Asian Journal of Chemistry; Vol. 30, No.

7 (2018), 1405-1412

ASIAN JOURNAL OF CHEMISTRY

https://doi.org/10.14233/ajchem.2018.20845

REVIEW
The Sol-Gel Method: Pathway to Ultrapure and Homogeneous Mixed Metal Oxide Nanoparticles

M. SHARMA*, M. PATHAK and P.N. KAPOOR

Department of Chemistry, Miranda House, University of Delhi, Delhi-110 007, India

*Corresponding author: E-mail: [email protected]

Received: 31 December 2017; Accepted: 22 April 2018; Published online: 31 May 2018; AJC-18903

This article includes an overview of current research on metal oxides and mixed (heterobi-) metal oxides prepared by sol-gel method
using variety of precursors which created interest among scientists and technologists due to their structure, reactivity as well as application
in almost every field of science. Sol-gel method is a soft-chemistry method requires mild reaction conditions, less equipments as well as
produces materials with ultra purity and therefore, widely used as compared to other methods. Authors have explained hydrolytic sol-gel
method with examples in the first section and compared the method with conventional solid state method. This section is further divided
into subsections explaining the process using metal salts such as chlorides, nitrates, etc. and metal-organic compounds as precursor with
chelating ligands, polyols, etc. The importance of using heterometallic alkoxides as precursor rather than using two different metal
precursors is also explained and finally the new advancement in sol-gel method.

Keywords: Hydrolytic sol-gel, Metal oxide, Mixed metal oxide, Sol-gel, Nanoparticles.

INTRODUCTION sol-gel method, etc. Among these methods, sol-gel method offers
many advantages over conventional heating method (solid-
Over past few years, sol-gel method have been attracted state method) viz., (a) high purity and homogeneous starting
key attention among scientists and technologists due to the wide materials give high purity and ultra homogeneous product,
applications of metal oxide in almost every areas of science (b) oxides prepared at much lower temperature and show greater
such as medical science, life science, material science, nano- homogeneity than prepared by traditional processes such as
science, etc. Earlier, metal oxides were prepared by mixing heating the mixture of oxides around 1100-1300 ºC. Hence
two or more metal powder reactants followed by heating (furnace prevents air pollution and save energy and, (c) product of desired
heating) to obtain desired product. But this method had some forms (monolith fibres, films, powder) can be obtained using
drawbacks which include inhomogeneity of starting material, controlled conditions.
lack of complete conversion to desired product, high tempera- Sol-gel method has a long history, starting with synthesis
ture required, release of ash particles which create air pollution of glass like material about 170 years ago. The term "Sol-Gel"
and difficult to control the morphology of the particles. Recently, was first proposed by Graham in 1864 [14] while doing research
solid state reaction has been used for the preparation of metal on silica sols, but actual sol-gel experiment was first carried out
oxides using their hydrated metal salts with either NaOH or by Ebelman [15] in 1846 when he observed that on exposure
NH4HCO3 in the solid form. Han et al. [1] prepared various of atmospheric moisture, Si(OEt)4 was converted into "glass
monometallic (Zn, In, Bi and Sn) oxides using solid state method like material". Later on, this process was used in the 1930 by
by mixing their chlorides with NaOH at room temperature the Schott glass company in Germany to produce metal oxides.
whereas Woodfield et al. [2] prepared several transition metal Thousands of papers, books and reviews [16-29] have been
oxides such as Fe, Cu, Ag, Zn, Mn, Co, Ni, Pd, Y, etc. by solid published on sol-gel method. A new journal "Journal of Sol-
mixing of their chlorides or nitrates and NH4HCO3 at room gel Science and Technology" has been launched since 1993,
temperature and characterized them by various techniques. in which the significance of this simple technique has been emp-
A wide range of solid, solution and vapour phase techni- hasized by Sakka [30] in1995. This method is not only for the
ques are available in literature for preparation of metal oxides preparation of metal oxides but also for non-oxide materials
include co-precipitation [3-5], hydro- and solvo-thermal method such as nitrides, carbides, sulphides, fluorides, etc. In present
[6-9], sonochemical [10,11], microemulsion method [12,13], review, our emphasis is on the preparation of metal oxide which
1406 Sharma et al. Asian J. Chem.

is basically an ionic bonded compound having electrostatic inter- xides and suggested that these can be used as precursors for
action between positively charged metal ions and negatively mixed metal oxide. Heterometallic alkoxides have stronger
charged oxide anions. In metal oxides, s-orbitals are completely M-O-M′ bond. These will certainly produce ultra homogeneous
filled which makes them thermally and chemical stable and and pure mixed metal oxide, which can be used in electronics
presence of vacant d-orbitals makes them excellent catalysts especially in semiconductors where ultra purity is required.
and their use in electronic devices. Because of their good electro- Hydrolysis and condensation: The main steps involved
chromic and optical properties, super-conductivity as well as in this method using metal alkoxide as precursor are hydrolysis
high band gap, metal oxides exhibit wide range of applications and condensation. The first step is hydrolysis and partial conden-
in the area of cosmetics [31,32], electroceramics [33,34], colour sation which results in the formation of homogeneous solution
pigments [35,36] in glass and ceramic industry, catalysis [37- (without precipitation). This homogeneous solution with chain
39], batteries [40,41], water and air purification [42-44], removal like material called sol on mixing precursor, water, alcohol and
of heavy metal ions [45,46], decontamination of chemical warfare with or without catalyst. A sol is actually a colloidal suspension
agents [47-49] and hence, their commercial value is increasing of solid particles in liquid. This colloidal suspension (sol) on
tremendously. Large amount of literature is available on mono- aging undergoes polycondensation to form thick, viscous or
metallic oxides but less work has been done on the preparation gelatinous material known as gel. High molecular weight inter-
of mixed metal oxides. Mixed metal oxides have improved mediates in sol lead to the formation of cross-linked three dimen-
properties as compared to monometallic oxides. Now-a-days, sional gel containing metal-oxygen-metal or metal-hydroxy-
these materials are prepared in nanosize rather than bulk material. metal bond. Gel is a two-component system that consists of a
Nanoparticles are those particles whose one of the dimensions continuous solid and fluid phase of colloidal dimensions. Gel
(length, width or diameter) is in the range of 1-100 nm. These consists of two parts one is solid part which contain three dimen-
nanoparticles exhibit unique chemical and physical properties sional cross linked high molecular weight material full with
because of their high surface to volume ratio. They show excellent solvent, second part is the liquid part i.e. solvent which is filled
properties as compared to properties of same oxide in bulk. in the vacant space (pores) between the solid part. Method of
Two types of sol-gel methods are available in the literature removal of solvent from the gel strongly affects the properties
based on the solvent used. Non-hydrolytic (non-aqueous) sol- of oxidic material. Removal of solvent from gel is done either
gel (NHSG) method uses organic solvent whereas hydrolytic by evaporation or by supercritical drying (Fig. 1). When solvent
(aqueous) sol-gel (HSG) method, as name suggests water is used is removed by simple evaporation at ambient temperature, the
as a solvent. In this review, authors have explained hydrolytic pores shrink which result in the formation of xerogel [69], which
sol-gel method in detail using all possible precursors with exam- on calcination forms dense ceramic or glass, whereas on drying
ples in the following sub-headings. under supercritical conditions results in the formation of an
Hydrolytic (aqueous) sol-gel method (HSG): Hydrolytic extremely porus form of light material called aerogel (Fig. 1).
sol-gel method method can be defined as the formation of Last step of HSG method is calcination or sintering by which
metal oxide by some chemical reactions including hydrolysis surface M-OH group can be removed by heating.
and condensation in aqueous medium under mild condition Prof. Pierre-Gilles de Gennes, a Nobel prize winner (1991)
followed by thermal treatment. In this process, precursor/s as in Physics, wrote a famous book "Scaling concepts in polymer
source of cations of required oxide, water as hydrolyzing agent, Physics" (Cornel University Press, 1979). In that book, he ment-
alcohol as solvent and acid or base as a catalyst or without ioned sol phase as "polymer solution" and conversion of sol
catalyst are mixed together nearly at room temperature. to gel as "sol-gel transition". Earlier, HSG method was used
Precursors: In conventional heating method, the precursor for the preparation of dense and bulk material. Now-a- day, this
minerals used were obtained by digging out from earth. These method is vastly used in the preparation of mixed metal oxide
minerals contained mixture of compounds, whereas in HSG nanoparticles as their activity is enhanced many times because
method, precursors used are synthetic chemical precursors high surface to volume ratio. One of the highly attractive features
which are pure and reproducible in their composition. Generally, of sol-gel process is the formation of material of desired physical
in sol-gel method, precursors used are either inorganic metal forms such as monoliths [70], films, fibers, monosized powders,
salts such as chlorides, sulphates, nitrates, soluble inorganic oxide spheres, etc.
or metal organic compounds (containing M-O-C bond) such Hydrolytic sol-gel method occurs in two ways depending
as alkoxides, acetylacetonates, carboxylates, acetates, etc. From on the nature of precursor. With inorganic metal salt as precursor
all possible precursors, metal alkoxides are considered as suit- in aqueous medium form a complicated condensed species on
able precursor mainly due to their easy purification, solubility changing the oxidation state, temperature and adjusting pH of
in organic solvents, high volatility and their extremely facile the solution. Furthermore, the role of counter ion is not exactly
hydrolyzability. Purification is generally carried out by distill- known which can change the morphology and chemical composi-
ation or recrystallization. Earlier, mixed metal oxide by sol-gel tion of the final metal oxides. Removal of these counter ions
method were prepared by complaxation of two homometallic from metal oxide is also very difficult. Many drawbacks using metal
alkoxide precursors but later on preparation of heterometallic salts as precursors for oxide preparation can be avoided by using
alkoxides [50-59] has opened the possibility of using it as "single metal organic precursors. In another method, precursor is metal
source precursors" and give ultra homogeneous mixed metal organic compound such as metal alkoxides or their derivatives.
oxide. Mehrotra et al. [60-68] prepared alkoxides of most of Because of extremely hydrolyzable nature of metal alko-
the elements in the periodic table and published several articles, xides, Mehrotra et al. [71,72] suggested oxo-alkoxides as better
books and reviews on homo, hetero (bi, tri, tetra)-metallic alko- precursors for the preparation of mixed metal oxide. They
Vol. 30, No. 7 (2018) The Sol-Gel Method: Pathway to Ultrapure and Homogeneous Mixed Metal Oxide Nanoparticles: A Review 1407

Solution of precursor using

water

Hydrolysis and
condensation

precipitation spinning
Powder Sol Fibre

aging coating

Gel Xerogel Film

supercritical
drying evaporation
heating

Aerogel Xerogel Dense Film

heating

Glass
Fig. 1. Scheme showing the formation of variety of forms by sol-gel process

called alkoxides and oxo-alkoxides as "single source precursors" high. But for less reactive metals, rate of hydrolysis can be
for preparation of mixed metal oxide. Kapoor et al. [73,74] as controlled by pH. In basic solution, reaction move in the
well as other researchers [75-78] also prepared mixed metal forward direction with the formation of oxo-bridged complex
oxide using alkoxides or oxo-alkoxide precursor. whereas in acidic solution, hydrolysis is either prevented or
Hydrolytic sol-gel using metal salts as precursor: Metal there will be a hydroxyl complex formation occur.
salts (chlorides, sulphates, nitrates, etc.) in aqueous medium Aqueous solution of many metal salts is very stable. Their
form hydrated species by coordination with water and form solution is homogeneous and does not resemble with gel. On
hydrated metal cation. This occurs via coordination of electrons heating or drying in air results either the formation of original
to bonding orbitals of metal ion. In the case of transition metals, metal salt or amorphous hydroxide/oxide with irregular particles.
electron density is transferred to vacant d-orbitals. This weakens To avoid this, small molecules such as chelating ligands or gelators
the O-H bond by the removal of H+ with the formation of hydroxo such as EDTA, citric acid, tartaric acid [79], glycolic acid [80],
species. Hydrated metal cation acts as Lewis acid hence undergo oxalic acid [81], synthetic [82] as well as biopolymers such as
olation (formation of metal-hydroxy-metal bond) and oxolation starch [83], chitosan [84], dextran [85], etc. and synthetic polymers
(formation of metal-oxy-metal bond) which results ultimately are added with metal salt. These chelating ligands form stable
in the formation of polymeric oxides in the solution. The exact complex with metal ion and the resulting homogeneous solution
series of reactions takes place in aqueous medium are complex. which resemble with gel. Removal of solvent from the solution
It may involve the formation of following hydrated species results in the formation of glassy solid which on heating give
such as aquo [M(H2O)n]z+, hydroxo [M(H2O)n(OH)m-n]z+ and more ordered metal oxides rather than precipitate. More detail
oxo [M(H2O)n(O)m-n]z+ ligands, etc. In these reactions, basic information was explained by Livage et al. [86].
aquo species [M(H2O)n]z+ displaces water from same neighbouring Citric acid, a weak tribasic acid, is the most common, low-
species with the formation of hydroxo- [M(H2O)n(OH)m-n]z+ cost and easily available gelator used in sol-gel method with
species and proton is released in aqueous medium. Hydroxy metal nitrates. In the preparation of metal oxides, metal salt
group in above species is bridged between two hydrated metal especially metal nitrate is mixed with citric acid and heated to
complexes [(H 2 O) n M(OH) M(H 2 O) n ] (2z-1)+. Subsequently, form viscous gel which on pyrolysis in air affords crystalline
deprotonation of hydroxyl species led to the formation of M- metal oxide powder. By this method, binary, ternary and
O-M bond. Polymerization in aqueous medium rarely proceeds quaternary metal oxides can also be prepared. Generally, type
smoothly, hence produce heterogeneous metal oxides. If metal of materials obtained by this method is porus and spongy because
in salt is more reactive then rate of hydrolysis will be very large amount of gases released on heating nitrates with organic
1408 Sharma et al. Asian J. Chem.

material. Some authors reported the use of ammonia and Pechini method: Pechini [93] developed this method for
ethylene diamine as base to modify the pH of the solution and to the synthesis of lead niobates and titanates. In a typical reaction,
enhance the complexation between metal ion and citrate. The aqueous solution of metal salt in the first step mixed with α-
pH of the solution has an important role in the synthesis to hydroxy carboxylic acid such as citric acid, tartaric acid, etc.
prevent the precipitation of hydroxides and stabilize the metal- or EDTA as chelating ligands to form complex. Stability of
citrate complex. Yue et al. [87] reported the synthesis of NiCuZn complex depends on pH and concentration of chelating ligand.
ferrite using nitrate/citrate precursors affords porus and more Most of the transition metals form stable complex with citric
open metal oxide at higher pH. The main advantage of this acid but some metals like barium does not form stable complex
method is the homogeneity of the starting material. Morphology hence an additional complexing agent EDTA also added. Formed
of nanoparticles is dependent on the concentration of reactants complex is then heated with polyol such as ethylene glycol
[88], pH, nature of the solvent, type and concentration of additive (Fig. 3) to form homogeneous gel. This is the key step of this
temperature of the reaction medium as well as pre- and post-heat method [94] i.e. trans-esterification (Fig. 4) which occur between
treatment to the material which has been proved in literature citrate complex and ethylene glycol and form covalently bonded
by their SEM studies. Some literature reported the synthesis polymeric network in which metal ions are trapped. The purpose
of ceramic/carbon composites carbon/FePO4 [89], an important of adding ethylene glycol is to form more controlled growth
cathode material for lithium ion batteries, using citrate method of ceramic materials by delaying thermal decomposition of
in inert atmosphere where citrate provides the carbon source. In organic surrounding. Recently, it has been observed that a mix-
citrate method, metal nitrates are preferred over other metal salts ture of -OH containing, poly(vinyl alcohol) and poly(ethylene
because of very sharp mass loss step with an exothermic peak glycol) proved good complexing agents as compared to carbo-
is involved in thermogravimetric analysis using nitrate/citrate xylic acid for the preparation of homogeneous oxide material
precursor. The mass loss occurs mainly at around 200 ºC in DTA such as indium tin oxide [95] and BiFeO3 [96].
which is associated with fast and self-propagating combustion
where counter ion, nitrate and citrate act as oxidant and organic CO2H CO2H
+ H2O
fuel, respectively. OH OH
OH OH
In order to get homogeneous gel, some researchers used CO2H CO2H
synthetic polymers or polyols such as poly(vinyl alcohol) [82], +
poly(vinyl pyrrolidone) [90], triethylene glycol [91] and poly- O OH HO O O
(ethylene glycol) [92]. Functional groups present in polymers
Fig. 4. Trans-esterification reaction between citric acid and ethylene glycol
have a strong tendency to form complex in which metal is homog-
eneously stabilized within the matrix. Cai et al. [91] prepared
Homogeneous gel is dried at 110-150 ºC to remove water
magnetite nanoparticles (Fig. 2) by using triethylene glycol
to get polymeric resin. During drying, precipitation is prevented
which acted as reducing agent, high boiling solvent as well as
otherwise, it will damage the homogeneity of the final product.
stabilizer to prevent agglomeration of nanoparticles.
Metal oxidic material is obtained after heating in furnace below
400 ºC where all organic part decomposes. Earlier, the excess
of polyol was added which required high temperature to remove
large amount of organic molecules but now a days, polyol is
added in the same ratio with that of carboxylic acid. Farbun et al.
[97] reported the change in the morphology of ZnO (Fig. 5)
with the change in the concentration of polyol [98].
Size of the final product particles and the stability of metal
citrate complex is also dependent on pH. Many scientists used
ammonium hydroxide, ammonia and other base used to optimize
pH. Low pH in result in protonation of citrate complex whereas
high pH lead to the formation of metal hydroxide precipitate.
Fig. 2. TEM and HRTEM images of magnetite NPs prepared by SG method.
Reproduced from [Ref. 91] with the permission of The Royal Society Abrue (Jr.) et al. [99] prepared Pb(Zr0.52Ti0.48)O3 using urea as
of Chemistry a base to rise the pH which slowly released ammonia to form

Fig. 3. Formation of MO by Pechini method {reproduced from [Ref. 94])

Vol. 30, No. 7 (2018) The Sol-Gel Method: Pathway to Ultrapure and Homogeneous Mixed Metal Oxide Nanoparticles: A Review 1409

Rate of hydrolysis is not same for all metal alkoxides. It

depends on the electronegativity of central metal, its ability to
increase coordination number, steric hinderence of alkoxy
group and molecular structure (whether monomeric or poly-
meric) of metal alkoxides. Generally, coordinatively unsaturated,
monomeric alkoxides with small or less sterically crowded
alkoxy group undergo fast hydrolysis. According to Livage
et al. [86], the rate of both hydrolysis and condensation in
tranition metal alkoxides is five times higher than in silicon
Fig. 5. SEM images of MO Nps prepared by using different ratio of ethylene
glycol: citric acid: metal ion. Reproduced from Ref. [98], copyright alkoxides. In transition metals, low electronegativity and presence
(2012) ACS of vacant d-orbitals make metal a highly electrophilic centre.
Transition metals are coordinatively unsaturated hence increase
their coordination number by several numbers when reacted
much smaller crystallites. This method not only used for the
with water. As a result, transition metal alkoxides are much more
preparation of metal oxides but also carbides.
reactive.
Advanced Pechini method has been reported by some group
Precipitation during hydrolysis results due to high react-
of scientists [100], where they had prepared YBCO super-
ivity of alkoxides towards water which can be prevented by
conductor YBa2Cu3O7-x by replacing citric acid by tartaric acid
slowing down the hydrolysis process. This can be done by carry-
or EDTA. This resulted in the formation of homogeneous and
ing out ligand exchange reaction [50,53,78]. In ligand exchange
larger particles which indicated that branching in polyester is
reactions, alkoxy group is replaced either by sterically more
responsible for altering the particles size [101].
crowded group (such as 2-methoxyethanol, tert-amyl alcohol,
Hydrolytic sol-gel using alkoxides as precursor: Metal
tert-butyl alcohol, etc.) or by chelating ligand (diethanolamine,
alkoxides M(OR)n are versatile molecular precursors for sol-
triethanolamine, β-diketones, etc.) which not only controls the
gel synthesis of metal oxides. Many alkoxides are soluble in
reactivity but also sometimes solubilize the metal alkoxides.
organic solvents, volatile and highly reactive towards nucleo-
Only few number of papers has been reported for the prep-
philic attack. Metal alkoxides are highly moisture sensitive
aration of mixed metal oxides using heterobimetallic alkoxides
compounds. They readily form precipitate rather than gels
and oxo-alkoxides [71-78] as precursors. Heterometallic alkoxides
when water is added. Hydrolysis undergoes by SN2 mechanism.
undergo hydrolysis via ligand exchange reaction and form
In hydrolysis, water is an essential solvent which initiate the
alkoxy-hydroxy sol and gel on aging. Centrifugation followed
reaction by coordinating itself through oxygen which contains
by heating gives ultra-homogeneous mixed metal oxides. Alter-
partial positive charge to the central metal centre. This coordi-
natively, two different metal alkoxides upon hydrolysis followed
nation causes instability in precursor molecule and imme-
by condensation gives M-O-M′ moiety (reaction 4).
diately undergoes transfer of proton from oxygen of water to
oxygen of alkoxy group. Cleavage of σ-bond between metal M(OR)x–n(OH)n + (HO)n(RO)x–nM′ →
and oxygen in M-OR then occurs by the addition of proton (OR)x–nM–O–M′(OR)x–n + H2O (4)
from water. Both steps (proton transfer and cleavage) takes Recent advances in sol-gel chemistry: Although this
place simultaneously, led to the formation of M-OH bond and method is considered to be almost ecofriendly but scientists
release of water. In HSG method, water is added just to initiate modified the process according as per their requirements. For
the reaction. Subsequent condensation step produces water example, fractures appear in the preparation of monolith silica
itself. Both hydrolysis and condensation are chain reactions. gel so conventional heating was shifted to microwave. Some
Very less amount of water is needed which depends upon the advancements in sol-gel methods are as follows:
amount of reactant. Addition of large amount of water may Conventional to microwave heating: In HSG method,
get precipitation immediately, which then difficult to form heating is required for the conversion of gel into desired material
homogeneous metal or mixed metal oxides. which is done either in air or in furnace. This takes more time
≡M–OR + H2O → ≡M–OH + ROH hydrolysis (1) with high energy consumption, sometimes reaction of gel with
crucible may occur as well as inhomogenity in heating which
≡M–OH + HO–M≡ → ≡M–O–M≡ + H2O oxolation (2) may afford inhomogenity in product. Therefore, conventional
≡M–OH + RO–M≡ → ≡M–O–M≡ + ROH alkoxolation (3) heating methods were shifted to modern microwave method.
Now a days, microwave assisted method is being used for the
Number of alkoxy group replaced by -OH group depends preparation of ceramic materials. The difference between conv-
upon the amount of water added forming -M(OH)x(OR)n-x. entional and microwave method is that in microwave assisted
Terminal alkoxy groups in precursor hydrolyse first. Conden- method reactants are heated by energy conversion which increases
sation reaction takes place by olation, oxolation or alkoxola- temperature of the reaction mixture very fast, uniformly as
tion. Olation is the condensation step in which hydroxyl group well as the heat is generated internally, whereas in conventional
is bridged between two metal atoms. There are various types method heating is done by energy transfer and requires external
of hydroxyl bridge forms reported in literature [86]. In general, source. For the first time, Komarneni and Roy [102,103] used
smaller the charge, larger the size of metal, greater will be the the microwave in liquid state synthesis for titania gel spheres.
rate of olation. Oxolation (reaction 2) is the condensation step Generally, in the preparation of monolith gel cracks appear
in which oxo bridge is formed between two metal centres. during aging and drying. But using microwave [104] not only
1410 Sharma et al. Asian J. Chem.

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