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APCBEE Procedia 3 (2012) 93 98

ICCCP 2012: 5-6 May 2012, Kuala Lumpur, Malaysia

Effects of Cationic Surfactant in Sol-gel Synthesis of Nano

Sized Magnesium Oxide
Mohd Sufri Mastulia,*, Noor Sabrina Ansaria, Mohd Azizi Nawawia, Annie Maria
Mahata
a

Faculty of Applied Sciences, Universiti Teknologi MARA, Shah Alam, Selangor, 40450, Malaysia

Abstract
In this study, sol-gel method was used to synthesize nano sized of magnesium oxide (MgO). Magnesium acetate
tetrahydrate and tartaric acid have been dissolved in ethanol and formed a precursor before calcined at 600 C for 6 h to
produce MgO nanoparticles. A cationic surfactant (cetyltrimethylammonium bromide, CTAB) had used in the sol-gel
reaction to reduce agglomeration of the nanoparticles. Two samples (MgO and MgO-CTAB) were characterized using
simultaneous thermogravimetric analyzer (STA), X-ray diffractometer (XRD), field emission scanning electron
microscope (FESEM) and nitrogen adsorption-desorption measurement. Formation of the samples via a sol-gel route is
discussed and confirmed using the STA results. The precursor formed was identified as magnesium tartrate and
decomposed to MgO and MgO-CTAB after the calcinations, and gave a single phase of samples as shown by the XRD
patterns. The used of CTAB in this sol-gel method gives the MgO nanoparticles with less agglomeration. This was proved
by the FESEM micrographs, the MgO-CTAB has spherical shape and the agglomeration seems to be less than the MgO. It
suggests that the cationic surfactant controls the morphology of the samples.

2012
2012 Published
Publishedby
byElsevier
ElsevierB.V.
B.V.
Selection
and/or
peer
review
under
responsibility
of Asia-Pacific

Selection
and/or
peer
review
under
responsibility
of Asia-Pacifi
c Chemical,
Chemical, &
Biological
& Environmental
Engineering Society
Biological
Environmental
Engineering Society
Keywords: MgO, Sol-gel, Nanoparticles, Cationic surfactant

1. Introduction
Magnesium oxide (MgO) is an important oxide material that used in many applications such as catalysis,
* Corresponding author. Tel.: +60-355436594; fax: +60-355444562.
E-mail address: mohdsufri@salam.uitm.edu.my.

2212-6708 2012 Published by Elsevier B.V. Selection and/or peer review under responsibility of Asia-Pacific Chemical,
Biological & Environmental Engineering Society
doi:10.1016/j.apcbee.2012.06.052

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catalyst supports, toxic wastes remediation, refractory materials and adsorbents [1-5]. The commercial MgO
particles have been prepared via thermal decomposition of magnesium salts or magnesium hydroxide [6, 7].
The resulting MgO has large particle size and small surface area which are disadvantages for use in some
applications. Therefore, many synthesis methods have been developed to prepare nano sized of MgO with
large surface area with controlled morphology as reported in [8-14].
A sol-gel method is one of the promising approaches due to its simplicity, cost-effective, high yield of final
product and low reaction temperature. The organic salts such as magnesium methoxide and magnesium
ethoxide are rare used in sol-gel reaction for formation of MgO nanoparticles and these discussed in a few
reports [15-20]. As an alternative, inorganic magnesium salts are reacted with different complexing agents
and give various precursors before decomposed to MgO [21-26]. However, the sol-gel method used is usually
caused agglomeration of MgO particles, which hinder its wide applications [27, 28]. It is highly required to
develop a surfactant-mediated synthesis method to overcome this limitation. A numbers of polymeric
surfactant have been used in sol-gel method [10, 27, 29-31]. A more spherical MgO with less agglomeration
was obtained by using cationic surfactant of cetyltrimethylammonium bromide (CTAB) in emulsion-phase
method [32]. So far, no studies on the use of CTAB in sol-gel method have been reported.
The controlled synthesis for MgO with specific morphology, small crystallite size and large surface area
are challenging aspects to be studied. Understanding the growth mechanism is also an important area for
study. The synthetic strategies by which size and shape of the nanostructures are tailored represent key issues
in the nanomaterials research. The prospect of easier to control the parameters of sol-gel method has
motivated us to synthesize nano sized MgO using sol-gel route assisted with CTAB as a surfactant to reduce
the agglomeration of their particles.
2. Experimental Details
All reagents used in the present work were analytical grade and directly used without further treatment.
Magnesium acetate tetrahydrate, Mg(CH3COO)2.4H2O (Merck, 99.5% purity); tartaric acid, C4H6O6 (Merck,
99.5% purity), cetyltrimethylammonium bromide or CTAB, C19H42BrN (Calbiochem, >98% purity); and
ethanol, C2H5OH (J. Kollin Chemical, 99.9% purity) were used in synthesis of the samples (MgO and MgOCTAB).
Mg(CH3COO)2.4H2O was initially dissolved in 0.001 M of CTAB under constant stirring until the solution
became transparent. Then, pH of the solution was adjusted to pH 5 using 1 M of C4H6O6 and stirred
vigorously until a thick gel was formed. The gel was left to stand overnight followed by oven drying at 100 C
for 24 h. Afterwards, the dried sol-gel product (precursor) was grinded into powder before calcined at 600 C
for 6 h to give MgO-CTAB. For comparison, CTAB-free of MgO had been prepared using the same method.
The decomposition behavior and thermal stability of the precursors were examined using simultaneous
thermogravimetric analyzer (STA; SETARAM SETSYS Evolution 1750). The precursors were heated from
room temperature to 800 C at a rate of 10 C min-1. The X-ray diffraction (XRD; PANalytical Xpert Pro
MPD) with CuK radiation was used to identify the phase of the samples (with and without CTAB). The
morphologies of these samples were observed using field emission scanning electron microscope (FESEM;
JEOL JSM-7600F). The nitrogen adsorption-desorption isotherm for the MgO and MgO-CTAB was obtained
from automated gas sorption instrument (Quantachrome AS1Win). Prior to the measurements, the samples
were degassed in a vacuum at 25 C for 9 h. Specific surface area of the samples were calculated using
Brunauer-Emmett-Teller (BET) method.
3. Results and Discussion

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In a sol-gel method, magnesium acetate tetrahydrate and tartaric acid were hydrolyzed in ethanol to form
magnesium (Mg2+) and tartrate (C4H4O62-) ions, respectively. These ions form complexes and have been
polymerized to form a thick gel and identified as magnesium tartrate (MgC4H4O6). This is known as a
precursor and calcined to produce MgO. The side products of the sol-gel reaction were acetic acid
(CH3COOH) and water (H2O) which were evaporated in oven during drying process. The chemical reactions
involved for formation of the MgO are shown in equations below. These are further confirmed using STA
results.
Weight loss of 41.06%
Mg(CH3COO)2.4H2O + C4H6O6
MgC4H4O6 + 2CH3COOH + 4H2O
(1)
MgC4H4O6 + 5/2 O2
MgCO3

Weight loss of 33.41%

Calcination

MgO + CO2

MgCO3 + 3CO2 + 2H2O

(2)
(3)

Fig. 1 shows decomposition behavior and thermal stability of precursors for both samples, MgO and MgOCTAB. For the precursor of MgO, there are two major stages of weight loss as shown in Fig. 1(a). The small
weight loss at below 100 C is attributed to the loss of ethanol that still remained in the precursor. In
temperature range of 100 425 C, a sharp endothermic peak at about 400 C with a weight loss of 40.08%
represents removal of acetic acid. This weight loss is closed to theoretical value as stated in equation (1). Next,
a weight loss of 34.17% takes place immediately after 425 C until 580 C with a broad endothermic peak at
about 450 C. It indicates decomposition of the precursor to magnesium carbonate before calcined to form
MgO. This decomposition should undergo a weight loss of 33.41% as proposed in equation (2). All the
predicted weight losses agree with the STA results. A broad exothermic peak is observed which starts at about
500 C corresponds to the phase transformation from the amorphous to the crystalline states of the MgO.
Therefore, calcinations of the precursor above this temperature should give a single phase of MgO.
The STA result of precursor for MgO-CTAB is shown in Fig. 1(b). It indicates a relatively similar to the
decomposition behavior and thermal stability of the MgO except one of additional weight loss about 100 C
for the decomposition of cationic surfactant (CTAB). It is worthy to mention that no weight loss occurred
above 600 C and reveal the MgO-CTAB should be formed.

Fig. 1. STA curve of precursor for (a) MgO; (b) MgO-CTAB

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The X-ray diffraction (XRD) patterns for MgO and MgO-CTAB are illustrated in Fig. 2. All the diffraction
patterns can be indexed as a face-centered cubic phase of periclase MgO (ICDD No.: 01-078-0430) with
space group of Fm-3m. The XRD peaks are assigned to (111), (200), (220), (311) and (222) reflections. No
diffraction peaks for impurities are present, which indicated the high purity of the samples. The XRD peaks as
shown in Fig. 2(a) showed broadening of peaks for MgO. This observation agrees with the value of full width
at half maximum (FWHM) of the peak (200) used to demonstrate the peak broadening. The broadening of the
MgO has smaller FWHM (0.2448) implying a larger crystallite size. This FWHM is increased to 0.2676 for
the MgO-CTAB, which means that the surfactant reduced the crystallite size. From the BET results, specific
surface area of the MgO and MgO-CTAB are 60.294 and 61.111 m2 g-1, respectively. The crystallite sizes are
also estimated from the BET results. The MgO crystallites are about 27.8 nm and this decreased to 27.4 nm
with CTAB added. The CTAB serves as dispersive and cohesive agents that caused different morphology
observed between MgO and MgO-CTAB.

Fig. 2. Powder XRD pattern for (a) MgO; (b) MgO-CTAB

This is confirmed by FESEM micrograph for the prepared samples as shown in Fig. 3. As can be seen, the
particles are agglomerated into bundles of flaky-spherical morphology, but it turns to heavy spherical shape
with less agglomeration due to presence of the CTAB. It is also observed that MgO-CTAB having smaller
crystallite size and this compliment its XRD pattern. This occurred because the precursor particles were
entrapped inside the CTAB micelles during the sol-gel reaction. Upon calcinations, the micelles were
removed and give a spherical shape of MgO as proposed below.

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Fig. 3. FESEM micrograph for (a) MgO; (b) MgO-CTAB

4. Conclusion
In the present work, MgO and MgO-CTAB have been synthesized using a sol-gel method. Both samples
have small crystallite size (< 100 nm) and different morphology. The present of CTAB in sol-gel reaction give
a spherical shape of MgO with less agglomerated.
Acknowledgements
The authors would like to thank the Malaysian Government for the research fund provided. This research
work has financially supported by the Fundamental Research Grant Scheme (600-RMI/ST/FRGS
5/3/Fst(200/2010) from the Ministry of Higher Education, Malaysia.
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