Chemical Engineering Communications

ISSN: 0098-6445 (Print) 1563-5201 (Online) Journal homepage: http://www.tandfonline.com/loi/gcec20

One-pot synthesis and modification of

silica nanoparticles with 3-chloropropyl-
trimethoxysilane assisted by microwave
irradiation

Juliana F. De Conto, Marília R. Oliveira, Matheus M. Oliveira, Thadeu G.

Brandão, Kelvis V. Campos, Cesar C. Santana & Silvia M. Egues

To cite this article: Juliana F. De Conto, Marília R. Oliveira, Matheus M. Oliveira, Thadeu G.
Brandão, Kelvis V. Campos, Cesar C. Santana & Silvia M. Egues (2018): One-pot synthesis and
modification of silica nanoparticles with 3-chloropropyl-trimethoxysilane assisted by microwave
irradiation, Chemical Engineering Communications, DOI: 10.1080/00986445.2017.1406349

To link to this article: https://doi.org/10.1080/00986445.2017.1406349

Published online: 08 Feb 2018.

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CHEMICAL ENGINEERING COMMUNICATIONS
https://doi.org/10.1080/00986445.2017.1406349

none defined

One-pot synthesis and modification of silica nanoparticles with

3-chloropropyl-trimethoxysilane assisted by microwave irradiation
Juliana F. De Conto, Marília R. Oliveira, Matheus M. Oliveira, Thadeu G. Brandão, Kelvis V. Campos,
Cesar C. Santana, and Silvia M. Egues
Institute of Technology and Research (ITP), Synthesis Materials and Chromatography Laboratory (LSINCROM), Tiradentes University (UNIT),
Aracaju, SE, Brazil

ABSTRACT KEYWORDS
Industry and academia have shown great interest in the synthesis of organic–inorganic hybrid CPTMS; microwave
material because the modification of inorganic supports with organic groups increases the options synthesis; one-pot synthesis;
for using these materials. Microwave irradiation as a heat source is an alternative tool compared silica
with conventional heating (oil bath or furnace) to reduce the reaction times during the synthesis of
these materials. Thus, the purpose of this work was to synthesize an organic–inorganic hybrid
material, more specifically silica nanoparticles modified with 3-chloropropyl-trimethoxysilane,
using microwave irradiation as the heat source. The hybrid materials were synthesized using the
sol–gel method, with microwave irradiation for 10, 25, and 40 min, at 300 W of power and
temperature of 40, 60, and 80°C. Elemental analyses, FTIR, and N2 adsorption–desorption isotherms
were developed to characterize the materials. It can be concluded that when microwave irradiation
is used as a heat source, the reaction rate is accelerated and the surface area of hybrid materials
increases considerably.

Introduction different characteristics in terms of pore diameter,

surface area, and ordered or disordered pores
The synthesis of mesoporous materials combined
(Hoffmann et al., 2006). Also, it is possible to
with organic compounds, metals, or oxides is an
obtain materials with specific properties as hydro-
area with great research potential. This combi-
phobicity, polarity, as well as catalytic, optical,
nation increases the efficiency and selectivity of
and electronic activity after the organofunctionali-
these materials, favoring several processes when
zation of silica (Kumar and Guliants, 2010).
they are used as a catalyst, adsorbent, or stationary
However, the synthesis of organic–inorganic
phase (Cao et al., 2009; Xun et al., 2014; De Conto
hybrid materials through conventional heating
et al., 2014; Sun et al., 2014). Combined materials
methods requires long reaction times (Cheng
with a mesoporous structure and high specific
et al., 2014; Su et al., 2014). Thus, researchers
surface area also offer opportunities in separation
around the world have proposed new methodolo-
processes. It is possible to use these materials
gies using microwave irradiation as the heat source.
in chromatography and adsorption techniques
This is a good alternative as it reduces operational
because they have high mechanical and thermal
costs, and is simple, fast, and shows high energy
stability, and appropriate porosity and selectivity
efficiency (Rao et al., 1999; Adachi et al., 2004).
(Passos et al., 2006; Van Meter et al., 2009).
Over the past 30 years, many reactions and chemi-
The synthesis of an inorganic porous matrix,
cal processes have been performed using micro-
and more specifically silica synthesis, is usually
wave irradiation as the heat source. However, the
performed using the sol–gel method, or by routes
interactions between microwaves and reagents dur-
using surfactants and hydrothermal treatment.
ing the synthesis of materials remain unclear. The
Depending on the initial feedstock, and variations
reaction mechanisms that result in fast heating
in conditions such as temperature, time, and type
are based on the dielectric heating that can occur
of synthesis, it is possible to obtain materials with

CONTACT Silvia M. Egues smsegues@gmail.com Institute of Technology and Research (ITP), Synthesis Materials and Chromatography Laboratory
(LSINCROM), Tiradentes University (UNIT), Av. Murilo Dantas, 300, CEP-490032-490, Aracaju, SE, Brazil.
© 2018 Taylor & Francis
2 J. F. DE CONTO ET AL.
in resonance adsorption or absorption mode or
relaxation mechanism, due to microwave dipole
alternation and polar species movement (Rao
et al., 1999).
Although practical and theoretical knowledge of
microwave interactions with the materials is still at
an early stage of development, there has been much
interest in the synthesis of hybrid materials using
microwaves for the previously mentioned reasons.
Furthermore, it is known that the parameters used
in the synthesis of silica assisted by microwaves,
such as temperature, power, and reaction time,
have an important influence on the size of particles
and the morphology of the materials (Celer and
Jaroniec, 2006). Moreover, one-pot synthesis using
microwave-assisted heating causes spectacular
accelerations in the reactions, mild reaction
conditions, and thus shorter reaction times (Ergun
et al., 2013).
Nevertheless, little is known about the synthesis
of organic–inorganic hybrid materials combining
one-pot synthesis and microwave irradiation. There-
fore, the purpose of this work was to synthesize an
organic–inorganic hybrid material, more specifically
silica nanoparticles modified with 3-chloropropyl-
trimethoxysilane, using one-pot synthesis and
microwave irradiation as the heat source.
Materials and methods
Synthesis of silica modified with
3-chloropropyltrimethoxysilane
The one-pot synthesis of organic–inorganic hybrid
material was carried out in a microwave-assisted
reactor (CEM (CEM corporation, model Discover
SP)—discovery synthesis) and we studied the
influence of temperature and reaction time in the
textural characteristic of material. The temperature
and reaction time were varied for each sample as
shown in Table 1. Silica synthesis was performed
using the sol–gel method adapted from De Conto
et al. (2014). The scheme of the silica synthesis
and functionalization is shown in Figure 1.
Tetraethylorthosilicate (TEOS, Aldrich �99%)
and 3-chloropropyltrimethoxysilane (CPTMS,
Aldrich �97%) were used as precursor reagents
in the silica synthesis (90% molar of TEOS and
10% molar of CPTMS). Hydrofluoric acid (Merck,
48%) was used as the catalyst. TEOS (5 mL) was
Table 1. Experimental conditions of silica synthesis assisted by
microwave irradiation.
Samples Temperature (°C) Time (min)
SiCPTMS-40/10 40 10
SiCPTMS-40/25 40 25
SiCPTMS-40/40 40 40
SiCPTMS-60/10 60 10
SiCPTMS-60/25 60 25
SiCPTMS-60/40 60 40
SiCPTMS-80/10 80 10
SiCPTMS-80/25 80 25
SiCPTMS-80/40 80 40
pre-hydrolyzed by adding 8 mL of ethanol and
2 mL of distilled water. Subsequently, the sample
was irradiated with microwaves for 1 h at 40°C
and 300 W of power under constant stirring. After
this, CPTMS (0.45 mL) and hydrofluoric acid
solution (1 mol L−1) were added. The mixture was
placed back in the microwave reactor and submit-
ted to the reaction conditions presented in Table 1.
In this step, the sample was kept under constant
stirring at a power of 300 W.
Subsequently, the hybrid material was placed for
gelation. Afterwards, the hybrid material was dried
in an oven at 80°C. In the nomenclature used in
this work, the first number in the sample name
refers to the temperature and the second number
the time.
Characterization
The silica characterization was performed using
different techniques. The specific surface area
and the pore size distribution were determined
using an N2 adsorption/desorption isotherm, in
Autosorb I—Quantachrome Instruments, using
the BET and BJH method, respectively. The sam-
ples were treated at 140°C for 3 h under vacuum.
FTIR analyses were performed in Varian 600
equipment in the region of 400–4,000 cm−1 with
a resolution of 2 cm−1 and 140 accumulations.
Pellets were prepared from the dispersion of solids
in KBr at the ratio of 1:100 and the analyses were
performed at room temperature. The sample
spectrum was obtained after heat treatment in
vacuum. The content of carbon, hydrogen, and
nitrogen was measured on a Perkin-Elmer
analyzer, model PE 2400. The analyses were run
in triplicate. The percentage of carbon, hydrogen,
and nitrogen is given as final results, by the
detector equipment.

Figure 1. Scheme of silica synthesis and functionalization steps.
Results and discussion
The adsorption/desorption isotherms of the
different silica materials obtained by microwave
irradiation are presented in Figure 2.
Figure 2(a) and (b) illustrates that the materials
synthesized at 40 and 60°C and irradiated with
microwaves for 10, 25, and 40 min showed
isotherm type IV, characteristic of mesoporous
materials (Sing, 1982; Thommes et al., 2015). On
the other hand, the materials irradiated by
Figure 2. Adsorption/desorption N2 isotherm of silica obtained
via microwave irradiation at 40 (a), 60 (b), and 80°C (c), 300 W of
power and 10, 25, and 40 min.
CHEMICAL ENGINEERING COMMUNICATIONS 3
microwaves at 80°C for 10 and 25 min showed
a combination of isotherm types I and IV
(Figure 2(c)). This type of isotherm I þ IV is a
characteristic of materials that contain micro-
and mesopores. However, the pore size distribution
in the silica is in boundary region of micropore and
mesopore, that is, between 5 and 10 nm. Thus,
increasing the temperature to 80°C altered the
textural characteristic of materials.
However, when the material was subjected to
microwave irradiation at 80°C for 40 min, the
isotherm reverted to type IV, as can be seen in
Figure 2(c). This can be attributed to the gelation
of the material under these conditions inside the
microwave reactor. Thus, the silica structuration
occurred quickly and, consequently, decreased the
specific surface area of the synthesized materials
(Ergun et al., 2013). According to Kannan and
Jasra (2000), when the microwave radiation is used
as heating source in short period of time, there is
an increase in the surface area. However, a
reduction in the surface area was observed after
submitting the sample long periods of times. So,
one can confirm that the main factor that deter-
mined the development of specific surface area is
the ageing process.
Table 2 shows the values of specific surface area
and pore volume of the samples synthesized in the
microwave reactor. As temperature increases from
40 to 80°C, the specific surface area of the sample
also increased for the reaction times of 10 and
25 min. However, this trend was not observed in
sample SiCPTMS-80/40, as explained previously.
Table 2 shows that the amount of carbon and
hydrogen in the samples exposed to microwave
irradiation at 40 and 60°C was around 6 and 2%,
4 J. F. DE CONTO ET AL.

Table 2. Textural and elemental analysis of silica.

N2 ads/des-isotherm Elemental analysis
2 −1 3 −1
Sample SBET (m g ) VBJH (cm g ) C (%) H (%) N (%) Amount of Organica(mmol g−1)
SiCPTMS-40/10 376 0.087 6.19 1.98 0.12 1.27
SiCPTMS-40/25 387 0.129 5.83 1.96 0.15 1.17
SiCPTMS-40/40 397 0.105 6.12 2.09 0.10 1.25
SiCPTMS-60/10 415 0.095 6.80 2.32 0.35 1.44
SiCPTMS-60/25 408 0.148 6.26 2.27 0.29 1.29
SiCPTMS-60/40 410 0.146 6.10 2.25 0.27 1.25
SiCPTMS-80/10 540 0.058 4.66 2.86 0.018 0.85
SiCPTMS-80/25 500 0.059 4.58 2.78 0.025 0.83
SiCPTMS-80/40 365 0.127 4.69 2.42 0.024 0.86
a
Obtained by elemental analysis, mmol of CPTMS group per gram of silica.

respectively. Therefore, at these temperatures, the
organic content bonded on the silica surface was
almost identical. Similar results were obtained by
Gu et al. (2015), for synthesis at 40 and 60°C under
microwave irradiation, with a carbon and hydro-
gen content in the material of 6 and 1.3%, respect-
ively. At 80°C, the carbon content decreased to
around 4.6%, and the hydrogen content increased
slightly, probably due to the presence of some
uncovered hydroxyl groups in the silica.
Figure 3 shows the results of the FTIR analysis
of all the samples synthesized by microwave
irradiation. The band in the region of 1,069 cm−1
corresponds to the Si–O–Si and Si–O–Si–C groups
and the band of 698 cm−1 can be assigned to the
C–Cl bond (Adam et al., 2009). These vibration
bands can be observed in all samples. The resulting
structure of the hybrid material is similar to that
obtained using the conventional heating process,
indicating that microwave irradiation could be
used in the synthesis and modification of silica
with organic groups. Besides, this process is
advantageous because it reduces the processing
time and energy consumption.

Figure 3. Absorption spectrum in FTIR of silica modified with
CPTMS obtained via microwave irradiation at 40 (a), 60
(b), and 80°C (c) under different conditions. Note: CPTMS,
3-chloropropyltrimethoxysilane.
Conclusion
According to the results obtained in this work, it is
possible to synthesize silica with CPTMS using
microwave irradiation. Increasing reaction tem-
perature from 40 to 80°C was observed to have an
increase in the specific surface area and a decrease
in the pore volume. From FTIR analysis, it was
possible to identify the organic groups present in
the silica. This proved that the functionalization
of the silica surface with CPTMS was effective.
The elemental analysis verified that the amount
of carbon in the SiCPTMS-40 and SiCPTMS-60
samples was close to 6%, indicating the presence
of the silane agent (CPTMS), while in the
SiCPTMS-80 sample the carbon content was
reduced to 4%, approximately. The hydrogen con-
tent increased with the reaction temperature,
which may indicate incomplete condensation of
TEOS with a larger number of silanol groups
(–OH) in place of the siloxane groups (–SiO).
Furthermore, it was possible to obtain a gelled
silica at the end of the reaction in the microwave

for the SiCPTMS-80 sample (80°C for 25 and
40 min), proving that the method is promising for
reducing the preparation time of these materials.
Funding
The authors are grateful to Coordenação de Aperfeiçoamento
de Pessoal de Nível Superior (CAPES) and Conselho Nacional
de Desenvolvimento Científico e Tecnológico (CNPq) (Grant
Number PDSE-12671/12-6) for financial support and
fellowships.
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