of
nanoparticles was used for laser light scattering experiment. QELS
measurements for determining the size of nanoparticles were performed using
photoCor-FC instrument with open modular architecture goniometer. Air
cooled He/Ne laser was operated at 633nm and 200mw was light source. The
time dependence of the intensity auto correlation function of scattering was
derived by using a 288 channel digital co-relator. All measurements were done
12

at 25C. The particle was automatically calculated from the autocorrelation

function using Strokes-Einstein equation.

1.2 Transmission Electron Microscope (TEM)

The Transmission electron Microscope (TEM) has evolved over many years
into a highly sophisticated instrument that has found widespread application
across the scientific disciplines. Because the TEM has has an unparalleled
ability to provide structural and chemical information over a range of length
scales down to the level of atomic dimensions, it has developed into an
indispensable tool for scientists who are interested in understanding the
properties of nano structured and in manipulating their behavior.
Image formation in TEM is more complicated in practice than in the case for
the optical microscope. Strong magnetic fields are needed for focusing the
electron beam, and these cause electrons to take a spiral trajectory through the
lens field. Modern day TEMs operating at 200 or 300KeV have resolution
limits well below 2.0A0, which is comparable to the spacing between atoms.
Individual columns of atoms thus can be resolved in crystalline materials,
which must first, however be oriented so that the incident electron beam is
aligned along some major crystallographic zone axis of the sample. In the
standard TEM operating mode, which is commonly referred to as amplitude or
diffraction contrast imaging, only a fraction of those electrons that have passed
through the sample are used to form the highly magnified final image.

1.3 Scanning Electron Microscope (SEM)

The Scanning Electron Microscope (SEM) is a microscope that uses electrons
rather than light to form an image. There are many advantages to using the
SEM instead of a light microscope. The SEM has a large depth, which allows a
large amount of the sample to be focus in one time. The SEM also produces
images of high resolution, which means that closely spaced features can be
13

examined at a high magnification. Preparation of samples is relatively easy

since most SEM only require the sample to be conductive. The combination of
higher magnification, larger depth of focus, greater resolution, and ease of
sample observation makes the SEM one of the most heavily used instruments
in research area today.
In light microscopy, a specimen is viewed through the series of lenses that
magnify the visible-light image. However, the scanning electron microscope
(SEM) does not actually view a true image of the specimen, but rather
produces an electronic map of the specimen that is displayed on the cathode ray
tube (CRT). The SEM has a secondary electron detector. The signals produced
by the secondary electrons is detected and sent to a CRT image.
The SEM has compensating advantages, though including the ability to image
a comparatively large area of the specimen; the ability to image bulk materials;
and the variety of analytical models available for measuring the composition
and nature of the specimen.

1.4 X-Ray Diffraction (XRD)

X-ray diffraction is a versatile, non-destructive analytical technique for
identification and quantitative determination of the various crystalline forms,
known as phases of the compounds present in the powdered and solid
samples. When a monochromatic X-ray beam with wavelength is incident on
the lattice crystals on lattice planes in a crystal at an angle , diffraction peaks
occur when the distance travelled by the ray reflected from successive planes
differs by a complete number n of wavelengths. This is described by Braggs
Equation:
n = 2d Sin
Where d is the spacing between the planes. By varying the angle , Braggs
equation is satisfied by different d spacing in polycrystalline material.

14

1.5 Thermogravimetric Analysis (TGA)

Thermal gravimetric analysis (TGA) is a method of thermal analysis in which
changes in physical and chemical properties of materials are measured as a
function of increasing temperature (with constant heating rate) or as a function
of time (with constant temperature and/or constant mass loss). TGA can
provide information about physical phenomena, such as second phase
transition, including vaporization, sublimation, absorption and adsorption and
desorption. Likewise, TGA, can provide information about chemical
phenomena including chemisorptions, desolvation (especially dehydration),
desorption and solid-gas reactions (e.g. oxidation and reduction). TGA is
commonly used to determine selected characteristics of material that exhibit
mass loss or gain due to decomposition, oxidation, or loss of volatiles (such aas
moisture). Common applications of TGA are:
1. Materials characterization through analysis of characteristic decomposition
patterns,
2. Studies of degradation mechanism and reaction kinetics,
3. Determination of organic content in a sample, and
4. Determination of inorganic (e.g. ash) content in a sample, which may be
useful for corroborating predicted material structures or simply used a chemical
analysis. It is an especially used technique for the study of polymeric materials,
including thermoplastics, thermosets, elastomer, composites, plastic films,
fibers, coating and paints. Discussion of the TGA apparatus, methods and trace
analysis will be elaborated upon below. Thermal stability, oxidation and
combustion, all of which are possible interpretations of TGA traces, can be
predicted.

15

Chapter 2:
Literature Survey

2.1 PEG Chemistry

PEG is also known as polyethylene oxide (PEO) or polyoxy ethylene(POE)
depending upon their molecular weight. Polyethylene glycol is the polymer of
non ionic ether with a molecular formula H-(-O-CH2-CH2)n-OH. PEG, PEO, or
POE refers to an oligomer of ethylene oxide. PEG has tended to refer to
oligomers and polymers with a molecular mass below 20,000g/ml, PEO to
polymers with a molecular mass above 20,000g/ml, and POE to a polymer of
any molecular weights. PEG and PEO are liquids or low melting solids
depending upon their molecular weights. PEGs are prepared by polymerization
of ethylene oxide and are commercially available over a wide range of
molecular weights from 300g/ml to 10,000,000g/ml. While PEG and PEO with
different molecular weights find use in different applications, and have
different physical properties (e.g.viscosity) due to chain length effects, their
chemical properties are nearly identical. Different forms of PEG are also
available, depending on the initiator used for the polymerization process-the
most common initiator is a monofunctional methyl ether PEG or
methoxypoly(ethylene glycol), abbreviated mPEG. Lower-molecular-weight
PEGs are also available as purer oligomers, reffered to as monodisperse,
uniform, or discrete. Very high purity PEG has recently been shown to be
crystalline, allowing determination of a crystal structure by x-ray diffraction.
Since purification and separation of pure oligomers is difficult, the price for
this type of quality is often 10-1000 fold that of polydisperse PEG.

Figure 2 . Polyethylene Glycol

16

PEGs are also available with different geometries:

1. Branched PEGs have three to ten PEG chains emanating from a central core
group.
2. Star PEGs have 10 to 100 PEG chains emanating from a central core group.
3. Comb PEGs have multiple peg chains normally grafted onto a polymer
backbone.
Polyethylene glycol is produced by the interaction or ethylene oxide with
water, ethylene glycol or ethylene glycol oligomers. The reaction is catalyzed
by acidic basic catalysts. Ethylene glycol and its oligomers are referable as a
starting material instead of water, because they allow the creation of polymers
with a low polydispersity (narrow molecular weight distribution). Polymer
chain length depends on the ratio of reactants.
HOCH2CH2OH+ n(CH2CH2O) HO(CH2CH2O)N+1H
Depending on the catalyst type, the mechanism of polymerization can be
cationic or anionic. The anionic mechanism is preferable because it allows one
to obtain PEG with a low polydispersity, polymerization of ethylene oxide is
an exothermic process. Overheating or contaminating ethylene oxide with
catalysts such as alkalis or metal oxides can lead to runaway polymerization,
which can end in an explosion after a few hours.
Polyethylene oxide, or high-molecular weight polyethylene glycol, is
synthesized by suspension polymerization. It is necessary to hold the growing
polymer chain in solution in the course of the polycondensation process. The
reaction is catalyzed by magnesium, aluminium or calcium-organoelement
compounds. To prevent coagulation of polymer chains from solution chelating
additives such as dimethyl glyoxime are used.
17

High molecular weight PEG(e.g.8000) has been shown to be a dietary

preventive agent against colorectal cancer in animal models.
The injection of PEG 2000 into the bloodstream of guinea pigs after spinal cord
injury leads rapid recovery through molecular repair of nerve membranes. The
effectiveness of this treatment to prevent paraplegia in humans after an
accident is not known yet.
PEG is being used in the repair of motor neurons damaged in crush or
laceration incidents in vivo and in vitro.
Since PEG is a flexible, water soluble polymer, it can be used to create very
high osmotic pressures (on the order of tens of atmospheres). It also is unlikely
to have specific interactions with biological chemicals. These properties make
PEG one of the most useful molecules for applying osmotic pressure in
biochemistry and biomembranes experiments, in particular when using the
osmotic stress technique.
PEG is used in a number of toothpastes as a dispersant. In this application, it
binds water and helps keep xanthun gum uniformly distributed throughout the
toothpaste. The generation and stabilization catalytically active nanoparticles in
water have several important advantages over both traditional homogeneous
and supported transition-metal catalysts in terms of low cost, absence of
expensive ligands and organic solvents.
1. Here, PEG act as a stabilizer, which absorb to the particle surface, control
particle size, and prevent agglomeration. The resulting material bearing longer
polyether chains has been successfully used as a stabilizer for the preparation
of water soluble palladium nanoparticles. Water is an excellent solvent for this
PEG capped nanoparticles in catalytic system.
2. Possibly the polar capping agent forms a more open structure in water, so
that reactants could easily get in contact with the metal surface.

18

3. Using highly biocompatible PEG molecules as reducing and stabilizing agent,

two types of water-soluble stable monometallic NPs (PEG8K-Pd) were
successfully synthesized.
4. The size of the resulting NPs was controllable by the concentration of
metal/polymer ratio precursors.
5. The electron transfer between the metal ions and hydroxyl groups of solvent
methanol and PEG polymer results in the reduction of metal ions to zero valent
metal.
6. The prepared polymeric nanoparticles can be preserved for months without any
change of physical and chemical properties. Thus, the polymer stabilized metal
NPs can be more effective catalysts for varied catalytic applications

2.2 Palladium Chemistry

Electronic

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
19

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).

2.3 Applications of Palladium

The largest use of palladium today is in catalytic converters. Palladium is also
used in jewelry in dentistry, watch making, in blood sugar test strip in aircraft
spark plugs and in the production of surgical instrument and electrical contacts.
Palladium is also used to make professional transverse flute. A large number of
carbon-carbon bond forming reactions in organic chemistry (such as the Heck
and Suzuki coupling) are facilitated by catalysis with palladium compounds. In
addition, palladium, when dispersed on conductive materials, proves to be
excellent electro catalyst for oxidation of primary alcohols in alkaline media.
Palladium is also a versatile for homogenous catalysis. Palladium itself has
been used as a precious metal in jewelry since 1939, as an alternative to
platinum for making white gold.
2.4 Transition Metal Nanoparticles
Transition metal nanoparticles have attracted a great deal of attention in the last
10 years, their preparation, structure determination, and applications are
20

capable of current interest. Nanoparticles are defined as having 1-50 nm

diameter a size range where metals can show size dependent properties. The
smaller the cluster of atoms, the higher the percentage of atoms are on the
surface, rendering nanoparticles very interesting in catalysis. Thus a
nanoparticle of 10nm diameter has about 10% of its atom in the surface, but
one of 1nm has 100%. The metal atoms constituting nanoparticles can be
generated by

(i) chemical reduction of a metal salt, (ii) thermal,

photochemical, or sonochemical decomposition of a metal (0) complex, (iii)

hydrogenation of a coordinating oelifinic moiety, and (iv) the vapor phase
deposition. To this list proposed by Bradley should be added (v)
electrochemical reduction of valent species of the metal. During the generation
of nanoparticles, the following steps have been identified (i) generation of
atoms as above; (ii) nucleation to form an initial cluster of atoms; (iii) growing
of cluster until a certain volume is reached; and (iv)surrounding the cluster by a
protecting shell that prevents agglomeration. Therefore, nanoparticles should
be formed in the presence of a protecting agent. These protectors can be
divided into two categories: those providing electrostatic and those providing
steric stabilization. The electrostatic stabilization is based upon the double
electric layer formed when the ions of the same sign are adsorbed at the
nanoparticle surface. The counter ions forms a second layer that repels the
neighboring nanoparticle; for example sodium citrate acts by this mechanism.
In other cases, protecting molecules of considerable length interact attractively
with the surface of the particles. The volume of these surrounding molecules
prevents mutual approach of metal surfaces at bonding distance. Popular
protecting agents are polymers (poly(vinylpyrrolidone)), cyclodextrins,
dendrimers, and so forth. Particularly well known is the mechanism of
stabilization by large molecules featuring functional groups with high affinity
for the metals, i.e. thiols, sulfides, amines or phosphines. Other common
stabilizers are ionic surfactants i.e. sodium dodecyl sulfate and lauryl trimethyl
ammonium chloride. These Compounds protect nanoparticles by both
electrostatic and steric mechanism.
21

Size and dispersity are important properties of nanoparticles. The

development of uniform nanometer sized particles have been intensively
pursued because of the many technological and fundamental scientific interests
associates with these nanoparticles. These nanoparticle materials often exhibit
very interesting electronic, optical, magnetic and chemical properties, which
are unachievable for their bulk counterparts. The formation of metal
nanoparticles is carried out by reduction of metal ions in the presence of
stabilizers like polymers, dendrimers, microgel, surfactants, and colloids which
prevent the nanoparticles from aggregation and serve as carriers. In general, the
catalytic properties of metal nanoparticles are a function of their size, crystal
lattice parameters and the properties of carrier systems.

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.

23

Controlling size and polydispersity of nanomaterials is a key requirement for

most of the applications. In this work we described the synthesis and
characterization of polymer PEG8K capped palladium nanoparticles of
smallest size with low polydispersity. The use of water as a solvent and design
of recyclable catalysts are some of the promising directions in this field.
Among water soluble catalysts, a great deal of attention has been focused on
the metal nanoparticles. Water-soluble Pd (0) nanoparticles are a promising
class of catalysts in some organic processes, mainly in hydrogenation,
oxidation and cross coupling reaction for the formation of C-C bonds. A wide
of stabilizers for the preparation of nanoparticles is known, in order to prevent
their aggregation. Polymer protected noble metal colloids are usually prepared
from suitable metal precursors by various in situ reactions, such as chemical
reduction, photo reduction and thermal decomposition.These protective
polymers employed should fulfill the following requirements:
1. They should be soluble in different solvents and be thermally stable at the
temperature used for the preparation and technical applications of the colloids.
2. There should be good protective function of the polymer for the stabilization of
metal colloids, therefore good interaction with the metal surface is essential.
3. The polymer should ideally interact with the metal precursor, for instance for
the complex and the ion-pair formation.
The number of nuclei formed at the very beginning of the determines the
number and size of the resultant particles. The atoms formed at the later period
are used mainly to the collision with the nuclei already formed instead of the
formation of new nuclei and therefore lead to the formation of larger particles.
Among them polymers provide stabilization by entrapment, both through their
steric bulk and through the weak dative bonds between the nanoparticle surface
and the hetero atoms present in the structure of the protecting agent.
In this context our work is focused on the use of polyethylene glycol (PEG) as
the stabilizing agents for metal nanoparticles. The PEG chains are
24

commercially available in various molecular weights which are soluble in

water and are insoluble in diethyl ether. In this work, it has been synthesized a
new PEG8K-Pd nanoparticles.
The resulting material bearing longer polyether chains has been successfully
used as stabilizer for the preparation of water soluble palladium nanoparticles.
A common method for the preparation of metal nanoparticles involves the
reduction of metal ions in the presence of stabilizers as surfactant and
polymers.
In the present study we used PEG8K as a stabilizer for palladium nanoparticles.
We report a facile and novel route for the preparation of Pd nanoparticles by
exploiting PEG, molecular weight 8000 (MW8K), which was found to act as
both reducing agent and stabilizer.
Preparation of polymeric PEG8K-Pd nanoparticles were achieved successfully
(Scheme 1) by the reaction of a solution of Pd(OAc)2 in 1,4-dioxane with
aqueous solution of PEG8K in methanol at room temperature in a 30ml closed
vial for 5 hours.
Pd(II)ions reduced to Pd(0) because of the presence of the terminal OH
functional present in methanol as reducing agent as well as solvent in the
system.
Pd(OAc)2 + PEG8000

R.T.,5hr
Methanol

PEG8K-Pd

Scheme 1: Synthesis of PEG8K-Pd nanoparticles

The experimental condition such as amount of protecting polymer, the

concentration of metal ions are systematically changed to achieve the smallest
size PEG8K-Pd nanoparticles.
The size and morphology of the resulting PEG8K-Pd nanoparticles are
sensitive to a number of different reaction conditions. These include the
polymer PEG8K used, the reducing agent employed (methanol), the reaction
time, the nature of the stabilizing ligand (polyethers), and the ratio of the
25

palladium (palladium acetate) precursor to the other reagents (PEG8K). In

general, to prepare small nanoparticles it is beneficial to use a large excess of
long chain polymer with an excess of reducing agent.

3.5 Experimental Procedure

Procedure for preparation of PEG8K-Pd nanoparticles
1. In the typical experiment a mixture of palladium acetate Pd(OAc) 2 (5.09 x 10-3
M in 1,4-dioxane solution) and molecular weight 8000 aqueous solution
(3.050%) in methanol (15ml).
2. The mixture is then allowed to for stirring on the magnetic stirrer for 5 hours.
3. With the course of time the color of the solution turned orange to brown and
finally turned black, indicating the formation of PEG8K capped Pd(0) metal
nanoparticles.
4. Size of the prepared nanoparticles were characterized by DLS technique. The
reduction of Pd2+ ions followed an analogous polyol process in the current
study. When Pd(II) ions were added into the methanol is solution,
electropositive palladium ions are rapidly trapped by electronegative oxygen
forming weak metal ion complex followed by analogous polyol process. In this
system electron transfer between metal ions and hydroxyl group leads to the
reduction of Pd2+ to Pd(0).
5. For TEM analysis the samples with best DLS results are re-prepared in 3sets,
again DLS of those samples is done and then sample is diluted and finally the
sample is analyzed through TEM.

3.6 Results
Characterization of prepared PEG8K-Pd nanoparticles by DLS
26

a.

b.
c.

d.

e.

f.

27

g.

h.

i.

Table 3.1: DLS data of prepared PEG8K-Pd nanoparticles

Sample Name

PEG8K (ml)

Pd(OAc)2 (ml)

Mean Size (nm)

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.

28

DLS data of re-prepared Samples

Table 3.2 : DLS data of reprepared samples

29

Sample Name

PEG8K (ml)

Pd(OAc)2 (ml)

Mean Size (nm)

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.

30

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.

References:
1. Berne, B. Pecora, R.: Dynamic Light Scattering with applications to chemistry,
biology and physics, Wiley-Interscience, New York
2. A. Moores and F. Goettmann, New J. Chem., 2006, 30 (8), 1121
3. M. C. Daniel, D. Astruc., Chem., Rev., 2004, 104, (1), 293
4. N. Semagina, N. Renken and L. Kiwi Minsker, J. Phy., Chem., C, 2007, 111, (37)
13933
5.O. M. Wilson, M. R. Knecht, J. C. Garcia-Martinez and R. M. Crooks, J. Am. Chem.
Soc., 2006, 128, (14), 4510
6. N. Dimitratos, F. Porta and L. Prati, Appl. Catal. A: Gen 2005, 291, (1-2), 210
7. Z. Hou, N. Theyssen, A. Brinkmann and W. Leitner, Angew Chem. Int. Ed. 2005, 44,
(9), 1346

31

32