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Materials Today: Proceedings 4 (2017) 350–357 www.materialstoday.com/proceedings

5th International Conference of Materials Processing and Characterization (ICMPC 2016)

Synthesis Methods of Mesoporous Silica Materials

Sunil Kumara, M.M. Malikb and Rajesh Purohitc *
a
Research Scholar, Centre for Nano Science and Engineering, MANIT, Bhopal, 462003, India.
b
Professor and Chairman, Centre for Nano Science and Engineering, MANIT, Bhopal, 462003, India.
c
Associate Professor, Mechanical Engineering Department, MANIT, Bhopal, 462003, India.

Abstract

From the discovery of mesoporous materials in 1992 at Mobil oil company, these materials are continuously gaining attraction
due to their superior properties like tunable pore structure, surface morphology, huge pore volume and ability of easy
functionalization. In this paper historical background of mesoporous silica materials and methods which are used to synthesize
these materials such as sol-gel method, microwave assisted technique, chemical etching technique, templating approach are
discussed. In templating approach a template (structure directing agent) is used to create hollow porous structure but chemical
etching technique uses a selective etching agent (basic/acidic) to create mesoporous structure, here no template (soft/hard) is
required. Microwave technique is used for rapid synthesis of mesoporous silica nanoparticles. In microwave technique self
assembly of organosilane precursors and blockcopolymer and successive hydrothermal treatment is carried out under the
microwave oven.
©2017 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of Conference Committee Members of 5th International Conference of Materials
Processing and Characterization (ICMPC 2016).

Keywords:Mesoporous materials, nanoparticle, synthesis, structure, porous;

1. Introduction

The materials havingsmall holes (ordered or disordered) are called porous materials. The skeletal portion of the
material is often called the "matrix" or "frame" (as shown in figure 1). Nano porous materials consist of a regular
organic or inorganic framework supporting a regular porous structure. Examples of porous materials include: dry
wall, wood, concrete, gunite, rubber, some plastic, porous silica nanoparticles, and porous carbon nanoparticles [1].

* Corresponding author. Tel.: 0755-4051610.

E-mail address:rpurohit73@gmail.com

2214-7853©2017 Elsevier Ltd. All rights reserved.

Selection and peer-review under responsibility of Conference Committee Members of 5th International Conference of Materials Processing and
Characterization (ICMPC 2016).
 Sunil Kumar et al./ Materials Today: Proceedings 4 (2017) 350–357 351

Nomenclature

MCM Mobil Crystalline Material

M41S Molecular 41 Sieves
MSNs Mesoporous Silica Nanoparticles
SBA-n Santa Barbara Amorphous Number
FDU Fudan UniversityShanghai Materials
IUPAC International Union of Pure and Applied Chemistry
HMS Hexagonal Mesoporous Silica

Fig 1. Porous materials

On the basis of their pore diameter IUPAC has classified porous materials into three categories shown in figure 2
[2].

Fig. 2. Classification of porous materials.

(I) Microporous materials are the materials with pore diameters less than 2 nm. Examples of microporous
materials include zeolites and metal-organic frameworks. (ii) Materials having pore diameter between 2-50
nanometer ranges are mesoporous materials. (iii) Materials having pore diameter greater than 50 nanometer are
macroporous materials.
From last two decades much interest ofresearchers are continuously growing towards mesoporous silica
nanoparticles (MSNs) because they are chemically and thermally stable with controllable morphology and porosity.
It is observed the internal and external surfaces of these nanoparticles can be selectively modified with multiple
organic and inorganic functional groups. On the basis of these features, the biocompatibility of silica, and
theirefficient uptake by mammalian cells, MSNs are proposed as the basis of nanodevices for the controlled release
of drugs and genes into living cells [3].For example recently chlorophyll entrapped luminescent mesoporous silica
nanoparticles were synthesized for biological imaging application [4].
352 Sunil Kumar et al./ Materials Today: Proceedings 4 (2017) 350–357

1.1. History of mesoporous silica materials

Mesoporous silica was first discovered in 1990 by researchers in Japan and later in 1992 it was synthesized in
Mobil Corporation Laboratories and named as molecular 41 sieves (M41S). These materials have regular cylindrical
pores with tunable range of pore diameter in ranges between 2 and 30 nm and, consequently, the large surface area
of these materials (700–1500 m2/g), along with the high chemical and thermal stability and easy functionalization of
silica, making them useful for supports as adsorption, catalysis, chemical separations, and biotechnology devices
applications. MCM-41, MCM-48 and MCM-50 are the widely known mesoporous silica materials in M41S family
which have different methods of synthesis and applications based on instability and limitation of mesoporous
structure. After the discovery of the above-mentioned materials, MCM-41 (Mobil Crystalline Materials), significant
research efforts have been started to achieve control over the characteristics of mesoporous silica with special
emphasis on pore size and morphology. These mesoporous silica are highly ordered, large specific surface area,
hexagonal array and uniform mesoporous channel. Especially for MCM-41 and MCM-48, the pore size can be
controlled and widely used as adsorbent, catalyst and support. MCM-41 is in hexagonal packed rod-shaped micelle
structure [1, 5,], whereas MCM-48 is in cubic and MCM-50 is in lamellar structure form as shown in figure 3.

Fig. 3. Structures of mesoporous M41S materials a) MCM-41 (2D hexagonal, space group p6mm), b) MCM-48 (cubic, space group Ia3d),
and c) MCM-50 (lamellar, space group p2).

Through this huge research, in 1995 new families of mesoporous silica material, such as SBA, [6] MSU, [7] and
FSM, [8] were developed with characteristic porosities and particle shapes. In 1998, an important research of
mesoporous material produces whichhave hexagonal array of pores namely as Santa Barbara Amorphous No.15
(SBA-15) with larger pore size from 4.6-30 nm was a research gambit in mesoporous material development.
Mesoporous materials are generally formed using a micelle-templating process, following either an electro
statically driven cooperative assembly pathway or a non-ionic route in the presence of uncharged surfactants as
structure directing agents. The first reported ordered mesoporous silica material was M41S which has Emerging
applications in catalysis, adsorption, and separation [9, 10]. In considering above mention applications other type of
Mesoporous silica nanoparticle was synthesized by researchers such as the SBA-16 [11], Fudan University Material
(FDU) [12], and Korea Institute of Technology (KIT) [13].

2. Mesoporous materials

IUPAC defines mesoporous material as material containing pores with diameters between 2 to 50 nm.
Mesoporous material can be ordered or disordered in a mesostructure. Mesoporous materials can be divided into two
categories 1) silicon-based mesoporous materials and 2) non-siliceous mesoporous materials. Silicon-based
mesoporous materials are called mesoporous silicates and further can be divided into two categories one is pure
silicates and other is modified ones. Pure silicate materials are MCM, SBA, HMS, while the Non-siliceous
mesoporous materials include transition metal oxides (such as zirconia, titanium dioxide, tin oxide, manganese
 Sunil Kumar et al./ Materials Today: Proceedings 4 (2017) 350–357 353

oxide, niobium oxide, tantalum oxide, etc.) and non-metallic oxides (such as phosphate, sulfate and mesoporous
carbon). Usual mesoporous materials are silica, alumina and transition metal oxides with fine mesopores [14].
Other type of porous materials that are not based on the silicate, are porous carbon, coordination solids or porous
heteropolyanion salts. Ordered porous carbon is an interesting material because of some unique properties such as
the hydrophobic nature of their surface, chemical inertness, good mechanical and thermal stability having
advantages to form membranes, tubes or fibers. Porous carbon can be synthesized by nanocasting with mesoporous
silicate as template. The non silica mesoporous materials are very important to be used as catalysts due to their
transition-state property. But however, these kinds of mesoporous materials are not stable. The mesopores of these
materials can be collapsed during synthesis. Calcinations and synthesis techniques are also complicated. Due to
above difficulties most of the researchers are focusing on silica mesoporous materials [15].
It has considered that porous silica and porous glasses are typically disordered mesoporous materials. They have
wide pore distribution and pore structure is disordered. It is seen thatM41S are highly ordered mesoporous materials
but they are not crystalline material, instead of they are amorphous materials like glass [15].
Some important characteristics of mesoporous materials are:
1) They have long range ordered porous structure.
2) Their pore size distribution is usually quite narrow and the pore size can be varied from 2 nm to 30 nm by
changing the composition of the synthesis mixture or surfactants;
3) They have large surface areas, enable them for sorption processes.
4) Different structure of these materials such as rods, sheets and 3D structures can be obtained by using different
surfactants.
5) High thermal stability and hydrothermal stability can be obtained after modification.
Porous materials can be ordered in the regard of their hosts or the pores or both. In most cases it has been
observed that atoms of the host structure are periodically arranged with long-range order. If the atoms of host are
completely ordered, then the pores of materials will also be ordered. These types of ordered materials are called
crystalline and produce sharp maxima in diffraction experiments with X-rays, electrons and neutrons. However,
there exist a variety of materials where the atoms of the host structure have only short-range order in this variety of
material the host is amorphous with the regard of X-rays, electrons and neutrons, but pores have a very narrow size
distribution and a high long-range order [2].

3. Synthesis methods

Mesoporous materials can be synthesized by different techniques such as:-

(1) Sol-Gel processing, (2)Template assisted techniques, (3)Microwave assisted techniques, (4)Chemical etching
technique

3.1. Sol-gel method

The sol-gel process is a wet chemical technique which is widely used in the fields of materials science and
ceramic engineering. Another name is used for this process is chemical solution deposition method. In the sol-gel
process, at starting a colloidal suspension (i.e. called sol) is prepared for the growth of inorganic network and then
gelation process of the sol is carried out to form a network in a continuous liquid phase (i.e. called gel). The
precursors used for synthesizing these colloids usually consist of a metal or metalloid element surrounded by various
reactive ligands. The starting material is processed to form a dispersible oxide and forms a sol in contact with water
or dilute acid. Removal of the liquid from the sol produces the gel; the particle size and shape are controlled by
sol/gel transition. Calcination of the gel produces the oxide. The reactions involved in the sol-gel chemistry are
mainly based on the hydrolysis following by condensation of metal alkoxides wherein corresponding oxides and
mixed oxides with different stoichiometry [16, 17]. Nowadays this method is widely used to synthesize mesoporous
materials with the different morphologies. For the synthesis of mesoporous material by sol-gel process, different
templates can be used as the structure directing agents such as cat-ion surfactants, triblock copolymers and organic
small molecules [18].
354 Sunil Kumar et al./ Materials Today: Proceedings 4 (2017) 350–357

3.2. Template assisted technique

Template Assisted Technique is a well known and cheaper technique to synthesize ordered mesoporous
materials. In this technique, template is used to synthesize mesoporous materials. It can be classified into two
categories one is exotemplate method (hard matter templating) and another is endotemplate (soft matter templating).
In endotemplate a surfactant (structure directing agent) is used as template for synthesis ordered mesoporous
materials [15]. In endotemplate no hard template solid is used and therefore it is also called soft matter templating
method which is shown in figure 4.

Fig.4. Endotemplate (soft matter templating) method for porous materials.

In exotemplate method (“nanocasting”), a porous solid is used as the template in place of the surfactant. Thus,
this method is also known as “hard-matter templating”.The hollow spaces that provide the exotemplate framework
are filled with an inorganic precursor, which is then transformed (cured) under suitable conditions. In this way, the
pore system of the template is copied as a “negative image” after removal of the filled exotemplate framework [15];
thenincorporated material is obtained with a large specific surface area (figure 5.)

Fig. 5. Exotemplate (hard matter templating approach)

3.2.1 Liquid crystal template approach

In LCTA method, surfactant molecules are used as template to direct the structure of silica phase; no solid
template is used in this method. Therefore, it is also named as soft matter templating method [19].
In 1992, this method was first introduced to synthesis MCM-41 and two different pathways were suggested for
the formation of mesoporous structure. In first pathway, surfactant creates hexagonal structure before the silica
precursor is added. The silica framework is precipitated around this template, forming the mesoporous structure.
Surfactant is removed by calcinations process and mesoporous structure is obtained. In second pathway, after adding
the silica source hexagonal structure was formed [20]. Later This Synthesis method was studied in more detail and
concluded that mesoporous structure is formed by second pathway [21]. Possible synthesis pathways for synthesis of
SBA-15 (LCTA technique) is shown in figure 6.
 Sunil Kumar et al./ Materials Today: Proceedings 4 (2017) 350–357 355

Fig. 6. Possible synthesis pathways for synthesis of SBA-15 (LCTA technique).

3.3. Microwave assisted technique

The microwave hydrothermal process was discovered in 1992 and this process is used for the rapid synthesis of
numerous ceramic oxides, hydroxylated phases, porous materials and metal powders. The microwave-assisted
synthesis for making molecular sieves is relatively a new technique in the field of research’s technology area. Using
this process several types of zeolite manufactured (zeolite A, Y, MCM-41 etc.) As compared to conventional
process there are many advantages of this technique such as rapid heating to crystallization temperature, fast super
saturation by the rapid dissolution of precipitated gels and a shorter crystallization time compared to conventional
autoclave heating have been acknowledged [22].
In this technique structure directing agent with demonized water is kept on stirring at 400C for 4–6 hour. Then
mixture of demonized water, HCL, and 1, 2-bis(triethoxysilyl)ethane (silica source with ethane group) is added with
continue stirring homogeneous solution. The resulting mixture was transferred to the Teflon vessels, which were
installed in microwave oven at 1000C temperature. The self-assembly of organosilane precursors and block
copolymer and the subsequent hydrothermal treatment, were carried out under microwave irradiation. In the first
step, the synthesis mixture was stirred using magnetic bars for 2–24 h at 400C. After initial stage, temperature was
increased to 1000C and kept for 8 48 h under microwave oven without magnetic stirring condition. Then resulting
product was filtered, washed with demonized water, and dried in the oven at 800C. Periodic mesoporous
organosilicas with ethane and disulfide groups [23], mesoporous hectorites [24] was successfully synthesized by
using microwave-assisted technique.
Microwave assisted techniques have also been accepted for the synthesis of mesoporous materials. It was
reported that, MCM-41 mesoporous materials can be obtained via microwave heating using the Cetyl Trimethyl
Ammonium Bromide (CTAB) as the template and found that the result by microwave heating, high ordered
mesoporous materials can be synthesized within a very short time [25]. The microwaves can provide high localized
heating that may be higher than the recorded temperature of the reaction vessel. Hence sometime, microwave is a
best way for synthesizing mesoporous materials as well as other nonomaterials.

3.4. Chemical etching technique

In this technique the hollow type mesopores are created on the basis of structural differences between the core
and the shell of a silica core/mesoporous silica structure to create hollow interiors. By using this technique highly
dispersed hollow mesoporous silica with controllable pore size can be synthesized, which can be used as a
transporter for high loading capacity (1222 mg/g) for anticancer drug (doxorubicin). This technique can be used to
prepare different kinds of heterogeneous hollow type nanostructures with inorganic nanocrystals, such as Au, Fe2O3,
356 Sunil Kumar et al./ Materials Today: Proceedings 4 (2017) 350–357

and Fe3O4 nanoparticles, as the core and mesoporous silica as the shell. However, traditional methods such as
soft/hard templating methods, materials self templating to prepare mesoporous materials have limited success in the
preparation of particle/pore size controlling, morphology controlling. In the Traditional soft/hard templating
methods for hollow materials fabrication of uniform soft/hard templates are require and their surface
functionalization is done by the deposition of heterogeneous shells and soft templating method calcination process
for removing the cores strongly depend on the compositional variations [26].
But in chemical etching technique, a homogeneous templating route, namely, “structural difference-based
selective etching”, is applied to fabricate porous structure and create unique core/ shell structure . When an
appropriate etching agent is used then selective etching takes place at the interior while the outer shell remains
mostly intact, and a hollow structure forms as shown in figure 7.

Fig. 7. Chemical etching process

Route “A” represents the selective-etching procedure in Na2CO3 solution and route “B” for that in ammonia
solution under hydrothermal treatment.
Cornelia Rosu et al. used base induced chemical etching technique to tailor the internal architecture of fluorescent
simple silica into fluorescent meso- and macroporous particles [27]. Tiantian Li et. al. synthesized kaolin based
mesoporous silica, with improved specific surface area (604 m2/g) and large pore size (4.41 nm) at the maximum
probability via the successive treatments of natural kaolin by calcination, alkali activation and acid etching [28].
Ellipsoid silica nano shells are synthesized by from silica nanoparticles by using wet chemical etching technique.
Wet-etching approach is an attractive alternate procedure for the following reasons because it is a facile, one-step
process that directly produces (without template) ellipsoidal silica nanoshells with dimension than 100 nm. By using
an appropriate etchant, the roughness of the silica shells can be well-controlled and it results in tunable, uniform size
particles with controllable shell thicknesses [29].

4. Conclusions

Mesoporous materials are continuously synthesized via various methods because they have large surface area,
large pore volume for higher loading capacity and ability to attach different functional group for different
applications. In this paper most popular methods for the synthesis of mesoporous silica have been reviewed.
Templating method is more popular than other method because pore size and surface area controlled by using
structure directing agent functional group easily attached via post grafting. In chemical etching technique a selective
 Sunil Kumar et al./ Materials Today: Proceedings 4 (2017) 350–357 357

etchant is required to create hollow structure, sometimes etchant can disturb the pore structure. Microwave
technique is found as rapid synthesis of mesoporous silica materials but sometimes due to rapid heating pore
structure can be reduced. So for specific application a particular method should be used. Researchers are
continuously decreasing the limitation of synthesis and developing new method for mesoporous materials.

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