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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:
DOI:
Reference:
S0001-8686(14)00280-2
doi: 10.1016/j.cis.2014.10.007
CIS 1490
To appear in:
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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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
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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
last decade, remarkable efforts have been made on the investigations for novel
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,
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
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
been successfully prepared using organic and inorganic templates. The soft template
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
discussed. The influence of reaction conditions such as temperature, pH, concentration
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,
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, Nanoengineered concrete
*Corresponding author: Fax: +91 1332 272272, E-mail: lpsingh@cbri.res.in
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Contents
1. Introduction03
2. Preparation of nanoparticles.05
2.1 Gaseous state preparation.05
2.1.1 Gas condensation....05
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1. Introduction
In the last two decades, material science and engineering has come out with some
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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
areas [4-10]. Recent advances in the preparation of SNPs (<100nm) are focusing the
morphological architecture such as spheres, hollow spheres, fibers, tubules, helical
fibers etc. At the moment, it is generally accepted that the reduction in size to sub-
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preparing nanoparticles. This strategy is faster, precise, energy efficient and therefore,
extensive research is going on towards the preparation of nanoparticles through this
route. Several techniques are available to synthesize SNPs viz., flame spray pyrolysis,
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these sol-gel process remains the most popular one, due to its ability to control the size,
distribution and morphology of the particles through systematic monitoring of the
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reaction parameters [11]. In 1864, the term sol-gel was firstly introduced by Graham
during his work on silica sols [12]. The sol-gel technique offers a low-temperature
method for synthesizing materials that are either purely inorganic or both inorganic as
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well as organic. The process, based on the hydrolysis and condensation reaction of
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].
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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
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The MSNPs have a regular porous structure with uniform pore size, large surface area
and superior thermal stability, therefore, they are suitable for a variety of applications in
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the diverse fields such as drug delivery, biosensors, molecular separations, catalysis,
HPLC etc.[21-26]. In drug delivery systems, MSNPs have been used as carrier of drug,
as guest molecules are simply adsorbed on the mesopore surface of the SNPs. As no
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functional group acts as a gate to control the release of the loaded substances, the
release is controlled either by the size or the morphology of the pores. The MSNPs are
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the material of interest, as the stationary phases due to their high connectivity,
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
enhance the thermal, mechanical, optical, abrasion resistance and surface hardness
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properties of composite coatings. In the construction sector, SNPs are the innovative
materials explored to enhance the strength and durability of cement based construction
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
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concrete for specific applications. The second, is the reduction of the amount of cement
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.
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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
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2. Preparation of nanoparticles
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approaches (Fig. 1). The bottom-up approach involves building up from the atom or
molecular constituents to meso-level and top-down approach involves making smaller
sizes through etching or grinding from the bulk materials. There are varieties of
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techniques available for preparing nanostructured materials and these can be divided
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The metallic, metal oxides and ceramic nanomaterials can be prepared by this method.
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and low energy electron beam. The clusters form in the vicinity of the source by
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 500C.
For vacuum deposition, a reasonable deposition rate can be achieved if the
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to 100 nm and called ultra-fine particles or clusters. The high deposition rates and
economy are the advantages of vacuum deposition process. However, the deposition of
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surface through a chemical reaction [32-33]. The activation energy, required to initiate
the process, can be provided by several methods like in thermal CVD, the reaction is
initiated at a high temperature (~1000C). In plasma CVD, the reaction is activated by
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plasma at a temperature range of 300-700C. In laser CVD, pyrolysis occurs when laser
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.
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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
the milling material, milling time and atmospheric condition. The energy transferred to
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the powder from refractory or steel balls depends on the rotational and/or vibrational
speed, size and number of balls, ratio of the ball to powder mass, the time of milling and
the milling atmosphere. The milling in cryogenic liquids can significantly increase the
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brittleness of powders influencing the fracture process. This process is limited for the
production of non-oxide materials because it requires the milling in an inert atmosphere
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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
process includes high energy ball mill, low energy tumbling mill, centrifugal type mill and
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vibratory type mill. The high energy ball milling is a well known method for the
preparation of nanostructured materials. The attrition ball mill, planetary ball mill,
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
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area, heterogeneous size, partially amorphous states of resultant powder are some of
the limitations of these processes. Apart from these, the contamination with iron is a
major drawback of these techniques.
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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
synthesised by employing micro-emulsion technique. Usually, in this process two types
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of emulsions are used; first is water-in-oil and second is oil-in-water. The microemulsions are thermodynamically stable colloidal nano-droplets which are stabilized by
surfactant film and act as nano-reactors for the formation of nanomaterials. The size
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and shapes of resulting nanomaterials are dependent upon the texture of these nanodroplets, reactant concentration, type of surfactant, concentration of capping agent etc.
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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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process, depending on the nature of the precursors, may be divided into two classes
namely inorganic precursors (chlorides, nitrates, sulfides, etc.) and alkoxide precursors.
The extensively used precursors are tetramethoxy silane and tetraethoxy silane. In this
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process, the reaction of metal alkoxides and water, in the presence of acid or base,
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 solgel includes four stages namely hydrolysis, condensation, growth and aggregation.
Si(OR)4 + H2O
Si(OR)3(OH) + ROH
Hydrolysis:
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release of water (oxolation). The reaction between a hydroxide and an alkoxide leads
to form M-O-M bonds following release of an alcohol (alkoxolation).
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[(OR)3SiOSi(OR)3] + HOH
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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together to form a three-dimensional network. The possible mechanisms for both acid
and base catalyzed reactions in case of silicon alkoxides are as shown in schemes. 1
and 2 [45-47].
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i.
Deposition of monomeric silica and surfactant ions onto existing primary particles in
a continuous process.
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manner.
An interesting work on the radial ordered mesoporous silica spheres using an anionic
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surfactant was done by Wang et al. [49]. A commercial anionic surfactant N-lauroylsar
cosin sodium (Sar-Na) was employed due to its biodegradability, low toxicity and lowcost. An isotropic morphology like elliptical, peanut like and trifurcate particles, instead
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of spheres, were obtained when the pH of reaction lowered to 5.8. The microscopic
studies revealed that MSNPs contains centrosymmetric radial mesopores. Further, it
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was concluded that the lowering of pH leads to an increase of specific surface area
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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aggregates were noticed to form larger spherical organic/inorganic hybrid. At this stage,
the surfactant/silica hybrid particles would be soft, i.e., the silica is less cross linked and
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
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be the preferential structure to minimize its surface free energy. Therefore, the final
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
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surfactant micelles and micellar rods were formed and then these rods self assemble to
the lamellar phase. Further, a mixed lamellar-hexagonal membrane, separated by water
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layers in the surfactant silicate system, was reported to be formed (Fig. 5).
Cai and others [51] presented a comprehensive study on the formation and control of
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nucleation involves interaction of silica with surfactant that facilitates the assembly of
rod like silicate micelles. The Inorganic/organic self assembled silicate micelles (SSMs)
were immediately formed as the two precursors (surfactant and inorganic solution
containing predominantly multiply charged silicate anion at a certain pH) mixed. The
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driving force for the formation of SSMs was provided by the ion exchange of silicates
oligomers with Br- and OH- anions. A sub-micron sized silica rod with 0.7-1m in length,
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Suzuki and co-workers [52] prepared SNPs with a well-ordered mesostructure having a
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uniform aperture (approx. 2nm), using a double surfactant system. Cationic surfactant
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).
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the SNPs employing organic or inorganic templates such as ionic and non-ionic
surfactants, polymers etc. Ding and associates [53] proposed a mechanism for the
preparation of silica hollow nanospheres. In this work, first, the authors prepared 3-
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The hollow silica nanospheres were prepared by Chen et al. [54] using surface initiated
atom transfer radial polymerization (ATRP). In this study, hollow silica nanospheres
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selectively removed after the synthesis of desired nanostructure. However, the soft
templates are normally involved in chemical synthesis procedure.
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In 1968, Stber and co-workers [55] developed a process capable of forming controlled
silica particles (500 nm-2 m) using tetraethoxysilane (TEOS) as silica precursor, water,
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ethanol and ammonia. The process was carried out at room temperature and higher pH
(~10). The silica particles had a narrow size distribution and could be controlled by
adjusting the pH of solution, composition of reactants and temperature. Guo and others
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[56] reported a method for the preparation of monodispersed SNPs (~10-100nm) using
one of the most affordable silica precursor i.e. elemental silicon. The ultrasonication
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technique in sol-gel process to prepare monodispersed and uniform size SNPs, for the
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
increasing concentration of ammonia and water. Yu et al. [58] prepared high purity
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dispersed silica nanocubes (~30nm) using tartaric acid as organic template by sol-gel
method. Sadasivan and associates [59] prepared ultrafine silica particles (20-60 nm) by
hydrolysis followed by condensation of TEOS in methanol medium.
mesoporous
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The
silica
particles
was
prepared
by
Liu
et
al.
[60]
using
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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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a dominant factor on the final size and polydispersity of SNPs as the particle size was
decreasing with increasing the rates of addition of TEOS. Kim et al. [65] prepared
nanoporous silica particle for enzyme support via a salt route. The silica particles with
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1-15 nm pore diameter were synthesized by acid decomposition reaction using the
silicate salt as a precursor. Arai and co-workers [66], using TMOS as silica source,
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prepared cocoon shaped SNPs having excellent abrasive properties. The effects of
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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Choa et al. [67] investigated metal oxide incorporated mesoporous SNPs and
Nanotubes. Edrissi et al. [68] prepared SNPs with an average particle size of about
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
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water. Low TEOS concentration and high temperature were found to be suitable for
producing smaller particle size of silica.
4.2 Soft (surfactant) template synthesis
The nanostructured materials are frequently synthesised through the surfactanttemplating 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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An amphiphilic molecule can arrange itself at the surface of the water in such a way that
the polar part interacts with the water and the non-polar part remains above the surface
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(Fig 9). The presence of these molecules on the surface disrupts the cohesive energy
at the surface and thus, lowers the surface tension. Another arrangement of these
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molecules can allow each component to interact with its favoured environment [70, 71].
The molecules can form aggregates, at critical micelle concentration (Fig 10), which are
called micelles.
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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-
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(1282 m2/g) was obtained by using CTAB as template in acidic conditions. Using CTAB
as a template, pore volume and average pore diameter increased with increasing
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surfactant content. Brij-56 templated silica in basic medium had the highest pore
diameter (14.4 nm). The use of Brij-56 as pore forming agent exhibited the same trend
of results as observed using CTAB. With increasing the SDS content the pore volume
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and average pore diameter observed to be decreased because SDS adhere together to
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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.
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(SDBS) were used as ionic templates. It was proposed that the charge of the surfactant,
CMC and the ionic strength of solution were responsible for the agglomeration of SNPs.
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The average particles size of the spheres using DTAB, SDS and SDBS were 230, 150
and 300 nm, respectively. Zhang and others [79] synthesized SNPs using CTAB,
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,
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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 <0.2m.
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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
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An interesting study on the effect of procedure of adding reagents was also examined.
According to this study, morphology of the resultant silica hollow sphere depended not
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only on the concentration of reagents but also on the procedure of adding them into the
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 - 2m, 100-300 nm, 200-400 nm,
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respectively.
Yu and others [84] presented an interesting method for the preparation of hierarchical
silica nanotubes. Self assembled chiral anionic surfactants [N-palmitoyl-L-alanine(C16-LAla), N-palmitoyl-L-valine(C16-L-val), N-palmitoyl-L-Leucine(C16-L-Leu), N-palmitoyl-L-
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isoleucine(C16-L-Ile),
N-palmitoyl-L-methionine(C16-L-Met),
N-palmitoyl-L-
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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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TEOS using CTAB followed by neutralization with dilute HCl. The microscopic studies
of synthesized silica showed that the particles were spherical and slightly faceted with
well defined edges with a mean size of 100nm. The mean particle size was 23 nm and
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degree of mesostructural order in the nanoparticles reduced when the length of time
between dilution and neutralization of reaction mixture allowed to be decreased.
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Haskouri and others [88] presented, for the first time, a generalized method for the
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
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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
and forming novel intermediate mesophases more easily than hydrocarbon, are now
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
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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
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SNPs were obtained. Singh et al. [97] analysed the effect of cationic surfactant
containing carbon chain (C15, C17 and C19) on average particle size and morphology.
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The average particle size of silica nanosphere dropped down from 150 to 50nm using
C19TAB surfactant.
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The biometric synthesis of silica nanotubes from self assembled ultra short peptide as a
template was reported by Wang et al. [98]. The studies on the effect of concentration of
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TEOS and pH on the morphology and size of silica nanotubes showed that the outer
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
formed. Buchel and others [99] prepared spherical mesoporous silica with average
pore
structure
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particle size 100 nm to 2m. The porosity was created by adding two different types of
directing
agent,
n-alkyltrialkoxysilon
and
n-alkyl
amine.
N-
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cm3/g, an average pore diameter between 2 and 6 nm and specific surface area 1019
m2/g were obtained.
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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
results of the studies showed that an increase in hydrocarbon chain length of surfactant
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led to decreases the particle size (Fig. 16). Further, an increase in the particle size of
SNPs as a result of increase in pH was also observed.
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Since the discovery of a novel family of MCM-48, by mobile researchers, there has
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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and bring about the long range ordering in the mesoporous materials. The final silica
mesoporous materials using tetramethylammonium bromide, tetraethylammonium
bromide and tetrabutylammonium bromide were designated as Si-MCM-41@TMA, SiMCM-41@TEA and Si-MCM-41@TBA, respectively. The specific surface areas of Si-
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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
CTAB as a template. Highly ordered SNPs were formed with CMC however, without
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Chen et al. [106] prepared MCM-48 silica using mixed cationic-anionic surfactants as
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templates. CTAB was used as a cationic surfactant and sodium laurate as an anionic
surfactant template. They proposed electrostatic templating route for the preparation of
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MCM-48 silica. The carboxylate anionic surfactant was reported to function as a polar
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
of anionic surfactant may not enter the micelles core, but were located at the
layer.
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hydrophobic- hydrophilic portion of the micelles and, therefore, formed a thick palisade
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symmetry by using mixed cationic and nonionic surfactants were prepared by Huang et
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.
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(2-3nm). Nan and co-workers [109] prepared MCM-41 mesopores silica using the self
assembly -cyclodextrin (-CD) and CTAB as structure directing agents. The pore
structure of the resulting mesoporous silica belonged to the two dimensional hexagonal
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structure (space group P6mm). The pore size and the pore wall thickness of the silica
increased with the rise of molar ratio of -CD to CTAB. The particles with elliptic shapes
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about 300 and 600nm diameter were obtained in the absence of -CD. The particles
transformed to uniform spheres in the presence of -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
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additive of -CD and reached the smallest size of about 200nm at molar ratio of 1.0.
The rod like mesoporous silica with hexagonal appearance using mixed surfactants of
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CTAB and CTACl was prepared by Han and associates [110]. At a molar ratio of 9:1
(CTAB-CTACl), regular rods like shapes were obtained. The rod like morphology had a
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-
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MSN) system through the utilization and combination of organic pore swelling agent.
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 poctylpolyethylene 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 hydrogenbonding 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
was significant in self-assembly procedure of micelles [113]. Le and others [114]
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reported a novel synthesis pathway for silica hollow nanosphere (40nm) with
mesoporous walls. The double-template (inorganic-organic) route was employed with
calcium carbonate as spherical template and hexadecyltrimethyl ammonium bromide
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nanospheres.
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
the silica nanospheres became bigger from 42-188 nm and more uniform in size with
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the increase of temperature from 298 to 368K. The use of cationic-nonionic composite
surfactant of CTAB and Brij 56 resulted into the improved dispersivity, spherical shape
and the decreased particle size from 188 to 72 nm. Further, multistep addition modes of
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TEOS contributed to the better monodispersivity and larger size of silica nanospheres.
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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
polymeric micelle as a template with core-shell-corna structure. ABC triblock copolymer
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~11 nm and the wall thickness of the shell was 10 nm. Zhao and others [120] reported
needle shape silica nanohollow structure with high specific surface area using needle
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Rahman and co-workers [121] observed the effect of anion electrolytes (NH4Cl, NH4Br,
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NH4I, NH4NO3 and (NH4)2SO4) on the formation of SNPs. The results showed that all
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.
The effect of molar ratio of TEOS/NH3 on particle size of SNPs was also examined. At
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TEOS/NH3 0.6, the particles (~30nm) were uniformly distributed. At TEOS/NH3 ratio
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.
Shimura and Ogawa [127] prepared dispersed nanoporous spherical SNPs by Stober
method combined with supra molecular templating approach. In this study methanol
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/TEOS ratio was used as a factor to control the particle size of silica particles. By
increasing the MeOH/TEOS ratio the particle size was noticed to be decreased from 1.5
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to 0.01 m. Ding and Pacek [128] done an interesting work on the effect of the type of
surfactants, polymer and pH on de-agglomeration of hydrophilic SNPs polyethylene
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5. Applications
5.1 Construction materials
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superplasticized cement mortar with SNPs. With the addition of appropriate dosages of
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. Rodrguez and others [143] measured
the effect of an alternative activator, modified with SNPs on the performance of alkaliactivated 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
process. Lin and associates [146] observed that the use of SNPs on sludge/fly ash
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with cement mortars was highly beneficial in improving the rheological properties of
drilling cement slurry; concurrently producing an increase in the compressive and
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flexural strengths of cement mortar. The pozzolanic activity of SNPs through highresolution 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, CSH gel formation and silica
polymerization in cement paste hydration. The mechanical, engineering and physio-
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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
different hydrophobic/hydrophilic properties, molecule weights and biomedical effects
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The properties of MSNPs as carriers for the hydrophobic drug Ibuprofen were studied
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by Munoz et al. [201]. The authors reported that the interactions between the cargo
Ibuprofen molecules and the SNPs were mainly attributed to the interactions between
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the carboxylic acid group on Ibuprofen and the silanol groups in the silica matrix. Lu and
others [202] studied the applications of non-gated MSNPs to deliver hydrophobic anticancer 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
phenyl boric acid-functionalized MSNPs served as an efficient co-delivery system for
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reported that the thermal properties were found decreased as the SNPs content was
increased.
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Due to their high surface area and organized porous structure, mesoporous silica is an
interesting material as stationary phases for HPLC. The mesoporous silica, constituted
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by loose particles agglomerates was the first material used in HPLC [219-221]. In the
field of biosensors, the mesoporous SNPs improve the sensitivity and response time of
sensors due to their high porosity [222-224]. Highly dispersed SNPs enhance the
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6. Conclusions
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
with narrow-size distribution using mild conditions is a frequently used process to
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synthesize SNPs. The morphology and texture of SNPs can be precisely controlled
using soft-templates. SNPs with various morphologies like lms, spheres, hollow
spheres, nanotubes and nanotube arrays etc. are prepared using cationic surfactants,
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polymers and electrolytes. The particle size, pore size, wall thickness and surface can
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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Figure Caption
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Figure 1
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Figure 12
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Figure 13
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Figure 14
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Figure 15
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Figure 16
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Figure 17
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Figure 19
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Schemes
OR
Si
+
+ H
fast
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Si
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Si
H + OH
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H2O
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OH + ROH + H
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Si
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Si
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Scheme 1 Representation of acid- (A) and base-catalyzed (B) hydrolysis reactions.
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Si
OH + H
+
O
Si
H
..
O
Si
+O
Si
O +
..
O +
Si
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..
O + H2 O
Si
Si
Si
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Tables
Table 1 High ( 1000 m /g) specific surface area (SSA), related pore diameter and
volume of SNPs.
2
Pore
diameter
(nm)
0.87
2.
1020
2.9
0.93
Basic
3.
1373
--
0.64
Basic
4.
1282
2.6
0.72
Acidic
5.
1095
3.2
2.54
Basic
6.
1260
3.9
1.20
7.
1029
3.05
1.54
8.
1070
3.2
0.85
9.
1136
22.6
10.
1055
2.9
11.
1120
12.
1267
13.
Basic
Basic
Basic
Basic
0.98
Basic
0.97
Basic
--
0.78
Basic
1237
2.6
--
Basic
14.
1105
4.5
0.99
Basic
15.
1217
--
0.84
Basic
16.
1056
2.1
1.9
Basic
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Na2SiO3/CTAB/H2O/EA
1/0.33/3557/1.87
NH4OH used as catalyst
H2O:NH4OH:CTAB:TEOS
525:69:0.125:1
Heterogeneous system
employed
TEOS:H2O:CTAB
1.0:1.0:0.25
Si:TEAH:CTAB:H2O
2.0:8.0:0.52:180
H2O:CTAB:TEOS:NaOH
2486:0.123:1.0:0.63
CTAB:Si:H2O
0.15:1:100
TEOS:CTMAB:NH3:H2O
1:0.035:2.8:141.2
Tetra-butyl ammonium
bromide as template
Mixed surfactant system
employed CTAB+SDS:Si
0.1681:1
25% mole percentage of
tetraethylene glycol ether
(C12EO4) used in
surfactant system
Cationic polymer poly
(allyamine hydrochloride)
PAACl used as a template
Molar ratio of
-CD:CTAB= 0.1
1,3,5-trimethyl benzene
(TMB) and CTAB used
pore swelling agent
Molar ratio of
OP-10:CTAB =0.08
CaCO3:C16TMAB 5:1
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Acidic
0.61
4.2
Remarks
References
Pore
volume
(cm3/g)
1.1
Medium
1.
BET
SSA
(m2/g)
1085
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S. No.
pore
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[73]
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[48]
[75]
[88]
[50]
[96]
[100]
[103]
[106]
[107]
[108]
[109]
[111]
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Polyurethane
2.
Epoxy
(DGEBA)
Epoxy
(DGEBF)
Polyimide
400
5070
90
17
20
1050
5.
Thermoplastic
polyurethane
10
6.
Epoxy
(DGEBA)
75 and
330
15
7.
Epoxy
(TGDDM)
12.5
8.
9.
Epoxy
1020
(DGEBA)
Acrylic polymer 1520
10.
Polyurethane
14260
14
11.
Polystyrene
25200
510
12.
Polypropylene
50110
15
3.
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5 and10
1070
1050
Ref.
[105]
[210]
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Nanosilica
incorporation
Size
Content
(nm)
(wt.%)
175, 395 110
and 730
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Polymer
matrix
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[208]
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[211]
[212]
[213]
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[215]
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Graphical abstract
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Schematic diagram for the preparation of silica nanoparticles via Sol-Gel process
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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.
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