1

III. 0-dimensional nanostructures

Small size
Monosized
Identical shape or morphology
Identical chemical composition and crystal
structure
No agglomeration
Required features of nanoparticles:
2
Bottom up approaches preferred:
1. Generation of supersaturation
Liquid
Vapor
Solid
2. Nucleation
Homogeneous nucleation
Heterogeneous nucleation
3. Subsequent growth
Confined space (micelle, microemulsion)

Many methods have been developed.
Synthesis of nanoparticles
3
1. Nanoparticles through homogeneous nucleation
Generation of supersaturation is a prerequisite:
Reduction of T of an equilibrium mixture
In situ chemical reaction by converting
highly soluble chemical into less soluble
chemicals.
1.1 fundamental of homogeneous nucleation
4
Reduction of Gibbs free energy is the driving
force for both nucleation and growth.
Two contributions to total Gibbs energy:
1. Phase transformation: supersaturated
solution has high Gibbs free energy. It will be
reduced by segregating solute from the solution.
The change of Gibbs free energy per unit volume
of the solid phase
5
2. Increase in liquid/solid interface surface
energy that will be created when solutes are
segregated.
Assuming a spherical nucleus with a radius of r,
is the surface energy per unit area.
<0 and nucleation occurs spontaneously.
when
(Or T<T
melting
, for physical transformation)
Gibbs free energy change:
6
the newly formed nucleus is stable only when its
radius exceeds a critical size, r*.
Total:
7
Energy barrier that a nucleation process must overcome.
Minimum size of a stable spherical nucleus
3
It also works for supersaturated vapor and a
supercooled gas or liquid
8
To reduce the critical size
Increase gibbs free energy
Increasing the supersaturation
Decrease surface energy
use of different solvent
additive in solution
incorporation of impurities into solid phase
9
10

Thermodynamics: Is nucleation possible ?
(energy minimization)
how small can you prepare?

Kinetics: How fast does it happen ?
(nucleation rate)
how small can you prepare in reality?
11
The rate of nucleation ,
is proportional to
(i) the probability
(ii) the number of growth species per unit volume,
n, which can be used as nucleation centers (in
homogeneous nucleation, it equals to the initial
concentration, C
o
)
(iii) the successful jump frequency of
growth species, from one site to another
12
high initial concentration or supersaturation
(so,a large number of nucleation sites)
low viscosity
low critical energy barrier
To form a large number of nuclei
For a given concentration of solute, a larger
number of nuclei mean smaller sized nuclei.
13
No nucleation in region I
(even above equilibrium C)
Nucleation when
supersaturation/concentration
reaches certain value (to
overcome certain energy
barrier to from nuclei)
Decrease of supersaturation
level.
When the concentration decreases below this specific
concentration, no more nuclei would form. Instead,
particle growth proceed until C falls below equilibrium C
or solubility
14
For the synthesis of nanoparticles with uniform size:
All nuclei should be formed at a short period of time.
- All nuclei are likely to have similar size and will
have the same subsequent growth.
In practice:
to achieve a sharp nucleation, the concentration
of the growth species is increased abruptly to a
very high supersaturation and then quickly
brought below the minimum concentration for
nucleation.
15
1.2 subsequent growth of nuclei
This determines the size distribution.
Two processes:
diffusion
it includes the generation, diffusion and
adsorption of growth species onto the growth
surface.
Surface growth
incorporation of growth species adsorbed on the
growth surface into solid structure.
Different controlling step will lead to different size
distribution.
16
1.2.1 growth controlled by diffusion
If controlled by the diffusion of growth species
from the bulk to the particle surface
Growth rate:
r is the radius of nucleus.
D is the diffusion coefficient of the growth species
V
m
is the molar volume of the nuclei
or
17
Differentiate
with respect to r
0
or
For two particles with initial radius difference ,
the radius difference , decreases as time
increases or particles grow bigger.
The diffusion controlled growth promotes
the formation of uniformly sized particles.
18
1.2.2 Growth controlled by surface process
Fast diffusion, no C gradient
Two mechanisms for surface growth:
Mononuclear growth (growth layer by layer).
Polynuclear growth (surface process is so fast
that second layer growth proceeds before the
first layer growth is complete).
19
Mononuclear growth
Growth rate:
This growth mechanism does not favor monosize
synthesis.
20
Polynuclear growth
The absolute radius difference remains constant
regardless of the growth time and the absolute
particle size.
This growth mechanism also favors the synthesis
of monosized particles.
21
the radius difference as functions of particle size
and growth time for all three mechanisms of
subsequent growth.
22
Some discussions on growth
Usually, the growth of nanoparticles involve all
three mechanisms.
monolayer growth
poly-nuclear growth
Diffusion limited growth

Different growth mechanisms can become
predominant when favorable growth conditions
are established.

e.g. when the supply of growth species is very slow,
predominantly by the diffusion-controlled process.
small nuclei

Large particles
23
to achieve diffusion-limited growth for monosize
synthesis:
low concentration of growth species (dilution after
nucleation stage).
Increase solution viscosity.
Introduction of diffusion barrier such as monolayer on
particle surface.
Controlled supply of growth species by reaction
control.
24
1.3 Synthesis of metallic nanoparticles
Reduction of metal complex in dilute solution
Advantages: easiness of
Stabilization of nanoparticles from agglomeration
Extraction of nanoparticles from solvent
Surface modification
Processing control
Mass production
25
Reduction of metal complex in dilute solution
Various precursors
Reducing agents (KBH4, alcohol, glycol, hydrogen,
ascorbic acid, sodium citrate)
Other chemicals (polymer, surfactant, pH adjusting)
Energy providing (heat, microwave, radiolysis, UV
illumination, sonication)
Objective: to promote/control reduction reactions,
so that it has fast initial nucleation and
subsequent diffusion controlled growth.
26
Au nanoparticles
Heat HAuCl4 aqueous solution to boiling
+
Sodium Citrate (reducing agent and diffusion barrier)
Color change
Excellent stability and uniform size.
A typical approach:
Turkevich method
(>50 years ago)
HOC (COONa) (CH2COONa)2
27
Concentration effect
28
Pt nanoparticles
Mix H2PtCl6+CH3OH+PVA
Reflux at 90C, pH adjustment
Color change
H2PtCl6+2CH3OH
->Pt+2HCHO+6HCl
a). Polymer
29
Mix H2PtCl6+CH3OH+SB12
Reflux at 90C, pH adjustment
Color change
b). surfactant
Other reducing agents: Hydrogen, KBH4, NH2OH
ascorbic acid
30
-
-
-
-
-
-
-
-
Colloid particle
SO
3
-

N
CH
3

CH
3

+
SO
3
-

N
CH
3

CH
3

+
SO
3
-

N CH
3

CH
3

+
SO
3
-

N CH
3

CH
3

+
CH
3

SO
3
-

N
CH
3

+
N
+
CH
3

SO
3
-

CH
3

SO
3
-

N
CH
3

CH
3

+
SO
3
-

N
CH
3

CH
3

+
*Schematic of a Surfactant-stabilized
Colloidal Catalyst Particle
SB12
31
c). Ethylene glycol
Serving as reducing agent and stabilizer.
No need for polymer and surfactant!
Reflux at 140C, pH adjustment
32
Ag nanoparticles
a). Untrasonication of an aqueous AgNO3 at
10C in Ar/H2.
The ultrasound resulted in decomposition of water
into hydrogen and hydroxyl radicals. Hydrogen
radicals would reduce silver ions into silver atoms,
which subsequently nucleate and grow to silver
nanoclusters.
Some hydroxyl radicals would combine to form
an oxidant, H2O2. Use H2 to remove it.
33
b). UV illumination of aqueous solution of AgClO
4
,
acetone, 2-propanol and polymer stabilizer.

Generate ketyl radicals
protolytic dissociation
reduction by radicals
34
Influence of reducing agents
a strong reduction reaction

favors the formation of more nuclei, therefore,
smaller nanoparticles.
leads to big size, in growth period.
a slow reaction may
result in wide size distribution, if it leads to
continuous formation of nuclei.
lead to diffusion limited growth and favors narrow
size distribution, if no further nucleation.

35
abrupt surge of concentration. More nuclei
36
Influence of polymer stabilizer
A strong adsorption would occupy growth sites.
A full coverage would reduce diffusion of growth
species.
Interaction with solute/catalyst/solvent, thereby
contributing to the reaction.
shape
Influence of
polymer/Pt ion ratio
37
Influence of other factors (concentration, T)
Ions that will affect reaction rate.
e.g. for the synthesis of Pt nanoparticles using an
aqueous methanol reduction of H2PtCl6, a high
concentration of chloride ions present in the
reaction mixture promoted monodispersity and
near-spherical shape
PtCl
6
2-
+ CH
3
OH -> PtCl
4
2-
+ HCHO + 2H
+
+ 2Cl
-
Slow supply of Pt atoms favors diffusion
controlled growth.
PtCl
4
2-
+ CH
3
OH -> Pt + HCHO + 2H
+
+ 4Cl
-
Control of pH is also very critical for many reactions
38
Sequence of adding reagent
e.g. Au nanoparticles formation:
HAuCl4+ ascorbic acid+ PDDA
adding AA firstly and followed by
adding HAuCl4 into PDDA
solution
adding HAuCl4 firstly and then
adding AA into PDDA solution
AuCl
4
-
+PDDA will form ion pairs
39
Seeding nucleation
Co
x
Ni
100-x
and Fe
z
[Co
x
-Ni
100-x
]
1-z
were
synthesized by reduction and precipitation from
metallic precursors dissolved in 1,2-propanediol
with an optimized amount of sodium hydroxide
e.g.
The particle formation is initiated by adding
a small amount of solution of K2PtCl4, or
AgNO3 as nucleating agent.
Increased C reduced mean particle size
40
1.4 Synthesis of semiconductor nanoparticles
Non-oxide semiconductor nanoparticles (CaSe,
CdS, InP) are commonly synthesized by

pyrolysis of organometallic precursor(s)
dissolved in anhydrate solvents
at elevated temperatures
in an airless environment
in the presence of polymer stabilizer or capping
material.
41
1). Temporally discrete nucleation is attained by
a rapid increase in the reagent concentrations
upon injection, resulting in an abrupt
supersaturation.
2). Ostwald ripening during aging at increased
temperatures promotes the growth of large
particles at the expense of small ones,
narrowing the size distribution.
3). Size selective precipitation is applied to
further enhance the size uniformity.
To form monodispersed semiconductor particle:
42
e.g. synthesis of InP nanoparticle.

Reaction of InCl and P(Si(CH3)3)3 in
trioctylphosphine oxide (TOPO) with
dodecylamine as capping material at elevated
temperatures in dry box (Ar).
Size selective precipitation can be an effective
way to narrow size distribution
Initial product contains wide size distribution as
it is a slow process in which nucleation and
growth occur simultaneously over long time
scales.

43
InP nanocrystals capped with dodecylamine are
soluble in toluene and insoluble in methanol.
Methanol is added stepwise. The solution is
filtered after each addition, isolating a
narrowed size distribution of nanocrystals,
which become successively smaller throughout
the precipitation series.
44
1.5 Synthesis of oxide nanoparticles
Sol-gel processing
Sol: A stable suspension of colloidal solid particles within a liquid.
Gel: A colloidal suspension of a solid in a liquid, forming a
jellylike material that keeps its shape in a more solid form
than a sol.
Sol-gel processing is a wet chemical route for the
synthesis of a colloidal suspension of solid particles or
clusters in a liquid, and subsequently for the formation of
a dual-phase material having a solid skeleton filled with a
solvent through sol-gel transition.
45

After evacuating the solvent, thin films and coatings,
powders, fibers and membranes can be obtained from the
gels.
The sol-gel process involves the evolution of networks
through the formation of a colloidal suspension (sol) and
gelation of the sol to form a network in a continuous liquid
phase (gel).
Sol-gel is a useful self-assembly process for
nanomaterials synthesis. (particularly oxide nanoparticles)


Advantages: low processing temperature and
molecular level homogeneity
46
47
Precursor: It includes inorganic salts and organic compounds.
Al(NO3)3, Al(OC4H9)3,Si(OCH3)4, Si(OC2H5)4,Ti(OC2H5)4,
Ti(OC3H7)4, Ti(OC4H9)4

Metal alkoxides and alkoxysilanes are most popular
precursors because they react readily with water.

The most widely used alkoxysilanes are tetramethyloxysilane
(TMOS) and tetraethoxysilane (TEOS), which form silica gels.

Alkoxides such as aluminates, titanates, and borates are also
commonly used in the sol-gel process, often mixed with TMOS
and TEOS.
48
Four stages:

Hydrolysis
Condensation and polymerization of
monomers to form nanoparticles
Growth of particles
Agglomeration of particles followed by
formation of networks that extend throughout
the liquid medium resulting in thickening, which
forms a gel
Sol-Gel Formation
49
Condensation results in the formation of nanoscale clusters of
metal oxide or hydroxide, often with organic group embedded
The size of the nanoscale clusters, along with the morphology and
microstructure of the final product, can be tailored by controlling the
hydrolysis and condensation reactions.
50
Hydrolysis and condensation of silica alkoxides are
relatively slow without addition of an external
catalyst. Therefore, acids (HCl, HNO3, HAc, etc.)
and bases (NH4OH, KOH, etc.) are commonly used
to speed up these processes.
51
52
53
Summary of acid/base sol-gel conditions
54
e.g. Stober approach for Silica nanoparticles
First, alcohol solvent,
ammonia, and a desired
amount of water were mixed,
and then silicon alkoxide
precursor was added under
vigorous stirring. The
formation of colloids became
noticeable just in a few
minutes.
55
Various silicon alkoxides with different alkyl
ligand sizes were used as precursors, and various
alcohols were used as solvents.

The reaction rate and particle size were strongly
dependent on solvents, precursors, amount of
water and ammonia.
Reaction rate: Methanol>n-butanol,
Final particle size: Methanol<n-butanol
smaller ligand has faster rate and smaller size
Ammonia gives spherical shape.
(condensation under a basic condition yield 3D
structure instead of a linear chain structure
under acidic condition.)
56
Different precursors have different chemical
reactivities. important for multi-component
colloids synthesis
a). The reactivity of a metal atom is dependent
largely on the extent of charge transfer and the
ability to increase its coordination number.
Reactivity
increases
57
b). For a given metal atom, large or more complex
organic ligand would result in a less reactive
precursor.
<
c). Multiple step sol-gel processing to ensure
hetero-condensation
The stabilization of colloids ->electrostatic
stabilization.
Size control? (low concentration, or controlled release, time)
58
Forced hydrolysis
The simplest method for the generation of
uniformly sized colloidal metal oxides
-- rapid and forced hydrolysis gives an abrupt
supersaturation.
e.g. Stober approach for Silica nanoparticles
(heat the solution before adding TEOS)
Increase T to increase hydrolysis rate.
59
1.6 Solid state phase segregation
Preparation of nanoparticles of metals and
semiconductors in glass matrix.
1. Precursors + liquid glass melt at high T.
2. Rapidly quenched.
3. Upon reheating, metallic ions are reduced to metallic
atoms by certain reduction agents and diffuse through
glass to form nuclei.
4. Nuclei grow further to form nanoparticles.

Metallic atom is not soluble in glass and gains
limited diffusivity with increased T > diffusion
limited growth > monosized particles
60
2.Nanoparticles through heterogeneous nucleation
consider a heterogeneous nucleation
process on a planar solid substrate:
growth species in the vapor phase impinge on
the substrate surface, these growth species
diffuse and aggregate to form a nucleus with a
cap shape

: surface energy
61
Change of Gibbs free energy
Contact angle defined by Youngs equation
62
Area=2tRh
h=R(1-cosu)
63
2
64
Compare homogeneous case
Substitute the geometric constants
wetting factor
u= 180, no wetting, homogeneous case.
u= 0, no energy barrier, the deposit is the same as
substrate.
u<180, wetting factor smaller than 1, -->
heterogeneous is easier
3
3
65
Nanoparticles by heterogeneous nucleation
Surface defects are active nucleation centers due to
high energy state.
To create surface defects on substrate:
thermal oxidation
Sputtering and thermal oxidation
Ar plasma and ulterior thermal oxidation
edge
66
Example: core-shell structure
seed-mediated growth method for Au-Pt catalyst synthesis
Synthesis of core Au
nanoparticles



Deposition of Platinum shell
on Au core

Citrate stabilized Au nanoparticles were
prepared from the reduction of
HAuCl4.3H2O with NaBH4
H2PtCl6 was mixed with aqueous
NH2OH.HCl and heated to 60
o
C, then
the Au hydrosol was added to start the
seed-mediated growth reaction
67
Average particle size (measured and
calculated)
3
2
3 3 3
[ ] and [ / ]
6000

- Pt Au
final
final core core
d nm gr cm
d
d d d


= =
( +

Should
form 1
complete
shell

Pt/Au
molar
ratio
measured
particle
size
(nm)
calculated
particle
size
(nm)
calculated
shell
t hickness
(nm)
specific Pt
surface
area
(m
2
/gr)
0 4.8 - - -
0.5 5.4 5.4 0.3 166
1 6 5.9 0.6 100
2 7 6.7 1.0 65
3 7.5 7.4 1.3 52
4 8.2 8.0 1.6 45

Pt atom diameter: 0.276nm
68
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
-0.4
-0.3
-0.2
-0.1
0.0
0.1
0.2


c
u
r
r
e
n
t

(
m
A
)
E (V vs SCE)
A
B
CV of (A) Au/C and (B) PtAu/C 4:1 in 0.5 M H2SO4 at 50mV/s
Au/C: typical features of
the Au electrode were
observed.
PtAu/C: above features
disappear an Pt oxide
formation/reduction
observed..

Voltammetry can be viewed as a surface sensitive technique, as it reflects only the
electrochemical properties of the surface rather than the bulk electrode
Cylic Voltammetry (CV) of Pt(shell)-Au(core)/C
69
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
-0.20
-0.15
-0.10
-0.05
0.00
0.05
0.10
0.15


c
u
r
r
e
n
t
(
m
A
)
E (V vs SCE)
2:1
1:1
1:2
3:1
Pt:Au
0.7 0.8 0.9 1.0 1.1

CV of PtAu/C with different Pt/Au ratios
Not epitaxial layer growth
Complete coverage for Pt:Au=2:1 and above
70
Core-shell Au-Pd prepared by sonochemical technique.
a: annular dark field scanning TEM
and b: TEM of Au-Pd nanoparticles
NaAuCl
4
2H
2
O and PdCl
2
2NaCl3H
2
O
Stabilized by sodium dodecyl sulfate (SDS)
* T. Akita, et al, Catalysis Today, 131 (2008), 90-97.

Atomic number:
Au (79)
Pd (46)
71
72
Reversible change of core-shell structure*
NO, O2
H2, CO
Rh-Pd system
Pd shell
Rh shell
In reducing (oxidizing) environment, Pd (Rh) shell forms.
The surface energy: Pd < Rh
Pd oxide > Rh oxide
* Gabor A. Somorjai, et al, Science, 322 (2008), 932.
73
3. Kinetically confined synthesis of nanoparticles
Spatially confine the growth so that the growth
stops when the limited amount of source
materials is consumed or the available space is
filled up.
(i) liquid droplets in liquid, such as micelle and
micro emulsion synthesis,
(ii) liquid droplets in gas phase
including aerosol synthesis and spray pyrolysis,
(iii) template-based synthesis,
(iv) self-terminating synthesis.
74
3.1 Synthesis inside micelles or using
Microemulsions (soft template)
by confining the reaction
in a restricted space.
When surfactant C
exceeds CMC, form self
assembly micelle.
Reverse-microemulsion:
Dispersion of water in
organic solvent.
Molecular Packing Parameter
75
3.2 Growth termination
Terminate the particle growth by occupying
growth sites with organic components or
alien ions.
thiophenol
an increasing amount of capping molecules
relative to sulfide precursor resulted in a
reduced particle size.
76
3.3 Template-based synthesis (hard template)
e.g.
Infiltration of precursor into porous polymer
matrix, or zeolite.
Formation of nanoparticle inside the template
by reaction.
Removal of the template
77
Suk Bon Yoon, et. al. Advanced Materials 14 (2002) 19
Paraformaldehye+phenol
78
SEM: Porous silica
TEM: Hollow carbon
BET surface area:
1345 m
2
/g.

Mesopore: 4 nm.
Micropore: 0.8 nm.
Micropore area: 345 m2
External area: 1000 m2
80% Pt/HC
79
3.4 Aerosol synthesis
An aerosol is defined as a suspension of
solid or liquid particles in a gas.
Aerosol processes in material synthesis
can be classified as:
Gas-to-particle conversion
Droplet-to to-particle conversion
80
81
82
83
84
85
86
87
88