Sol-Gel processing of silica nanoparticles and their applications

L.P. Singh, S.K. Bhattacharyya, S. Ahalawat, R. Kumar, G. Mishra, U.

Sharma, G. Singh

PII: S0001-8686(14)00280-2
DOI: doi: 10.1016/j.cis.2014.10.007
Reference: CIS 1490

To appear in: Advances in Colloid and Interface Science

Please cite this article as: Singh LP, Bhattacharyya SK, Ahalawat S, Kumar R, Mishra
G, Sharma U, Singh G, Sol-Gel processing of silica nanoparticles and their applications,
Advances in Colloid and Interface Science (2014), doi: 10.1016/j.cis.2014.10.007

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 ACCEPTED MANUSCRIPT

Sol-Gel processing of silica nanoparticles and their applications

L.P. Singh*, S. K. Bhattacharyya, S. Ahalawat, R. Kumar, G. Mishra, U. Sharma, G. Singh
CSIR-Central Building Research Institute
Roorkee, 247667, India

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ABSTRACT

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Recently, silica nanoparticles (SNPs) have drawn widespread attention due to their
applications in many emerging areas because of their tailorable morphology. During the

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last decade, remarkable efforts have been made on the investigations for novel

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processing methodologies to prepare SNPs, resulting in better control of the size,
shape, porosity and significant improvements in the physio-chemical properties. A
number of techniques available for preparing SNPs namely, flame spray pyrolysis,

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chemical vapour deposition, micro-emulsion, ball milling, sol-gel etc. have resulted, a
number of publications. Among these, preparation by sol-gel has been the focus of
research as the synthesis is straightforward, scalable and controllable. Therefore, this
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review focuses on the recent progress in the field of synthesis of SNPs exhibiting
ordered mesoporous structure, their distribution pattern, morphological attributes and
applications. The mesoporous silica nanoparticles (MSNPs) with good dispersion,
varying morphology, narrow size distribution and homogeneous porous structure have
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been successfully prepared using organic and inorganic templates. The soft template
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assisted synthesis using surfactants for obtaining desirable shapes, pores, morphology
and mechanisms proposed has been reviewed. Apart from single template, double and
mixed surfactants, electrolytes, polymers etc. as templates have also been intensively
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discussed. The influence of reaction conditions such as temperature, pH, concentration

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of reagents, drying techniques, solvents, precursor, aging time etc. have also been
deliberated. These MSNPs are suitable for a variety of applications viz., in the drug
delivery systems, high performance liquid chromatography (HPLC), biosensors,
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cosmetics as well as construction materials. The applications of these SNPs have also
been briefly summarized.

Keywords: Silica nanoparticles, Sol-gel method, Polymer, Drug delivery system, Nano-
engineered concrete

*Corresponding author: Fax: +91 1332 272272, E-mail: [email protected]

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Contents

1. Introduction…………………………………………………………………………03
2. Preparation of nanoparticles…………………………………………………….05
2.1 Gaseous state preparation…………………………………………………….05

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2.1.1 Gas condensation……………………………………………………....05
2.1.2 Vacuum deposition and vaporization…………………………………06

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2.1.3 Chemical vapour deposition…………………………………………..06

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2.2 Solid state preparation ………………………………………………………..07

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2.2.1 Mechanical milling ……………………………………………………..07
2.3 Liquid state preparation…………………………………………………….....07

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2.3.1 Micro-emulsion Method………………………………………………..08
2.3.2 Sol-Gel Process………………………………………………………..08
3. Control of geometry and porosity……………………………………………..09
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4. Management of size and shape…………………………………………… .....12
4.1 Reaction kinetics…………………………………………………………........13
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4.2 Soft (surfactant) template synthesis………………....…………………...... 14

4.2.1 Single Template………………………………………………….........15
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4.2.2 Double/Mixed template………………………………………………..20

4.3 Hard template synthesis………………………………………………….......24
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5. Applications………………………………………………………………………..25
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5.1 Construction materials……………………………………………………......25

5.2 Drug delivery systems………………………………………………………...26
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5.3 Polymer nanocomposites……………………………………………………..27

5.4 Other applications……………………………………………………………..28
6. Conclusions ..............................………………………………………………28
Acknowledgement............................................................................................29
References ………………………………………………………………………….........30

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1. Introduction

In the last two decades, material science and engineering has come out with some
excellent nanomaterials exhibiting novel features due to their unique physio-chemical

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properties [1-3]. The preparation of nanoparticles like silica, alumina, titania, zirconia,

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silicon nitride, silicon carbide with improved properties has been successful in several

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areas [4-10]. Recent advances in the preparation of SNPs (<100nm) are focusing the
morphological architecture such as spheres, hollow spheres, fibers, tubules, helical

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fibers etc. At the moment, it is generally accepted that the reduction in size to sub-
atomic or nanolevel cannot be achieved with the conventional top-down methods,

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therefore, the bottom-up approach has been widely accepted as a promising route for
preparing nanoparticles. This strategy is faster, precise, energy efficient and therefore,
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extensive research is going on towards the preparation of nanoparticles through this
route. Several techniques are available to synthesize SNPs viz., flame spray pyrolysis,
chemical vapour deposition, sol-gel process, micro-emulsion etc., however, among
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these sol-gel process remains the most popular one, due to its ability to control the size,
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distribution and morphology of the particles through systematic monitoring of the

reaction parameters [11]. In 1864, the term ‗sol-gel‘ was firstly introduced by Graham
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during his work on silica sols [12]. The sol-gel technique offers a low-temperature
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method for synthesizing materials that are either purely inorganic or both inorganic as
well as organic. The process, based on the hydrolysis and condensation reaction of
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organometallic compounds in alcoholic solutions, offers many advantages for the

synthesis of nanoparticles including excellent control of the reaction kinetics, ease of
compositional modifications, customizable microstructure, introduction of various
functional groups etc. [13-16]. In the sol-gel process, there are two distinct stages
during the synthesis; the first stage is a colloidal suspension of particles in a liquid
medium that is referred to as the sol. The particles react with each other forming a
cross linked 3D polymeric chain which converts into gel in the second stage [17-19].

A number of modifications/developments in sol-gels process like the use of

surfactants/polymers as a template, varieties in precursors, reaction conditions, drying
techniques etc. have been reported in recent years [20]. Quaternary ammonium
cationic surfactants such as cetyltrimethylammonium bromide (CTAB) were the first
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used as templates to prepare highly ordered MSNPs. Since the applications of cationic
surfactants as template, this method has been widely used to prepare SNPs with high
surface area, tunable pore sizes, large pore volume etc.

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The MSNPs have a regular porous structure with uniform pore size, large surface area

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and superior thermal stability, therefore, they are suitable for a variety of applications in
the diverse fields such as drug delivery, biosensors, molecular separations, catalysis,

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HPLC etc.[21-26]. In drug delivery systems, MSNPs have been used as carrier of drug,

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as guest molecules are simply adsorbed on the mesopore surface of the SNPs. As no
functional group acts as a gate to control the release of the loaded substances, the

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release is controlled either by the size or the morphology of the pores. The MSNPs are
the material of interest, as the stationary phases due to their high connectivity,
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accessibility, defined porous structure and large surface area for HPLC applications. In
biosensors field, MSNPs improve the sensitivity and response time of sensors due to
their high porosity that allows large amount of sensing molecules encapsulated on the
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surface for quick response time and low detection limit. Highly dispersed SNPs
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enhance the thermal, mechanical, optical, abrasion resistance and surface hardness
properties of composite coatings. In the construction sector, SNPs are the innovative
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materials explored to enhance the strength and durability of cement based construction
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products. The use of SNPs in cement based products leads to three distinct
advantages. The first one is the production of ultra high strength and more durable
concrete for specific applications. The second, is the reduction of the amount of cement
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required in concrete of comparable strengths and thereby, decreasing the impact of

construction materials on environment. The third advantage is the reduction of
construction time as SNPs can produce high-strength concrete with less curing time.

To present an overview of recent research progress in the field of the preparation of

SNPs using sol-gel method exhibiting featured morphologies, uniform pore system, high
specific surface area etc., this review article is organized as follows:
The review outlines a general introduction of nanomaterials and classification of
preparation methods namely instrumental, mechanical and chemical. Next, the
influence of the reaction conditions like temperature, pH, concentration of reagents,
drying techniques, solvents, precursors, aging time etc. has been discussed.
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Thereafter, in the next section, the control of morphology and size of the SNPs using
soft templates viz., surfactants, electrolytes, polymers etc. has been extensively
reviewed. Finally, the applications of SNPs have been briefly summarized.

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2. Preparation of nanoparticles

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The manufacturing of nanomaterials can be classified as bottom-up and top-down
approaches (Fig. 1). The bottom-up approach involves building up from the atom or

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molecular constituents to meso-level and top-down approach involves making smaller

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sizes through etching or grinding from the bulk materials. There are varieties of
techniques available for preparing nanostructured materials and these can be divided

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into three based categories: MA
2.1 Gaseous state preparation
The metallic, metal oxides and ceramic nanomaterials can be prepared by this method.
This method involves:
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2.1.1 Gas condensation

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In this technique, a metallic or inorganic material is vaporized using thermal evaporation

sources such as a Joule heated refractory crucibles or electron beam evaporation
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devices, in an atmosphere of 1-50 m bar. The ultrafine particles are formed by collision
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of evaporated atoms with residual gas molecules requiring a gaseous pressure of more
than 3 MPa (10 torr). The vaporization sources may be resistive heating, high energy
and low energy electron beam. The clusters form in the vicinity of the source by
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homogenous nucleation in the gas phase grew by incorporation of atoms in gas phase.
It comprises of an ultra-high vacuum system fitted evaporation source, a cluster
collection device of liquid nitrogen filled cold finger scrapper assembly and compaction
device. During heating, atoms condense in the supersaturation zone, close to Joule
heating device. The nanoparticles are removed by scrapper in the form of a metallic
plate. The method is very slow and has limitations like a source-precursor
incompatibility, temperature ranges and dissimilar evaporation rates in an alloy [27-29].

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2.1.2 Vacuum deposition and vaporization

In the vacuum deposition process, elements, alloys or compounds are vaporized and
deposited in a vacuum [30-31]. The vaporization source vaporizes the materials by
thermal process. The process is carried out at a pressure of less than 0.1 Pa (1 m Torr)

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and 10-0.1 MPa in vacuum. The substrate temperature ranges from ambient to 500°C.

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For vacuum deposition, a reasonable deposition rate can be achieved if the
vaporization rate is fairly high. A required deposition rate is obtained at a vapour

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pressure of 1.3 Pa (0.01 Torr). The vapour phase nucleation can occur in a dense

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vapour cloud by multi body collisions. The resulted nanoparticles are in the range of 1
to 100 nm and called ultra-fine particles or clusters. The high deposition rates and

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economy are the advantages of vacuum deposition process. However, the deposition of
many compounds is difficult and nanoparticles produced from a supersaturated vapour
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are usually longer than the cluster [30].

2.1.3 Chemical vapour deposition

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To produce nanostructured materials and composite, chemical vapour deposition (CVD)

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is a well established method. In this method, a solid material is deposited on a heated

surface through a chemical reaction [32-33]. The activation energy, required to initiate
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the process, can be provided by several methods like in thermal CVD, the reaction is
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initiated at a high temperature (~1000°C). In plasma CVD, the reaction is activated by

plasma at a temperature range of 300-700°C. In laser CVD, pyrolysis occurs when laser
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thermal energy heats the absorbing material. In photo laser CVD, the chemical reaction
is initiated by ultra-violet radiation which has sufficient energy to break the chemical
bonds.

A typical bench-top instrument to prepare nanoparticles covering a wide range of

elements of periodic table is nanopowder synthesizer (NPS10). This technique is based
on flame spray pyrolysis that allows the production of a broad range of metal oxides
nanoparticles (SiO2, TiO2, Al2O3, Fe2O3 etc.). The flame spray pyrolysis is a single step
process. In this process a metal precursor, dissolved in an organic solvent, is sprayed
with an oxidizing gas into a flame zone [34-35]. The size and morphology of metal oxide
nanoparticles depend upon the nature of precursor and the operating conditions.

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2.2 Solid state preparation

2.2.1 Mechanical milling
The preparation of SNPs using mechanical milling (MM) method falls in top-down
approach. The MM is performed using high energy shaker, planetary ball or tumbler

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mills [36-37]. The physical and chemical properties of resultant material depend upon

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the milling material, milling time and atmospheric condition. The energy transferred to
the powder from refractory or steel balls depends on the rotational and/or vibrational

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speed, size and number of balls, ratio of the ball to powder mass, the time of milling and

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the milling atmosphere. The milling in cryogenic liquids can significantly increase the
brittleness of powders influencing the fracture process. This process is limited for the

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production of non-oxide materials because it requires the milling in an inert atmosphere
to prevent oxidation. The MM method of synthesis is suitable for producing amorphous
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or nanocrystalline alloy particles, elemental or compound powders. If the mechanical
milling imparts sufficient energy to the constituent powders, a homogeneous alloy can
be formed. Based on the energy of milling process and the thermodynamic properties of
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the constituents, the alloy can be rendered amorphous by this processing. The MM
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process includes high energy ball mill, low energy tumbling mill, centrifugal type mill and
vibratory type mill. The high energy ball milling is a well known method for the
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preparation of nanostructured materials. The attrition ball mill, planetary ball mill,
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vibrating ball mill etc. are common examples of high energy ball mills. Generally, the
amorphous alloys are produced using these high energy ball mills [38-39]. Low surface
area, heterogeneous size, partially amorphous states of resultant powder are some of
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the limitations of these processes. Apart from these, the contamination with iron is a
major drawback of these techniques.

2.3 Liquid state preparation

The chemical synthesis technique, to produce nanomaterials, is an extensively used
bottom-up approach. Usually, a chemical method is better than instrumental or physical
methods as the size and shape of materials can be precisely controlled at nano and
micro levels. This approach has some advantages such as low cost, higher productivity,
environmentally benign etc. For the preparation of SNPs through chemical route, two
methods namely microemulsion and sol-gel are generally used.

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2.3.1 Micro-emulsion Method

The micro-emulsion method is a widely used technique to prepare materials with novel
and unique properties at nano and micro levels [40-41]. The pure, bimetallic and multi-
metallic nanoparticles can be synthesised using this method. The nanoparticles of SiO2,

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CdSe, TiO2, ZnS, CaCO3 etc. with different size and shapes have been successfully

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synthesised by employing micro-emulsion technique. Usually, in this process two types
of emulsions are used; first is water-in-oil and second is oil-in-water. The micro-

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emulsions are thermodynamically stable colloidal nano-droplets which are stabilized by

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surfactant film and act as nano-reactors for the formation of nanomaterials. The size
and shapes of resulting nanomaterials are dependent upon the texture of these nano-

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droplets, reactant concentration, type of surfactant, concentration of capping agent etc.

2.3.2 Sol-Gel Process

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The sol-gel process, a frequently used technique for the preparation of SNPs, involves
the development of networks through an arrangement of colloidal suspension (sol) and
gelation to form a system in continuous liquid phase (gel) [42-43]. A sol is basically a
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dispersion of colloidal particles (1–100 nm) in a liquid and a gel is an interconnected

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rigid network with pores of sub-micron dimensions and polymeric chains. The sol-gel
process, depending on the nature of the precursors, may be divided into two classes
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namely inorganic precursors (chlorides, nitrates, sulfides, etc.) and alkoxide precursors.
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The extensively used precursors are tetramethoxy silane and tetraethoxy silane. In this
process, the reaction of metal alkoxides and water, in the presence of acid or base,
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forms a one phase solution that goes through a solution-to-gel transition to form a rigid,
two-phase system comprised of solid metal oxides and solvent filled pores. The
physical and electrochemical properties of the resultant materials largely depend on the
type of catalyst used in the reaction. In the case of silica alkoxides, the acid catalyzed
reaction results in weakly cross-linked linear polymers. These polymers entangle and
form additional branches leading to gelation. Whereas, base-catalyzed reaction, due to
rapid hydrolysis and condensation of alkoxide silanes, forms highly branched clusters
(Fig. 2) [44].

This difference in cluster formation is due to the solubility of resultant metal oxides in
reaction medium. The solubility of the silicon oxide is more in alkaline medium which

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favors the inter-linking of silica clusters than acidic medium. A general procedure of sol-
gel includes four stages namely hydrolysis, condensation, growth and aggregation.

Hydrolysis: Si–(OR)4 + H2O Si–(OR)3(OH) + ROH

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The complete hydrolysis to form M(OH)4 is very difficult to achieve. Instead,

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condensation may occur between either two –OH or M–OH groups and an alkoxy group
to form bridging oxygen and a water or alcohol molecule. A condensation reaction

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between two –OH with the elimination of water is shown below. The condensation

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reaction between two hydroxylated metal species leads to M-O-M bonds following
release of water (oxolation). The reaction between a hydroxide and an alkoxide leads

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to form M-O-M bonds following release of an alcohol (alkoxolation).

Condensation: (OR)3–Si-OH + HO–Si–(OR)3 [(OR)3Si–O–Si(OR)3] + H–O–H

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The hydrolysis and the polycondensation reactions are initiated at numerous sites and
the kinetics of the reactions are therefore complex. When a sufficient number of
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interconnected M–O–M bonds are formed in a particular region, they interact

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cooperatively to form colloidal particles or a sol. With time the colloidal particles link
together to form a three-dimensional network. The possible mechanisms for both acid
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and base catalyzed reactions in case of silicon alkoxides are as shown in schemes. 1
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and 2 [45-47].

3. Control of geometry and porosity

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There is a great deal of interest in exploring the use of surfactants for the refinement of
porous structure of SNPs. Nooney et al. used both cationic CTAB and non-ionic
surfactants (n-dodecylamine) as templates and showed that MSNPs with a wide range
of diameters, varied from 65 to 740 nm, were synthesized by simply varying the TEOS–
surfactant ratio under dilute conditions [48]. When an aprotic co-solvent was used to
create a homogeneous condition, spherical MSNPs with smooth surfaces were
observed to be formed. Further, they proposed a mechanism for the formation of
ordered MSNPs using CTAB as a template (Fig. 3). According to this mechanism
particle growth may occur through one of the following possible mechanisms.

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i. Deposition of monomeric silica and surfactant ions onto existing primary particles in
a continuous process.
ii. Directional aggregation in which primary particles orderly agglomerate together.
iii. Non-directional aggregation where primary particles agglomerate in a disordered

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manner.

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An interesting work on the radial ordered mesoporous silica spheres using an anionic
surfactant was done by Wang et al. [49]. A commercial anionic surfactant N-lauroylsar

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cosin sodium (Sar-Na) was employed due to its biodegradability, low toxicity and low-

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cost. An isotropic morphology like elliptical, peanut like and trifurcate particles, instead
of spheres, were obtained when the pH of reaction lowered to 5.8. The microscopic

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studies revealed that MSNPs contains centrosymmetric radial mesopores. Further, it
was concluded that the lowering of pH leads to an increase of specific surface area
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from 325 to 775m2/g, pore volume from 0.32 to 0.77cm2/g and pore diameter from 3.1
to 3.3 nm, respectively. They proposed a re-alignment self assembly mechanism for the
formation of the SNPs with radial mesopores (Fig. 4). In this mechanism, clusters of
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organic–inorganic composite were reported to form due to self-organization between

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the silica precursors and the surfactant micelles. In addition to this, the clusters
aggregates were noticed to form larger spherical organic/inorganic hybrid. At this stage,
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the surfactant/silica hybrid particles would be soft, i.e., the silica is less cross linked and
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the composite is liquid-like and liable to be shaped. For the spherical shape,
centrosymmetric radial array of the silica-coated micelles (a hybrid mesophase) would
be the preferential structure to minimize its surface free energy. Therefore, the final
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ordered structure of the spherical morphology exhibited a radial mesoporous

orientation.

A novel mesoporous silica sphere with uniform diameter and starburst like mesopore
canals, using CTAB as a templating agent, was synthesized by Zhang et al. [50]. The
arrangement of pore diameter of the sphere was tailored by altering the concentration
of ethanol. Ethanol may acts as a ‗spacing agent‘ to adjust the interaction between
ethanol and the cationic surfactant and the hydrophilic-hydrophobic balance of the self
assembly system. The group proposed a ‗Liquid Crystal Initiated Templating‘
mechanism for the hexagonal array of the micellar rods. In this mechanism, initially
hydrolysis of alkoxide occurs in a regular fashion following self organisation of

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surfactant and finally, surfactant combines with silica oligomers. This mechanism is
suitable for the formation of mesoporous silica MCM-41. Further, a mechanism for the
preparation of mesoporous silica with egg-shell and starburst pore canal structure was
proposed. According to this mechanism, firstly, in a very dilute aqueous solution,

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surfactant micelles and micellar rods were formed and then these rods self assemble to

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the lamellar phase. Further, a mixed lamellar-hexagonal membrane, separated by water
layers in the surfactant silicate system, was reported to be formed (Fig. 5).

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Cai and others [51] presented a comprehensive study on the formation and control of
morphologies of MCM-41 using a cationic surfactant CTAB as a template. In this

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mechanism, deposition of self assembled rod like silicate micelles controls the
morphologies of MCM-41. The formation of mesoporous silica particles followed by the
nucleation involves interaction of silica with surfactant that facilitates the assembly of
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rod like silicate micelles. The Inorganic/organic self assembled silicate micelles (SSMs)
were immediately formed as the two precursors (surfactant and inorganic solution
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containing predominantly multiply charged silicate anion at a certain pH) mixed. The
driving force for the formation of SSMs was provided by the ion exchange of silicates
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oligomers with Br- and OH- anions. A sub-micron sized silica rod with 0.7-1μm in length,
0.3-0.6 μm in diameter was synthesised.
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Suzuki and co-workers [52] prepared SNPs with a well-ordered mesostructure having a
uniform aperture (approx. 2nm), using a double surfactant system. Cationic surfactant
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as a templating agent and nonionic surfactant (triblock copolymer pluronic F-127) as a

suppressant of gain growth were used. The microscopic studies of synthesized SNPs
with well-ordered hexagonal mesostructure revealed that the average particle size of
SNPs, using a non-ionic surfactant, was 20-50 nm. A mechanism for the formation of
well ordered hexagonal mesostructure (approx. 2 nm) using a double surfactant system
was also proposed. In this mechanism, acidic condition endorses hydrolysis of alkoxide
and decreases the residual ethoxy groups. The subsequent addition of base catalyst
(ammonia) was found to be effective in the formation of well-ordered mesostructures
through steady self-assembly of negative charged silicates and positive charged
surfactant micelles. Due to this slow assembly of negative charged silicates and

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positive charged surfactant, hexagonal structure was predominantly constructed

regardless of the presence of non-ionic surfactant (Fig. 6).

Continuous efforts are being made in the direction of preparation of various

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morphologies/textures such as nano-spheres, submicron size oblate particles,

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micrometer size nanorods, cubic and spherical hollow nanoparticles, nanotubes etc. of
the SNPs employing organic or inorganic templates such as ionic and non-ionic

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surfactants, polymers etc. Ding and associates [53] proposed a mechanism for the

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preparation of silica hollow nanospheres. In this work, first, the authors prepared 3-
methactyloxylpropyl trimethoxysilane (KH570) and polystyrene (PS) polymer particles

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by the dispersion copolymerization. In the second step, a core of silica was prepared on
KH570/PS polymer particles by polycondensation of TEOS in ethanolic ammonia
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suspension. Further, the polymers particles were calcined at 800°C to obtain hollow
silica nanospheres (Fig. 7).
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The hollow silica nanospheres were prepared by Chen et al. [54] using surface initiated
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atom transfer radial polymerization (ATRP). In this study, hollow silica nanospheres
were synthesized in three steps: surface functionalization of inorganic or polymer
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particles, conversion of functional groups into an outer layer or shell and removal of the
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template core. First, polyvinylbenzyl chloride (PVBC) latex particles (~100nm) were
prepared by emulsion polymerization. The silyl functional group was introduced onto the
PVBC nanoparticles templates via surface initiated ATRP of 3-(trimethoxysilyl) propyl
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methacrylate. The silyl group was then converted into silica shell (~20nm) via a reaction
with TEOS in ethanolic ammonia. Hollow silica nanospheres were finally produced by
thermal decomposition of PVBC template core (Fig. 8).

4. Management of size and shape

The size, shape and morphological features of SNPs can be controlled by reaction
kinetics, use of templates such as cationic, non-ionic surfactant, polymers, electrolytes
etc. A variety of templates have been successfully demonstrated for the formation of
nanomaterials. Generally, these templates are classified as ‗soft template and hard
template‘. The hard templates remain physically involved and, hence, need to be

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selectively removed after the synthesis of desired nanostructure. However, the soft
templates are normally involved in chemical synthesis procedure.

4.1 Reaction kinetics

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In 1968, Stöber and co-workers [55] developed a process capable of forming controlled

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silica particles (500 nm-2 μm) using tetraethoxysilane (TEOS) as silica precursor, water,
ethanol and ammonia. The process was carried out at room temperature and higher pH

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(~10). The silica particles had a narrow size distribution and could be controlled by

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adjusting the pH of solution, composition of reactants and temperature. Guo and others
[56] reported a method for the preparation of monodispersed SNPs (~10-100nm) using

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one of the most affordable silica precursor i.e. elemental silicon. The ultrasonication
technique in sol-gel process to prepare monodispersed and uniform size SNPs, for the
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first time, was used by Rao et al. [57]. The effects of temperature and concentration of
TEOS, ammonia, water, ethanol on the texture of SNPs were also systematically
analysed. The particle size of SNPs was reported to be increased with a rise in the
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concentration of TEOS and ethanol. A decrease in particle size was observed with
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increasing concentration of ammonia and water. Yu et al. [58] prepared high purity
dispersed silica nanocubes (~30nm) using tartaric acid as organic template by sol-gel
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method. Sadasivan and associates [59] prepared ultrafine silica particles (20-60 nm) by
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hydrolysis followed by condensation of TEOS in methanol medium.

The mesoporous silica particles was prepared by Liu et al. [60] using
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poly(ethyleneoxide) – poly(propylene oxide) – poly(ethylene oxide) as a template with

sodium silicate and TEOS in a buffer solution (pH~4.4). By changing the molar ratio of
sodium silicate / TEOS, highly ordered mesoporous silica particles with pore diameter
of around ~15nm and the cage size of 14-36 nm were obtained. Gu and others [61]
prepared mesoporous SNPs based on suppressed growth strategy in a TEOS-CTAB-
NH4OH- formaldehyde system. In this system, formaldehyde formed a polymer shell on
the outer surface of SNPs to control the particle size. Zhang et al. [62] investigated a
facile synthesis of MSNPs with controlled morphologies using ammonia catalysed
hydrolysis of TEOS in a water-acetone medium at room temperature. The morphology
of the obtained SNPs was tailored from nanorods to nanospheres by simply adjusting
the water to acetone molar ratio.
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Wang et al. [63] reported an economical method to prepare uniform sized (12-36 nm)
SNPs using primary amines as base catalyst. The size of SNPs was observed to be
decreased with an increase in pH of reaction mixture. Nozawa and others [64] prepared

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monodisperse SNPs by using a single parameter procedure of the progressive addition

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of a diluted TEOS solution in ethanol. The rate of addition of TEOS was considered as
a dominant factor on the final size and polydispersity of SNPs as the particle size was

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decreasing with increasing the rates of addition of TEOS. Kim et al. [65] prepared

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nanoporous silica particle for enzyme support via a salt route. The silica particles with
1-15 nm pore diameter were synthesized by acid decomposition reaction using the

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silicate salt as a precursor. Arai and co-workers [66], using TMOS as silica source,
prepared cocoon shaped SNPs having excellent abrasive properties. The effects of
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temperature and rate of supply of reactants were also examined. The diameter and
shape were strongly dependent upon the temperature. The particles with high aspect
ratio and the small diameter were obtained at high temperature. The size of SNPs was
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found to be increased with rising supply rate of reactants.

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Choa et al. [67] investigated metal oxide incorporated mesoporous SNPs and
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Nanotubes. Edrissi et al. [68] prepared SNPs with an average particle size of about
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13nm with narrow size distribution by the ultrasonic assisted sol-gel method. The
particle size of SNPs was decreased with increasing the concentration of ammonia and
water. Low TEOS concentration and high temperature were found to be suitable for
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producing smaller particle size of silica.

4.2 Soft (surfactant) template synthesis

The nanostructured materials are frequently synthesised through the surfactant-
templating approach in which silicate species (inorganic part) are jointly congressed
with amphiphilic molecules (surfactant) via non-covalent interactions i.e. hydrogen
bonding and electrostatic interactions in aqueous media. These interactions, between
silicates and surfactant are the key factors to tune the sizes, morphology and a large
variety of mesoporous structure. The surfactants have two distinct regions in their
chemical structure, one is hydrophilic and the other is hydrophobic. These molecules
are referred to as amphiphilic or amphipathic molecules. Amphiphilic surfactants are

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characterized by the hydrophilic-lipophilic balance (HLB), a relative ratio of polar and

non-polar groups in the surfactant. This means the balance between the oil soluble and
water soluble moieties in a surface active molecule. Compounds with a high HLB >12
are principally hydrophilic and water-soluble. Those with very low HLB values are

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hydrophobic and water-insoluble [69]. The surface activity of a particular surfactant

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depends on the balance between its hydrophilic and hydrophobic properties.

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An amphiphilic molecule can arrange itself at the surface of the water in such a way that

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the polar part interacts with the water and the non-polar part remains above the surface
(Fig 9). The presence of these molecules on the surface disrupts the cohesive energy

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at the surface and thus, lowers the surface tension. Another arrangement of these
molecules can allow each component to interact with its favoured environment [70, 71].
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The molecules can form aggregates, at critical micelle concentration (Fig 10), which are
called micelles.
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4.2.1 Single Template

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Two burgeoning areas of current research in the chemistry of nanomaterials are

manufacturing the nano-scale devices and synthesis of nano-structures with ordered
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meso-porosity. The soft template assisted preparation is a comfortable way to obtain

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materials at nano level. Hoshikawa and co-workers [72] prepared dispersed MSNPs of
40-80nm size in alcoholic medium by simultaneous trimethylsilylation modified
extraction. The authors used 1,3,5-trimethybenzene (TMB) as a swelling agent to
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enhance the porosity of the nanoparticles. SEM and TEM micrographs of three samples
prepared with molar ratios of TMB/CTAB 0, 2 and 4, respectively are illustrated in Fig
11. The increase in pore diameter by addition of TMB was evident. Ekloffa et al. [73]
developed a procedure for the synthesis of mesoporous silica with regular morphology
and bimodal silica (BMS) containing pore size of about 3-30 nm. This new procedure
was based on the ethyl acetate hydrolysis for achieving uniform acidification during the
precipitation of silica controlled by the structure directing agent i.e. CTAB. SEM
micrographs (Fig 12) of BMS1, BMS2 and BMS3 containing 15, 25 and 35 ml of ethyl
acetate, indicated that BMS3 had a spherical morphology. The ‗end effect‘ mechanism
of cylindrical micelles for the development of worm-like morphology was also proposed
[74].
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Boonamnuayvitaya et al. [75] studied the effect of type and concentration of surfactant
in acidic and basic medium. They used CTAB, sodium dodecyl sulphate (SDS) and Brij-
56 as a cationic, anionic and non-ionic surfactant, respectively. A large surface area

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(1282 m2/g) was obtained by using CTAB as template in acidic conditions. Using CTAB

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as a template, pore volume and average pore diameter increased with increasing
surfactant content. Brij-56 templated silica in basic medium had the highest pore

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diameter (14.4 nm). The use of Brij-56 as pore forming agent exhibited the same trend

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of results as observed using CTAB. With increasing the SDS content the pore volume
and average pore diameter observed to be decreased because SDS adhere together to

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a mass on increasing the SDS content [76-77].
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Whitsitt and Barron [78] investigated the effect of surfactant type and concentration on
the particle morphology for liquid phase deposition (LPD) of SNPs.
Dodecyltrimethyammonium bromide (DTAB), SDS and sodium dodecylbenzyl sulphate
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(SDBS) were used as ionic templates. It was proposed that the charge of the surfactant,
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CMC and the ionic strength of solution were responsible for the agglomeration of SNPs.
The average particles size of the spheres using DTAB, SDS and SDBS were 230, 150
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and 300 nm, respectively. Zhang and others [79] synthesized SNPs using CTAB,
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having hexagonal-like mesoporous structures with average pore size ranging from 2.7
to 3.3 nm and surface area from 806-1055 m2/g. The morphology of mesoporous silica,
from nanococons to nanorods to nanospheres, was controlled by decreasing molar ratio
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of water-to-acetone.

The mesoporous silica nanotubes (30-100 nm) were prepared by Lin et al. [80]. The
nanotubes and gyroidal spheres of silica, using C18TMAB as a structure directing agent,
were obtained in acidic medium [81]. The authors observed that employing template not
only controlled the morphology but also gave high yield (90%) of SNPs. The average
diameter and length were 80-150 nm and 300-400nm, respectively. The results
revealed that the silica nano-ropes looked like multi-walled carbon nanotubes. During
the preparation of gyroidal spheres followed by hydrothermal treatment of ammonia,
many of the gyroidal spheres were broken, revealing the interior as hollow with a centre
pillar. The thickness of hollow gyroidal spheres shells was <0.2µm.
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Yuan and others [82] fabricated nanosized hollow spheres of silica by introducing
polystyrene. They employed emulsifier- free emulsion for the preparation of nano-sized
polystyrene particles. Subsequently, hollow nanospheres of silica were formed through

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a simultaneous ‗coating – etching‘ process. The nanoparticles of polystyrene (PS)

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showed a zeta potential of +4.94 mV under neutral condition. The coupling effect of
polyvinylpyrrolidone (PVP) rather than electrostatic interaction was responsible for

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porous silica shell formation. The results revealed that the thickness of silica shell

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increased from 2 to 7 nm as the concentration of TEOS increased from 0.1 to 0.3 ml.
An interesting study on the effect of procedure of adding reagents was also examined.

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According to this study, morphology of the resultant silica hollow sphere depended not
only on the concentration of reagents but also on the procedure of adding them into the
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medium. Vankatathri synthesized mesoporous silica nanospheres using different
templates such as CTAB, CTACl, n- octylamine and tetrapropylammonium bromide
(TPABr) [83]. The SNPs obtained using CTAB, CTACl and n-octylamine were spherical
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in shape and average diameters were 500nm - 2µm, 100-300 nm, 200-400 nm,
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respectively.
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Yu and others [84] presented an interesting method for the preparation of hierarchical
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silica nanotubes. Self assembled chiral anionic surfactants [N-palmitoyl-L-alanine(C16-L-

Ala), N-palmitoyl-L-valine(C16-L-val), N-palmitoyl-L-Leucine(C16-L-Leu), N-palmitoyl-L-
isoleucine(C16-L-Ile), N-palmitoyl-L-methionine(C16-L-Met), N-palmitoyl-L-
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phylalanine(C16-L-Phe), N-palmitoylglycine(C16-Gly) and N- palmitoyl-2-aminoisobutyric

acid C16-Z-AIBA] were used. The nanotubes with average lengths, ranged from 1-3μm,
and inner diameters ~94nm were synthesized at molar ratios 0.45 and 0.3 of HCl/ C14-
L-AlaS & TMAPS/ C14-L-Al, respectively (Fig. 13). SEM analysis revealed that silica
nanotubes with different pore system were prepared using various anionic carboxylate
surfactants namely C16-L-Leu, C16-L-Ile, C16-L-Met, C16-L-Ala, C16-L-Val and C16-L-
Phe.

A report on the preparation of various morphologies such as double helical mesoporous

silica nanofibers, single-strand coiled mesoporous silica nanofibers and twisted
mesoporous silica ribbons, using chiral surfactant as a template, was presented by
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Yang et al. [85]. Sadasivan and others [86] investigated the model for the nucleation of
mesoporous SNPs under specific conditions. The results indicated that the nucleation
of SNPs occurred heterogeneously by a disorder-order phase transition within silica-
surfactant micellar aggregates less than 50nm in size. Fowler and co-workers [87]

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prepared thermally stable mesostructured SNPs with average diameter of 15nm at

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room temperature. MCM-41 silica was prepared by hydrolysis and condensation of
TEOS using CTAB followed by neutralization with dilute HCl. The microscopic studies

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of synthesized silica showed that the particles were spherical and slightly faceted with

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well defined edges with a mean size of 100nm. The mean particle size was 23 nm and
degree of mesostructural order in the nanoparticles reduced when the length of time

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between dilution and neutralization of reaction mixture allowed to be decreased.
Haskouri and others [88] presented, for the first time, a generalized method for the
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preparation of bimodal porous silica with organically modified surfaces. CTAB was used
as a single structural directing agent. The nucleation and crystal growth process led to
primary mesostructured nanosized particles (20-40nm) which were linked together
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through covalent Si-O-Si bonds. This special morphology was obtained at pH~ 9.3.
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The fluorinated surfactants, due to their unique assembling capacity into aggregates
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and forming novel intermediate mesophases more easily than hydrocarbon, are now
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being employed as a template for the preparation of porous inorganic materials. Tan et
al. [89] presented a comprehensive investigation on controlling the pore size and shape
of silica nanomaterial using cationic fluorinated surfactants. A homologous series of
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perfluoroalkylpyridinium chloride surfactants (UKA6-1, UKA8-1, UKA9b-1, UKA10-1,

UKA11b-1, UKA12-1) with tail lengths between 6-12 carbons were synthesized and
used for SNPs preparation (Fig. 14). TEM analysis showed that using UKA6-1 irregular
morphology and uniform worm hole-like pore structure, ordered 2D hexagonal structure
with UKA8-1; spherical morphology with worm hole-like pores structure using UKA 9b-
1, elongated particles with a highly ordered layered pore structure using UKA 10-1,
spherical morphology at nanolevel using UKA11b-1 and composed crumbled sheet of
silica using UKA12-1 were obtained. Trewyn et al. [90] prepared fluorescein-labeled
MSNPs consisting of spherical and tube-shaped particles.

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The MSNPs were synthesized using a variety of silica precursors like n-alkoxysilanes,
n-alkylamines, sodium silicate aerosol etc. [91-95]. Yu et al. [96] synthesized ordered
MSNPs using iron ore tailings as a silica source and n-hexadecyltrimethyl ammonium
bromide as a template. Microscopic studies revealed that ribbon like morphology of

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SNPs were obtained. Singh et al. [97] analysed the effect of cationic surfactant

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containing carbon chain (C15, C17 and C19) on average particle size and morphology.
The average particle size of silica nanosphere dropped down from 150 to 50nm using

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C19TAB surfactant.

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The biometric synthesis of silica nanotubes from self assembled ultra short peptide as a

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template was reported by Wang et al. [98]. The studies on the effect of concentration of
TEOS and pH on the morphology and size of silica nanotubes showed that the outer
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diameter seem to increase slightly, but more and more random precipitation occur with
increasing TEOS concentration. At pH-5, tubular morphology of silica precipitates was
observed. A subsequent increase to pH-7 led to silica deposition mainly on the surface
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of the peptide template. At pH-9 tubular silica structures with uniform diameter was
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formed. Buchel and others [99] prepared spherical mesoporous silica with average
particle size 100 nm to 2μm. The porosity was created by adding two different types of
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pore structure directing agent, n-alkyltrialkoxysilon and n-alkyl amine. N-

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alkyltrialkoxysilane was covalently bonded to the silica framework, however, n-alkyl

amine acted as a non-ionic template. After treatment a specific pore volume of 0.8
cm3/g, an average pore diameter between 2 and 6 nm and specific surface area 1019
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m2/g were obtained.

Lelong et al. [100] investigated the effect of surfactant (CTAB) concentration on

morphology and texture of MCM-41 (Fig. 15). A non-organised worm-like porosity which
was progressively replaced by hexagonal packing of cylindrical pores was observed at
5% concentration of surfactant. At 2.3% concentration, large domains of channels
organized into honeycomb structure were obtained. By decreasing the surfactant
concentration to 1% the wide domains disappeared gradually to form smaller particles
with a more rounded shape. For the 0.1% concentration close to CMC, the spherical
particles become more homogeneous in size with a smaller mean diameter (125 nm). A
decrease in CTAB concentration led to an increase in sphericity.
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The amino-modified, ordered SNPs, using CTAB as template, were prepared by

Puanngam and Unob [101]. 2-(3-(2-aminoethylthio) propylthio) ethanamine was used to
functionalize silica. Singh et al. [102] prepared uniform silica nanospheres of about

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70nm size using a series of non-ionic surfactant (span 20, span 40 and span 60). The

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results of the studies showed that an increase in hydrocarbon chain length of surfactant
led to decreases the particle size (Fig. 16). Further, an increase in the particle size of

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SNPs as a result of increase in pH was also observed.

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4.2.2 Double/Mixed template

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Since the discovery of a novel family of MCM-48, by mobile researchers, there has
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been a considerable interest in the use of mixed doubled surfactant system as a
template for the synthesis of SNPs with unique mesostructure. Jana et al. [103]
established a new synthesis route for the preparation of pure mesoporous silica
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materials having a rod like morphology. In this new procedure a series of

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tetraalkylammonium salts, in addition to CTAB, were employed to enhance the stability

and bring about the long range ordering in the mesoporous materials. The final silica
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mesoporous materials using tetramethylammonium bromide, tetraethylammonium

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bromide and tetrabutylammonium bromide were designated as Si-MCM-41@TMA, Si-

MCM-41@TEA and Si-MCM-41@TBA, respectively. The specific surface areas of Si-
MCM-41@TMA, Si-MCM-41@TEA and Si-MCM-41@TBA were found to be 1136, 957
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& 350 m2/g, respectively. SEM studies of Si-MCM-41@TBA revealed that the calcined
bulk solid of Si-MCM-41@TBA contained primarily 36-40 µm long single crystal like
particles exhibiting rod like morphology. Some of the rods had sharp hexagonal ends,
while the others rounded ends. The outcomes of these studies showed that a semi-
hexagonal face of the rod was observed at a lower resolution and at higher
magnification pores consist of hexagonal voids of the Si-MCM-41@TBA. Venkatathri
and Nanjundan prepared mesoporous silica nanostructure by employing polystyrene
and cetyltrimethylchloride as templates [104]. A mechanism proposed for the
preparation of mesoporous silica nanosphere showed that first polystyrene particles got
isolated. These isolated polystyrene spheres were surrounded by surfactant. The silica
layers were formed over surfactant layers giving silica nanosphere. On calcination, the
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polystyrene and surfactant were removed and the hollow silica nanospheres obtained.
The microscopic studies revealed that particle size and shape were uniform with a core
size of 300nm and shell size 50nm. Maybodi and Vahid [105] prepared well ordered
hexagonal pores structure of SNPs using sodium carboxy methyl cellulose. Sodium

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silicate solution was used as silica source and carboxy methyl cellulose (CMC) with

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CTAB as a template. Highly ordered SNPs were formed with CMC however, without
CMC the formation of conventional MCM 41 was observed.

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Chen et al. [106] prepared MCM-48 silica using mixed cationic-anionic surfactants as
templates. CTAB was used as a cationic surfactant and sodium laurate as an anionic

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surfactant template. They proposed electrostatic templating route for the preparation of
MCM-48 silica. The carboxylate anionic surfactant was reported to function as a polar
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organic co-solvent in this system. There were two kinds of forces between cationic and
anionic surfactants namely Vander Waals force between hydrocarbon chains in the
mixed micelles and electrostatic attraction between quaternary ammonium ion and
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carboxyl ion. As a result of the balance between the two forces, the hydrocarbon chains
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of anionic surfactant may not enter the micelles core, but were located at the
hydrophobic- hydrophilic portion of the micelles and, therefore, formed a thick palisade
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layer.
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The helical mesoporous SNPs functionalized by mercaptopropyl group with C2mm

symmetry by using mixed cationic and nonionic surfactants were prepared by Huang et
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al. [107]. CTAB was used as a cationic surfactant and tetraethylene glycoldodecyl ether
(C12EO4) as non-ionic surfactant. The mesostructure transformed towards P6mm phase
when the amount of mercaptopropyl trimethoxysilane was increased and a reverse
P6mm to C2mm transformation took place as the mole percentage of C 12EO4 was
further increased. A mechanism based on the kinetics of the cooperative assembly of
silicate species and the micelles of mixed surfactants was proposed. Upon being added
into the synthesis solution, TEOS and MPTMS readily hydrolysed to form anionic
silicate species that diffuse and preferentially absorb onto (CTA+) cations in the
micelles.

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Pang and workers [108] synthesized mesoporous silica using a cationic surfactant
(CTAB) and an anionic sulphonated aromatic poly ether ether ketone (SPEEK) or
cationic poly allylamine hydrochloride (PAACl) as co-template under basic conditions.
The use of CTAB/SPEEK as structure directing agent resulted in hierarchical

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mesoporous silica that contained hexagonally ordered mesopores (20-50nm). On the

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other hand the use of CTAB/PAACl resulted into mesoporous silica with unimodal pores
(2-3nm). Nan and co-workers [109] prepared MCM-41 mesopores silica using the self

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assembly β-cyclodextrin (β-CD) and CTAB as structure directing agents. The pore

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structure of the resulting mesoporous silica belonged to the two dimensional hexagonal
structure (space group P6mm). The pore size and the pore wall thickness of the silica

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increased with the rise of molar ratio of β-CD to CTAB. The particles with elliptic shapes
about 300 and 600nm diameter were obtained in the absence of β-CD. The particles
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transformed to uniform spheres in the presence of β-CD at molar ratio of 0.1, 1.0, 2.0
and to irregular shape at molar ratio of 5.0. The size of particles changed by varying the
additive of β-CD and reached the smallest size of about 200nm at molar ratio of 1.0.
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The rod like mesoporous silica with hexagonal appearance using mixed surfactants of
CTAB and CTACl was prepared by Han and associates [110]. At a molar ratio of 9:1
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(CTAB-CTACl), regular rods like shapes were obtained. The rod like morphology had a
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regular hexagonal appearance with the decrease of molar ratio of CTAB from 9:1 to 8:2.
Zhang et al. [111] presented a pore size enlarged magnetic mesoporous SNPs (M-
MSN) system through the utilization and combination of organic pore swelling agent.
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CTAB and 1, 3, 5-triisopropyl benzene (TMB) was used as a template and pore swelling
agent, respectively. The pore size was increasing with the addition of a limited amount
of TMB, while further addition led to particle coalescence and random pore structure.
The resultant M-MSN materials had particle size (about 40-70nm in diameter), tunable
pore sizes (3.8-6.1nm), high surface areas (700-1100m2/g) and large pore volume
(0.44-1.54 cm2/g).

By using a mixed cationic-nonionic surfactant and varying pH, Zhai and others [112]
prepared a high quality MCM-48. CTAB was used as cationic surfactant and p-
octylpolyethylene glycol phenyl ether (OP-10) as non-ionic surfactant. The use of mixed
surfactants allowed better condensation and higher ordering of the cubic mesostructure.
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A reaction mechanism was proposed and according to it, OP-10 dissolved easily in
water and formed mixed micelles with cationic CTAB molecules through hydrogen-
bonding and strong Vander-Waals forces. The hydrocarbon chains of the OP-10 were
oriented into the interior of the micelles and big polar head group were located

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preferentially at the exterior interface. OP-10 played a role of auxiliary modifier which

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was significant in self-assembly procedure of micelles [113]. Le and others [114]
reported a novel synthesis pathway for silica hollow nanosphere (40nm) with

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mesoporous walls. The double-template (inorganic-organic) route was employed with

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calcium carbonate as spherical template and hexadecyltrimethyl ammonium bromide
(C16TMAB) as mesostructure directing agent for the preparation of silica hollow

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nanospheres. MA
He and co-workers [115] prepared dispersed mesoporous silica nanosphere with
controllable size under a neutral condition using CTAB and Brij 56 as structure directing
agent. The effects of temperature, structure directing agent and multistep addition mode
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on particle size and the dispersivity of SNPs were examined.The results showed that
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the silica nanospheres became bigger from 42-188 nm and more uniform in size with
the increase of temperature from 298 to 368K. The use of cationic-nonionic composite
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surfactant of CTAB and Brij 56 resulted into the improved dispersivity, spherical shape
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and the decreased particle size from 188 to 72 nm. Further, multistep addition modes of
TEOS contributed to the better monodispersivity and larger size of silica nanospheres.
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Ohkubo and others [116] developed a method to obtain precisely controlled

mesoporous silica particles using a cationic and anionic mixed surfactant system. The
pore structure of the synthesized silica particles was controlled between 3.22-3.66 nm
with the mixed surfactant system. Mori et al. [117] prepared micro-mesoporous SNPs
with a particle diameter of 40-90 nm by a two step reaction based on the polymerization
of TEOS confined to the mixed surfactant hexagonal structured liquid crystal template.
The nonaethylene glycol dodecylether (C12EO9) and polyoxyethlene (20) sorbiton
monostearate (Tween 60) or eicosaethyleneglycol octadecyl ether (C 18EO20) were used
as templates.

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4.3 Hard template synthesis

The preparation of hollow silica nanoparticles by polystyrene latex as a template was
reported by Cornelissen et al. [118]. The microscopic studies on silica coated latex
revealed that the thickness of shell varied between 3-10 nm and diameter of SNPs was

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between 25-40 nm. Khanal et al. [119] have prepared silica hollow nanoparticles using

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polymeric micelle as a template with core-shell-corna structure. ABC triblock copolymer
micelles with a core-shell-corna architecture were used as a template. The microscopic

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studies of hollow silica nanoparticle revealed that all the hollow silica had a spherical

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shape with smooth shell and average outer diameter of the hollow (void space) mass
~11 nm and the wall thickness of the shell was 10 nm. Zhao and others [120] reported

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needle shape silica nanohollow structure with high specific surface area using needle
shaped calcium carbonate nanoparticles as structural template. The microscopic
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analysis revealed that uniform hollow silica nanotubes were obtained in a regular
pattern. The length of the hollow tubes ranged from 200 to 300nm with an inside
diameter of about 20 μm. The thickness of the tube was around 10nm.
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Rahman and co-workers [121] observed the effect of anion electrolytes (NH4Cl, NH4Br,
NH4I, NH4NO3 and (NH4)2SO4) on the formation of SNPs. The results showed that all
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ammonium salts were able to reduce the particle size in the following order Cl-<Br-<I-
<NO3-<SO4--. The enhanced particles size, due to particle aggregation was observed.
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The effect of molar ratio of TEOS/NH3 on particle size of SNPs was also examined. At
TEOS/NH3 ≥ 0.6, the particles (~30nm) were uniformly distributed. At TEOS/NH3 ratio
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≤ 0.6, mixtures of large and small particles were observed with a wider distributions of
particles ranging from 90-250nm. A similar type of work, using mono-valent electrolytes
(NaOH, NaCl, NaI, KCl, CsCl and CsI), had been reported by Kim et al. [122]. The
results of these studied revealed that without additives, the particle size varied from 35
to 100 nm. The addition of small amount of electrolytes reduced the particle size upto
17.5nm. Yang et al. [123], using silica coated magnetic assemblies, prepared hollow
silica nano-containers as drug delivery vehicles. The core cavity was obtained by
removal of Fe3O4 phase with hydrochloric acid and subsequent calcination at high
temperature. The average particle size of hollow SNPs was ~83 nm. The synthesis of
uniform spheres in the nanometer to micrometer scale range, with tailored structure
exhibiting enhanced optical and surface properties was intensively pursued for a wide
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range of applications [124-125]. The high specific surface area (≥ 1000 m2/g) of silica
nanoparticles, achieved using different templates, is presented in Table 1. An
interesting work on the shape controlled synthesis of hollow SNPs by an inorganic
template was reported by Fuji et al. [126], wherein, a variety of shapes such as cubic,

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spherical and rod like particles of CaCO3 were used as templates for shape control of

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SNPs.

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Shimura and Ogawa [127] prepared dispersed nanoporous spherical SNPs by Stober

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method combined with supra molecular templating approach. In this study methanol
/TEOS ratio was used as a factor to control the particle size of silica particles. By

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increasing the MeOH/TEOS ratio the particle size was noticed to be decreased from 1.5
to 0.01 μm. Ding and Pacek [128] done an interesting work on the effect of the type of
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surfactants, polymer and pH on de-agglomeration of hydrophilic SNPs polyethylene
glycol (PEG), polyvinylpyrrolidone (PVP), and SDS were used as surfactants.
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5. Applications
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5.1 Construction materials

In the construction sector, the capability to give a mechanical reinforcement to a cement

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based material is one of the most preferred properties of SNPs (Fig. 17) [129-138].
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Zapata and co-workers [139] studied the rheological and hardened properties of
superplasticized cement mortar with SNPs. With the addition of appropriate dosages of
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superplasticizer SNPs caused to increases the compressive strength of mortar. Aly and
others [140] evaluated the properties of colloidal SNPs/waste glass cement composites.
The nanosize of silica allows reacting more readily with the calcium hydroxide, thereby
increasing C-S-H conversion. Senff et al. [141] assessed the effect of addition of SNPs
on the rheological behavior and the hardened properties of cement mortars. The results
showed that the mortars exhibited visible differences in the rheological behavior. The
values of torque, yield stress and plastic viscosity of mortars increased significantly with
the addition of SNPs.
Kontoleontos and co-workers [142] reported that the addition of SNPs led to increase
the compressive strength up to ~62% at 28 days. Rodríguez and others [143] measured
the effect of an alternative activator, modified with SNPs on the performance of alkali-
activated fly ash binders. The results showed that the gel was more tightly bound with
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the partially reacted fly ash in the case of the SNPs-derived activator, consistent with
the reduced porosity. The colloidal SNPs hastened cement hydration through an
acceleration of the dissolution of cement particles and a preferred hydration and
hydrates precipitation on colloidal SNPs surface [144]. Ltifia et al. [145] reported that

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SNPs made cement paste and mortar thicker and accelerate the cement hydration

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process. Lin and associates [146] observed that the use of SNPs on sludge/fly ash
mortars compensated the negative effects of sludge incorporation in terms of setting

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time and initial strength. The SNPs showed a faster formation of structures during the

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rheological measurements. Choolaei et al. [147] mentioned that the mixing of SNPs
with cement mortars was highly beneficial in improving the rheological properties of

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drilling cement slurry; concurrently producing an increase in the compressive and
flexural strengths of cement mortar. The pozzolanic activity of SNPs through high-
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resolution TGA and XRD was studied by Tobon et al. [148]. The studies indicated that
using SNPs, from the first day of curing, a larger quantity of C-S-H and C-A-H in the
pastes was found. Bjornstrom and others [149] studied the accelerating effects of
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colloidal silica on the rate of C3S phase dissolution, C–S–H gel formation and silica
TE

polymerization in cement paste hydration. The mechanical, engineering and physio-

chemical properties such as compressive strength, split tensile strength, flexural
P

strength, setting time, of the cement based building materials were noticed to be
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increased using SNPs [150-179].

5.2 Drug delivery systems

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The ability of SNPs to encapsulate different types of drug molecules within their pore
channels and controlled drug release mechanism are the two major advantages of
MSNPs as drug delivery system [180-181]. The drug molecules are incorporated by the
particles through adsorption. In addition, SNPs are developed for a host of biomedical
and biotechnological applications such as cancer therapy, DNA transfection, drug
delivery and enzyme immobilization [182-188]. Barik et al. [187] recently reviewed the
impact of SNPs on basic biology, medicine and agro-nanoproducts. Among the different
types of inorganic nanomaterials, MSNPs have emerged as promising multifunctional
platforms for nanomedicine (Fig. 18) [188].

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The exclusive topology of SNPs allows distinguishing three well-defined domains viz.
silica framework, mesopores and outermost surface. Owing to the remarkable
characteristics of MSNPs they are excellent platforms to integrate several multi-
functionalities for therapy and diagnostic of different pathologies [189-194]. The MSNPs

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have been used as drug delivery systems for a variety of pharmaceutical drugs of

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different hydrophobic/hydrophilic properties, molecule weights and biomedical effects
(Fig. 19) [195-200].

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The properties of MSNPs as carriers for the hydrophobic drug Ibuprofen were studied
by Munoz et al. [201]. The authors reported that the interactions between the cargo

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Ibuprofen molecules and the SNPs were mainly attributed to the interactions between
the carboxylic acid group on Ibuprofen and the silanol groups in the silica matrix. Lu and
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others [202] studied the applications of non-gated MSNPs to deliver hydrophobic anti-
cancer drugs, namely camptothecin (CPT) and paclitaxel (Taxol), to human cancer
cells. The MSNPs were reported to be delivered anticancer drugs into human
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xenografts in mice and suppress the tumor growth [203]. Zhao et al. [204] reported that
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phenyl boric acid-functionalized MSNPs served as an efficient co-delivery system for

saccharideresponsive controlled release of insulin.
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5.3 Polymer nanocomposites

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The application of SNPs in the preparation of polymer nanocomposites is one of the

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prominent applications of SNPs. These SNPs act as a filler or reinforcement in

advanced composite materials with improved thermal, mechanical, physical and
chemical properties. The SNPs reinforcement in polymer matrixes leads to improve
properties significantly as shown in Table 2 [205-216]. Kang et al. [206] observed that
the addition of 400nm silica particles into epoxy caused an increase (13%) in the
thermal properties. On the other hand the damping behaviour of composite decreased
with the increase in SNPs content. Ragosta and co-workers [211] reported that the
epoxy groups reacted with the silanol groups present on silica surface, leading to an
increased interfacial adhesion of composite. The strong interfacial adhesion increased
the fracture toughness of silica-epoxy nanocomposite. Zhang et al. [217] reported that
the polyacrylamide- (PAAM-) modified SNPs slightly enhanced the cure reactions of
epoxy and wear resistance in silica-epoxy nanocomposite. Preghenella et al. [218]
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reported that the thermal properties were found decreased as the SNPs content was
increased.

5.4 Other applications

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Due to their high surface area and organized porous structure, mesoporous silica is an

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interesting material as stationary phases for HPLC. The mesoporous silica, constituted
by loose particles agglomerates was the first material used in HPLC [219-221]. In the

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field of biosensors, the mesoporous SNPs improve the sensitivity and response time of

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sensors due to their high porosity [222-224]. Highly dispersed SNPs enhance the
thermal, mechanical, optical, abrasion resistance and surface hardness properties of

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composite coatings [72, 225,226]. MA
6. Conclusions

The silica nanoparticles have been prepared by bottom-up as well as top-down

approach. The bottom-up approach is preferably used for the controllable synthesis of
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ordered SNPs. Sol-gel method due to its ability to produce monodispersed particles
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with narrow-size distribution using mild conditions is a frequently used process to

synthesize SNPs. The morphology and texture of SNPs can be precisely controlled
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using soft-templates. SNPs with various morphologies like films, spheres, hollow
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spheres, nanotubes and nanotube arrays etc. are prepared using cationic surfactants,
polymers and electrolytes. The particle size, pore size, wall thickness and surface can
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be tailored by simply changing the reaction conditions i.e. concentration of reagents,

temperature, pH, drying method, mixing of reagents etc. The porous inorganic material
show good stability under extreme physical and chemical conditions. Interestingly, both
of these characteristics are present in mesoporous SNPs. The mesoporous SNPs have
a regular porous structure with uniform pore size, high surface area and superior
thermal stability, therefore, they have applications in the fields like drug delivery,
polymer composites, construction etc. Finally, we hope that this review will provide an
insight for researchers working on the synthesis of SNPs by sol-gel process.

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Acknowledgement
The present work is supported by joint INDO-UK research programme under UKIERI
scheme. Authors Ms G Mishra and Ms G Singh are thankful to CSIR-CBRI Roorkee for
the financial support. Fellowship awarded by UGC, New Delhi to Ms Usha Sharma is

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also gratefully acknowledged.

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Figure Caption

Figure 1 Approaches for the preparation of nanoparticles.

Figure 2 Schematic presentation of acid catalyzed linear weakly cross-linked (A)
and base catalyzed hydrolysis of highly branched clusters (B).

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Figure 3 The upper pathway corresponds to a monomeric silica addition (mechanism 1) and

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the lower pathway corresponds to the primary particles directionally aggregate to form
particles with ordered mesopore morphology (mechanism 2) [48].

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Figure 4 Illustration of the formation of ordered mesoporous silica sphere with centrosymmetric
radial pore channels [49].

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Figure 5 Possible mechanistic pathways for the formation of meso-silica materials with
nanospheres, eggshell and starburst pore canals [50].
Figure 6 Schematic representations of the functions of two surfactants [52].

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Figure 7 Schematic illustrations for the synthesis of hollow silica nanoparticles [53].
Figure 8 Schematic illustration of the step involved in the coating reaction of silyl-
functionalized PVBC latex particles with silica and the formation of hollow silica
nanospheres [54].
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Figure 9 Representation of two possible ways of surfactant interaction with water.
Figure 10 Relation between surfactant concentrations (SC) and surface tension (ST) and CMC
of surfactant.
Figure 11 FE-SEM (left) and TEM images (right) of TMS-MSNs prepared
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with TMB/CTAB ratios of (a) 0, (b) 2, and (c) 4 [72].

Figure 12 SEM micrographs of (i) MCM-41, (ii) BMS-1, (iii) BMS-2 and (iv) BMS-3, respectively.
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The lengths of the bars correspond to 2, 5, 5 & 10 µm respectively [73].

Figure 13 SEM and low- and high-magnified TEM (L-TEM and H-TEM) images of the
calcined mesoporous silica nanotubes synthesized with different HCl/C14-L-AlaS
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(sample a and b) and different TMAPS/C14-L-AlaS (sample b and c) molar ratios

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[84].
Figure 14 TEM images of samples (a) UKA6-1, (b) UKA8-1 with inset showing
FFT of hexagonal region, (c) UKA9b-1, (d) UKA10-1, (e) UKA11b-1,
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and (f) UKA12-1 [89].

Figure 15 TEM micrographs showing the evolution of the morphology and texture of
the mesoporous silica with decreasing CTMABr concentration. The tube
like images comes from the carbon supporting grids [100].
Figure 16 SEM micrographs of n-SiO2 particles (80-200nm) prepared without
surfactant (A), span 20 (B), span 40(C) and span 60 (D), respectively [102].
Figure 17 Application of silica nanoparticles in cement and concrete [128].
Figure 18 Mesoporous silica nanoparticles as nanomedical multifunctional
nanoplatforms [188].
Figure 19 Mesoporous silica nanoparticles as versatile drug delivery systems
for a variety of therapeutic agents including pharmaceutical drugs
(ibuprofen, doxorubicin, and docetaxel), therapeutic genes (plasmid
DNA,antisense oligonucleotides, and siRNA), and therapeutic proteins
and peptide (cytochrome C and peptide) [200].

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Schemes

Si OR + fast +
+ H Si O R

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R H
+ .. +
Si OR + HOH O Si Si OH + ROH + H

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H H
H

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(A)

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. +
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R O Si O H R O Si O H
Si OR + OH
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Scheme 1 Representation of acid- (A) and base-catalyzed (B) hydrolysis reactions.

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+ +
Si OH + H Si O H

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Si O H + +O Si Si O Si + H2O + H

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Scheme 2 Representation of acid- (A) and base-catalyzed (B) condensation reactions.

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Tables
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Table 1 High (≥ 1000 m /g) specific surface area (SSA), related pore diameter and pore
volume of SNPs.

S. No. BET Pore Pore Medium Remarks References

SSA volume diameter

T
(m2/g) (cm3/g) (nm)

IP
1. 1085 1.1 0.87 Acidic Na2SiO3/CTAB/H2O/EA [73]
1/0.33/3557/1.87

R
2. 1020 2.9 0.93 Basic NH4OH used as catalyst [51]
H2O:NH4OH:CTAB:TEOS

SC
525:69:0.125:1
3. 1373 -- 0.64 Basic Heterogeneous system [48]
employed

NU
4. 1282 2.6 0.72 Acidic TEOS:H2O:CTAB [75]
1.0:1.0:0.25
5. 1095 3.2 2.54 Basic Si:TEAH:CTAB:H2O [88]
2.0:8.0:0.52:180
MA
6. 1260 3.9 1.20 Basic H2O:CTAB:TEOS:NaOH [50]
2486:0.123:1.0:0.63
7. 1029 3.05 1.54 Basic CTAB:Si:H2O [96]
0.15:1:100
D

8. 1070 3.2 0.85 Basic TEOS:CTMAB:NH3:H2O [100]

1:0.035:2.8:141.2
TE

9. 1136 22.6 0.61 Basic Tetra-butyl ammonium [103]

bromide as template
10. 1055 2.9 0.98 Basic Mixed surfactant system [106]
P

employed CTAB+SDS:Si
CE

0.1681:1
11. 1120 4.2 0.97 Basic 25% mole percentage of [107]
tetraethylene glycol ether
AC

(C12EO4) used in
surfactant system
12. 1267 -- 0.78 Basic Cationic polymer poly [108]
(allyamine hydrochloride)
PAACl used as a template
13. 1237 2.6 -- Basic Molar ratio of [109]
β-CD:CTAB= 0.1
14. 1105 4.5 0.99 Basic 1,3,5-trimethyl benzene [111]
(TMB) and CTAB used
pore swelling agent
15. 1217 -- 0.84 Basic Molar ratio of [112]
OP-10:CTAB =0.08
16. 1056 2.1 1.9 Basic CaCO3:C16TMAB 5:1 [114]

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Table 2 Applications of SNPs in the polymer composites.

S. Polymer Nanosilica Major property changes Ref.

No. matrix incorporation (with increasing filler content)

T
Size Content

IP
(nm) (wt.%)
1. Polyurethane 175, 395 1–10 Constant glass transition temperatures [105]
and 730 (Tg) at different particle size and

R
concentrations

SC
2. Epoxy 400 50–70 (i) Decreased CTE and increased Tg [106]
(DGEBA) (ii) Increased brittleness
3. Epoxy 90 1–7 (i) Increased fracture toughness [207]
(DGEBF) (ii) Larger deformation resistance

NU
4. Polyimide 20 10–50 (i) Increased dielectric constant [208]
(ii) Enhanced thermal stability
5. Thermoplastic 7 10 (i) Increased shear and storage modulus [209]
MA
polyurethane (ii) Increased tensile and peel strength
6. Epoxy 75 and 1–5 (i) Increased aggregation level [210]
(DGEBA) 330 (ii) Increased elastic modulus
(iii) Higher modulus for smaller
D

particles
(i) Decreased Tg, constant Tβ
TE

7. Epoxy 12.5 5 and10 [211]

(TGDDM) (ii) Increased elastic and yield modulus
(iii) Increased brittle fractureness
P

8. Epoxy 10–20 10–70 (i) Decreased Tg [212]

(DGEBA) (ii) Increased thermal stability
CE

9. Acrylic polymer 15–20 10–50 (i) Increased thermal stability [213]

(ii) Enhanced hardness
(iii)Excellent optical transparency
AC

10. Polyurethane 14–260 1–4 (i) Increased Tg [214]

(ii) Decreased surface and interface
free energies
11. Polystyrene 25–200 5–10 (i) Strong interaction between silanes [215]
group and polymer chains
12. Polypropylene 50–110 1–5 (i) Larger thermal degradation [216]
stabilization
(ii) Larger elastic modulus

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Graphical abstract

T
R IP
SC
NU
MA
D
P TE
CE

Schematic diagram for the preparation of silica nanoparticles via Sol-Gel process
AC

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Highlights
This review focuses on
 Synthesis of silica nanoparticles using surfactants for desirable size and shape.
 Mechanism proposed for the synthesis of SNPs.
 Influence of temperature, pH, concentration, drying techniques, solvents etc.
 Applications of SNPs in drug delivery, HPLC, biosensors, construction etc.

T
R IP
SC
NU
MA
D
P TE
CE
AC

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