Sol-gel Synthesis

of
Nanomaterials
Yu-Guo Guo

Synthesis of Nanomaterials through

Sol-gel Method
Contents
Part I
Part II
Part III

Introduction to the sol-gel method

Basic principles in the sol-gel synthesis
Synthesis of nanomaterials by sol-gel method

Introduction to the sol-gel method

Introduction
Development of the sol-gel synthesis
Several conceptions & definitions in sol-gel synthesis
Synthetic process in the sol-gel method
Apparatus used in sol-gel synthesis
Technical process of sol-gel method
Advantages & Disadvantages of sol-gel synthesis

Introduction

The sol-gel process is a wet-chemical technique (also

known as Chemical Solution Deposition) widely used
recently in the fields of materials science and ceramic
engineering. Such methods are used primarily for the
fabrication of materials (typically a metal oxide)
starting from a chemical solution (sol, short for solution)
which acts as the precursor for an integrated network
(or gel) of either discrete particles or network polymers.

Development of the sol-gel synthesis

In the 1930s, W.Geffcken
used metal alkoxides to
prepare oxide films
In 1846, Ebelmen
found the gelation
phenomenon

After the 1980s, the preparation

of functional ceramic materials
with glass and oxide coatings,
composite oxide ceramic materials

In 1971, Dislich prepared

the SiO2-B2O-Al2O3-Na2OK2O multicomponent glass

In 1975, Yoldas and Yamane

prepared monolithic ceramic
and transparent alumina
membrane

Several conceptions & definitions in solgel synthesis

Colloid: A colloid is a type of mixture in which one substance is

dispersed evenly throughout another. A colloidal system consists
of two separate phases: a dispersed phase (or internal phase) and
a continuous phase (or dispersion medium). Generally, the
gravity of the dispersed phase is negligible, and the interaction
between particles is always a short-range interaction.
Sol: A sol is a colloidal suspension of solid or macromolecular
particles (1 - 1000 nm in size) in a liquid.
Gel: A gel a colloidal system of solid properties, in which the
dispersed substances form continuous and crosslinked networks
within liquid or gas. The content of dispersed phase in the gel is
very low (between 1% to 3%).

Several conceptions & definitions in solgel synthesis

Comparison between sol and gel:
Sol

Gel

Unfixed
shape

Particles in the solid phase can move freely

Particles in the solid phase are fixed in

Fixed shape accordance with certain network structure and
cannot move freely

* The special network structure gives the gel extremely high specific surface area *

Synthetic process in the sol-gel method

1) Use the compound containing components of high chemical
activities as the precursor;
2) Uniformly mix the raw materials in the liquid phase;
3) Carry out hydrolysis and polycondensation reactions so as to form
stable and transparent sol system;
4) Colloidal particles slowly aggregate after the aging of sols to form
gels with three-dimensional network structures, meanwhile, the
solvent without fluidity is filled in the gel network;
5) After various processes such as drying and sintering, materials with
microstructures even nanostructures can be prepared.
Dissolve

Polycondensation

Hydrolysis

Aging

Precursor

Solution

Sol

Gel

Aged gel

Synthetic process in the sol-gel method

Typical precursors: Metal alkoxides & Metal chlorides

(which undergo various forms of hydrolysis and
polycondensation reactions).
Formation of the gel:
The formation of a metal oxide involves connecting the metal
centers with oxo (M-O-M) or hydroxo (M-OH-M) bridges,
therefore generating metal-oxo or metal-hydroxo polymers in
solution.
Thus, the sol evolves towards the formation of a gel-like
biphasic system containing both a liquid phase and a solid
phase whose morphologies range from discrete particles to
continuous polymer networks.

Synthetic process in the sol-gel method

Removal of the liquid phase

The volume fraction of particles (or particle density) in the colloid may be
so low that a significant amount of fluid may need to be removed initially
for the gel-like properties to be recognized.
Approaches: Sedimentation or Centrifugation (more efficient)
After that, a drying process is required to remove the remaining liquid
(solvent) phase, which is typically accompanied by a significant amount of
shrinkage and densification.
Finally, a thermal treatment, or firing process, is often necessary in order
to favor further polycondensation and enhance mechanical properties and
structural stability via sintering, densification and grain growth.

Apparatus used in sol-gel synthesis

2
2

3
3
4
5

7
5

Schematic drawing of the electric

stirring sol-gel synthesis
1.Reflux device 2.Motor stirrer 3.Thermometer
4.Container 5.Hydrothermal equipment

Schematic drawing of the magetic stirring

sol-gel synthesis
1.Container 2.Cover plate for sealing 3.Reaction solution
4.Stirrer 5.Heater plate of the magnetic stirrer
6.Temperature regulator 7.Rotating speed regulator

Technical process of sol-gel method

Sol-gel
Synthetic
Materials

Mechanical mixing of
ultrafines and solution to
form the glue solution

Solution - Solation

Gelation - Shaping

Hydrolysis of metallic
inorganic compounds
or metal alkoxides

Hydrolysis of
organometallic

Curing process

Drying

compounds

Technical process of sol-gel method

Heat treatment

Technical process of sol-gel method

Precursor solution
Water and catalyst

Transparent sol

Film forming process Fiber forming process

Film

Fiber

Pulverization and
collection

Wet gel

Powder

Dried gel

Curing process
Final product
Gel-casting process

Advantages of sol-gel synthesis

Starting materials are in molecular level, and final products

prepared are homogeneous;
Products are relatively higher in purity;
Have rheological behavior, which may be used in the preparation
of products with different applications;
Controllable degree of porosity;
Easy to prepare various shapes;
Cheap and convenient to carry out;
Enable synthesis at a low temperature;
Allow for fine control of the products chemical composition,
especially suitable for preparing multicomponent materials;
Enable small quantities of dopants to be introduced in the sol and
end up uniformly dispersed in the final product;

Disadvantages of sol-gel synthesis

Relatively higher in the cost of raw materials;
Micropores may be left after the synthesis;
Relatively longer in reaction times;
Organic solvents may be harmful to the human
body.

Basic principles in the sol-gel synthesis

Stability principle of colloids - DLVO Theory

The DLVO theory is named after Derjaguin and Landau,
Verwey and Overbeek.

Stability mechanism of sols

Basic principles of the sol-gel synthetic method

Stability principle of colloids - DLVO Theory

Electric double layer & potential

In the sol system, the existence of electrostatic attraction will force the counterions
in solution move close to the particle surface, and repel homo-ions; solid surface
charges and coutercharges in solution may together form the structure of electric
double layer.
The adsorbed ions may firmly bind to the solid surface, therefore, when relative
movement happens between solid and liquid, a small portion of counterions may
slip with the solid, AB plane is the practical sliding plane at the occurrence of
electrokinetic phenomena, and potential is the potential on the sliding plane.
When potential equals to zero, the pH value becomes the isoelectric point.
+

+
+
+
+
+
+
+
+

+ - +- +
- - +
- + + liquid -

Particle Surface charge

+
+
+

Distance x from surface

Stability principle of colloids - DLVO Theory

Interparticle
Van der Waals force

Electric double layer

electrostatic repulsive energy

Interparticle total
interaction energy

VT = V A + VR

A sol is a colloidal system in which solid or macromolecular particles

disperse in the liquid phase, and there exists a considerable large interface in
the sol; therefore, the Gibbs free energy of interfacial atoms is higher than that
of internal atoms, and particles have a tendency of agglomeration to lower the
surface energy.
During the integration of particles, increase the energy barrier required to
overcome in the system may make them stable in kinetics. Generally, there are
three basic ways to increase the energy barrier between particles: (1) surfacely
charged the colloidal particles; (2) utilize the steric effect; (3) utilize the solvent
effect.

Stability mechanism of sols

The surface charge of colloidal particles comes from the selective ionization of lattice
ions in the colloidal particle, or the selective adsorption of ions in the solvent.
For metal oxide hydrosols, H+ or OH- will be preferentially adsorbed. When pH >
PZC (point of zero charge), the surface of colloidal particles will be negatively charged;
otherwise it will be positively charged.
According to the DLVO theory, colloidal particles will be affected by both the
repulsion force from the electric double layer and the long range Van der Waals force,
besides, interactions between colloidal particles may also include intermolecular Van
der Waals force and short range Bonn repulsion force, which is caused by the
overlapping of surface valence electrons.

64n0 Tr02 nx
A
e

n
12H 2

Basic principles of the sol-gel

synthetic method
1. Hydrolysis - condensation reaction of alkoxides

Hydrolysis reaction:
M(OR)n + xH2O M(OH)x(OR)n-x + xR-OH

Polycondensation reaction:
(OR)n-1M-OH + HO-M(OR)n-1 (OR)n-1M-O-M(OR)n-1 + H2O
m(OR)n-2 M(OH)2 [(OR) n-2M-O]m + mH2O
m(OR)n-3 M(OH)3 [(OR) n-3M-O]m + mH2O + mH+

Condensation reaction may be also observed between hydroxyl groups

and alkoxyl groups:
(OR)n-x(HO)x-lM-OH + ROM(OR)n-x-l (OH)x
(OR)n-x(OH)x-1M-O-M(OR)n-x-l (OH)x + R-OH

Basic principles of the sol-gel

synthetic method
1. Hydrolysis - condensation reaction of alkoxides
Conventional alkoxides in sol-gel synthesis

Cation

M(OR)n

Anion

M(OR)n

Si

Si(OCH3)4
Si(OC2H5)4

Ge

Ge(OC2H5)4

Al

Al(O-iC3H7)3
Al(O-sC4H9)3

Zr

Zr(O-iC3H7)4

Ti

Ti (O-iC3H7)4
Ti(OC4H9)4
Ti(OC5H7)4

Y(OC2H5)3

B(OCH3)3

Ca

Ca(OC2H5)2

Basic principles of the sol-gel

synthetic method
2. Hydrolysis - condensation reaction of inorganic salts

Hydrolysis reaction: Mn+ nH2O M(OH)n nH+

Dehydrated gelation

Gelation
Alkalic gelation

Colloidal particles dehydrate,

electrolyte concentration in the
diffusion layer increases, energy
barrier in gelation gradually
decreases

xM(H2O)nz+ + yOH- + aA- MxOu(OH)y-2u(H2O)nAa(xz-y-a)+ + (xn+u-n)H2O

A- acid ions added during the gelation process.
When x=1, mononuclear polymer will form;
When x>1, multinuclear polymer will form;
Mz+ can bridge with ligands by O2-, OH-, H2 or A-.

Basic principles of the sol-gel

synthetic method
2. Hydrolysis - condensation reaction of inorganic salts:
Concentration method & Dispersion method

Sols can be
prepared at
relatively
higher
temperatures
through
controllable
nucleation
effect and
crystal growth.

The metal salts

hydrolyzed quickly
to form gelatinous
precipitates, and
excessive electrolytes
may be washed off,
then strong acid may
be added at
relatively higher
temperatures to
form the sol.

Synthesis of nanomaterials by Sol-gel

method

Synthesis of nanoparticles (e.g.,spheres) through sol-gel

method
Synthesis of nanofibers through sol-gel method
Synthesis of nanofilms through sol-gel method
Synthesis of aerogels through sol-gel method
Synthesis of nanoporous carbon containing LiFePO4
nanoparticles through sol-gel method

Monodisperse silica spheres prepared from hydrolysis

of tetraethyl orthosilicate (TEOS)

SiO2 prepared in Guos group

Synthesis of nanopowders through sol-gel method

Lithium orthosilicate (Li4SiO4) and its solid solution are known as fast Li-ion
conductors. As a CO2 catalytic/sorbent, Li4SiO4 also exhibits excellent
performance. Recently, Li4SiO4 has been selected as one of the most
promising candidates for solid tritium breeding materials in fusion reactors
because of its high lithium atom density and favorable tritium release
behaviors.
In the synthesis of Li4SiO4, traditional solid state reaction or precipitation
methods require high temperature (usually 900 C) and lead to many
problems including volatilization and lack of control of the microstructure and
composition. Also, the combustion method could hardly produce pure Li4SiO4
because of the deficiency of oxygen or the formation of Li2CO3.
The sol-gel method is a preferred choice to synthesize ceramic powders, since
it offers an opportunity for not only synthesizing a material at low
temperatures but also the possibility to control its morphology and
microstructure.

X. Wu et al. Journal of Nuclear Materials, 392 (2009) 471-475

Synthesis of nanopowders through sol-gel method

With LiOHH2O and aerosil SiO2 as the starting
materials and citric acid (C6H8O7H2O) as the
chelating agent, Li4SiO4 powders with particle
size as small as 100 nm were successfully
synthesized at the temperature as low as 675 C.
DSC/TG analysis results of the gel precursors

The sol-gel procedure for the

preparation of Li4SiO4 powders

X. Wu et al. Journal of Nuclear Materials, 392 (2009) 471-475

Synthesis of nanopowders through sol-gel method

SEM images of the Li4SiO4 powders synthesized by

(a) solid state reaction
and (b) the water-based solgel method.
As seen, the samples obtained by solid state reaction (900 C for 4 h) show irregular grains. The
grain size had a wide distribution, mainly ranging from 10 to 20 m with a few grains as large as
30 m. The samples prepared by the water-based sol-gel method (675 C for 4 h) displayed
different morphology. The grains were spherical and the grain size had a homogeneous
distribution. The average grain size was about 100 nm, which was much smaller than that of the
samples obtained by solid state reaction.

X. Wu et al. Journal of Nuclear Materials, 392 (2009) 471-475

Synthesis of nanopowders through sol-gel method

The experimental results showed
that the powders obtained by the
water-based sol-gel process (SG)
possessed excellent sinterability,
exhibiting a linear shrinkage of
5.2% while sintered to 900 C,
more than 3 times that of the
powders obtained by solid state
reaction (SSR). The higher
sinterability was attributed to the
smaller particle size and higher
specific surface area of the
powders. The high sinterability
was beneficial to obtain dense
Li4SiO4 ceramics, which was an
important aspect of the tritium
breeding materials.

Thermal shrinkage behaviors of Li4SiO4 powders fabricated by (a)

solid state reaction and (b) the water-based solgel method.

X. Wu et al. Journal of Nuclear Materials, 392 (2009) 471-475

Synthesis of nanopowders through sol-gel method

The equivalent circuit was composed of a resistance R1 in
series with a component consisting of another resistance R2 in
parallel to a CPE element. As seen from Fig. (a), the grain
interior resistance was comparable for SSR and SG samples, but
the bulk resistance was much lower for the SG samples. The
conductivity values of the bulk conductivity (b) can be
calculated with b = d/SRb, where d is the sample thickness, S,
the area of the electrode and Rb, the bulk resistance. From Fig.
(b), it is clear that The bulk conductivity of the SG sintered
bodies was much higher than that of the SSR samples at the
same testing temperature, and the bulk conductivity enhanced
significantly with the increase of temperature, the conductivity
data are found to be linear and well fit the Arrhenius equation,
bT = Aexp(-E/kT).

(a) Cole-Cole-Diagram of Li4SiO4 ceramics at

300 C, (b) Arrhenius plots of the bulk
conductivity for the Li4SiO4 samples.
X. Wu et al. Journal of Nuclear Materials, 392 (2009) 471-475