Synthesis of Nanomaterials

Nanomaterials deal with very fine structures: a nanometer is a billionth of a meter.

This indeed allows us to think in both the bottom up or the top down
approaches (Fig. 1) to synthesize nanomaterials, i.e. either to assemble atoms
together or to dis-assemble (break, or dissociate) bulk solids into finer pieces until
they are constituted of only a few atoms. This domain is a pure example of
interdisciplinary work encompassing physics, chemistry, and engineering upto
medicine.

Fig. 1: Schematic illustration of the preparative methods of nanoparticles.

Bottom-up and Top-down Syntheses of Nanomaterials

There are two approaches to the synthesis of nanomaterials: bottom-up and top-
down. In the bottom-up approach, molecular components arrange themselves into
more complex assemblies atom-by-atom, molecule-by-molecule, cluster-by-cluster
from the bottom (e.g., growth of a crystal). In the top-down approach,
nanoscale devices are created by using larger, externally-controlled devices to
direct their assembly.

The top-down approach often uses the traditional workshop or microfabrication

methods in which externally-controlled tools are used to cut, mill and shape
materials into the desired shape and order. Attrition and milling for making
nanoparticles are typical top-down processes.

Bottom-up approaches, in contrast, arrange molecular components themselves

into some useful conformation using the concept of molecular self-assembly.
Synthesis of nanoparticles by colloid dispersions is an example of the bottom-up
approach.

The bottom-up approach has been well-known to the chemists for a long time.
This approach plays a very important role in preparing nanomaterials having very
small size where the top-down process cannot deal with the very tiny objects. The
bottom-up approach generally produces nanostructures with fewer defects as
compared to the nanostructures produced by the top-down approach. The main
driving force behind the bottom-up approach is the reduction in Gibbs free energy.
Therefore, the materials produced are close to their equilibrium state.

In spite of the defects, the top-down approach plays an important role in the
synthesis and fabrication of nanomaterials. The present state of nanoscience can be
viewed as an amalgamation of bottom-up chemistry and top-down engineering
techniques.
 Following are mainly the synthetic methods reported so far for the synthesis of
various nanomaterial systems.

Bottom-up Syntheses (Chemical Methods)

1) Sol-gel
2) Precipitation
3) Chemical reduction
4) Thermal decomposition
5) Microemulsion
6) Hydrothermal
7) Chemical Vapor Deposition
8) -ray irradiation

Top-down Syntheses (Physical Methods)

1) Ball milling
2) Laser ablation
3) Electron beam evaporation

Bottom-up processes are discussed below.

1) Sol-gel technique

The sol-gel process, involves the evolution of inorganic networks through the
formation of a colloidal suspension (sol) and gelation of the sol to form a network
in a continuous liquid phase (gel). A sol is a colloidal (the dispersed phase is so
small that gravitational forces do not exist; only Van der Waals forces and surface
charges are present) or molecular suspension of solid particles of ions in a solvent
(Fig. 2a). A gel is a semi-rigid mass that forms when the solvent from the sol
begins to evaporate and the particles or ions left behind begin to join together in a
continuous network (Fig. 2b).

Fig. 2: Photo images of (a) sol, (b) gel.

The precursors for synthesizing these colloids consist usually of a metal or

metalloid element surrounded by various reactive ligands. The starting material is
processed to form a dispersible oxide and forms a sol in contact with water or
dilute acid. Removal of the liquid from the sol yields the gel, and the sol/gel
transition controls the particle size and shape. Calcination of the gel produces the
oxide.

Sol-gel processing refers to the hydrolysis and condensation of alkoxide-based

precursors such as Si(OEt)4 (tetraethyl orthosilicate, or TEOS). The reactions
involved in the sol-gel chemistry based on the hydrolysis and condensation of
metal alkoxides M(OR)z can be described as follows:

MOR + H2O MOH + ROH (hydrolysis)

MOH + ROM M-O-M + ROH (condensation oxolation)

MOH + HOM M-O-M + H2O (condensation olation)

Sol-gel method of synthesizing nanomaterials is very popular amongst chemists

and is widely employed to prepare oxide materials. The sol-gel process can be
characterized by a series of distinct steps.

Fig. 3: Schematic representation of sol-gel process of synthesis of nanomaterials.

1. Formation of different stable solutions of the alkoxide or solvated metal
precursor.

2. Gelation resulting from the formation of an oxide- or alcohol- bridged network

(the gel) by a polycondensation reaction that results in a dramatic increase in the
viscocity of the solution. The kinetics of olation are usually faster than those of
oxolation.

3. Aging of the gel (Syneresis), during which the polycondensation reactions

continue until the gel transforms into a solid mass, accompanied by contraction of
the gel network and expulsion of solvent from gel pores. Ostwald ripening (also
referred to as coarsening, is the phenomenon by which smaller particles are
consumed by larger particles during the growth process) and phase transformations
may occur concurrently with syneresis. The aging process of gels can exceed 7
days and is critical to the prevention of cracks in gels that have been cast.

4. Drying of the gel, when water and other volatile liquids are removed from the
gel network. This process is complicated due to fundamental changes in the
structure of the gel. The drying process has itself been broken into four distinct
steps: (i) the constant rate period, (ii) the critical point, (iii) the falling rate period,
(iv) the second falling rate period. If isolated by thermal evaporation, the resulting
monolith is termed a xerogel. If the solvent (such as water) is extracted under
supercritical or near super critical conditions, the product is an aerogel.

5. Dehydration, during which surface- bound M-OH groups are removed, there by
stabilizing the gel against rehydration. This is normally achieved by calcining the
monolith at temperatures up to 800oC.

6. Densification and decomposition of the gels at high temperatures (T>800oC).

The pores of the gel network are collapsed, and remaining organic species are
volatilized. The typical steps that are involved in sol-gel processing are shown in
the schematic diagram.

2) Precipitation process

Numerous nanomaterials have been prepared via precipitation methods such as

homogeneous precipitation, co-precipitation, etc. Various precipitating agents such
as urea, sodium hydroxide, ammonium hydroxide, and ammonium hydrogen
carbonate are used in the precipitation reactions.

In the precipitation process, a supersaturation of the growth species is created.

The supersaturation can be achieved by a reduction in temperature of a saturated
solution or by a chemical reaction in situ, i.e. the factors effecting the formation of
precipitate are pH, temperature and duration of the reaction. A solution that is in
equilibrium with the solid phase is called saturated with respect to that solid.
However, it is easy to prepare a solution containing more dissolved solid than that
represented by the saturation condition. Such a solution is known as supersaturated
with respect to the dissolved solid. The state of supersaturation is a
prerequisite for all crystallization processes.

The electrostatic repulsion between the particles can prevent the

nanoparticles in the solution against their agglomeration. This electrostatic
repulsion can be caused due to the adsorption of charged species on the
surface of the particles. Also, when charges present on the surface of the
particles there will be repulsion between the particles and agglomeration
will be prevented. These surface charges prevent the particle from
agglomerating and in turn keep the size of the particles small, which is
most important in order to synthesize nanomaterials. The other way is
using capping agents or ligands or surfactants that provide steric
hinderance.

Given below, an example of formation of cobalt hydroxide nanopetals by

precipitation of Co2+ ions using urea as precipitating agent. Reactions
involved are shown below.

3) Chemical reduction

In this method, reducing agents such as sodium borohydride, 1,2-hexadecanediol,

ethylene glycol, hydrazine, etc will be used for the reduction of the metal ions (e.g.
Co2+, Fe2+, Fe3+) to metals.

For example, bi-functional core-shell Fe3O4 Au nanocomposites prepared by

the reduction of Au3+ ions on the surface of Fe3O4 particles using sodium
borohydride, are shown in Fig. 4.
Fig. 4: Schematic representation of the synthesis of Fe3O4 -Au core-shell
nanoparticles by chemical reduction.

Following is another example where silver nanoparticles are prepared using

ethylene glycol reduction method.

In the above reaction, acetate ions formed in the reaction will adsorb on the surface
of silver nanoparticles and control their growth.
4) Thermal decomposition / Solvothermal

In the solvent mediated thermal decomposition method (solvothermal), metal

precursors such as iron oleate, iron pentacarbonyl, nickel acetylacetonate,
manganese acetylacetonate, iron acetylacetonate, etc will be decomposed in
high boiling point solvents (e.g. 1-octadecene, benzyl ether, diphenyl ether,
eicosane, docosane, 1,2-hexadecanediol) at high temperatures (~ 200o -350oC)
to yield nanomaterials.

For example, schematic representation of synthesis of silica-iron oxide

nanocomposites by thermal decomposition method, is shown below.

In the above case, iron oxide nanoparticles were prepared by thermal

decomposition of iron acetylacetonate (metal precursor) in diphenyl ether (high
boiling point solvent) on the surface of silica spheres. Later, phase
transformation of maghemite to hematite on silica surface has also been shown.

Silver acetate can be used for the synthesis of silver nanoparticles by

solvothermal method, as indicated by the following reaction.

Formation of nanoparticles by thermal decomposition process can be

understood as follows. Precursor materials with very low vapor pressure such
as organometallics, decompose at elevated temperatures in the solvent to
produce a condensable material. The hot atoms of the evaporated matter lose
energy by collision with the molecules of the solvent and undergo condensation
into small clusters via homogeneous nucleation. Thus formed clusters will grow
in the solvent to form nanoparticles. This growth can be controlled by in situ
capping agents or the surfactants which can be added externally.

Solid-state thermal decomposition can also followed for the preparation of

nanomaterials. In this process, the metal precursor taken in a crucible will be
fed into the furnace. A schematic representation of solid state thermal
decomposition process is shown in Fig. 5.
 Fig. 5: Schematic representation of gas phase process of synthesis of single
phase nanomaterials from a heated crucible.

5) Microemulsion technique

Micro-emulsion method is one of the recent and ideal techniques for the
preparation of inorganic nano-particles. Oil and water are immiscible and they
separate into two phases when mixed, each saturated with traces of the other
component. An attempt to combine the two phases requires energy input that
would establish water-oil association replacing the water-water/oil-oil contacts.
The interfacial tension between bulk oil and water can be as high as 30-50
dynes/cm. This can be overcome by the use of surface-active molecules known as
surfactants. Surfactants contain water-loving (hydrophilic) and oil-loving
(lipophilic) moieties. Owing to this characteristic, they tend to adsorb at the water-
oil interface. If enough surfactant molecules are present, they align and create an
interface between the water and the oil by decreasing the interfacial tension.

An emulsion is formed when a small amount of an appropriate surfactant is

mechanically agitated with the oil and water resulting in a two-phase dispersion
where one phase exists as droplets coated by surfactant that is dispersed throughout
the continuous, other phase. These emulsions are milky or turbid in appearance due
to the fact that the droplet sizes range from 0.1 to 1 m. As a general rule, the type
of surfactant used in the system determines which phase is continuous. If the
surfactant is hydrophilic, oil will be emulsified in droplets throughout a continuous
water phase. The opposite is true for more lipophilic surfactants. Water will be
emulsified in droplets that are dispersed throughout a continuous oil phase.

Emulsions are kinetically stable, but are ultimately thermodynamically

unstable, and will begin to separate back into their two phases. The droplets would
merge together, while the dispersed phases will sediment. At this point, they
degrade back into bulk phases of pure oil and pure water with some of the
surfactant dissolved preferentially in one of the two.

Emulsions versus Microemulsions

If a surfactant possessing balanced hydrophilic and lipophilic properties is used in

the right concentration, a different oil and water system will be produced. The
system remains an emulsion, but exhibits some characteristics that are different
from the milky emulsions discussed earlier. These new systems are
microemulsions. The interfacial tension between phases, amount of energy
required for formation, droplet sizes, and visual appearance are only a few of the
differences seen when comparing emulsions to microemulsions.
 Hence, microemulsions can be defined as homogenous, transparent,
thermodynamically stable dispersions of water and oil, stabilized by a surfactant,
usually in combination with a co-surfactant (Fig. 6).

Fig. 6: A schematic view of formation of Microemulsion.

The major differences between emulsions and microemulsions are given in the
following table.
Types of microemulsions

Microemulsions are of 3 types. They are

i) O/W microemulsion (oil in water)

ii) W/O microemulsion (water in oil)
iii) Bicontinuous Microemulsion

Oil-in-water (o/w) microemulsions are droplets of oil surrounded by a

surfactant (and possibly co-surfactant) film that forms the internal phase
distributed in water, which is the continuous phase. Water-in-oil
microemulsions are made up of droplets of water surrounded by an oil
continuous phase. These are generally known as reverse-micelles.Bi-
continuous microemulsion where in micro domains of oil & water are
inter dispersed within the system. In all the three types of
microemulsions, the interface is stabilized by an appropriate
combination of surfactants and/or co-surfactants. The structures of three
microemulsions are shown in Fig. 7.

Fig. 7: Three structures of microemulsions

For example, formation of nanoparticles in W/O Microemulsion system can

be explained as follows.

When the microemulsions material including reactants are mixed together,

reactants exchange takes place during the colliding of water droplets in
microemulsion. The reactant exchange is too fast and precipitation reaction
occurs in the nanodroplets, which is followed by nucleation, growth, and
coagulation of primary particles, resulting in the formation of the final
nanoparticles surrounded by water and/or stabilized co-surfactants. Because the
exchange of aqueous contents between the Microemulsion droplets or the
intermicellar material exchange is closely related to the formation process of
nanoparticles in reverse micelles, it is necessary to consider how the
intermicellar exchange influences various aspects of the nanoparticle formation.

Fig. 8: Possible mechanisms of nanoparticles formation by micro-emulsion

route.

As shown in the Fig. 8, at the first route, reactant diffusion is taken place
through oily phase into aqueous droplets including the second reactant. While
the particles achieve their final size, molecules of surfactant stick to particles
surface, and cause their durability, stability and maintenance in a certain level
and prevent more growing of particles. On the other hand, reactant ions
exchange may be occurred because of coalescence of two droplets with each
other (second route). In this case, the contact of reactants and subsequent
reaction can be regarded as a number of sequential steps:

1. Diffusion and convection to bring the emulsion droplets together,

2. Surfactant layer opening and coalescence,

3. Diffusion of the solubilizate molecules in the temporary dimeric aggregate,

4. Reaction between solubilizate molecules,

5. Nucleation and crystal growth of precursor particles, and

6. Decoalescence to return as smaller droplets.