Chemistry of Nanoscale

Materials
Synthesis, Properties and Applications
Potential Impacts of Nanoscale Materials

Pharmacy Water purification

Therapeutic drugs Catalysts
Tagging DNA and DNA chips Sensors
Information Storage Nanostructured Electrodes
Chemical/Optical components Improved polymers
Environmental/Green Chemistry Smart magnetic fluids
Solar Cells Improved National Security
Environmental remediation
 Definitions
Nanoparticle: A solid particle in the 1-1000 nm range that could be
noncrystalline, an aggregate of crystallites, or a single crystallite
Nanocrystal: A solid particle that is a single crystal in the nanometer
size range.
Quantum dot. A particle that exhibits properties of quantum
confinement.
Nanostructured/ Nanophase/ nanoscale material:
Any solid material that has a nanometer dimension;
Colloid: A stable liquid phase containing particles in the 1-1000
nm range. A colloidal particle is one such 1-1000 nm sized particle
Cluster: A collection of units (atoms or reactive molecules) of up
to about 50 units. Cluster compounds are such moieties
surrounded by a ligand shell that allows isolation of a molecular
species (stable, isolable, soluble)
Size Relationships of Chemistry, Nanoparticles,
and Condensed Matter Physics

Nanoscale Condensed
Atoms/Molecules Matter
Particles
1 125 70,000 6 x 106 ∞
Diameter 1-10 nm Diameter 100-∞ nm
Solid State
Quantum Chemistry ? Physics

In the nanoscale regime, neither quantum chemistry nor

classical laws of physics hold
Factors Affected by Size Reduction:
Bulk vs. Nano

Melting Points
Optical properties
Colors
Surface Reactivity
Magnetic properties
Conductivity
Specific heats
About 2/3 of the Chemical Elements
are Metals
Matter has Unusual Properties on the nm Scale

If you take gold and 
make particles about  ruby­red 
10 nm in diameter, it  stained glass 
looks wine­red or  from gold
blue­gray, depending  nanoparticles
on how close the 
particles are together
Preparation of Au Nanoparticles by a
Chemical Route

Reducing agent

Capping agent
Au nanoparticles
Au3+ Salt
Transmission Electron Microscopy Images of Au Nanoparticles
 Gold Nanospheres with Increasing
Diameter Size

Bulk Au
4 nm 12 nm 25 nm 37 nm

• Optical properties of metal nanoparticles depend on their shape and size

• Particle functionalization can be done on the surface
• Visible optical changes occur
 Origin of the Properties

Bulk Metal Nanoscale metal

Unoccupied Decreasing
states the size…

occupied
states
Separation between
Close lying bands the valence and
conduction bands

Unbound electrons have Electron motion becomes

motion that is not confined confined, and quantization sets in

Particle size < mean free path

of electrons
 Band Structure in Metals

EF (Fermi Level)
EF depends on the density
Density ρ = N/V (where N = Number of electrons, V = volume)

Assuming all energy levels have the same number of electrons,

δ = EF / N
Since N ∝ V

Therefore, δ ∝ 1/V
V = L3 (where L = side length of the particle)
Hence,
δ ∝ EF/L3

As the side length of the particle decreases the energy level spacing increase
 Gold Nanospheres with Increasing
Diameter Size

Bulk Au
4 nm 12 nm 25 nm 37 nm

• Optical properties of metal nanoparticles depend on their shape and size

• Particle functionalization can be done on the surface
• Visible optical changes occur
Surface Plasmon Absorption of Au Nanoparticles

Surface plasmon absorption in metal nanoparticles arises from the collective

oscillations of the free conduction band electrons that are induced by the
incident electromagnetic radiation.
Factors that Affect the Surface Plasmon
Absorbance of Metal Nanoparticles
Plasmon absorption of metal nanoparticles is
sensitive to the surrounding environment

3. Dielectric of the surrounding medium

5. Solvents (nature of the solvent)

 Dielectric Constant and its Effect of the
Surface Plasmon Absorption Band

Position of the plasmon absorption band can be discussed

within the framework of the Drude model

λ2 = λp2 (ε∝ = 2εm)

Where λp is the bulk plasma wavelength, ε∝ is the high frequency dielectric
constants due to interband and core transitions, and εm is the medium dielectric
constant

The refractive index is directly related to its dielectric constant

n = (εm)1/2
 Normalized surface plasmon absorption
band of Au nanoparticles in cyclohexane
and o-dichloromethane

J. Phys. Chem. B. 2002, 106, 7729

Inset shows the dependence of the square of the observed peak position of the surface plasmon
band as a function of twice the medium dielectric function. ( m was determined from the
expression, m = n2)
 How Does SP Band of Alkanethiolate-Au
Clusters Vary with Refractive Index

The optical dielectric of the

ligand shell, and not that of the
solvent, dominates the Au cluster
dielectric environment

Langmuir 1998, 14, 17

Dodecanethiolate-stabilized Au cluster
 Melting Points
Property is a consequence of the averaged coordination number
of the participating atoms

Typically, for bulk materials, surface atoms form a negligible

part of the total number of atoms

The smaller a particle becomes, the more the proportion of

surface atoms increases
Full shell clusters are constructed by successively packing layers
– or shells – of metal atoms around a single metal atom
The number of atoms per shell is
(Sum of atoms + 10n2 + 2)
where n = number of shell
The Relation Between the total number of atoms in
Full shell (‘Magic Number’) clusters and the
percentage of surface atoms
Full-shell Total Surface
Clusters Number of Atoms (%)
Atoms
1 Shell 13 92
2 Shells 55 76
3 Shells 147 63
4 Shells 309 52
5 Shells 561 45
7 Shells 1415 35
 Relation Between the Size of Gold
Particles and Their Melting Point

1200
1000
Melting Point (oC)

800
600
400
200
0
0 1 2 3 4 5 6 7 8 9 10
Particle Radius (nm)
Other Important Properties of Metal
Nanoparticles

Gold nanoparticles have been shown to be

photoluminescent

Unique electrochemical properties

Gold nanoparticles have shown electron – acceptor

properties

Enhanced catalytic properties

 Semiconductor Nanoparticles
Group 14 (old group IV) Si, Ge

III-V Materials: GaN, GaP, GaAs, InP, InAs

II-VI Materials: ZnO, ZnS, ZnSe, CdS, CdSe, CdTe

Quantum dots are

semiconductors particles
that has all three
dimensions confined to the
1-100 nm length scale

Colloidal CdSe quantum dots dispersed in hexane

 Energy Diagrams Illustrating the
Situation for a Nanoparticle, in Between
a Molecule and a Bulk Semiconductor
NANOPARTICLE

MOLECULE

LUMO BULK SOLID

CB
Energy

∆E Eg
∆E
VB
HOMO
 Quantum Confinement in
Semiconductor Nanoparticles

Eg (quantum dot) = Eg(bulk) + ( h2/8R2) (1/me + 1/mh) – 1.8e2/4πε 0εR

Eg = bandgap energy of a quantum dot or bulk solid

R = quantum dot radius
mc = effective mass of the electron in the solid
mh = effective mass of the hole in the solid
ε = dielectric constant of the solid
ε0 = permittivity of a vacuum
 Room-Temperature Spectra of CdSe
Quantum Dots

(a) Absorption and

photoluminescence spectra
as a function of diameter

(c) Quantum yield of

photoluminescence as a
function of size. Squares
represents deep-trap
emission, and circles
represent band-edge
emission

Murray, C. B. Synthesis and characterization of II-VI quantum dots and their

assembly into 3D quantum ot superlattices. Ph.D Thesis, MIT, Cambridge , MA 1995
 Inorganic Semiconductors

Trap states are caused by defects, such as vacancies, local

lattice mismatches, dangling bonds, or adsorbates at the
surface
Chemical Synthetic Routes for
Metal and Semiconductor
Nanoparticles and Structures

Additional Synthetic Approaches

• Sonochemical
• Electrochemical
• Photochemical
• Chemical Vapor Deposition
 Aspects of Nanoparticle Growth in
Solution
Arrested precipitation
Precipitation under starving conditions: a large number
of nucleation centers are formed by vigorous mixing of
the reactant solutions.

If concentration growth is kept small, nuclei growth is

stopped due to lack of material.
Particles had to be protected from Oswald Ripening by stabilizers
Oswald Ripening
The growth mechanism where small particles dissolve,
and are consumed by larger particles. As a result the
average nanoparticle size increases with time and the
particle concentration decreases. As particles increase
in size, solubility decreases.
 Synthetic Approaches for Metal and
Semiconductor Nanoparticles
via Chemical Routes
1. Metal Compound
• Positively charge metal salt, or
• Metal centers of complexes

2. Solvents (depends on the nature of the salt)

• Water
• Polar organic solvents
• Non-polar organic solvents
3. Reducing agent (determined by the nature of the metal compound)
• Gaseous hydrogen
• Hydridic compounds
• Reducing organics, e.g. alcohols
Many others
Stabilization of Nanoclusters Against
Aggregation
1. Electrostatic stabilization
Adsorption of ions to the + - - - - -- + - - - +
- - - -
-- δ+ δ+ - - δ+ δ+ --
δ - δ
+ +
surface. Creates an electrical
double layer which results in a - δ+ δ+ -+ δ+ δ+ -
+ -- - --- - -- - +
Coulombic repulsion force - + -
between individual particles

2. Steric Stabilization
Surrounding the metal center
by layers of material that are
sterically bulky,
Examples: polymers,
surfactants, etc
 Synthetic Approaches for Metal and
Semiconductor Nanoparticles
via Chemical Routes
4. Stabilizers
Role of stabilizers:
Stabilizing agents/ligands/capping agents/passivating agents
• prevent uncontrollable growth of particles
• prevent particle aggregation
• control growth rate
• controls particle size
• Allows particle solubility in various solvents
 Other Common Stabilizers
1. Organic ligands
• Thiols (thioethanol, thioglycerol, mercaptoethylamine, etc)
• Amines
• phosphates

2. Surfactants

3. Polymers

4. Solvents
ether
thioether

5. Polyoxoanions
Schematic Procedure for Cluster Synthesis

Add
+ ++ electron donor •• •••• •••••• •••••••
•
• • ••• •• •
•
++ +
•••••••••••••••••
Metal cations Metal atoms in Cluster
in solution solution formation

Ligand
• ••••• •••••••••• Isolation in
•••••
molecules (•) ••••••• •••••••••• solid form •
•••••••
•••••••••••••••••• ••••••••••••
 Schematic Procedure for Cluster
Synthesis

Add Add
Ligand electron
molecules (•) donor
++ + + + + + •••••• •••••• ••••••
•• •• ••
•••••••••••••••••
+ ++ ++ • +• • • + •• ••
••••• • •••••
•••••••••••••• ••••
•• • • • •• •
• + +• •••••••••••••• •••••• ••••••••
••• •• ••• •• •••
•• ••••• •••
Metal cations
in solution Stabilized
Metal particles
in solution
 Synthesis of Metal Nanoparticles in
Organic Media
Biphasic reduction procedure

Add phase
transfer reagent Extract
e.g. tetraoctyl
ammonium
Aqueous bromide
(TOAB)
solution of
metal salt Add
Reducing
agent
TEM Image of Au Nanoparticles Prepared
in the Presence of a Surfactant (CTAB)

CTAB = cetyltrimethylammonium bromide

J. Phys. Chem. B. 2001, 105, 4065
 Nucleation and Growth
Homogeneous nucleation occurs via a stepwise sequence of
bimolecular additions until a nucleus of critical size is obtained.
a. Nucleation from supersaturated solution

nS Sn
b. Diffusion-Controlled Growth

Sn + S Sn+1

LaMer et al. J. Am. Chem. Soc. 1950, 72, 4847

Highly monodisperse nanoparticles are formed if the processes

of nucleation and growth can be successfully separated

• Nucleation process must be fast

• Growth process must be slow
 Nucleation
Nucleus Radius is calculated as follows:
∆G = 4πσ(r2 – [2r3 / 3r*])

Where r = nucleus radius

r* = critical nucleus radius
σ = surface tension

∆G(nucleus) = n(∆G formation, bulk – ∆G formation, free atom) + σA

Where A = particle surface area

 Dendrimer-Templated Nanocluster
Synthesis
Structure of poly(amidoamine) dendrimer (PAMAM)

Generation 2 PAMAM Dendrimer

Dendrimer-Templated Nanocluster Synthesis
Pioneered in 1998, by
Donald A. Tomalia (Michigan Molecular Institute
Richard M. Crooks (TAMU)

Hydrazine
PAMAM + CuAc2 1 x 10-4 mol
1 x 10-6 mol Cu Nanoclsuters
1 x 10-5 mol

Formation of Cu nanoclusters
can be monitored by UV-vis
spectrophotometry

Reaction is pH dependent:
Presumably H+ ions compete
with Cu2+ ions for the tertiary
amine sites
J. Am. Chem. Soc. 1998, 120, 4877
J. Am. Chem. Soc 1998, 120, 7355
 Reverse Micelles
Water-in-oil droplets

[H2O]
Water pool w =
[surfactant]
Particle size is controlled by the size of the water
droplets in which synthesis takes place

Consider that: V = volume , R = radius,

R = 3V/A A = surface area

3Vaq[H2O] σ = head polar group area

Rw = Vaq = volume of water
σ[s]
Parameters Affecting Particle Growth/
Shape/ Structure

• Type of capping agent/stabilizers

• Concentration of the reactants
• pH value of the solution
• Duration of heat treatment
 Sonochemical Approaches for
Nanoscale Particle Synthesis
Rectified Diffusion

‘area’ effect ‘shell’ effect

+ Bubble
Acoustic
pressure

Liquid shell
-
Bubble
 Sonochemical Approaches for
Nanoscale Particle Synthesis
Step 1:
• Bubble expands when surrounding medium experiences –ve
pressure

• Bubble collapses when surrounding medium experiences +ve

pressure

• Bubble collapse leads to extreme temperatures (5,000 – 50, 000

K), and pressure (100 atm) within the bubble

Step 2:
Solvent or solute molecules present within the bubbles are
decomposed under these extreme conditions and generate highly
reactive radicals
Formation of Highly Reactive Radicals
Depending on the liquid medium, sonication leads to the
generation of oxidizing and reducing radicals

In aqueous solution
H2O • H + •OH

M+ + H • M + H+

In solutes like alcohols, sonication leads to secondary radicals

RHOH + H• (OH• ) ROH• + H2(H2O)

ROH • + M+ M + RO + H+
 Examples of Metal Nanoparticles
Prepared by Sonication
Ag nanoparticles prepared in aqueous solution at 1 MHz
H2O • • H + OH

Ag+ + H • Ag + H+

J. Phys. Chem. 1987, 91, 6687

Au nanoparticles prepared by sonication

ROH •
AuCl4- Au + Products

Langmuir 2002, 18, 7831-7836

Synthesis of CdS Nanoparticles
General:
Anionic or
Cd(II) salt + Lewis basic + Sulfide 1-10 nm
polymers source CdS

Sodium
Cd(NO3)2.4H2O + polyphosphate + Na2S CdS
2 x 10-4 M 2 x 10-4 M 2 x 10-4 M

Chem. Mater. 1999, 11, 3595

 Synthesis of CdSe Nanoparticles

General: High
Phosphine oxide
Cd(CH3)2 + Se reagent + temperature
surfactant CdSe

HAD-TOPO-TOP
Cd(CH3)2 + (C8H17)3PSe CdSe

HAD-TOP-TOP = hexadecylamine-trioctylphosphine oxide-trioctylphosphine

J. Am. Chem. Soc. 1993, 115, 8706
 Synthesis of ZnSe Nanoparticles

Zn(CH3CH2)2 + (C8H17)3PSe Zn/Se TOP

Solution
Zn/Se TOP + Hexadecylamine 270 C
o
ZnSe
Solution
J. Phys. Chem. B. 1998, 102, 3655

TOPO binds too strongly to Zn

TOP binds too weakly
Amines, however have intermediate strength
 Synthesis of III-V Semiconductor
Nanoparticles
Synthesis of III-V semiconductor nanoparticles is quite complex
Requires high temperature

370 – 400 oC
GaCl3 + tris-(trimethylsilyl)phosphine + TOPO-TOP GaP

GaP particles prepared in this manner lacked monodispersity

GaCl3 + As(SiMe3)3 ~ 700 oC GaAs

Chem. Mater. 1989, 1, 4
J. Am. Chem. Soc. 1990, 112, 9438
 Synthesis of InP and InCl3
260 oC, TOP InP nanocrystals
InCl3 + [(CH3)3Si]3P

Synthesis of InAs via Dehalosilylation

Me3SiCl Me3SiCl Me3SiCl
evolved evolved evolved
InCl3 + (Me3Si)3As InAs
3 days, rt 70-75 C
o
150 C
o

4 days 4 days

Chem. Mater. 1989, 1, 4

 Factors Affecting the Nature of the
Nanoparticle

• Particle size and shape

• Surface properties
• Particle-solvent interactions
• Particle-particle interactions
 Common Methods for Nanoparticle
Characterization
Surface state

Particle Surface Surface Surface

Size Area composition structure;
Topography
Surface
Complexes
Electron Microscopy
X-ray diffraction LEED
Magnetic Measurements AES, SEM
XPS, TEM
SIMS, EXAFS
EPMA,
EXAFS

IR, UV-Vis, ESR, NMR, Raman

 UV-Visible Spectroscopy
• Particularly effective in characterizing semiconductor and
metal particles

• Useful for metal nanoparticle characterization whose surface

plasmon absorbance lies in the visible range, e.g. Cu, Au, Ag

• Can be used to determine particle size:

(For semiconductor nanoparticles: as the radius decreases, the
band gap increases and λmax shifts to lower energy.

• Particle aggregation

• Information about the surface, e.g. presence of adsorbates

 Infrared Spectroscopy
IR has been used as a surface probe for nanostructures

Example illustrated by Bardley:

Adsorbing CO onto the metal nanoparticle surface resulted in IR
depending on particle size

More face:
More edge:
bridged CO
linear CO is
is stable
stable 2.5 nm 4 nm 6 nm

As particle size increased, the ratio of terminal CO to bridging

CO decreased
Bradley, et al. Chem. Mater. 1992, 4, 1234
 Nuclear Magnetic Resonance (NMR)
Two uses:
2. Probing the ligands that surround metal core
3. Probing the intra-core metallic atoms (difficult)

Probing the intra-core metallic atoms

Nuclear spin relaxation time, and nuclear resonance frequency,
are sensitive to any metallic property the particle may exhibit
Change in frequency (known as ‘Knight shift’) is a consequence
of the interaction of the metal nucleus with the conduction band
electrons
If particles are very small, in favorable cases, the Knight shift
allows resonances for surface and interior metal particles to be
identified
 Microscopy

• TEM: High voltage beam passes through a very thin

sample. The sample areas that do not allow passage of
electrons allow image to be presented

• STM: Involves dragging a sharp needlelike probe across a

sample very close to the surface. The tunneling current
between the sample and probe tip can be monitored . As
probe approaches an elevated portion, the probe moves up
and over, and produces a surface map.

• AFM: The probe tip is essentially touching the surface,

and the surface can be mapped by the weak interaction
between the tip and the sample.
 Transmission Electron Microscopy
• Provides direct visual information of size, shape, dispersity,
structure and morphology

• Routine magnifications > 40,000 to 0.2 nm

Drawbacks
• Samples are dried and examined under high vacuum conditions

• Therefore, no direct information is gained on how particles exist in

solution

• Only a finite number of particles can be examined and counted,

which may not be a representative of the sample as a whole

• Requires electron beam in which case, some nanoparticles may

undergo structural rearrangement, aggregation or decomposition.
Scanning Tunneling Microscopy (STM)

Makes possible the determination of the total diameter of the

nanoparticle, including the stabilizing ligand shell
Effective probe of the electronic properties of nanoparticles
Reetz et al. Science 1995, 267, 367-369

A combined STM/TEM study of Pd nanoparticles stabilized by

R4N+Br-.

Determined thickness of stabilizing ligand shell by subtracting

the STM determined diameter from the TEM determined
diameter
 Shortcomings to STM
• Nanoparticles may not stick well to the substrate surface,
preventing good images from being obtained

• Geometry of the tip shape may lead to inaccurate

measurements or artifacts in the image

• Tunneling mechanism is not well understood

• Samples have to be dried

• Specific techniques applied to imaging are not mature, i.e.

standard literature protocols have not been established
 Atomic Force Microscopy
• Technique is purely mechanical
– A cantilevered tip attached to a spring is dragged across
a sample
– Increase or decrease in tip height is measured yielding a
surface height profile as a function of distance
– Can be carried out on non-conducting samples

Shortcomings
• Can reliably determine particle height but not diameter

• Cannot distinguish between subtle shape differences, or

image particles that are not spatially close to each other
 High Aspect Ratio Nanoparticles
• What is a high aspect ratio nanoparticle?

• Aspect ratio refers to the ratio of a particles length to its

width
Aspect ratio = length
width

• High aspect ratio nanoparticles have elongated structure

Examples: nanotubes, nanowires, nanorods

• Often have distinctive properties as opposed to the bulk

materials or even spherical particles

e.g. Chemical, electrical, magnetic, optical, etc.

 Types of High Aspect Ratio Nanoparticles
Nanowires Aspect ratio
Synthetic Method
Ni, Au, Pt, Ag, Co, Cu, ZnO Templated electrodeposition Up to 250
TiO2, ZnO, SiO2 Sol-gel 250
Silicon Nanocluster-mediated vapor-liquid- > 100
solid growth > 20
MnO2, Fe2O3, Cu2O, Pd, Electrodeposition on graphite
Cu, Au, Ag surface
Nanotubes
Gold Templated electroless deposition 250
Silica Sol-gel 250
Carbon High temperature: laser > 100
ablation, arc discharge, others

Nanorods
Gold Surfactant/seed mediated synthesis ~20
CdSe Surfactant/seed mediated synthesis 2-10
Cu Micellar growth 1.7-3.7
Se Crystal growth > 100
UV-Visible Absorption Spectrum of
Au Nanorods with Aspect Ratio 3.3

J. Phys. Chem. B. 1999, 103, 3073

 Synthesis of Au Nanorods
1. Formation of 4 nm “seed” by reduction of HAuCl4

HAuCl4 NaBH4
solution
+ Sodium citrate

1. Seed-mediated growth in the presence of cetyltrimethylammonium

bromide (CTAB) produces rod-like Au spheroids and nanorods

HAuCl4
Solution + ascorbic acid
in CTAB
1. Seed-mediated growth in the presence of cetyltrimethyammonium
bromide (CTAB) of rod-like Au nanoparticles leads to Au nanorods

HAuCl4
Solution + ascorbic acid
in CTAB

CTAB = cetyltrimethylammonium bromide (a surfactant)

Increase in Intensity of the Longitudinal
Plasmon Band with Increase in Nanorod
Concentration

Chem. Mater. 2003, 15, 1957

 TEM Image of Au Nanorods Prepared
by a Seed-Mediated Growth Method

Aspect Ratio = 13

J. Phys. Chem. B. 2001, 105, 4065

Gold Nanoparticles with Increasing
Aspect Ratio

Increasing aspect ratio

1
18

Obare, S. O.; Jana, N. R.; Murphy, C. J. Unpublished results

 Increase in Aspect Ratio of Au
Nanoparticles Shifts the Longitudinal
Plasmon Band to the NIR

Chem. Mater. 2003, 15, 1957

Calculated absorption spectra of Au nanoparticles
with Varying Medium Dielectric Constant

Link, S.; Mohamed, M. B.; El-Sayed, M. A. J. Phys. Chem. B. 1999, 103 (16), 3073-3077
Synthesis of Ag Nanorods and Nanowires
Formation of 4 nm “seed” by reduction of AgNO3

AgNO3 NaBH4
solution
+ Sodium citrate Ag seed

Formation of Ag nanorods; aspect ratio was varied by changing the

seed
concentration; pH is higher ~ 11.8
AgNO3
solution + ascorbic acid NaOH

Formation of Ag nanowires; pH is low

AgNO3 + ascorbic acid

solution NaOH

CTAB = cetyltrimethylammonium bromide (a surfactant)

TEM Images of Silver Nanorods and
Nanowires

Chem. Commun. 2001, 617

Silver Nanoparticles with Increasing
Aspect Ratio

Increasing aspect ratio

1 10

Murphy, C. J.; Jana, N. R. Adv. Mater. 2002, 14, 80

 Electrochemical Synthesis of
Nanoparticles
Synthesis of High Aspect Ratio Nanoparticles
Nanoporous Membrane Templated Fabrication

SEM image of typical

alumina membrane.

Typically membranes consists of

3. Anodized alumina
4. Track etch polycarbonate www. whatman.com
J. Vac. Sci. Technol. B 2003, 35, 1097
Nanowire Synthesis by Electrodeposition

Sputter Place membrane in

copper on aqueous solution of
bottom metal salt

Nanoporous alumina membrane

M+
Apply potential
ee- -
M+(aq) + e- M(s)

Remove copper Dissolve alumina

with CuCl/HCl in warm .5 M
solution KOH
 Current–Time Transient for the Deposition of 60 nm
Nickel Nanowires into a 6 µm Polycarbonate Template

Science 1993, 261, 1316

 The Sol-Gel Process
M-O-R + H2O → MOH + R-OH (Hydrolysis)

M-OH + HO-M → M-OH + H2O (Condensation)

Sol Gel
Metal
Hydrolysis Gelling
Alkoxide
Solution
 Sol-Gel Synthesis for High Aspect
Ratio Fabrication

Materials synthesized by sol-gel method:

TiO2: Chem. Mater. 1997, 9, 2544, Adv. Mater. 1994, 8, 857.

CdS: Adv. Mater. 2001, 13, 1393.
SiO2: Chem. Mater. 1997, 9, 2544. J. Am. Chem. Soc. 1995, 117, 2651
In2O3: J. Mater. Chem. 2001, 11, 2901.
Ga2O3: J. Mater. Chem. 2001, 11, 2901.
V2O5: Chem. Mater. 1997, 9, 2544
MnO2: Chem. Mater. 1997, 9, 2544
WO3: Chem. Mater. 1997, 9, 2544
 SEM Image of TiO2 Nanostructures
Prepared by the Sol-Gel Process

SEM image of TiO2 nanostructures obtained by immersing the template membrane in the
sol for (A) 5, (B) 25, and (C) 60 s.
SEM Image of MnO2 Nanostructures
Prepared by the Sol-Gel Process

SEM image of MnO2 fibers prepared in the 200-nm-pore-diameter alumina

template membrane
SEM Image of V2O5 Nanostructures
Prepared by the Sol-Gel Process

SEM images of the template-synthesized V2O5 microstructures

SEM Image of Co3O4 Nanostructures
Prepared by the Sol-Gel Process

SEM image of Co3O4 fibers prepared in the 200-nm-pore-diameter

alumina template membrane
 Synthesis of Carbon Nanotubes
Synthesis of carbon
nanotubes involves high
temperature approaches
A single walled carbon nanotube
Carbon nanotubes are cylindrical
structures consisting of rolled-up
graphene sheets with fullerene
caps.
1993, Nature 1993, 363, 603
Iijima an coworkers first synthesized carbon
nanotubes via the thermal decomposition of
hydrocarbons.
High temperature decomposition of vapors such
as benzene or acetylene, in the presence of Co,
Fe, or Ni catalysts, formed single walled carbon
nanotubes.
1996, Science 1996, 273, 483
Laser Ablation method (Smalley and coworkers)
Method produced nanotubes formed into ropes of
100-500 carbon nanotubes, at yields of more than
70%.
2002, Nano Lett. 2002, 2, 1043
Catalyst-free synthesis (Avouris and coworkers)
Method developed for carbon nanotube synthesis
on a silicon surface. Advantage is that catalyst
removal is not necessary for purification.
 Ligands and the Surfaces they are
Reported to Functionalize
Ligand Name Surface Proposed
modified linkage
R–S–H Thiols
Au, Ag, Cu, Hg, Fe
R–S–S–R Disulfides
R–C N Isocyanides Pt, Pd
Carboxylic acids Metal oxides
Phosphonates Metal oxides
Siloxanes Metal oxides
Hydroxamic acids Metal oxides
Selective Functionalization

1-butaneisocyanide

2-mercaptoethylamine

Adv. Mater. 1999, 11, 1021

 Applications of High Aspect Ratio
Nanoparticles
Several applications of high aspect ratio nanoparticles have been
shown, and many others continue to be unfolded

Applications is areas such as:

•Biology
•Gene therapy
•Bioseparations
•Separations
•Catalysis
•Sensing
•Electronics
•Optical applications
Etc.
Nanowire Synthesis by Electrodeposition

Sputter Place membrane in

copper on aqueous solution of
bottom metal salt

Nanoporous alumina membrane

M+
Apply potential
ee- -
M+(aq) + e- M(s)

Remove copper Dissolve alumina

with CuCl/HCl in warm .5 M
solution KOH
 Au-Ni-Au Nanorods Bound and Unbound
to Fluorescein-tagged Poly-His
Confocal fluorescence
image of Au-Ni-Au after
modification of Ni portion
with Fluorescein-tagged
poly-His

SEM image of Au-Ni-Au

Nanowires

Angew. Chemie. Int. Ed. 2004, 43, 3048

 Exposure of Fluorescein-tagged Poly-His
Proteins to Au-Ni-Au Nanorods

Left: Fluorescein-tagged poly-His

solution

Right: Fluorescein-tagged poly-His

Solution after exposure to Au-Ni-Au
Nanorods Angew. Chemie. Int. Ed. 2004, 43, 3048
Separation of His-tagged Proteins
from a Non-His-tagged Structures

a. Solution of IgG protein (no

a b c His)-Green Alexa dye
mixed with His-tagged
protein-Red Alexa Dye

c. After exposure to Au-Ni-

Au; (non-His protein
remains in solution)

e. Separated Au-Ni-Au from a

in solution

Angew. Chemie. Int. Ed. 2004, 43, 3048

Smart Nanotubes for Bioseparations
and Biocatalysis

J. Am. Chem. Soc. 2002, 124, 11864

 Smart Nanotubes for Bioseparations
and Biocatalysis
Nanotubes preferentially
reside in cyclohexane due to
Vial containing cyclohexane the outer hydrophobic
(upper) and water (lower) surface

Add nanotubes A
cyclohexane

H 2O

Nanotubes A. Dansylamide on inner void and C18 on outer surfaces

Danyslamide dye fluoresces green J. Am. Chem. Soc. 2002, 124, 11864
 Smart Nanotubes for Bioseparations
and Biocatalysis

Nanotubes preferentially
Vial containing cyclohexane reside in Aqueous phase due
(upper) and water (lower) to the outer hydrophilic
surface

Add nanotubes B
cyclohexane

H 2O

Nanotubes B. Quinineurethan on inner and no silane on outer surfaces

Quinineurethan dye fluoresces blue J. Am. Chem. Soc. 2002, 124, 11864
 Smart Nanotubes for Bioseparations
and Biocatalysis
Nanotubes A preferentially
reside in Organic phase while
Vial containing cyclohexane
nanotubes B reside in the
(upper) and water (lower)
aqueous phase

Add nanotubes A
cyclohexane Add nanotubes B

H 2O

Nanotubes A. Dansylamide on inner void and C18 on outer surfaces

Nanotubes B. Quinineurethan on inner and no silane on outer surfaces
J. Am. Chem. Soc. 2002, 124, 11864
 Multifunctional Nanorods for Gene Delivery
Nature Materials 2003, 2, 668
Goal of gene therapy: to introduce foreign cells into somatic cells to
supplement defective genes, or provide additional biological functions

H2N H2N
S-S S-S DNA*
HOOC OOC

Au Ni
HN-DNA* HN-DNA*
S-S S-S
OOC S-T OOC
HS-Transferrin

Observations
2. Nanorods were internalized into the cell but did not
enter the nucleus
3. GFP was observed in the nucleus indicating
delivery of the reporter gene to the nucleus
Human kidney cell 4. Au-S-T served to promote cellular uptake
5. Disulfide linkage acts as a cleavable point to
promote release of DNA within the cell
DNA* = DNA plasmids which encodes Green fluorescent Protein GFP
 What is Nanoparticle
Engineering/Surface Modification
Tailored synthesis of core-shell nanoparticles
with defined morphologies and properties

shell

core
 Why Surface Modification?
1. The shell can alter the charge, functionality, and
reactivity of the surface

3. The shell can enhance the stability and dispersibility

of the colloidal core

5. Magnetic, optical, or catalytic functions may be

readily imparted to the dispersed colloidal core

7. Encasing colloids in a shell of different composition

may also protect the core from extraneous chemical
and physical changes
 Effects of Surface Modification
Chemical and Colloidal Stability
• Nanoparticle degradation through chemical etching
• Agglomeration caused by strong van der Waals attractive forces

Tuning of Physical Properties

For example, the optical properties of metal nanoparticles are
influenced by their environments. Controlled surface modification can
alter these properties

Control of Interparticle Interactions Within Assemblies

• Collective properties of nanoparticle assemblies are influenced to a
large extent by the separation between the particles.

• Coating the particles with a uniform shell of inert material could

control the distance between the particles
Types of Core-Shell Nanoparticles

• Metal-Polymer
• Metal-Metal
• Semiconductor- Semiconductor
• Semiconductor-Metal
• Metal - Semiconductor
 Polymers on Metals

• Main reason is for nanoparticle stabilization

• Could also be used to assemble nanoparticles

• Examples:
– Chem. Mater. 1998, 10, 1214
– J. Am. Chem. Soc. 1999, 121, 8518
– Adv. Mater. 1999, 11, 34
– Adv. Mater. 1998, 10, 132
– Chem. Commun. 1998, 351
– Adv. Mater. 1999, 11, 131
– J. Am. Chem. Soc. 1999, 121, 10642
– Nano Lett. 2002, 2, 3
 Sketch of the surface reactions involved in
the formation of a thin silica shell on citrate-
stabilized gold particles

Langmuir 1996, 12, 4329

 UV-visible spectra of sodium citrate-
stabilized, 15 nm diameter gold colloids 1
day after addition of different amounts of
APS
APS: polymerization initiator
3-aminopropyltrimethoxysilane

Langmuir 1996, 12, 4329

 15 nm gold particles coated with thin
silica layers

18 hours after addition 42 h after addition 5 days after addition

of active silica
The silica shell keeps on growing, but eventually small silica particles also nucleate out
of the solution.
Langmuir 1996, 12, 4329
 Silica-Coated Au Nanoparticles

Langmuir 1996, 12, 4329

Transmission electron micrographs of silica-coated gold particles produced during the extensive
growth of the silica shell around 15 nm Au particles with TES in 4:1 ethanol/water mixtures. The
shell thickness are (a, top left) 10 nm, (b, top right) 23 nm, (c, bottom left) 58 nm, and (d, bottom
right) 83 nm
Influence of thin silica shells on the UV-
visible spectra of aqueous gold colloids

Experimental Calculated

Langmuir 1996, 12, 4329

Influence of thick silica shells on the UV-
visible spectra of ethanolic gold colloids

Experimental Calculated
Langmuir 1996, 12, 4329
 Effect of Solvent Refractive Index on the
Color of Dispersions of 15 nm Gold Particles
with a 60 nm Silica Shell

The solvent refractive indices (left to right) are 1.45, 1.42, 1.39, and 1.36

Langmuir 1996, 12, 4329

 Silica Coating of Silver Colloids
NaBH4
AgClO4 + sodium citrate 10 nm Ag nanoparticles

Ag + 3-aminopropyltrimethoxysilane + sodium silicate Ag@SiO2

nanoparticles
Silicate ion concentration
0.02 % 0.01 % 0.005 %

Langmuir 1998, 14, 3740

 Emulsion Polymerization
Emulsion polymerization is a type of polymerization that takes place in an
emulsion typically incorporating water, monomer, and surfactant. The most
common type of emulsion polymerization is an oil-in-water emulsion, in
which droplets of monomer (the oil) are emulsified (with surfactants) in a
continuous phase of water.

In aqueous solution

surfactant

Monomer + free radical initiator → Polymer

 Polymer-Coated Silver Nanoparticles

TEM images of silver particles: (A) uncoated particle, (B) polystyrene/methacrylate

coated particles, (C) polystyrene/methacrylate coated particles with a covalently bound
BSA layer, and (D) the same as panel C after exposure to gold colloids. Negative staining
by phosphotungstic acid used for all images

J. Am. Chem. Soc. 1999, 121, 10642

 Preparation of Polymer-Coated
Functionalized Silver Nanoparticles

Extinction spectra of silver particles: (A) uncoated particles and (B) polystyrene coated
particles. Solid line: suspension in water. Dotted line: suspension in water, after 1 h in 1.8 M
NaCl
J. Am. Chem. Soc. 1999, 121, 10642
 Synthetic Protocols for the Synthesis of Coupled
1D Nanoparticle Arrays

Procedures for (A) Ppy-

linked Au Colloids

Alkyldithiolate-Linked
Au Colloids

Ppy = poly(pyrrole)

Chem. Mater. 1998, 10, 1214

 Au Colloids Linked by PPy

Transmission electron microscope images of 1D and near-

1D arrays of Au colloids linked by Ppy
Chem. Mater. 1998, 10, 1214
 Semiconductor on Semiconductor
Tailoring optical properties

Enhancing the luminescence

Shell

Energy
Core core
shell
shell core
Energies of Various Semiconductors

TiO2
GaP
Energy (eV)

GaAs CdS
CdSe ZnO TiO2
WO3
1.4 3.0
2.25
1.7 2.5
3.2 3.2
3.2

Values at pH = 1
 Inorganic Semiconductors

Trap states are caused by defects, such as vacancies, local

lattice mismatches, dangling bonds, or adsorbates at the
surface
 Examples for Semiconductor-
Semiconductor Core-Shell Nanoparticles
Examples include:
ZnS on CdSe
CdS on CdSe
CdSe on CdS, etc

J. Phys. Chem. B. 1997, 101, 9463

J. Phys. Chem. B. 1998, 102, 1884
J. Phys. Chem. 1993, 97, 5333
J. Phys. Chem. 1996, 100, 6381
J. Phys. Chem. 1996, 100, 8927
J. Phys. Chem. 1996, 100, 13226
J. Phys. Chem. 1996, 100, 20021
 CdSe Coated with ZnS Nanoparticles
Me2Cd + TOPSe CdSe
300 oC
(TMS)2/Me2Zn/TOP

∆T

ZnS

CdSe

J. Phys. Chem. 1996, 100, 468 TEM picture of (CdSe)ZnS nanocrystals

 CdSe Coated with ZnS Nanoparticles
J. Phys. Chem. 1996, 100, 468

Absorption spectrum of the (CdSe)TOPO

(dotted line) and the (CdSe)ZnS Normalized fluorescence spectra of CdSe-TOPO
nanocrystals (solid line). The fluorescence (dotted line) and CdSe@ZnS (solid line) with
of the (CdSe)ZnS is also shown (solid line) 470 nm excitation
Observations on the Optical Characteristics
of CdSe/ZnS Nanoparticles

Fluorescence of CdSe-TOPO shows the broad tail, due to

surface traps.

CdSe/ZnS fluorescence spectrum has a flat baseline; this

indicates that the ZnS reduces the traps present on the CdSe
(TOPO) surface

Fluorescence of CdSe (CdSe/ZnS) was stable for months

compared to uncapped CdSe

No reduction in the CdSe quantum yield was observed for

months with the CdSe/ZnS nanoparticles
J. Phys. Chem. 1996, 100, 468
 Synthesis of HgS/CdS Core-Shell
Nanostructures
J. Phys. Chem. 1993, 97, 5333
HgScore CdSshell
HgCl2 + H2S + sodium polyphosphate → HgS

HgS + Cd(ClO4)2 + H2S → HgS/CdS

CdScore HgSshell

Cd(ClO4)2 + H2S + sodium polyphosphate → CdS

CdS + HgCl2 + H2S → CdS/HgS

Note: Due to the much lower solubility of HgS compared with CdS
particles result in an exchange of Cd2+ by Hg2+
(CdS)n + mHgCl2 → (CdS)n-m(HgS)m + mCdCl2
 CdS/HgS Mixed Colloids
J. Phys. Chem. 1993, 97, 5333

HgS nanoparticles HgS coated with CdS

Absorption Spectra of Core-Shell CdS
on HgS Nanoparticles
J. Phys. Chem. 1993, 97, 5333

A = HgS
Fluorescence Spectra of Core-Shell
CdS on HgS Nanoparticles
HgS nanoparticles do not
fluoresce

CdS coated HgS nanoparticles

fluoresce:
Possibly due to
removal of traps for
nonradiative recombinations
or
Fluorescence could
arise from band to
band recombination in
HgS core

J. Phys. Chem. 1993, 97, 5333

CdS/HgS Mixed Colloids

J. Phys. Chem. 1993, 97, 5333

 Metal – Metal Core-Shell
Nanostructures
Examples reported in the literature

Au/Ag : J. Chem. Phys. 1964, 41, 3357-3363

Au/Cd : Ber. Bunsenges. Phys. Chem. 1994, 98, 180-189
Au/Pb : Ber. Bunsenges. Phys. Chem. 1994, 98, 180-189
Au/Sn : J. Phys. Chem. 1994, 98, 6931-6935
Au/Tl : Ber. Bunsenges. Phys. Chem. 1994, 98, 180-189
Ag/Pb : Ber. Bunsenges. Phys. Chem. 1992, 96, 754-759
Ag/Cd : J. Phys. Chem. 1994, 98, 6931-6935
Ag/In : Ber. Bunsenges. Phys. Chem. 1992, 96, 2411-2414
Au/Pt : J. Phys. Chem. B. 2000, 104, 2201-2203
 Pt/Au Core-Shell Nanoparticles
Synthesis of Aucore Ptshell Nanoparticles
High T
NaAuCl4 + sodium citrate Au nanoparticles (~ 20 nm)
H2
PtCl 4
2-
+ Au nanoparticles Au/Pt

Synthesis of Ptcore Aushell Nanoparticles

H2
PtCl4 + sodium polyacrylate
2-
Pt nanoparticles (~12 nm)
γ-rays
Pt nanoparticles + K2Au(CN)
MeOH
2 Pt/Au

J. Phys. Chem. B. 2000, 104, 2201-2203

 PtcoreAushell Nanoparticles

Pt nanoparticles 1:1 Pt/Au nanoparticles 1:2 Pt/Au nanoparticles

J. Phys. Chem. B. 2000, 104, 2201-2203

 Pt/Au Core-Shell Nanoparticles
J. Phys. Chem. B. 2000, 104, 2201-2203

Absorption spectra of Pt nanoparticles

before and after deposition of various
amounts of gold. Overall Pt
concentration is 1 x 10-4 M
Concentration of Pt:Au is given on the Absorption spectra of Au nanoparticles
curves before and after deposition of various
amounts of Pt. Overall Au concentration:
3 x 10-4 M Molar of Au:Pt is given on the
curves
 AucorePtshell Nanoparticles

Electron micrograph of Au core particles before (left) and after (right)

deposition of Pt in the ratio 1:2
J. Phys. Chem. B. 2000, 104, 2201-2203
 Metal-Semiconductor Core-Shell
Nanoparticles
Metals can be used as templates to make hollow semiconductor
nanostructures

Fabrication of composite nanoparticles with a large electronic

capacitance, i.e. a large difference in the Fermi level of the core relative
to the conduction band edge of the shell will enable electrons to diffuse
through the shell and be trapped in the core for a long time

Examples:
Au/CdSe: J. Mater. Res. 1998, 13, 905-908
Au/CdS: J. Phys. Chem. B. 1997, 101, 7675
Ag/TiO2: Langmuir 2000, 16, 2731-2735
Au/TiO2: J. Phys. Chem. B. 2000, 104, 10851
TiO2/Ag: Langmuir 1999, 15, 7084-7087
ZnO/Au: J. Phys. Chem. B. 2003, 107, 7479-7485
Au/CdS Composite Nanoparticles

Au nanoparticles Au/CdS composite

nanoparticles
J. Phys. Chem. B. 1997, 101, 7675
 Synthesis of CdS-Capped Au
Nanoparticles

High T
NaAuCl4 + sodium citrate Au nanoparticles (~ 20 nm)

MNA = 2-mercaptonicotinic acid

J. Phys. Chem. B. 1997, 101, 7675
Absorption Spectra of Au/CdS
Nanocomposites

Absorption properties
of Au/CdS are not the
result of a simple
addition of the
spectra of two
nanoclusters, but
rather an influence of
the CdS on the Au.
Au
Au/CdS
Au/MNA
CdS

J. Phys. Chem. B. 1997, 101, 7675

 Emission Spectra of Au/CdS
Nanocomposites

Emission quenching of CdS is

indicative of the occurrence of
electron transfer from excited CdS
into the Au core.

Conduction band energy for CdS =

- 1.0 V vs. NHE

Fermi level of Au = + 0.5 V vs. J. Phys. Chem. B. 1997, 101, 7675

NHE