Journal of Sol-Gel Science and Technology 35, 175181, 2005

c 2005 Springer Science + Business Media, Inc. Manufactured in The Netherlands.

Sol-Gel Synthesis of Nanoscaled Spinels Using Propylene Oxide

as a Gelation Agent
HONGTAO CUI, MARCOS ZAYAT AND DAVID LEVY
Instituto de Ciencia de Materiales de Madrid, C.S.I.C, 28049 Cantoblanco, Madrid, Spain
htcui@icmm.csic.es
marcos.Zayat@icmm.csic.es
d.levy@icmm.csic.es

Received October 14, 2004; Accepted March 31, 2005

Abstract. Spinel nanoparticles of CoAl2 O4 (blue), CoCr2 O4 (bluish green), ZnFe2 O4 (brown) and CuCr2 O4
(black) were synthesized by a sol-gel route with propylene oxide as a gelation agent. This method has proven to be
an effective route to synthesize mixed oxide nanoparticles, especially for that with one of metal ion having a formal
charge of less than +3. Transmission electron micrographs show the small particle size (less than 60 nm) of the
four pigments and their narrow particle size distributions.
Keywords: sol-gel, nanoparticles, mixed oxide, epoxide

1.

Introduction

Mixed oxides with spinel structure (AB2 O4 ) are important inorganic metalloid materials, widely used as
catalysts [1], cathode materials [2], heat-resistant pigments [3], etc. Spinels are usually synthesized by
the conventional high temperature method of solidstate chemistry [4], which results in spinel particles with low surface areas. In order to synthesize
spinels with high surface area, different wet chemistry
techniques have been attempted such as coprecipitation [5], polymeric gel [6], hydrothermal method [7],
microemulsion [8], heterogeneous precipitation [9],
sonochemical method [10], combustion [11], sol-gel
[12], etc. These methods allow a substantial reduction
of the temperature of processing, minimizing therefore, the undesired aggregation of the particles during
calcination.
Among these methods, the sol-gel process shows
promising potential for the synthesis of mixed oxides,
owing to its high purity, good chemical homogeneity,
To

whom all correspondence should be addressed.

low calcination temperatures, etc. The major disadvantages of using the metal alkoxide based sol-gel process are its moisture sensitivity and the unavailability of suitable commercial precursors especially for
mixed-metal oxides. The sol-gel synthesis of mixed
oxides from alkoxide mixture usually suffers from the
different hydrolysis susceptibilities of the individual
components and the benefits of improved homogeneity can be lost during the hydrolysis of the alkoxides,
which may ultimately lead to component segregation
and mixed phases in the final materials. To achieve
homogeneous mixed oxides with predetermined compositions, the difference in reactivity has been minimized by controlled prehydrolysis of the less reactive
precursor [13], by chemical modification of the precursors [14], by using single-source heterobimetallic
alkoxide precursors [15], or by non-hydrolytic sol-gel
processes [16]. Non-alkoxide sol-gel process, involving hydrolysis and condensation of metal salts, avoids
the disadvantage of alkoxide sol-gel process (high sensitivity to moist environment), however, has still the
disadvantage of different hydrolysis susceptibilities of
the individual components.

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Cui, Zayat and Levy

(1)
Another non-alkoxide sol-gel route involves the usage of an epoxide as a gelation agent. This procedure
requires relatively few steps to obtain metal oxides,
and is low-temperature and low-cost. The epoxide acts
as an acid scavenger through protonation of the epoxide oxygen and subsequent ring opening by the nucleophilic anionic conjugate base. According to the reaction Eq. (1), epoxide consumes protons from the aqua
complexes [M(H2 O)x ]n+ , which promotes the hydrolysis and condensation of the complexes resulting in the
formation of a gel [17]. Some metal oxide aerogels [17
20] and nanoparticles [2123] have been prepared by
this process. For mixed oxides, only lanthanide-silicate
gels were prepared at Lawrence Livermore National
Laboratory [24], silicate-aluminate by Itoh et al. [25]
and yttrium doped zirconia by Xie et al. [21]. However,
no work has been reported on the synthesis of bimetallic mixed oxides by the epoxide method in which one
of metal ions has a formal charge of less than +3. As
stated by Gash et al. [17, 18], metal oxide gels cannot be prepared from aqueous metal ions that have a
formal charge of less than +3 by the epoxide method.
Gash claimed that the acidities of the aquo complexes
[M(H2 O)x ]n+ of M2+ ions are much lower than those
of the Mn+ ions with (n = 3, 4, 5, 6). This would slow
down the protonation of the added epoxide with a subsequent rise in the pH. The slow rate of the process may
allow alternative side reactions to occur to a significant
degree and cause precipitation to take place.
The aim of this work is to apply the sol-gel epoxide
route for the preparation of spinel nanoparticles, using propylene oxide as the gelation agent. In order to
show the capability of this method for the preparation
of different mixed oxides, several pigments with spinel
structure, such as CoAl2 O4 (blue), CoCr2 O4 (bluish
green), ZnFe2 O4 (brown) and CuCr2 O4 (black) will be
prepared, all of them having one of metal ions with a
formal charge of less than +3.
2.
2.1.

Experimental Section
Materials

Cobalt nitrate hexahydrate (Co(NO3 )2 6H2 O), chromium nitrate nonahydrate (Cr(NO3 )3 9H2 O), ferric

nitrate nonahydrate (Fe(NO3 )3 9H2 O), zinc nitrate

hexahydrate (Zn(NO3 )2 6H2 O) and propylene oxide (PPO) were obtained from Aldrich; Aluminium
nonahydrate (Al(NO3 )3 9H2 O) and copper nitrate
hemipentahydrate (Cu(NO3 )2 2.5H2 O) were from
Fluka; Ethanol absolute was from merck. All these
reagents were used as received.

2.2.

Preparation of Pigments Nanoparticles

All syntheses were performed under the same experimental conditions except for the different calcination
temperatures (see Table 1). In a typical synthesis of
CoAl2 O4 nanoparticles, a 15 ml clear pink ethanol solution was obtained by dissolving 0.62 g Co(NO3 )2 6H2 O
3+
and 2.59 g Al(NO3 )3 9H2 O ([M2+
Co + MAl ] =
1
0.6 mol l ) in ethanol. After the addition of 4.96 g
3+
propylene oxide (propylene oxide/(M2+
Co + MAl ) = 10)
to the ethanol solution, an exothermic reaction occurred
within several minutes, followed by a gradual gel formation from the top to the bottom of the solution. The
gel formation time, which depends on the metal ions,
metal ion concentration and mol ratio of propylene oxide, varied from a few seconds to several hours. In the
above-mentioned case of CoAl2 O4 , the gel formation
occurred within 3 minutes and the gel became light purple within several minutes. The gel was aged in a closed
vessel at 50 C for 3 hours, dried in an open vessel at
50 C for 24 hours and then treated at 100 C for 12 additional hours. The resulting xerogel was ground to powder and calcined at the given temperature for 1 hour to
obtain nanoparticles. In order to obtain nanoparticles,
the calcination temperature of each pigment should be
Table 1. Gel formation time, calcination temperature and
particle size obtained by TEM.
Approximate gel
formation time

Calcination
temperature ( C)

Particle
size (nm)

CoAl2 O4

3 minutes

750

1050

CoCr2 O4

21 minutes

700

1020

Sample

CuCr2 O4

21 minutes

700

2060

ZnFe2 O4

a few seconds

700

820

Sol-Gel Synthesis of Nanoscaled Spinels Using Propylene Oxide as a Gelation Agent

the lowest temperature needed for the formation of the

specific clean colored phases, reducing the aggregation
of the particles during calcination.

177

The thermal behaviour (TG/DTA) of the samples was

studied by a Seiko SSC/5200 (TG/DTA 320U) in static
air atmosphere from ambient temperature to 1200 C at
a heating rate of 10 C/min. The XRD patterns of the
samples were measured in a Philips PW 1710 diffractometer using Cu K radiation. The morphology of the
particles was observed by a JEOL 2000 transmission
electron microscope working at 200 kV, and the particle size and size distribution were estimated in the
TEM micrograph.

deteriorating the coloration of the bulk pigment. In the

CoAl2 O4 pigment, an excess of the white Al2 O3 will
reduce the intensity of the blue coloration of the pigment, while excess cobalt oxide will form a segregated
Co3 O4 black phase, resulting in an important darkening of the pigment coloration, which will be discussed
in the following part.
The processes of gels formation of CoCr2 O4 ,
CuCr2 O4 and ZnFe2 O4 are very different from that
of CoAl2 O4 . The formation of CoCr2 O4 and CuCr2 O4
gels took at least 21 minutes, while only a few seconds
is required for the formation of ZnFe2 O4 gel.
In general, it is very interesting, that mixing M2+ and
3+
M ions in the ethanol solution prevented the precipitation of the M(OH)2 when the propylene oxide was
added to the mixture.

3.

3.2.

2.3.

3.1.

Characterization

Results
Gel Formation

In multimetallic systems, phase segregation is usually

observed due to the different hydrolysis rates of the hydrated metal ions of the different components. In the
case of CoAl2 O4 , the hydrolysis and condensation rate
of Al3+ alone in ethanol solution was rather fast, forming gels within a few minutes; on the contrary, that
of Co2+ alone in solution was much slower, giving a
precipitate about 10 minutes after the propylene oxide
was added. However, it is very interesting that a gel
was formed without any precipitation in the ethanol
mixture solution of Al3+ and Co2+ ions after the addition of propylene oxide. The colour of the mixed
ions gel changed from pink to light purple within several minutes after the gel was formed. After aging at
ambient temperature for several hours, a layer of pink
solution appeared on the upper part of the gel, showing
that the hydrolysis of the Co2+ was not complete. After two days of aging at ambient temperature, the pink
colour of the solution disappeared, accounting for the
complete hydrolysis of the Co2+ . The same effect was
observed when the gel was aged at 50 C for 3 hours.
The different hydrolysis rates of individual precursor
ions may lead to certain inhomogeneity and formation
of zones in the oxide gel that are rich in the ions exhibiting faster hydrolysis and condensation rates, resulting
in a partial segregation of the phases and the formation
of single oxides. This is particularly important for the
preparation of pigments, where even using stoichiometric ratios, one of the metal oxides can be in excess

TG-DTA Analysis

The four DTA/TG curves (Fig. 1) of the thermal

degradation of the CoAl2 O4 , CoCr2 O4 , CuCr2 O4 and
ZnFe2 O4 precursor powder with stoichiometric composition show a progressive weight loss from room
temperature to around 100 C accompanied by a broad
endothermic peak, which is attributed to the evaporation of free water. Above this temperature, two
weak exothermic peak around 177, 244 C and a very
strong and sharp exothermic peak around 280 C, accompanied by a steep weight loss, are observed in the
DTA/TG curve of CoAl2 O4 precursor due to the burning of the organic matter. The thermal behaviour of
CoCr2 O4 , CuCr2 O4 and ZnFe2 O4 precursors is very
different from that of CoAl2 O4 precursor. Only one
strong and sharp exothermic peak, accompanied by
a steep weight loss, is found in their DTA curves at
188 C for CoCr2 O4 , 210 C for CuCr2 O4 and 226 C
for ZnFe2 O4 due to the burning of organics. Above
these temperatures only a small weight loss is observed,
which is attributed to the release of water arising from
condensation reactions.

3.3.

Coloration and Crystallographic Analysis

3.3.1. CoAl2 O4 . Samples were synthesized using different Co:Al mol ratios (0.034 Co/Al 0.67) and
calcined at 750 C which is the lowest temperature for
the formation of the bright blue CoAl2 O4 phase. This
calcination temperature is lower than that reported for
other preparation methods [3].

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Cui, Zayat and Levy

Figure 2. XRD patterns of CoAl2 O4 particles prepared with different Co/Al values and calcined at 750 C.

All samples, except for the amorphous sample

(Co/Al = 0.034), show the spinel structure of CoAl2 O4
(JCPDS 44-0160) even for the cobalt rich sample
(Co/Al = 0.67) (Fig. 2). Due to the similar ionic radius of Co3+ and Al3+ , Co3 O4 and CoAl2 O4 have the
same spinel structure and it is very difficult to distinguish them from the diffraction lines of XRD patterns.
The cobalt rich samples (Co/Al = 0.67 and 0.58)
exhibited black coloration. According to the literature,
the most stable cobalt oxide at room temperature is the
mixed-valence black Co3 O4 that has the same spinel
structure as the aluminate; above 950 C, the oxide is
reduced to CoO [3]. Therefore, the black coloration of
the two cobalt rich samples can only be attributed to the
presence of Co3 O4 . Then, the dark blue coloration of
the stoichiometric sample (Co/Al = 0.5) and samples
(Co/Al = 0.43 and 0.36) is attributed to the mixture of
black Co3 O4 and blue CoAl2 O4 . The bright blue coloration of the aluminium rich samples (0.15 Co/Al
0.30) accounts for the presence of the blue CoAl2 O4
phase alone.

Figure 1. DTA-TG curves of stoichiometric CoAl2 O4 , CoCr2 O4 ,

CuCr2 O4 and ZnFe2 O4 precursors.

3.3.2. CoCr2 O4 , CuCr2 O4 and ZnFe2 O4 . For CoCr2

O4 CuCr2 O4 and ZnFe2 O4 , on the contrary to what we
observed in CoAl2 O4 samples, the pure spinel structure could only be obtained using the spinel stoichiometric M2+ /M3+ = 0.5 atomic ratio. Figure 3 shows
the XRD pattern of CoCr2 O4 prepared with different
Co/Cr values. In addition to the spinel CoCr2 O4 phase
(JCPDS 22-1084), samples prepared with Co/Cr values
below 0.5 show a second phase that could be assigned to
Cr2 O3 (JCPDS 38-1479). Samples with Co/Cr = 0.67

Sol-Gel Synthesis of Nanoscaled Spinels Using Propylene Oxide as a Gelation Agent

Figure 3. XRD patterns of CoCr2 O4 prepared with different Co/Cr

values and calcined at 700 C.

and 0.5 show the pure spinel CoCr2 O4 structure. Due

to the similar ionic radius of Co3+ and Cr3+ , it is very
difficult to distinguish between Co3 O4 and CoCr2 O4
from the diffraction lines. Then, sample (Co/Cr = 0.67)
is most probably a two phases mixture of CoCr2 O4 and
Co3 O4 phases.
A similar behaviour was observed in CuCr2 O4 and
ZnFe2 O4 samples. Stoichiometric (Cu/Cr = 0.5 and
Zn/Fe = 0.5) samples showed only the spinel phase:
CuCr2 O4 (JCPDS 34-0424) and ZnFe2 O4 (JCPDS
22-1012) respectively, while any deviation from stoichiometry resulted in the presence, in addition to the
spinel phase, of the corresponding oxide in excess: CuO
(JCPDS 44-0706) or Cr2 O3 (JCPDS 38-1479) in the
case of CuCr2 O4 (Fig. 4) and ZnO (JCPDS 36-1451)
or Fe2 O3 (JCPDS 33-0664) in the case of ZnFe2 O4
(Fig. 5).
3.4.

179

Figure 4. XRD patterns of CuCr2 O4 prepared with different Cu/Cr

values and calcined at 700 C.

Figure 5. XRD patterns of ZnFe2 O4 calcined prepared with different Zn/Fe values and calcined at 700 C.

Transmission Electron Microscope Analysis

4.

Transmission electron micrographs of the four pigments are shown in Fig. 6. The Fig. 6(a)(c) show
non-agglomerated and well-crystallised nanoparticles
of CoAl2 O4 (Co/Al = 0.30), ZnFe2 O4 (Zn/Fe = 0.5)
and CuCr2 O4 (Cu/Cr = 0.5) respectively having their
narrow particle size distribution (see Table 1). Although Fig. 6(d) shows slightly agglomerated CoCr2 O4
(Co/Cr = 0.5) particles between 50150 nm, it could
be clearly seen that the agglomerated particles are composed of small particles between 1020 nm.

4.1.

Discussion
CoAl2 O4

The process of CoAl2 O4 gel formation, together with

the existence of the black Co3 O4 phase in the samples with Co/Al between 0.43 and 0.5 and the existence of only a bright blue CoAl2 O4 phase in the aluminium rich samples (0.15 Co/Al 0.30) suggest
the following result: in the process of gel formation, an
alumina gel was formed first without the formation of

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Cui, Zayat and Levy

Figure 6. Transmission electron micrographs of CoAl2 O4 (Co/Al = 0.30) (a), ZnFe2 O4 (Zn/Fe = 0.5) (b), CuCr2 O4 (Cu/Cr = 0.5) (c) and
CoCr2 O4 (Co/Cr = 0.5) (d).

cobalt hydroxide precipitate and the hydrated cobalt

ions were then hydrolysed and condensed with the aluminium hydroxide at the surface of the alumina gel surface. During the calcination, an excess of cobalt, for the

formation of a layer of stoichiometric CoAl2 O4 on the

alumina surface, results in the formation of a mixture
layer of Co3 O4 and CoAl2 O4 in samples with Co/Al
values between 0.36 and 0.5. In samples with a lower

Sol-Gel Synthesis of Nanoscaled Spinels Using Propylene Oxide as a Gelation Agent

amount of cobalt (samples with Co/Al between 0.15

and 0.30), only a thin layer of stoichiometric CoAl2 O4
was formed on the alumina surface. The core-shelltype CoAl2 O4 particles obtained here in samples with
0.15 Co/Al 0.30 are composed of an alumina core
and a CoAl2 O4 shell. However, the XRD patterns of
these samples showed only the diffraction patterns of
CoAl2 O4 , suggesting that under the synthetic conditions the alumina in the core remains amorphous.

181

of the required calcination temperatures, as compared

with previously reported methods, minimizing the undesired aggregation of the particles. This method was
found to be an effective route to synthesize mixed oxide
nanoparticles with narrow size distribution.
The route described here can also be applied for the
synthesis of mixed oxides with other structures and
more than two metal components.
References

4.2.

CoCr2 O4 , CuCr2 O4 and ZnFe2 O4

For CoCr2 O4 and CuCr2 O4 , the difference in hydrolysis and condensation rates between Co2+ , Cu2+ and
Cr3+ in ethanol is not large, resulting in the formation
of homogeneous CoCr2 O4 and CuCr2 O4 gels. This is
supported by the experimental results in which the pure
spinel structure could only be obtained for M2+ /M3+
= 0.5 and secondary phases were formed for other
M2+ /M3+ values as shown in XRD patterns of CoCr2 O4
and CuCr2 O4 .
The hydrolysis and condensation rate of Fe3+ alone
in ethanol solution was fast and iron oxide gels were
formed within a few seconds after propylene oxide had
been added, while precipitate was observed in Zn2+
solution at least 5 minutes after addition of propylene
oxide. According to the explanation given for CoAl2 O4
gels, the formation of ZnFe2 O4 gels should be similar to that of CoAl2 O4 resulting on the formation of
core-shell particles. However, when a mixture of Zn
an Fe ions (Zn/Fe = 0.5) were treated with propylene
oxide, a homogeneous gel was obtained within a few
seconds, giving pure ZnFe2 O4 particles after calcinations as shown in the XRD patterns of ZnFe2 O4 . It is
very clear that the presence of Fe ions in the mixture
enhances the reactivity of Zn ions resulting in simultaneous hydrolysis and condensation of the two ions
and hence, in the formation of homogeneous ZnFe2 O4
gels.
5.

Conclusions

In summary, spinel nanoparticles with one of the metal

ions having a formal charge of less than +3 were successfully synthesized through a sol-gel method that
uses propylene oxide as a gelation agent. One of the
advantages of this method is the important reduction

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