Review

[Link]/IECR

Colloidal Silica Particle Synthesis and Future Industrial

Manufacturing Pathways: A Review
Emily D. E. R. Hyde,† Ahmad Seyfaee,† Frances Neville,†,‡ and Roberto Moreno-Atanasio*,†
†
School of Engineering, and ‡School of Environmental and Life Sciences, The University of Newcastle, Callaghan, NSW 2308,
Australia

ABSTRACT: Colloidal silica is used in many applications

including catalysis, pharmaceuticals, and coatings. Although
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naturally formed silica materials are widely available, they are

often in forms that are difficult to process or are even harmful
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to health. Therefore, uniform colloidal silicas are generally

manufactured using synthetic chemical processes. While
established high temperature gaseous synthesis methods fall
out of favor in our energy conscious society, liquid synthesis
methods are current industrial leaders. The precipitated silica
method provides the majority share of commercially produced
specialty silicas with its economic advantages predicted to
continue to grow in the future. The biomimetic method and
microemulsion methods of synthesis provide a superior level
of surface chemistry and morphological control than current industrial processes and are the major focus of current silica
synthesis research. Movement toward more tailor-made products and ecologically friendly production methods will likely provide
incentive for biomimetic methods, in particular, to take more of a market share. However, the lack of procedures to viably scale
up the biomimetic and microemulsion methods still forms significant gaps in the literature. In this review, the current methods of
colloidal silica synthesis are discussed alongside significant models and mechanisms of silica formation.

1. INTRODUCTION potential uses of colloidal silica include utilization as drug

Silicon oxides, also known as silicates, are by far the most carriers, 23−31 biosensor supports, 29,32−35 catalytic sup-
common component of the Earth’s surface.1 One form of ports,11−13,36−40 antifouling coatings,6,41−44 and additives to
silicate, known as silica, refers to a vast number of solid paints/lacquers/coatings.45−47
materials which possess the general chemical formula of SiO2 or Owing to the large number of uses it is unsurprising that
SiO2·xH2O. colloidal silica production has become a significant industry. In
Silica, due to its accessibility and ease of recovery, has been 2012, commercial silica production had a market value of
used extensively throughout history to manufacture glass, approximately 3.6 billion US dollars with an estimated
ceramics, and silicones.1 Silica also forms the basis for concrete, production rate of 2.4 million tonnes globally.48 According to
mortar, and sandstone and has been used widely in the a report by The Freedonia Group,49 global demand for
construction of buildings and roadways.2,3 More recently, specialty silica is expected to continue to increase, reaching a
colloidal silica has factored significantly in nano- and micro- production rate of approximately 2.9 million tonnes by 2018.
particle research.4 Herein, we will define colloids as possessing a For the majority of applications, the commercial marketplace
size between 1 nm and 1 μm; according to Bergna,4 particles requires colloidal silica to be produced cheaply and uniformly,
within this size range are large enough to retain an “individual with an ability to tailor the properties of the product. Mineral
identity”4 in solution without being overtly influenced by silicas, although common, are generally highly contaminated
gravitational forces. The focus of this review is on the synthesis with various metal ions and thus not suitable for use in colloidal
of spherical silica colloids. The research interest in colloidal
silica applications, such as the scientific and industrial uses
silica is due partially to the large number of advantageous
mentioned previously.50 Also mineral silica typically exists (with
properties they possess, including a relatively large surface area,
low toxicity, apparent biocompatibility, well established a few exceptions) in the less useful (due to the diminished
chemistry, optical transparency, relative chemical and thermal surface area) and, when colloidal sized, potentially health
stability, and high colloidal stability in many conditions and damaging, crystalline form.2,51 Therefore, for most applications
solvents.5−7
The possible uses of colloidal silica have been expanded even Received: May 13, 2016
further with the advent of in situ or postsynthesis surface Revised: July 30, 2016
modification5,8−17 and/or the use of silica as a coating agent for Accepted: August 3, 2016
various core materials.6,7,12,18−22 Common commercial and Published: August 3, 2016

© 2016 American Chemical Society 8891 DOI: 10.1021/[Link].6b01839

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silica produced through various chemical synthesis methods is unintentional byproduct of silicon or silicon alloy production58
preferential. and beyond the scope of this review.
A number of different synthesis routes of colloidal silica have The following sections will discuss the methodology and
been developed. The main colloidal silica synthesis processes, chemistry of the fumed silica approach (section 2.1), and the
both those used commercially and those still in the research properties and applications of fumed silica (section 2.2).
phase of development, are presented in Figure 1. 2.1. Fumed (Pyrogenic) Silica Synthesis Process. Flame
aerosol processes are one of the few colloidal synthesis methods
able to cope with the large throughput required to make the
process viable on an industrial scale.58 With production rates of
up to 25 t h−1,62 industrial plants are still employing the flame
aerosol method to manufacture fumed silica along with carbon
black, pigmentary titania, and alumina.63−65 The method to
produce fumed silica was originally developed in the early
1940s in Germany,59,66,67 where fumed silica was designed as an
alternative to the widespread tire filler, carbon black.
For the purpose of this review the basics of the fumed silica
synthesis process will be outlined alongside a schematic
detailing the basic process in Figure 2. Unfortunately, industrial

Figure 1. Different colloidal silica production methods.

For convenience, the routes of chemical synthesis of colloidal

silica in Figure 1 are categorized by the phase of the silica
feedstock, that is, gaseous and liquid routes. Within these two
major categories are a number of distinct synthesis methods
each having advantages and disadvantages in terms of
production and the properties of the final product. Previous
literature reviews have focused mainly on the research aspects
of developing synthesis methods, such as microemulsion7,52,53
and biomimetic synthesis,6,54,55 and/or specific areas of
application5,22,29,50,56 for colloidal silica. In contrast to these
reviews, the current work will focus on exploring and Figure 2. Schematic of the general industrial synthesis process used to
contrasting the major synthesis routes currently utilized produce fumed silica.
industrially and/or in the research stage. In addition, this
review will also explore the mathematical models and the
confidentiality has made it difficult to obtain information about
corresponding proposed mechanisms of colloidal silica particle
current industrial practice; however, the details of a particular
formation. This review will focus on the synthesis of colloidal
plant specific set up in the 1960s can be found in Mezey.59 The
spherical silica and thus methods specific to different
fumed silica synthesis technique employs volatile liquid silicon
morphological features, for example; gels and mesoporous
tetrachloride as the silicon feedstock.59 This silicon tetra-
silica will not factor significantly in this work. The review of
chloride feedstock can be purchased as a byproduct of the
Singh and co-workers57 provides a more comprehensive
polysilicon industry and/or prepared on site through the
discussion on mesoporous silica processing.
treatment of silicon carbide at high temperatures with HCl
2. GASEOUS METHODS (Figure 2).2,59,67 As HCl is a byproduct of the fumed silica
reaction, HCl can easily be sourced and recycled for use from
In this section colloidal silica made through gaseous methods later in the process, as can be seen in Figure 2.
will be discussed. A number of gaseous synthesis methods have To begin the synthesis process, the silicon tetrachloride is
been developed; however, only two have retained commercial vaporized in a hydrogen and oxygen flame (Figure 2) at
longevity, namely the arc silica and fumed silica methods.58 Of temperatures exceeding 1000 °C (generally 1100−1800
the other gaseous methods of silica production that have been °C).68−70 The reaction proceeds via condensation polymer-
attempted over the years, none appear to have a current market ization and/or oxidation of the SiCl4 feed stock (eq 1).2,68−71
share.58,59
> 1000 ° C
The production of arc silica involves an endothermic reaction 2H 2(g) + O2(g) + SiCl4(g) ⎯⎯⎯⎯⎯⎯⎯⎯⎯→ SiO2(s) + 4HCl(g) (1)
and thus requires extreme energy input; hence, the arc silica
methodology has been largely abandoned by modern The silica product forms as molten silica nuclei, which grow as
processing.58,60,61 For example, in 1990 arc silicas contributed the reaction continues into molten, spherical, nonporous
less than 1% of the silica market share.58 In view of the “subparticles” (7−40 nm diameter, 2.2 g cm−3 density). High
declining popularity of the arc silica method, this section will temperature fusion and partial sintering of these “subparticles”
focus on fumed silica synthesis. It is important to note that result in their agglomeration into larger, mesoporous silica
“fumed silica” should not to be confused with “silica fume”, aggregates with a higher specific surface area (BET, 50−380 m2
which is a noncrystalline low purity silica produced as the g−1) and wider size distribution.2,61,68−73 Overall, the formation
8892 DOI: 10.1021/[Link].6b01839
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reaction is exothermic, so little additional fuel is needed to keep The synthesis of high purity silica is highly desirable for many
the reaction vessel at the required temperature.74 It is important applications and can be achieved through high purity reactants,
to note that a low residence time within the flame is essential to complete combustion, and careful handling.72 In most cases,
ensure only amorphous silica is produced.2 metallic elements (e.g., aluminum, calcium, zinc, etc.) in trace
Once formed, fumed silica must be extracted from the concentrations are the only significant contaminants.72 Because
vaporous HCl byproduct (eq 1). Generally, the separation is of the lack of ionic impurities fumed silica showed favorable
achieved first by mechanical means, i.e. cyclones or filters, then dielectric properties72 which could prove useful in electronic
through the treatment of silica with water-saturated hot air to applications.
remove adsorbed HCl2,74 (Figure 2). As mentioned earlier, the Dispersions of fumed silica also display excellent thixotropic
HCl byproduct may be used as a source of chlorine to produce (shear thinning) properties due to the relatively low number of
the silicon feedstock (i.e., silicon tetrachloride) and the H2 gas surface silanol groups.86 In static conditions, these surface
resulting from the silicon tetrachloride production can be used silanols increase viscosity via weak interaction with the fluid
as fuel for the hydrogen flame (Figure 2).2,67 A vacuum through hydrogen bonds. Owing to the relatively low number
deaeration step may follow the purification phase to increase of silanols available for hydrogen bonding, these interactions
the density of the powder for ease of transportation (Figure 2).2 ease within a dynamic environment as even the strain of a light
Control of particle size, size distribution, and surface area shear force can break the connection between fluid molecules
may be achieved by varying the concentration of reactants, and silica.87
flame temperature, and retention time.59,75,76 Depending on In recent years, the bulk of research has focused on the
which properties are favored for a particular application, milling development of fumed silica products for modern research
can be employed to reduce aggregates to their spherical applications, such as biosensors.88−91 The preparation of
nonporous subparticle sizes of 7−40 nm (Figure 2). Additives nanoparticle composites utilizing fumed silica as the core
introduced during or after the flame process may be used to material has been suggested for a number of applications. These
alter the surface properties allowing the creation of mixed metal applications include acting as a conductive nanomaterial for
microelectronics,89 a shielding component of transparent
oxides, hydrophilic silicas, and hydrophobic silicas.2,68 Pratsi-
protective films90 and a support for photoluminescent
nis74 provides a thorough overview on controlling reaction
compounds for use as molecular detection tools.88,91 However,
conditions and additives to achieve particular desired properties
the in situ entrapment of sensitive molecules is unachievable in
in the fumed silica product.
pyrogenic synthesis due to the extreme temperatures and
Despite significant environmental disadvantages due to its conditions required.
high energy consumption, the fumed silica methodology makes Overall, the dry synthesis of gaseous methods means that
use of the pollutant byproduct of the polysilicon industry, pyrogenic silicas are completely anhydrous and in possession of
SiCl4.77 Thus, the utilization of this chemical as the silicon a relatively low number of surface silanol groups when
source for silica production is still highly attractive. With this in compared with silica synthesized via liquid methods.86 These
mind a number of studies78,79 have attempted to pioneer properties are beneficial when silica is to be used as a
gaseous synthesis of silica at lower temperatures achieving reinforcing filler in rubber.84,92 However, these properties make
mixed results in terms of product size distribution and purity. pyrogenic silicas difficult to disperse in water without the aid of
The Yan et al.80 synthesis method was the first to demonstrate wetting agents or surface modifications.1 Silicas produced via
that a silica product of high purity (99.89% SiO2), large surface pyrogenic methods also differ from liquid-method silicas by
area (342 m2 g−1), and low polydispersity (0.221) could be often possessing a higher purity and consisting of pore-free
produced through low-temperature gaseous phase synthesis. In primary particles.86 However, the high energy requirements and
the study of Yan et al.80 the hydrolysis of vaporized SiCl4 with harsh reaction conditions of pyrogenic synthesis restrict its
water vapor was carried out at the relatively low temperature of usefulness in the current energy and environmentally conscious
150 °C. In addition, studies have also examined the society; hence, recent studies on pyrogenic silica are sparse. In
employment of the SiCl4 reactant in the liquid (sol−gel) contrast, liquid silica synthesis methods have a significantly
synthesis method.50,77,81 However, no studies have been lower energy cost; these methods will be discussed in the
published examining the possibility of industrialization of this following section.
method.
2.2. Properties and Applications of Fumed Silica. 3. LIQUID METHODS
Currently, fumed silica enjoys commercial use in many A vast number of liquid synthesis methods exist with much
industries, as a rheological control additive, polisher, flowing research dedicated to increasing the economy and the
aid, and even as dental filler.71,82 In particular, the high purity environmental sustainability of various methods.93−99
(>99.8 wt % SiO2), low moisture content, and transparency of Liquid silica synthesis methods produce silica through the
fumed silicas mean they are ideal for the production of silicone supersaturation and resultant polymerization of silicic acid,
rubber for medical applications and electrical wire/cable/ Si(OH)4, to form gel networks and discrete particles, as is
building insulation.73,83,84 Fumed silica is used as a reinforcing illustrated in Figure 3. Although the condensation polymer-
agent, particularly in concrete, and is also highly valued because ization of silicic acid occurs at neutral pH, acidic or basic
of its fine particle size (7−40 nm “subparticles” after milling of conditions increase the rate of polymerization.100 Generally,
the aggregates) offering a high degree of reinforcement and the acidic conditions favor the production of gels (Figure 3), as the
ability to accelerate hydration for ultrahigh performance silica formed in acidic solutions possesses little or no surface
concrete.3,85 However, because of its high cost when compared charge and thus facilitates flocculation/connectivity between
to silica produced via commercial liquid synthesis methods (i.e., silica particles.1 Basic conditions give silica a highly negative
precipitated silica), fumed silica is rarely used in the current surface charge and thus stabilize the suspension allowing the
manufacture of tires or mechanical rubber goods.85 production of individual particles which grow under Oswald
8893 DOI: 10.1021/[Link].6b01839
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industrially as more environmentally friendly synthesis

alternatives are cultivated.
Commercial precipitated silica is generally produced in a
batch or semibatch process from sodium silicate and sulfuric
acid as per eq 2.48
Na 2O·2.6SiO2 + H 2SO4 → 2.6SiO2 + Na 2SO4 + H 2O
(2)
To a preheated aqueous solution of sodium silicate, sulfuric
acid is added to achieve the desired pH (usually pH 8−10).111
While maintaining the required pH, simultaneous or alternating
additions of sodium sulfate and sulfuric acid are added to the
mixture. To ensure the formation of discrete particles instead of
a gel, intermittent stirring is used during the reaction time.
Preheating of the mixture and control of the level of
supersaturation also helps prevent gel networks from forming.
After the reaction is complete, the precipitate is filtered,
washed, dried, and milled to the size range appropriate for the
product’s application.48
Figure 3. Schematic of the formation of silica gels and particles during The chemical properties of the precipitated silica, such as
liquid synthesis from silicic acid under different values of pH without porosity and particle size, are most influenced by variations in
accounting for high electrolyte concentrations. pH, reaction temperature, reactant concentration, and stirring
rate.2,48,95,99,112,113 The physical characteristics of precipitated
silica are generally 30−800 m2 g−1 BET surface area, 2−20 nm
ripening1 (Figure 3). The electrolyte concentration can also average primary particle size, 1.9−2.1 g cm−3 density of primary
influence the morphology of the silica particles produced. particles, and mean pore diameter exceeding 30 nm.75,114
Adsorption of a cationic electrolyte to the silica particle surface Precipitated silicas are slightly less pure than pyrogenic silicas
reduces the repulsion between particles and thus acts as a having a SiO2 content by weight of 98−99%116 compared with
flocculant producing gels or large aggregates of particles.1,54 >99.8% for fumed silica.2,68,69 The lower energy consumption
There are a number of methods to precipitate silica gel or and reduced cost, when compared with gaseous silica processes,
particles, these include precipitated silica, microemulsion,7,52,53 means that precipitated silicas are utilized in many colloidal
Stöber method,101−104 and biomimetic silica syntheses.6,54,55 silica applications. The precipitated silica method, however,
The precipitated silica and Stöber methods both rely on highly offers only scarce control over particle properties making the
basic conditions to induce particle silica formation. Particle tailoring of the silica for specific purposes difficult.
formation can also be facilitated in neutral or acidic conditions The particulars of current operating procedures are difficult
by use of microemulsions or certain coprecipitating (biological to obtain due to confidentiality issues.48 However, patent
or biomimetic) molecules; these factors are the basis for the literature reveals that existing processes generally operate at pH
microemulsion and biomimetic silica synthesis methods, 8−10, have a residence time of 60 to 240 min and a reaction
respectively. The microemulsion method confines the silica temperature range of 60 °C to greater than 170
polymerization reaction within spherical droplets, which act to °C.2,48,111,115−117 Ranges of reactant concentration, stirrer
prevent particle interlinking/gel formation.105 In the case of rate, and feed rate were not available publicly through patents.
coprecipitating molecules, such as used in the biomimetic Continuous processes have been developed,118,119 but are
method, the molecules generally contain amine groups that are difficult to viably scale-up because of the loss in associated
encapsulated within the silica being formed. These amine yield.48
groups thus impart the silica formed with a strong positive The precipitated silicas are currently used in a wide variety of
surface charge in acidic and neutral pH, thus stabilizing the applications which include acting as reinforcing agents for
silica sol, so particles may grow individually through Oswald rubber manufacture,2,85,120,121 catalytic supports,122,123 flow
ripening.1 regulators,124 and absorbents.125 Tailoring the properties of
3.1. Precipitated Silica Synthesis. The “precipitated precipitated silica for particular applications has been the
silica” synthesis method is based on the neutralization of a subject of much of the ongoing research into the precipitated
soluble silicate with an acid which generates a silicic acid silica product.50,121,126−130 Of particular interest in the literature
concentration greater than the solubility limit of silica leading is improving the properties of precipitated silica in an effort to
to its polymerization and precipitation out of solution.48 better enhance the mechanical and thermal properties of rubber
Precipitated silica, formed from sodium silicate, has the largest products.121,126−129
share of the global specialty silica market.48,49 The precipitated There are also a number of recent studies aimed at expanding
silica (or neutralization) method is expected to maintain this the uses of precipitated silica even further, a few of which will
position and enjoy the most rapid growth in the next decade or be briefly touched upon here. The production of precipitated
so.48,49 A number of press releases have documented the amine-functionalized porous silica (or silica composite) colloids
continuous expansion of various companies’ precipitated silica has proven highly successful at promoting a regenerative CO2
empire.106−110 However, despite indications that the precipi- adsorbing product with a high absorption capacity for potential
tated silica market will continue to grow in the near future, the for use in carbon capture technology.18,131,132 Quang et al.133
harsh conditions required for precipitated silica synthesis will had also utilized the amine-functionalized precipitated silicas to
likely hinder the continuing expansion of this method attract a silver coating allowing for the manufacture of silica−
8894 DOI: 10.1021/[Link].6b01839
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silver core−shell nanocomposites for catalysis and antibacterial A very high or very low water-to-surfactant molar ratio caused
applications. Further improvement of the control over pore size microemulsion instability, resulting in a bimodal size
and size distribution of precipitated silica during the synthesis distribution or flocculation of particles, respectively.142 The
and drying stages has also been studied in recent years.134 diameters of synthesized silica could be further influenced by
The precipitated silica method is highly cost-effective and the ammonia concentration, with higher ammonium concen-
with continued improvements has even approached the purity trations causing a minimum in achievable mean particle
obtained by the fumed silica synthesis route. However, diameter even with increased water/surfactant ratio.139 An
ultimately methods that offer greater control over the product emulsion of the immiscible phases: aqueous nitric acid and
properties and milder reaction conditions are likely to TEOS, was found to produce large spherical silica particles with
eventually supersede the current industrial monopoly enjoyed an average diameter of 10 μm.146
by the precipitated silica synthesis method. Chattopadhyay and Gupta147 pioneered a microemulsion
3.2. Microemulsion Method Synthesis. Microemulsions method which makes use of a supercritical antisolvent to
are thermodynamically stable dispersions of two or more synthesize nanosized silica. This method utilizes supercritical
immiscible phases.7 To decrease the interfacial energy the CO2 as both reactant and antisolvent with the aim of reducing
dispersed phase may form spherical droplets. To stabilize these the reaction time of the microemulsion process. A W/O
emulsions, surfactants are added which assemble at the microemulsion of aqueous sodium silicate, an oil phase of n-
interface of the droplets and continuous phase, forming heptane or isooctane and an anionic surfactant was prepared.147
micelles, which further lower the interfacial energy.7 A microemulsion was then injected into the supercritical CO2
In the production of colloidal silica, often a surfactant- at 35 °C, whereupon the solvent was extracted and the exposed
stabilized water-in-oil (W/O) microemulsion, also referred to surface of the aqueous droplets reacted with the CO2 producing
as a reverse microemulsion, is used.7 By conducting the nanosized silica within the size range of 20−800 nm depending
nucleation and growth of silica within the aqueous droplets, the on the reactant concentrations.147 This process has con-
silica product can be templated by the size and shape of the sequently been used in the development of silica coating
droplet. The microemulsion environment also acts to sterically procedures148,149 and silica−polymer composite synthesis.150
stabilize the growing silica inhibiting cross-particle polymer- More recent work has focused on developing pre-existing
ization (i.e., irreversible particle coagulation).105 This enables microemulsion synthesis methods for specific
the generation of much smaller silica particles than are usually uses.126,135,151−153 For example, a significant number of drug
able to be produced from other liquid synthesis methods.105 molecules are unstable in the highly basic conditions employed
Overall, the microemulsion method offers a large degree of by most colloidal silica synthesis techniques.138 Through the
control to be exercised over important properties of the addition of fluoride to the microemulsion system, the
synthesized silica, such as, the degree of aggregation, size, condensation of monomeric silica species was allowed to
shape, particle size distribution, and porosity.93,97,135 Additional proceed within acidic conditions (as low as pH 1.07).154,155
additives such as various metal salts may also be included within Analogous to the W/O emulsions, oil in ionic liquid
the reaction to achieve one-pot synthesis and surface microemulsions have also received attention.156 These micro-
modification.136 emulsions have the ability to template and produce hollow silica
In 1978, 1−10 μm diameter silica particles were prepared by spheres156 which are of particular importance as molecular (e.g.,
the reaction of aqueous sodium silicate and ammonium sulfate drugs, dyes, and inks) transportation systems.156,157 Recently,
at the interface of a water-in-benzene emulsion, using a uniform hollow silica spheres have also been prepared using a
nonionic surfactant for stabilization.137 Yamauchi et al.138 W/O microemulsion. Ammonia catalyzed co-condensation of
produced nanometer-sized (14−71 nm) silica by the addition the alkoxysilanes, TEOS, and 3-aminopropyltriethoxysilane
of the alkoxysilane, tetraethoxysilane (TEOS), to a W/O (APTS), resulted in a solid silica product able to be etched
microemulsion of an anionic surfactant, isooctane and aqueous by heated water to produce hollow nanospheres.158
ammonia liquid. In a process similar to the Stöber method (to Mesoporous colloidal silica templated through micro-
be discussed in section 3.3) the TEOS, within the water emulsions have also received a great deal of research
droplets, was catalyzed by ammonia to hydrolyze and attention.135,159−163 For example, one method of micro-
polymerize into silica. Interestingly it was found that the size emulsion mesoporous silica preparation utilizes the hydro-
of the silica produced exceeded the size of the aqueous droplets phobic silica source tetrabutoxysilane (TBOS), which is
(typically 6−8 nm diameter), the authors138 suggested this may mechanically dispersed in a highly basic aqueous phase using
be the result of adjacent droplets coalescing during the early a cationic surfactant such as cetyltrimethyl ammonium bromide
stages of silica formation. (CTAB).135,164,165 As the TBOS is hydrolyzed the organic
Osseo-Asare and Arriagada have conducted extensive work to dispersed phase of the microemulsion becomes composed of
characterize and model synthesis of silica from TEOS in W/O TBOS and butane from which mesoporous silica is
microemulsion systems stabilized by nonionic surfac- polymerized.135 The microemulsion synthesis method is also
tants.139−143 Spherical silica with a size range of 50−70 nm being adapted for the creation of core−shell particles with the
and a narrow size distribution (below 8.5% standard deviation silica as the shell or core depending on the application.19,166−173
from the particle mean diameter) were produced from a system The microemulsion method provides significant control over
of nonionic surfactant/ammonium hydroxide/cyclohexane.143 particle size, morphology, and dispersity. However, the oil
The same procedure with the use of an anionic surfactant, phase of the microemulsion method poses difficulties environ-
sodium bis(2-ethylhexyl) sulfosuccinate (AOT), was found to mentally and for entrapment of sensitive molecules.
produce only highly polydisperse particle distributions or 3.3. Stö ber Method Synthesis. In 1968, Stöber et al.104
gels.144 developed a robust method of silica production, hereby known
Increasing the molar ratio of alcohol to water was as the Stöber method, which allowed the controlled synthesis of
demonstrated to decrease particle size from 1.5 to 0.1 μm.145 spherical, monodisperse, nano- to micrometer-size silica. The
8895 DOI: 10.1021/[Link].6b01839
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Stöber method of synthesis is achieved by the hydrolysis and Bogush et al.102 also worked to define the reactant
condensation polymerization of alkoxysilanes, detailed in concentration ranges required to produce monodisperse silica.
Schemes 1 and 2, respectively.100,174 In this method a Bogush et al.102 systematically studied the effect of reagent
concentrations (i.e., the concentration of water, ammonia, and
Scheme 1. Hydrolysis of Alkoxysilanes TEOS) within the mixture on particle size and particle
distribution. Keeping the TEOS concentration constant,
variations in water and ammonia concentration revealed that
a maximum particle size, of around 800 nm, could be obtained
at a water concentration of 7 M and ammonia concentration of
Scheme 2. Condensation Polymerization of Alkoxysilanes 2 M.102
There have been continued efforts over recent years to
further improve synthesis efficiency and control over material
properties.175,177 Wang et al.177 examined systems with a high
TEOS concentration (0.22−1.24 M) and low ammonia
combination of a short chained alkanol and water is used as concentration (0.81 M) to produce silica within the 30−1000
the medium, and the reaction is performed in the presence of nm size range. Ibrahim et al.176 investigated the effect of TEOS
the basic catalyst, ammonia.102,104 Since the invention of the and NH3 concentrations on the nucleation and growth
Stöber method of synthesis, the conditions of reaction and their processes of the Stöber synthesis. The authors176 observed
effect on particle properties have been thoroughly re- that increasing the TEOS or NH3 concentration resulted in a
searched.101−103,174−177 faster/shorter nucleation period and an increased growth rate,
Stöber et al.104 demonstrated the synthesis of silica with both increases resulting in larger silica particles. Whereas,
mean diameters ranging between 0.05 and 2 μm. The first step Plumeré et al.175 varied the reaction conditions (such as reagent
of the method involved obtaining the required concentration of concentration and temperature) in order to optimize the size,
dissolved ammonia within the alcoholic medium. This was dispersity, porosity, and aggregation behavior of Stöber silica
achieved either by bubbling ammonia through the medium at 0 for postsynthesis redox modifications.
°C or by the addition of a saturated ammonium hydroxide A number of modified Stöber synthesis methods have been
solution to the mixture. To the reaction mixture the developed for particular purposes,101,178,179 of which a few
alkoxysilane (commonly tetraethoxysilane, TEOS) was added examples will be presented here. Bazula et al.101 produced
and agitation was used throughout the reaction. Typically, microporous silica to improve the surface area characteristics of
clouding of the reactant mixture was observed within the 1−5 the silica product. In the modified method, micropores were
min following alkoxysilane addition, indicating silica formation. generated in the nonporous Stöber silica after synthesis,
However, a total reaction time of 120 min was used for all through alternating steps of washing in water and incubation
experiments.104 in alcohol.101 Functionalization of the silica surface during
The alkyl chain lengths of the alcohol medium and synthesis was possible through the coprecipitation of traditional
tetraalkoxysilane branches were systematically studied for alkoxysilanes (i.e., TEOS) with organosilanes (e.g., 3-
their effect on particle size and reaction rate.104 Faster reaction mercaptopropyltrimethoxysilane, vinyltriethyoxysilane, 3-ami-
rates were observed for the shorter chained alcohol media, with nopropyltriethoxysilane) possessing a desired functional group
alongside hydrolyzable and polymerizable alkoxysilane
methanol producing the fastest reaction and the slowest of the
branches.178−182
studied reactions performed in butanol. However, the faster
In 2001, Dingsøyr and Christy98 determined that the
reacting short chained alcohol media had a tendency to widen
ammonia catalyst used in the Stö ber method of silica
particle size distributions when compared with longer chain
production could be replaced with sodium hydroxide
length alcohol media.104 A similar trend was observed when (NaOH). The basic catalyst, whether it be a product of the
comparing the chain lengths of the tetraalkoxysilane reactant NH3/H2O equilibrium (such as in the original Stöber method)
used. By increasing the alkyl-chain length of the alkoxysilane or directly supplied NaOH98 acts to increase the concentration
used, the condensation polymerization reaction rate became of hydroxyl groups, driving the hydrolysis and condensation
slower and the silica produced decreased in size.104 reactions forward and thus promoting silica fabrication.174
Van Helden et al.103 characterized Stöber silica via dynamic However, both the Stöber method and Dingsøyr-Christy
light scattering (DLS) and transmittance electron microscopy method require the use of harsh chemicals and organic solvent
(TEM) demonstrating the high sphericity, low polydispersity, which may become a safety and environmental concern for the
and large size range available through this technique. Moreover, commercial scale-up.
the van Blaaderen group174 studied the effect of chemical Another synthesis technique183,184 utilized a 25 mM
microstructure on morphology in a combination of techniques concentration of the NaOH catalyst to induce silication of
including 29Si nuclear magnetic resonance (NMR) spectrosco- the nontoxic alkoxysilane (trimethoxymethylsilane, TMOMS)
py, TEM, and DLS. in an aqueous mediated reaction. The NaOH-silica synthesis
Bogush et al.102 further developed the Stöber method by method rapidly produced silica colloids (∼950 nm) with a low
exploring the effect of temperature within the range of 9−55 polydispersity while circumventing the need for an organic
°C. A distinct decrease in mean particle size was observed with solvent or toxic reactant species.183 The particle size
increasing temperature. Higher temperatures also increased the distribution and SEM image of the silica product reported on
monodispersity of the silica even for high concentrations of the by Hyde et al.183 are shown in Figure 4.
common alkoxysilane, tetraethoxysilane (TEOS), which were The Stöber process has also been adapted for coating
found to have a wide distribution when synthesized at room purposes. Mine et al.185 developed a seeded polymerization
temperature. technique based on the Stö ber method whereby gold
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silication, biological organisms use a number of silica inducing

and generally coprecipitating biomolecules whose clever
chemical structures, honed over millennia of evolution, control
and promote silica formation in vivo.55,190 Learning from these
biomolecules and their silication mechanisms has allowed
materials scientists to develop new biomimetic silica synthesis
methods.54
3.4.1. Biosilication. The mechanisms of biosilication (the
formation of biological silication) have received significant
research attention, especially those employed by diatoms and
siliceous marine sponges.190−205 In this section, the key
biomolecules and mechanism involved in their biosilication,
as it is currently understood, will be discussed as a background
to the in vitro biomimetic processes they have inspired. A
number of additional biomolecules which influenced the
morphology of the precipitated silica but do not possess
intrinsic silication activity themselves will also be touched upon.
However, a detailed discussion of the mechanistic features of
these morphological molecules is outside the scope of the
current review. For a more detailed discussion on morphology
please see the following reviews.54,55,190,206,207
Diatoms are unicellular organisms capable of synthesizing
elaborate species-specific biosilica cell walls with ornate
microscale structures and nanoscale patterning. Synthesis of
Figure 4. Hydrodynamic particle diameter distribution of NaOH− the cell walls is performed within the highly controlled acidic
silica particles and their visualization via SEM.183 Reprinted from ref environment of a specialized silica deposition vesicle
183. Copyright 2015 American Chemical Society. (SDV).191,204,208−210 As the SDV itself has so far eluded
isolation, 2 1 1 biosilica chemical extraction techni-
nanoparticles were coated with a silica shell without the need ques193,194,196,199,200,202−205 and intracellular analysis of the
for pretreatment of the gold surface. In the coating process, the diatom genome192,195 have been utilized to determine the
gold nanoparticles were first mixed with TEOS, water, and mechanism of diatom biosilication. So far these techniques have
ethanol with vigorous stirring. The synthesis of the silica shell identified a number of coprecipitating organic molecules that
was then initiated by addition of aqueous ammonia. The shell are believed to be responsible for the growth and arrangement
thickness could be tuned through varying the TEOS of these intricate biological structures, including long chain
concentration. Silver nanoparticles were coated through a polyamines (LCPAs), specialized proteins (silaffins, silacidins
similar process; however, an amine solution of ammonia, and cinguliums), and saccharides (e.g., chitin).
methylamine, and dimethylamine was necessary to engender In vitro activity of LCPAs in physiologically relevant
silication.186 conditions (pH 5.5) was dependent on the presence of a
Khan et al.187 successfully demonstrated the Stöber method multivalent anionic species.201 A phase separation model was
synthesis of uniform silica colloids in laboratory-scale proposed as the mechanism of LCPA mediated silication.190,212
continuous microfluidic chemical reactors in an effort to In the proposed model, the amphiphilic character of the LCPAs
showcase the favorable operation of microfluidic chemical and the ionic/H-bonding cross-linking role of the multivalent
reactors. Apart from this laboratory scale study, there is a anionic species allowed multiple LCPA molecules to assemble
considerable lack of significant literature exploring scale-up of into amine-anion-rich microdroplets.201,213,214 In fact, the
the Stöber process. It is likely that the advantages of enhanced ability to form a supramolecular amine-rich microphase appears
size control and increased monodispersity afforded by the to be vital for silica precipitating activity in all soluble organic
Stöber method, when compared to the leading “precipitated diatom biomolecules discovered so far.190,196,200−202,204 The
silica” production route, are not enough to offset the cost of role of multivalent anions is generally assumed by phosphate in
using the alkoxysilane reactant in place of the naturally in vitro tests.190,201 In vivo the multivalent anions component is
abundant sodium silicate feedstock. In addition, although the believed to be fulfilled by anionic polypeptides called
Stöber method does not require the high temperatures of the silacidins,193,196 heavily phosphorylated saccharide species,215
“precipitated silica” method the reaction still requires highly and/or Type-2 silaffins.199,200 Once supramolecular micelles are
basic conditions and/or an organic solvent. assembled, silicic acid polymerization is induced at the amine-
3.4. Biomimetic Sol−Gel Synthesis. Biomimetic sol−gel rich aqueous interface of the micelle where the cationic amine
synthesis methods are silication techniques inspired by the groups electrostatically attract silicic acid mono/oligo-mers and
mechanisms certain biological organisms employ to create uncharged amine groups act as acid−base catalyst polymer-
elaborate silica structures for the purposes of protection and ization.54,204,205,216 Additionally, selection of the LCPAs within
structural stability.188,189 a particular diatom species appears to play a role in biosilica
Biological silica synthesis (biosilication) in organisms, such as nanopatterning in vivo.190,212,217,218
diatoms and siliceous sponges, outstrip current synthetic silica Recent studies indicate that the anionic component of the
production methods by possessing superior control over silica system may have a role beyond ionic cross-linking during
structure/patterning and the ability to rapidly produce silica in aggregation, that is, may assist in inducing silica-
mild reaction conditions.54,190 To achieve these advantages in tion.191,193,219,220 In particular, Wallace et al.220 demonstrated
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how an NH3+/COO−-terminated surface induced silica 3.4.2. Biomimetic Silication. Bioextracts pose difficulties in
nucleation where NH3+ only surfaces did not. their extraction, availability and purification, thus are not ideal
Silaffins (so named due to their affinity to silica) are for probing the mechanistic features of biosilication or
polypeptides rich in lysine and serine residues with a high endeavors to manufacture silica on a large scale.55 As discussed
degree of post-translation modification (PTM).190,197 Unlike (section 3.4.1), biomolecule extracts, such as Type-1 silaffins,
the LCPAs which are found ubiquitously in diatom cell walls, so native LCPAs, and silicateins, possess silication activity in vitro
far only nine silaffin proteins have been identified in two diatom when exposed to a silicic acid source (generally hydrolyzed
species.211,221 Of the silaffins identified, only three native silaffin TEOS or tetramethoxysilane (TMOS)) under acidic/neutral
proteins, silaffin-1A1, silaffin-1A2, and silaffin-1B (denoted pH and ambient temperatures.190,201−205,234,239 Hence, utilizing
Type-1 silaffins), are able to directly mediate in vitro formation knowledge on how bioextracts promote and control silication
of spherical silica in acidic conditions.54,197,222 in vivo and in vitro a number of bioextract mimics
Type-1 silaffins are believed to employ a similar mechanism (biomimetic) molecules have been developed for synthetic
to the LCPA mediated silication.190 However, unlike LCPAs, silication. These synthetic equivalents or approximates allow for
the specialized zwitterionic structure of these silaffins allows the the advantages of the biosilication to be retained while
assembly of multimolecular aggregation (with a reported 700 circumventing the difficulties associated with the extraction of
molecules per aggregate) required for silication activity without the original biomolecules. For instance, a system of
anionic additives.190,202 The zwitterionic character of these polyethylenimine (PEI) and phosphate buffer (PB) is used as
silaffins is supplied through the high degree of modification a Type-1 silaffin mimic. The silaffin and PEI structures are
made to the polypeptide backbone of the molecule, with shown in Figure 5. In the PEI/PB system the PEI acts to mimic
positively charged polyamine groups attached to the lysine
residues and negatively charged phosphorylation of the serine
residues.190,202,223
A number of other biomolecules have been identified which
do not possess the ability to individually precipitate silica,
including Type-2 silaffins,199,200,211,221 saccharides,54,194,224 and
other proteins species.54,192 These biomolecules are believed to
provide a cross-linking role and/or impart some degree of
morphological control on the deposited silica resulting in the
elaborate nanopatterning observed in vivo.
Sponges are the other major biosilica producing organism.
Two classes of sponges, demosponges and hexactinellids, form
needle-like silica structures known as spicules for defense and
structural support. In both classes, the vesicles of specialized
sclerocyte cells produce an axial protein filament onto which
the formation and deposition of a soft gel-like biosilica is
facilitated by specialized biomolecules.225 A dehydration
process follows, causing the biosilica to solidify and shrink
into the characteristic spicule morphology.226,227 In addition to
LCPAs (detailed earlier in relation to diatoms),197,228 sponges
possess a number of other silication specific biomolecules
including the enzymatic catalysts (silicateins) and silicatein- Figure 5. Structure of (A) silaffin peptide, which contains
interacting proteins (silintaphins). polyaminated hydrocarbon chains that have a similar structure to
(B) branched polyethylenimine.240 Reprinted from ref 240. Copyright
A number of silicatein (so named as they are silica proteins) 2011 American Chemical Society.
isoforms have been identified in siliceous sponge spe-
cies.225,229−233 In vitro silicatein is able to mediate the the long chained polyamine chains substituents of the silaffin
hydrolysis and polycondensation of low concentrations of molecule, while the phosphate ions in the biomimetic PEI/PB
silica precursors (e.g., orthosilicates, TEOS) under mild system play a similar role to the phosphorylate modifications of
reaction conditions (near neutral pH and ambient temper- the silaffin molecule (Figure 5).240
atures), producing soft gelatinous silica nanospheres.234 Biomimetic molecules developed for the purpose of silicic
However, in contrast to the previous biomolecules discussed, acid polycondensation include the R5 peptide241−245a
silicateins mediate polycondensation of silicic acid through synthetic peptide possessing the amino acid sequence of one
enzymatic catalysis; a descriptive mechanism for this catalytic of the repeat units of the silaffin-1 precursor;205 various cationic
polymerization was proposed by Schröder and co-work- polypeptides/peptides (e.g., poly-L-lysine (PLL), poly-L-argi-
ers.206,235 Moreover, silicateins are believed to self-assemble nine (PLAr), poly-L-ornithine (PLO))191,233,244,246−255 and
in vivo providing some degree of structural guidance for silica copolypeptides;256,257 a number of synthetic polyamines (e.g.,
deposition177,236 a role which has been backed up by in vitro PEI, poly(allylamine hydrochloride) (PAH), polyallylamine
evidence.237 The two silica-interacting proteins, denoted (PAA));214,217,244,258−265 surfactants;255 short chained alkyl-
silintaphin-1 and silintaphin-2, have been identified in spicules amines;216,266 and amine-terminated dendrimers (e.g., poly-
of S. Domuncula species of sponge and are believed to assist in propylenimine (PII) and polyamidoamine (PAMAM)).213,267
the assembly of silicateins.206 Silintaphin-1 has also been shown Typically, an anionic counterion is required to be present for
to significantly enhance the polymerization ability of silicatein silication activity, which is believed to assist in cross-linking214
in vitro.237,238 and/or surface charge neutralization for particle growth
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through aggregation.213,268 In addition, a number of silicatein- nontoxic alkoxysilane possessing a relatively high silication
mimics, including copolypeptides (e.g., cysteine-lysine)269 and activity.16 This modified Stöber method (also known as the
enzymes (lysozyme, specific members of the cathepsin L PEI−silica method) has been shown to produce spherical
family) 270,271 are capable of both the hydrolysis and silica.268,272 Fabrication of silica prefunctionalized with thiol
condensation alkoxysilanes.269 groups is also possible using the modified Neville et al.16
Similar to in vitro experiments using biosilication molecules, synthesis method, which in 2015 led to a novel postsynthesis
the majority of these biomimetic molecules produce spherical functionalization method to be described.15 The nucleation/
silicas.205,213,242−244,247,250,253,256,262,264,266,267,269,272 The biomi- growth mechanism and reactant concentration dependence of
metic silication mechanism also generally appears reminiscent the PEI-TMOMS silica production has been thoroughly
of native biosilication whereby amine-rich multimolecular explored through in situ experiments.272,306−308
aggregates are formed through cross-linking with an intrinsic Limited effort to industrialize biomimetic processes has been
anionic element or separate multivalent anionic additive made so far. In 2011, He et al.309 published a bench-scale study
species.246,250,256,262,273 These assemble then act as morpho- of the microfluidic synthesis of PEI-mediated silica from a
logical templates and silication promotors. The primary hydrolyzed TMOS silica source. He et al.309 reported particle
particles formed though the templating action of the size and distribution could be precisely tuned through
biomimetic aggregates in some conditions produce larger deliberate variations in reaction conditions. It was also observed
(micrometer-sized) particles through flocculation facilitated by that the microfluidic unit enhanced silica yield and narrowed
the presence of electrolytes in solution.54 Thus, control over particle distribution when compared with batch processes at the
product particle size and distribution can be exercised through same scale.309
selection of the chemistry and relative concentrations of the Three factors contributing to the struggle of scaling up the
cationic and anionic components of the template as well as the biomimetic methods may be the cost, availability, and toxicity
presence of additive electrolytes which may promote of the reactants. As discussed, a significant number of synthetic
flocculation.241,246,250,256,262,273 biomimetic molecules have been reported on in the literature,
Although in vitro silication techniques have not yet fully thus the selection of the most appropriate mediator for scale-up
achieved the high degree structural control observed in may be made easier by the shear amount of options available.
biological silicas,274 a number of robust techniques have been However, just as important to the scale-up feasibility is the
developed which are able to induce the production of a variety selection of the silicon source, and here there is considerably
of nonspherical ordered silica morpholo- less choice. None of the alkoxysilane sources currently
gies.219,241,243,245,247,249,251−253,259−261,269,275−280 As an exam- investigated (TEOS, TMOS, or TMOMS) are able to be
ple, hollow silica nanospheres have significant applications in naturally sourced. In addition, these alkoxysilanes do not
drug delivery and as general molecular cargo carriers.281,282 provide an accurate model of the reactivity held by naturally
Hollow nanospheres were synthesized through the templating available sodium silicate, which is relatively cheaply and
effect of multimolecular assembles of block copeptides or abundantly available, and thus the most favorable choice of
polyamines micelles.216,217,257 In basic pH, lysozyme-mediated silica precursor for potential industrial scale-up.255
silication under sonication can also produce hollow silica Biomimetically induced precipitation of sodium silicate has
nanospheres.283,284 been reported on only a few occasions. PLL and PLAr induced
As the template is entrapped during synthesis, the surface the unorganized gelation of dilute sodium silicate.254 Utilizing
chemistry of the silica product can be tailored through selection arginine-derived surfactants as the silication-mediator produced
of the anionic/cationic components of the molecular an interconnected network comprising meso-to-macroporous
template.246 For example the PEI/PB-mediated silication silica from sodium silicate.255 A silica precipitate was also
reaction results in positively charged amine-functionalized silica obtained from a lysozyme/bovine serum albumin/sodium
due to the entrapment of the polyamine PEI template.240 silicate solution at neutral pH.310 Whereas, Annenkov et al.311
In addition, the mild reaction conditions available through mimicked the in vivo concentrating effect of biological
biomimetic silica synthesis are also an advantage in molecular desiccating agents through increasing the gravity during
encapsulation studies. In contrast to previous silica meth- synthesis (centrifugation), allowing the synthesis of a bimodal
ods,285−287 biomimetic synthesis allows for the effective in situ distribution of silica nanospheres from a sodium silicate and
entrapment of sensitive molecules without significant loss of poly(acrylic acid) solution. In 2015, nonpurified lysozyme
activity.16,35,223,240,271,272,285,288−301 The silica casing can thus sourced directly from egg shells was also found to induce the
act as a carrier, protector, and/or capture device enhancing the rapid precipitation of sodium silicate; however, the morphology
stability of the molecule and aiding the recovery of the of the resultant silica was not reported.289
molecules from solution.288,292,295,297−299 This encapsulation Overall, biomimetic silication offers a number of advantages
technique has potential applications in a variety of fields when compared with other silica synthesis techniques,
including drug delivery, imaging, enzymatic catalysis, antifoul- including mild reaction conditions, an aqueous solvent, the
ing, and environmental cleanup.54,289,302−304 ability to tune surface properties, and the capacity to
3.4.3. Silica Source and Potential Industrialization. Many successfully entrap and protect a number of sensitive biological
of the published biomimetic procedures utilize the alkoxysi- molecules. Additionally, the dual templating and silication
lanes, TEOS, or TMOS, as the silica source. However, there are inducing nature of the biomimetic catalysts present materials
number of issues associated with these common precursors. scientists with an unprecedented degree of control over
TMOS is a toxic compound, whereas the nontoxic TEOS has a precipitated silica morphology and size distribution. This
low reactivity and thus often requires much longer reaction morphological control is clearly demonstrated by the intricate
times.16,301,305 Neville et al.16,240,268 developed a polyethyleni- nano- and microscale structures produced by in vivo
mine (PEI)-mediated silication technique utilizing acid hydro- biosilication.191 However, despite these favorable character-
lyzed trimethoxymethylsilane (TMOMS). TMOMS is a istics, the commercial feasibility of biomimetic methods,
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Figure 6. A general representation of particle growth based on (A) monomer addition and (B) aggregation mechanisms.272 Note that different
authors have defined nuclei at different stages of particle growth (for further details please refer to Table 1). Adapted from ref 272. Copyright 2013
American Chemical Society.

Table 1. Summary of the Proposed Models on Silica Particle Formation

prediction of prediction of
nuclei definition/proposed particle growth mechanism/ PSD with particle size with
refs model for nuclei formation quantitative approach growth limiting phenomenon time time
LaMer322 sulfur rings/monomer monomer addition/Fick’s law diffusion of monomer no yes
addition
Flory,324,325 densification/monomer monomer addition/statistical approach diffusion of monomer yes (weight yes (i mer)
Stockmayer325 addition fraction)
Matsoukas and dimer of hydrolyzed silica monomer addition/rate equation surface reaction yes yes
Gulari100,321 species/monomer kernel
addition
Harris et al.320 stable particle/aggregation aggregation at early stages and diffusion of monomer no no
of unstable subparticles monomer addition at final stages/
rate equation
Bogush and densification/monomer aggregation/Smo-luchowski equation- primary particle production (diffusion related) yes yes
Zukoski318,319 addition Randolph and Larson
Bailey and densification/monomer monomer addition/rate equation diffusion of monomer no no
Mecartney317 addition
van Blaaderen et stable particles/ monomer addition/rate equation surface reaction no yes
al.316 aggregation of small
silica moieties
Giesche315 nanosized subunits/ aggregation at early stages and surface reaction no yes
aggregation monomer addition at final stages
Nagao et al.314 nanosized subunits/no aggregation/Smoluchowski equation primary particle reaction limited at early stage yes yes
mechanism proposed and primary particle diffusion limited at final
stages
Nozawa et al.313 seed particle/no monomer addition/Ostwald ripening surface reaction limited at early stages and no yes
mechanism proposed diffusion limited at later stages
Zao et al.327 stable particles/qualitative monomer addition/qualitative diffusion of monomer no no
(monomer addition) (monomer addition)
Seyfaee et PEI molecules/monomer primary particle aggregation/rate primary particle diffusion (aggregation) no yes
al.307,308 addition equation

especially in comparison to precipitated silica synthesis, still addition of monomers, surface reaction,326 and interparticle
presents an obstacle to scale-up. In addition, insufficient interactions. This section will address the most highly cited
understanding of biosilication mechanisms means biomimetic models of formation of colloids that can be directly or indirectly
methods have yet to fully realize the potential in morphological applied to predict the formation of synthesized silica in liquids.
and rate control successfully demonstrated by in vivo The models discussed here (except Lamer and Dinegar,322
biosilication. Flory324,325 and Stockmayer323) were developed for silica
synthesized via the Stöber method104 utilizing a tetraethox-
4. PROPOSED MODELS FOR SILICA PARTICLE ysilane (TEOS) silica precursor, unless otherwise indicated.
SYNTHESIS The comparatively low reactivity of TEOS allows indicators
The majority of the reported particle growth mechanisms and of silica formation, such as change in solution transparency, to
their related theoretical models100,307,312−325 were developed be easily observed. In contrast to the tens of minutes required
for liquid phase synthesis. Some of these models were for TEOS silication, reactions utilizing tetramethoxysilane
developed for colloids other than silica. However, their (TMOS) as the silicon precursor undergo silication at an
application to silica growth is straightforward as there are accelerated rate, such that silica is effectively produced
common physicochemical similarities such as diffusion and immediately after reaction initiation.240 The observable reaction
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rate of TEOS has meant that it is the preferable silica precursor method synthesis is also a concern and reveals a large gap in the
candidate in the majority of theoretical studies. Another silica current literature.
precursor examined by more recent theoretical studies307,272 is More detailed explanations of each reported model in Table
trimethoxymethylsilane (TMOMS). TMOMS molecules have 1 are provided in the following subsections of this review. Since
three reactive alkoxy groups and a methyl group in their the major focus of this modeling section is on particle growth,
structure in contrast to TEOS and TMOS that have four we have categorized the aforementioned research, based on the
reactive alkoxy groups. particle growth mechanism. Therefore, the following sub-
All of the suggested colloidal particle formation mod- sections consider first the models based on monomer addition
els100,307,312−325 agree that the reaction begins with the (section 4.1), later the models based on aggregation (section
formation of particle nuclei (as the most basic structure of a 4.2) and finally the models that considered a combination of
particle) and continues with the increase in particle size with both mechanisms (section 4.3). Since the models are complex
time. However, the central differences among models are found and sometimes combine components of the two main models,
on the definition of nuclei and particles and the mechanisms of the current literature is presented in Table 1 in chronological
their formation and growth. Here we endeavor to communicate order.
the essential components of the most cited models that are 4.1. Monomer Addition Growth Models. The pioneer-
either directly or indirectly applicable to sol−gel silica colloidal ing model of particle growth due to monomer addition was
particle formation. established by LaMer and Dinegar.322 These authors originally
There are two main proposed mechanisms for silica particle proposed their model to predict the formation of mono-
growth (Figure 6). One is the monomer addition growth model dispersed sulfur hydrosols. They assumed that nuclei formed
which is based upon LaMer’s original model322 and the second after slow decomposition of sodium thiosulfate using hydro-
is based on aggregation. In the monomer addition model of chloric acid as a catalyst. This model,322 suggests that the
particle growth,100,321−325 generally, nucleation is described as increasing concentration of sulfur eventually reached super-
homogeneous, that is, once supersaturation is reached the saturation causing the spontaneous assembly of solid cyclo-
precipitable material falls out of solution in a quick outburst, octasulfur (S8) rings as nuclei. The number of nuclei was
(Figure 6A). However, different authors have used different assumed to be equal to the number of particles, which implies
definition of nuclei (for more information on the definition of each particle formed individually and grew only through
nuclei, please refer to Table 1). Particle growth occurs via the monomer addition without any significant particle aggrega-
polycondensation of monomers on the surface of the newly tion.322 It was suggested that the growth of particles was
proportional to the amount of the total diffusible sulfur. LaMer
formed nuclei or existing particles. In the second model (Figure
and Dinegar,322 also assumed that the total amount of
6B), nucleation and growth of particles is proposed to occur via
molecular sulfur that diffused toward the nucleus to be a
an aggregation mechanism314,318,319 through the flocculation of
function of time only. So, through integration of Fick’s first law
nanometer-sized particles which are referred to as subpar-
of diffusion, LaMer and Dinegar,322 succeeded in expressing the
ticles316,320 or primary particles.307,318,319
molecular concentration profile of the sulfur precursor as a
At first glance these two mechanisms appear incompatible.
function of time and distance from the growing particle surface.
However, studies have shown that both models are useful to Furthermore, the change in the concentration profile was
describe particle formation and growth in different situations. directly related to the change in the volume of growing particle.
For example, the fact that particle growth can be described by a The LaMer model322 cannot predict the particle size
first order rate equation using a hydrolysis reaction constant as distribution and reports only one value for particle diameter,
well as the observation of an induction period, allows particle which in practice can be taken as an average, at any given time.
growth to be modeled via the monomer addition mecha- Flory−Stockmayer theory323−325 was developed to model
nism.316 On the other hand, if the silica product has an the molecular weight distribution of polymers (weight fraction)
ultramicroporous structure315,318,319 it is likely that the as a function of the degree of polymerization. Their theory can
aggregation mechanism is a better fit to model the particle be applied to understand the growth of silica as these particles
growth. In cases where the product is influenced by parameters form as a result of the polymerization of the silica
such as ionic strength, pH, and solvent properties including the precursor.272,326 Nucleation in Flory−Stockmayer theory was
dielectric constant and viscosity, then aggregation is likely the defined as the point at which the polymer becomes unstable
dominant growth mechanism.315,318,319 However, independent and undergoes phase separation forming small dense particles.
of the growth mechanism, confining the nucleation process to The reason for the polymer instability is either that the
occur only at the early stages of the reaction may lead to an polymer’s internal cross-linking density, or the molecular
increase in the final particle size and a narrow particle size weight increased324,325 to such an extent that the polymer−
distribution.315,316,318,319,322 solvent interactions were no longer strong enough to solvate
Overall this section reports upon the most well-known the polymer. Nuclei were then presumed to grow via the
models of silica particle formation and growth, to date. A monomer addition mechanism.
summary is provided in Table 1. The particle formation and Matsoukas and Gulari100 also suggested a monomer addition
growth are complicated phenomena. We have endeavored to mechanism for silica formation and growth as in the model of
increase the correlation between the observed experimental LaMer and Dinegar. 322 In the Matsoukas and Gulari
results and prediction of the published developed models. More model100,321 nuclei formation is defined as the point at which
recent models have attempted to improve the predictive power two hydrolyzed TEOS molecules join together. Matsoukas and
of their theoretical models by adapting older models.307,312,327 Gulari100 suggested that the narrow particle size distribution
Nevertheless, no silication model has yet to perfectly match all (PSD) of the Stöber-method synthesized silica indicated that
experimental data. The lack of specialized models developed for nucleation was likely terminated during the early stages of the
particle formation and growth outside of the TEOS Stöber reaction. Matsoukas and Gulari100 assumed the basic hydrolysis
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to be the rate limiting step and not the condensation reaction. Utilizing a competitive growth procedure, van Blaaderen et
Therefore, the change in mass of particles with time was shown al.316 investigated the growth of silica particles in a series of
to be proportional to the hydrolysis constant. bimodal seeded experiments using aged silica. In contrast to
Matsoukas and Gulari,100 further developed their model by their expectations, they observed an induction time in silica
considering three main irreversible chemical reactions. A first growth in seeded experiments. Fleming328 stated that a
order rate equation was used to describe each chemical contradiction such as this could be due to the difference in
reaction. The first described a hydrolysis reaction in which the the solubility of fresh and aged silica. Hence, for the
silica precursor maintained its monomeric structure and alkoxy precipitation reaction to happen in seeded growth, a level of
groups were substituted with reactive hydroxyl groups. The supersaturation roughly twice as high as the equilibrium
second involved a nucleation reaction in which two hydrolyzed concentration was required.328
monomers polymerized to form a nucleus (or dimer). A growth Van Blaaderen et al.216 suggested that the hydrolysis reaction
reaction was described in the third equation where an active was the rate limiting step. They also stated that the total particle
monomer (hydrolyzed monomer) was added to an oligomer of growth can be expressed using the hydrolysis coefficient of the
i monomers (denoted as an “i”-mer), thus producing an “i+1”- precursor via a first order rate equation. However, the authors
mer. Each rate constant was uniquely devoted to describe each believed that the condensation was limited by the surface
reaction and as a result a kernel (matrix) of rate constants was reaction condensation of hydrolyzed monomer and oligomers.
created. A power law dependency of the growth kernels on the According to their proposed mechanism, small siloxane
number of i-mers was assumed. The power law index was moieties, subject to the ionic strength and the surface potential
assumed to be given any value between zero and 1 where these of silica, were able to aggregate and form colloidally stable
values represented molecular diffusion limited and surface nuclei. If the formed nuclei were stable (low ammonia
reaction limited growth, respectively. To solve the rate concentration) aggregation ceased at relatively early stages of
equations, the method of moments321 was utilized. This the reaction. This led to an increase in the final particle number
model321 showed that in the hydrolysis rate limiting step density, a decrease in the final particle size, and a roughness of
reactions, the evolution of particle mass was independent of the surface of the particle product. In contrast, higher ammonia
whether the reaction was diffusion or reaction limited. concentrations resulted in a decrease in the number of stable
However, the final particle average size and standard deviation particles, which in turn increased the time needed for
were sensitive to the growth kernel and hence whichever aggregation. Longer aggregation times resulted in a lower
mechanism was limiting. Overall, the Matsoukas and Gulari321 particle number density and increased the final particle
diameter. Also the surface of the particles became smoother
model is able to predict the particle size distribution as well as
as there were more hydrolyzed silica species available.316
the evolution of particle size with time.
Nozawa et al.313 investigated the effect of continuous
Bailey and Mecartney,317 probed the mechanisms proposed
addition of TEOS on silica particle growth in seeded
by LaMer and Dinegar,322 Bogush and Zukoski,318,319 and
experiments. In the proposed model, they used a growth
Harris et al.320 using cryo-TEM and Si NMR techniques. The
deterministic parameter that related the surface reaction of
silication reaction was based on the Stöber method. Bailey and
silicic acid to its diffusion coefficient. It was argued that when
Mecartney317 suggested that different particle formation the concentration of silicic acid started to build up in the
mechanisms can be examined by observation of growing solution and passed a critical supersaturation value, nucleation
particles using the cryo-TEM technique. The NMR results of spontaneously occurred. As particle growth also proceeded at
Bailey and Mecartney317 showed that the main species in the this stage, there was monomer competition for nucleation and
reaction were monomeric TEOS and its first and second particle growth. Since silicic acid was still accumulating in the
hydrolyzed product (one or two hydrolyzed groups, system, the supersaturation reached a maximum. However,
respectively). Hence, the proposed model, based on rate soon after the reaction began, the silicic acid concentration
equations, consisted of two reaction rates for the first and decreased due to its consumption in nucleation or growth and
second hydrolysis reactions (TEOS with one or two hydroxyl reached a value lower than the critical supersaturation
groups) and one rate equation for the condensation reaction. concentration. After passing this point nucleation ended and
On the basis of the NMR and cryo-TEM results,317 the supersaturation continued to decline to reach to a quasi-steady
authors suggested that roughly123 silica atoms formed, in a state (known as the free growth stage).313 The silica formed in
random expanded polymeric coil, what the authors called a low the free growth stage continued to grow by Ostwald ripening1
density particle, or microgel particle. The microgel particles until the system reached the saturation concentration. On the
were presumed to grow via the monomer addition mechanism, basis of their experimental observation it was stated that the
while simultaneously intramolecular condensation bonds molecular diffusion of silicic acid was the rate limiting step of
formed within the gel resulting in densification. The densifying the particle growth in the final stages of the reaction.
particles grew further until they reached a collapse point which Combining their experimental observation with the proposed
resulted in them precipitating out of solution. The monomer model they expressed that the final particle diameter was
addition and densification processes ultimately resulted in the proportional to the cubed root of the inverse addition rate of
“intramolecular enthalpic attraction” overcoming the “entropic TEOS.313
solvation effect”,317 producing particle collapse. The authors Zhao et al.312 proposed a modified LaMer and Dinegar
suggested that colloidally stable particles continued to grow by model322 to explain the bimodal size distribution that they
monomer addition while no aggregation due to double layer observed experimentally. Zhao et al.312 added an ethanol
repulsion existed. A disadvantage of the Bailey and Mecartney containing TEOS solution dropwise into an ethanol and
model317 is that it only qualitatively describes the formation of ammonia solution mixture. They concluded that the particle
silica particles and thus is unable to report on particle size growth was by monomer addition and was limited by diffusion
variation with time as well as a particle size distribution. of the hydrolyzed precursor. The proposed modified
8902 DOI: 10.1021/[Link].6b01839
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Industrial & Engineering Chemistry Research Review

mechanism consisted of four consecutive steps named density function with respect to time was considered to be
prenucleation, nucleation, secondary nucleation, and growth.312 equal to the net summation of an aggregative birth, an
In the prenucleation step, the concentration of the dehydrated aggregative death, and a nucleation term. To include particle−
silica (precipitable material) accumulated with time. The particle interactions, the kernels for both birth and death terms
nucleation region started when the concentration passed a were considered to be a function of van der Waals, electrostatic
critical supersaturation level and nuclei formed and grew. After and solvation interactions. The comparison of the model and
this, during the third region (secondary nucleation) the experimental data318,319 in the homogeneous reactions showed
accumulated concentration of precipitable materials dropped that using the aggregation mechanism one may be able to
below the critical supersaturation value. The addition of TEOS predict the particle radius and particle size distribution
during this stage hindered the drop in concentration of correctly. The model by Bogush and Zukoski319 remains one
dehydrated silica and thus prolonged the nucleation period. It of the most popular models to describe particle formation and
was argued that if the production rate of precipitable materials growth.
due to TEOS addition to the system was higher than the Nagao et al.314 modified the Smoluchowski aggregation
consumption of the growing particles, a new generation of equation used by Bogush and Zukoski319 to study silica
nuclei appeared. As a result of this secondary nucleation stage, formation and growth in homogeneous and seeded experi-
in the growth region of the reaction (step 4), newly formed ments. In the modified model, the aggregation kernel was
small particles grew alongside the particles from the first assumed to be a function of both diffusion and surface reaction
generation nuclei. In contrast, if the number of nuclei during of aggregative particles. This modified model considered both
the first nucleation step was high enough, a second nucleation birth and death kernels to be only a function of the electrostatic
step was not generated, and the product was found to be and van der Waals interactions. They used the same nucleation
monodispersed. Zhao et al.312 justified their observation by function as Bogush and Zukoski.318 Their model was able to
using the aforementioned model. However, they did not demonstrate the effect of ionic strength on particle growth. In
express their proposed model quantitatively. addition, they demonstrated the hindering of formation of new
4.2. Models Based on the Aggregation Mechanism. particles by adding 2 mM KCl to the seeded experiments.314
Models based on an aggregation mechanism consider a binary Seyfaee et al.307,308 investigated the formation and growth of
collision of fine particles (e.g., primary particles, or subparticles) TMOMS derived PEI−silica particles. In their study, they
that may lead to the formation of larger colloids. stated that TMOMS diffused on to the surface of PEI
The first model of silica particle formation that considered molecules (nuclei) and polymerized there and primary particles
particle growth based on aggregation is by Bogush and started to form. Growth of nuclei by monomer addition led to
Zukoski.318,319 These authors developed their model on the precipitation of primary particles.308 They stated that the
basis of the results of their experiments which considered both production of primary particles was present throughout the
seeded and homogeneous conditions. Bogush and Zukos- reaction.308 Here it was assumed that silica formed due to
ki318,319 studied the changes in final particle size, total silica aggregation of primary particles (<25 nm).306−308 A model was
concentration, TEOS concentration, solution conductivity, and developed based on rate equations consisting of two terms,
solution volume, using TEM, atomic absorption spectropho- representing both production and consumption of primary
tometry, and Si NMR techniques as well as measuring the particles.307 The rate constant of their model was found to be a
volume of the reacting solution. function of silica precursor and biomimetic catalyst (PEI)
To investigate whether silica growth in seeded experiments concentration. To develop their model, Seyfaee et al.307
followed a monomer addition mechanism or aggregation assumed the reaction medium to consist of unit cells. Each
mechanism, Bogush and Zukoski318 used three equations to unit cell contained only one growing particle. Primary particles
express the hydrolysis of TEOS, the mass balance of silica, and were assumed to drop out of solution and to aggregate into a
the evolution of particle population for a given size range. The central growing particle. Using a mass balance, the concen-
hydrolysis of TEOS was considered to be represented by first tration of primary particles within each cell was related to the
order reaction kinetics. The mass balance equation related the mass of the forming particle.
change in the concentration of hydrolyzed silica with respect to Seyfaee et al. 307 also suggested that using a high
time to the net summation of hydrolysis reaction of precursor, concentration of precursor might lead to oscillation(s) in the
the deposition of hydrolyzed precursor on the surface of seeds particle diameter evolution. It was suggested that these
(by monomer addition) and a term representing nucleation. oscillations might be due to the coexistence of more than
Finally, the time evolution of the particle population as a one particle population with different growth rates. Hence,
function of size was equal to the negative gradient of the multiple types of unit cell with different growth rates were
product of the total rate of particle growth and its considered. The average particle diameter at any given time was
corresponding population.329 a function of both the quantity of different populations and
The set of three equations described above were solved for their average diameters. Moreover, the quantity of each
different scenarios considering the possibility of only monomer population was connected to its aggregation rate. Finally
addition or pure aggregation. The comparison of Bogush and using an averaging formula, the model was able to report the
Zukoski’s model and the experimental data318 verified the particle diameter versus time in a way that correlated well with
assumption that further growth of seeds was due to the experimental dynamic light scattering (DLS) results.307
aggregation of newly formed particles (nuclei) with the surface 4.3. Mixed Growth Mechanisms. The final type of
of seed particles. growth mechanisms considers that particle growth is due to
Assuming a purely aggregative mechanism, Bogush and both aggregation (at the early stages of growth) and monomer
Zukoski319 applied the Smoluchowski equation330 to describe addition (at the later stages of growth). These models are more
the formation and growth of silica particles from a complex in nature than those that are purely based on
homogeneous solution. The evolution of the particle number monomer addition or aggregation.
8903 DOI: 10.1021/[Link].6b01839
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Harris et al.320 stated that new particles kept on forming 5. CONCLUSION

throughout the reaction. They also measured the concentration For the majority of applications of silica, the physical and
of silicic acid to be more than three times greater than its chemical attributes of the material are paramount for
equilibrium concentration, and therefore nucleation continued performance.1 Colloidal silica produced via different methods
throughout most of the reaction period. Harris et al.320 may possess variations in hydration, purity, the number of
assumed the size of unstable nuclei, based on the optimization surface silanol groups, and porosity, which can have a
of Gibbs free energy, to be approximately 1−5 nm. During the significant impact on their appropriateness for particular
first half of the reaction period, these small nuclei were applications.2 For each application, the method of production
suggested to aggregate with each other very quickly to form used is chosen as a result of a trade-off between cost,
larger more stable particles or to deposit on to the surface of environmental imprint, availability, and suitability of the silica
existing particles. However, during the second half of the properties. So while one method may be appropriate for the
reaction the monomer addition mechanism was the dominant production of silica for laboratory scale projects, another may
process by which particles grew. Moreover, they claimed that be more appropriate for a particular commercial application.
the greater portion of silicic acid deposited on the silica surfaces This is the reason many methods of silica production are still
by a monomer addition mechanism at the midfinal stages of the relevant and in use.
reaction where nucleation ceased as variation of the number Current synthesis techniques encompass both gaseous and
density of particles was negligible. liquid media. Gaseous synthesis techniques are unique in their
In the research published by Harris et al.320 it was assumed ability to produce silica colloids of a very high purity. However,
that the basic hydrolysis of TEOS had a nucleophilic as continuous improvements of liquid synthesis methods bring
mechanism (OH- attacked silicon atom in TEOS). So, it was these liquid synthesized silicas closer to achieving the same or
suggested that lower order alkoxy groups around the silicon better measures of purity, this advantage diminishes. In
atom resulted in faster hydrolysis. Harris et al.320 assumed that addition, liquid method syntheses require less energy and
that the hydrolysis reaction of TEOS was a first order have a larger capacity for modifications to produce silica with
irreversible reaction and the condensation reaction was application-specific properties. Hence liquid synthesis methods
assumed to be a first order reversible reaction and to only have a greater proportion of the current scientific literature
occur between fully hydrolyzed species (silicic acid). Therefore, devoted to their study and improvement.
the change in the concentration of silicic acid was related to the Of the liquid synthesis techniques, only precipitated silica has
net summation of TEOS hydrolysis, condensation to silica, and made the leap to commercial production as it has the lowest
reverse condensation terms. In addition, in their proposed rate production costs. However, the Stöber, biomimetic sol−gel,
equations, a parameter for the total surface area of particles was and microemulsion methods continue to be studied in detail
considered. On the basis of their experiments the authors stated and used widely in the development of novel silica
that the particle growth mechanism switched from aggregation technologies. Most promising is the biomimetic sol−gel
to monomer addition when particle diameter reached method which combines mild reaction conditions with a high
approximately 135 nm as the particle number density remained degree of morphological control, however financial feasibility of
constant. The model by Harris et al.320 focused on predicting scale up is still a major obstacle for scale up.
the decrease in total soluble silica (TEOS and silicic acid) and Despite the extensive research into colloidal silica synthesis,
did not provide any information regarding evolution of particle the area still requires continued scientific attention. Optimiza-
diameter or particle size distribution. tion of current methods to provide increase cost effectiveness
Giesche315 performed an extensive study on silica synthesis. and decrease energy and material wastage is essential maintain
It was assumed that particle growth could be best described by to commercial techniques in the current market and launch
a first order rate equation in which the rate constant was equal laboratory methods into industrial scale production. Continued
to that of the TEOS hydrolysis reaction. Their experiments pioneering of novel synthesis techniques will be necessary to
showed that the hydrolysis reaction of silica was the rate increase the environmental sustainability of silica production in
limiting reaction.315 Giesche315 reported that the critical size of a more environmentally conscious society and to cater to new
silica nuclei was about 1 to 2 nm and that the time needed for markets for the colloidal silica product, such as the manufacture
these nuclei to form particle subunits (primary particles) was of medicinal and catalytic supports.
responsible for the observed induction or nucleation period. A number of mechanisms and corresponding mathematical
The latter is similar to the experimental results of Seyfaee et models have been proposed for the formation of sol−gel silica
al.308 Giesche315 continued that the nanosized subunits (nuclei) particles. In the majority of cases the Stöber method of
that were formed at the very early stages of the reaction, synthesis was utilized as the basis for model development;
aggregated and formed larger particles through a surface however, the basics should apply to most sol−gel synthesis
reaction limited condensation. The final size and number of processes. Most models hinged on whether silica growth
particles was determined by the colloidal stability and occurred through monomer addition or aggregation of nuclei/
aggregation rate of the nuclei. It was suggested that in the subparticles. The period of nucleation was also a contentious
later stages of the reaction, the growth mechanism changed and subject between models, some suggested nuclei continued to
particles continued to grow by monomeric or dimeric addition form throughout the reaction while others proposed significant
of silicic acid to their surfaces. nucleation only occurred for a short period after reaction
In conclusion, it is clear that a large amount of literature initiation. Overall, current understanding of silication suggests
exists for modeling the formation of silica particles. However, that reaction conditions are the deciding factor as to which
the models are complex and differ depending on the model best represents particle formation for a particular system.
experimental conditions of the synthesis and so are the subject The wealth of mechanisms and formulations available in the
of future work as new silica synthesis methods are developed. literature allows the user to make an informed decision as to
8904 DOI: 10.1021/[Link].6b01839
Ind. Eng. Chem. Res. 2016, 55, 8891−8913
Industrial & Engineering Chemistry Research Review

which model best represents their particular synthesis reaction. (8) Mugica, L. C.; Rodríguez-Molina, B.; Ramos, S.; Kozina, A.
Once an accurate model is selected for a particular system a Surface Functionalization of Silica Particles for Their Efficient
multitude of predictive tools are available, allowing the Fluorescent and Stereo Selective Modification. Colloids Surf., A
exploration and optimization of sol−gel methods without the 2016, 500, 79−87.
(9) Qiao, B.; Liang, Y.; Wang, T.-J.; Jiang, Y. Surface Modification to
time and resource expenses of experimental work.
Produce Hydrophobic Nano-Silica Particles Using Sodium Dodecyl
This paper provides an overview of current industrial and Sulfate as a Modifier. Appl. Surf. Sci. 2016, 364, 103−109.
laboratory-based colloidal silica synthesis methods, each of (10) Zhong, B.; Jia, Z.; Luo, Y.; Jia, D. Surface Modification of Silica
which possess their own advantages and disadvantages with N-Cyclohexyl-2-Benzothiazole Surfenamide for Styrene-Buta-
dependent on the desired application of the product. Significant diene Rubber Composites with Dramatically Improved Mechanical
models of the silica synthesis methods have also been presented Property. Mater. Lett. 2015, 145, 41−43.
herein. These models provide a tool allowing for a deeper (11) Xie, W.; Hu, L.; Yang, X. Basic Ionic Liquid Supported on
understanding of the mechanics of silica synthesis and thus the Mesoporous SBA-15 Silica as an Efficient Heterogeneous Catalyst for
ability to better tailor synthesis conditions for particular Biodiesel Production. Ind. Eng. Chem. Res. 2015, 54, 1505−1512.
product specifications. (12) Nasir Baig, R. B.; Varma, R. S. Magnetic Silica-Supported

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Palladium Catalyst: Synthesis of Allyl Aryl Ether in Water. Ind. Eng.
Chem. Res. 2014, 53, 18625−18629.
AUTHOR INFORMATION (13) Chen, L.; Hu, J.; Qi, Z.; Fang, Y.; Richards, R. Gold
Corresponding Author Nanoparticles Intercalated into the Walls of Mesoporous Silica as a
*E-mail: [Link]-Atanasio@[Link]. Versatile Redox Catalyst. Ind. Eng. Chem. Res. 2011, 50, 13642−13649.
(14) Zarabadi-Poor, P.; Badiei, A.; Fahlman, B. D.; Arab, P.; Ziarani,
Notes G. M.; Mohammadi Ziarani, G. One-Pot Synthesis of Ethanolamine-
The authors declare no competing financial interest.

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Modified Mesoporous Silica. Ind. Eng. Chem. Res. 2011, 50, 10036−
10040.
ACKNOWLEDGMENTS (15) Hyde, E. D. E. R.; Seyfaee, A.; Moreno-Atanasio, R.; Aubin, J.;
Neville, F. Covalent Surface Modification of Biomimetic Silica
The authors wish to acknowledge the University of Newcastle
Particles. In Proceedings of Asia Pacific Conference of Chemical
Electron Microscope X-ray Unit. E.D.E.H. and A.S. are the Engineering Congress 2015: APCChE 2015, incorporating CHEME-
recipients of the Australian Postgraduate Award scholarship.

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CA 2015, Melbourne, Australia, September 27−October 1, 2015;
Engineering Australia: Melbourne, pp 918−928.
ABBREVIATIONS (16) Neville, F.; Pchelintsev, N. A.; Broderick, M. J. F.; Gibson, T.;
PEI = polyethylenimine Millner, P. A. Novel One-Pot Synthesis and Characterization of
TMOMS = trimethoxymethylsilane Bioactive Thiol Silicate Nanoparticles for Biocatalytic and Biosensor
Applications. Nanotechnology 2009, 20, 055612.
TMOS = tetramethoxysilane (17) Bagwe, R. P.; Hilliard, L. R.; Tan, W. Surface Modification of
TEOS = tetraethoxysilane Silica Nanoparticles to Reduce Aggregation and Nonspecific Binding.
PB = phosphate buffer Langmuir 2006, 22, 4357−4362.
SEM = scanning electron microscopy (18) Osei-Prempeh, G.; Ingles, J.; Keffer, M.; Dunlap, D.; Thomas,
ATR-FTIR = attenuated total reflectance Fourier transform G.; Davari, A. Influence of the Polymer Surface Charge on the
infrared spectroscopy Synthesis and Properties of Polymer-Silica Composites. Ind. Eng.
DLS = dynamic light scattering Chem. Res. 2015, 54, 11295−11301.
W/O = water in oil microemulsion (19) Zhang, J.; Li, B.; Yang, W.; Liu, J. Synthesis of Magnetic Fe3O4@
APTS = 3-aminopropyltriethoxysilane hierarchical Hollow Silica Nanosphere for Efficient Removal of
NMR = nuclear magnetic resonance spectroscopy Methylene Blue from Aqueous Solution. Ind. Eng. Chem. Res. 2014,
LCPAs = long chained polyamines 53, 10629−10636.
(20) González-Ruiz, V.; Olives, A. I.; Martín, M. A. Core-Shell
TEM = transmission electron microscopy

■
Particles Lead the Way to Renewing High-Performance Liquid
Chromatography. TrAC, Trends Anal. Chem. 2015, 64, 17−28.
REFERENCES (21) He, D.; Wang, S.; Lei, L.; Hou, Z.; Shang, P.; He, X.; Nie, H.
(1) Iler, R. K. The Chemistry of Silica; John Wiley & Sons: New York, Core-Shell Particles for Controllable Release of Drug. Chem. Eng. Sci.
1979. 2015, 125, 108−120.
(2) Wason, S. K. Synthetic Silicas. In Handbook of Fillers for Plastics; (22) Knopp, D.; Tang, D.; Niessner, R. Review: Bioanalytical
Katz, H. S., Milewski, J. V., Eds.; Van Nostrand Reinhold: New York, Applications of Biomolecule-Functionalized Nanometer Sized Doped
1987; pp 165−201. Silica Particles. Anal. Chim. Acta 2009, 647, 14−30.
(3) Oertel, T.; Helbig, U.; Hutter, F.; Kletti, H.; Sextl, G. Influence of (23) Geszke-Moritz, M.; Moritz, M. APTES-Modified Mesoporous
Amorphous Silica on the Hydration in Ultra-High Performance Silicas as the Carriers for Poorly Water-Soluble Drug. Modeling of
Concrete. Cem. Concr. Res. 2014, 58, 121−130. Diflunisal Adsorption and Release. Appl. Surf. Sci. 2016, 368, 348−359.
(4) Bergna, H. E. Colloid Science. In Colloidal Silica Fundamentals (24) Wang, A.; Yang, Y.; Qi, Y.; Qi, W.; Fei, J.; Ma, H.; Zhao, J.; Cui,
and Applications; Bergna, H. E., Roberts, W. O., Eds.; CRC Press: Boca W.; Li, J. Fabrication of Mesoporous Silica Nanoparticle with Well-
Raton, 2006; pp 575−588. Defined Multicompartment Structure as Efficient Drug Carrier for
(5) Liberman, A.; Mendez, N.; Trogler, W. C.; Kummel, A. C. Cancer Therapy in Vitro and in Vivo. ACS Appl. Mater. Interfaces 2016,
Synthesis and Surface Functionalization of Silica Nanoparticles for 8, 8900−8907.
Nanomedicine. Surf. Sci. Rep. 2014, 69, 132−158. (25) Rajanna, S. K.; Kumar, D.; Vinjamur, M.; Mukhopadhyay, M.
(6) Wang, J.; Shah, Z. H.; Zhang, S.; Lu, R. Silica-Based Silica Aerogel Microparticles from Rice Husk Ash for Drug Delivery.
Nanocomposites via Reverse Microemulsions: Classifications, Prep- Ind. Eng. Chem. Res. 2015, 54, 949−956.
arations and Applications. Nanoscale 2014, 6, 4418−4437. (26) Hao, X.; Hu, X.; Zhang, C.; Chen, S.; Li, Z.; Yang, X.; Liu, H.;
(7) Guerrero-Martínez, A.; Pérez-Juste, J.; Liz-Marzán, L. M. Recent Jia, G.; Liu, D.; Ge, K.; Liang, X. − J.; Zhang, J. Hybrid Mesoporous
Progress on Silica Coating of Nanoparticles and Related Nanomateri- Silica-Based Drug Carrier Nanostructures with Improved Degrad-
als. Adv. Mater. 2010, 22, 1182−1195. ability by Hydroxyapatite. ACS Nano 2015, 9, 9614−9625.

8905 DOI: 10.1021/[Link].6b01839

Ind. Eng. Chem. Res. 2016, 55, 8891−8913
Industrial & Engineering Chemistry Research Review

(27) Kempen, P. J.; Greasley, S.; Parker, K. A.; Campbell, J. L.; Ultrafiltration Membranes with Antifouling Properties. J. Membr. Sci.
Chang, H. Y.; Jones, J. R.; Sinclair, R.; Gambhir, S. S.; Jokerst, J. V. 2012, 423−424, 362−370.
Theranostic Mesoporous Silica Nanoparticles Biodegrade After Pro- (45) Jo, K.; Ishizuka, M.; Shimabayashi, K.; Ando, T. Development of
survival Drug Delivery and Ultrasound/Magnetic Resonance Imaging New Mineral Oil-Based Antifoams Containing Size-Controlled
of Stem Cells. Theranostics 2015, 5, 631−642. Hydrophobic Silica Particles for Gloss Paints. J. Oleo Sci. 2014, 63,
(28) Zhang, Q.; Wang, X.; Li, P. Z.; Nguyen, K. T.; Wang, X. J.; Luo, 1303−1308.
Z.; Zhang, H.; Tan, N. S.; Zhao, Y. Biocompatible, Uniform and (46) Puig, M.; Cabedo, L.; Gracenea, J. J.; Jiménez-Morales, A.;
Redispersible Mesoporous Silica Nanoparticles for Cancer-Targeted Gámez-Pérez, J.; Suay, J. J. Adhesion Enhancement of Powder
Drug Delivery In Vivo. Adv. Funct. Mater. 2014, 24, 2450−2461. Coatings on Galvanised Steel by Addition of Organo-Modified Silica
(29) Bitar, A.; Ahmad, N. M.; Fessi, H.; Elaissari, A. Silica-Based Particles. Prog. Org. Coat. 2014, 77, 1309−1315.
Nanoparticles for Biomedical Applications. Drug Discovery Today (47) Jensen, K. A.; Saber, A. T. Case Study: Paints and Lacquers with
2012, 17, 1147−1154. Silica Nanoparticles. In Safety of Nanomaterials along Their Lifecycles:
(30) Tang, F.; Li, L.; Chen, D. Mesoporous Silica Nanoparticles: Release, Exposure and Human Hazard; Wohlleben, W., Kuhlbusch, T.
Synthesis, Biocompatibility and Drug Delivery. Adv. Mater. 2012, 24, A. J., Schnekenburger, J., Lehr, C. M., Eds.; CRC Press: Boca Raton,
1504−1534. 2015; pp 381−398.
(31) Yang, P.; Gai, S.; Lin, J. Functionalized Mesoporous Silica (48) Drummond, C.; McCann, R.; Patwardhan, S. V. A Feasibility
Materials for Controlled Drug Delivery. Chem. Soc. Rev. 2012, 41, Study of the Biologically Inspired Green Manufacturing of Precipitated
3679−3698. Silica. Chem. Eng. J. 2014, 244, 483−492.
(32) Wang, K.; Liu, P.; Ye, Y.; Li, J.; Zhao, W.; Huang, X. Fabrication (49) The Freedonia Group. World Speciality Silicas·Demand and Sales
of a Novel Laccase Biosensor Based on Silica Nanoparticles Modified Forecasts, Market Share, Market Size, Market Leaders; The Freedonia
with Phytic Acid for Sensitive Detection of Dopamine. Sens. Actuators, Group: Cleveland, OH, 2014.
B 2014, 197, 292−299. (50) Rahman, I. A.; Padavettan, V. Synthesis of Silica Nanoparticles
(33) Zhao, W.; Fang, Y.; Zhu, Q.; Wang, K.; Liu, M.; Huang, X.; by Sol-Gel: Size-Dependent Properties, Surface Modifications and
Shen, J. A Novel Glucose Biosensor Based on Phosphonic Acid- Applications in Silica-Polymer Nanocomposites − A Review. J.
Functionalized Silica Nanoparticles for Sensitive Detection of Glucose Nanomater. 2012, 2012, 1−15.
in Real Samples. Electrochim. Acta 2013, 89, 278−283. (51) Jaganathan, H.; Godin, B. Biocompatibility Assessment of Si-
(34) Ma, F.; Zhou, L.; Tang, J.; Wei, S.; Zhou, Y.; Zhou, J.; Wang, F.; Based Nano- and Micro-Particles. Adv. Drug Delivery Rev. 2012, 64,
Shen, J. A Facile Method for Haemoglobin Encapsulation in Silica
1800−1819.
Nanoparticles and Applications in Biosensors. Microporous Mesoporous (52) Malik, M. A.; Wani, M. Y.; Hashim, M. A. Microemulsion
Mater. 2012, 160, 106−113.
Method: A Novel Route to Synthesize Organic and Inorganic
(35) Choi, O.; Kim, B. C.; An, J. H.; Min, K.; Kim, Y. H.; Um, Y.; Oh,
Nanoparticles. Arabian J. Chem. 2012, 5, 397−417.
M. K.; Sang, B. I. A Biosensor Based on the Self-Entrapment of
(53) Uskokocić, V.; Drofenik, M. Synthesis of Materials within
Glucose Oxidase within Biomimetic Silica Nanoparticles Induced by a
Reverse Micelles. Surf. Rev. Lett. 2005, 12, 239−277.
Fusion Enzyme. Enzyme Microb. Technol. 2011, 49, 441−445.
(54) Lechner, C. C.; Becker, C. F. W. Silaffins in Silica
(36) Chermahini, A. N.; Omran, M. K.; Dabbagh, H. A.;
Biomineralization and Biomimetic Silica Precipitation. Mar. Drugs
Mohammadnezhad, G.; Teimouri, A. Application of a Functionalized
2015, 13, 5297−5333.
Mesoporous Silica Catalyst to the Synthesis of Tetrazoles. New J.
(55) Patwardhan, S. V. Biomimetic and Bioinspired Silica: Recent
Chem. 2015, 39, 4814−4820.
Developments and Applications. Chem. Commun. 2011, 47, 7567−
(37) Jin, C.; Wang, Y.; Wei, H.; Tang, H.; Liu, X.; Lu, T.; Wang, J.
Magnetic Iron Oxide Nanoparticles Coated by Hierarchically 7582.
(56) Slowing, I. I.; Trewyn, B. G.; Giri, S.; Lin, V. S. -Y. Mesoporous
Structured Silica: A Highly Stable Nanocomposite System and Ideal
Catalyst Support. J. Mater. Chem. A 2014, 2, 11202−11208. Silica Nanoparticles for Drug Delivery and Biosensing Applications.
(38) Yang, X.; Chen, D.; Liao, S.; Song, H.; Li, Y.; Fu, Z.; Yunlan, S. Adv. Funct. Mater. 2007, 17, 1225−1236.
High-Performance Pd-Au Bimetallic Catalyst with Mesoporous Silica (57) Singh, L. P.; Bhattacharyya, S. K.; Kumar, R.; Mishra, G.;
Nanoparticles as Support and Its Catalysis of Cinnamaldehyde Sharma, U.; Singh, G.; Ahalawat, S. Sol-Gel Processing of Silica
Hydrogenation. J. Catal. 2012, 291, 36−43. Nanoparticles and Their Applications. Adv. Colloid Interface Sci. 2014,
(39) Margelefsky, E. L.; Zeidan, R. K.; Davis, M. E. Cooperative 214, 17−37.
Catalysis by Silica-Supported Organic Functional Groups. Chem. Soc. (58) Ferch, H. K. Industrial Synthetic Silicas in Powder Form. In
Rev. 2008, 37, 1118−1126. Colloidal Silica Fundamentals and Applications; Bergna, H. E., Roberts,
(40) Bérubé, F.; Khadhraoui, A.; Janicke, M. T.; Kleitz, F.; Kaliaguine, W. O., Eds.; CRC Press: Boca Raton, 2006; pp 187−199.
S. Optimizing Silica Synthesis for the Preparation of Mesoporous Ti- (59) Mezey, E. J. Pigments and Reinforcing Agents. In Vapor
SBA-15 Epoxidation Catalysts. Ind. Eng. Chem. Res. 2010, 49, 6977− Deposition; Powell, C. F., Oxley, J. H., Blocher, Jr., J. M., Eds.; John
6985. Wiley and Sons: New York, 1966.
(41) Lin, J.; Ye, W.; Zhong, K.; Shen, J.; Jullok, N.; Sotto, A.; der (60) Saevarsdottir, G.; Bakken, J. A. Current Distribution in
Bruggen, B. V. Enhancement of Polyethersulfone (PES) Membrane Submerged Arc Furnaces for Silicon Metal/Ferrosilicon Production.
Doped by Monodisperse Stöber Silica for Water Treatment. Chem. In Proceedings of the Twelfth International Ferroalloys Congress
Eng. Process. [Online early access]. DOI 10.1016/[Link].2015.03.011 Sustainable Future, Helsinki, Finland, June 6−9, 2010; Vartiainen, A.,
Published Online: March 11, 2015. [Link]/science/ Ed.; Outotec Oyj: Finland, 2010; pp 717−728.
article/pii/S0255270115000574 (accessed July 25, 2015). (61) Deutsche Forschungsgemeinschaft (DFG). Silica, Amorphous.
(42) Zhu, L. J.; Zhu, L. P.; Jiang, J. H.; Yi, Z.; Zhao, Y. F.; Zhu, B. K.; In MAK Collection for Occumpational Health and Saftey; Wiley-VCH:
Xu, Y. Y. Hydrophilic and Anti-Fouling Polyethersulfone Ultra- Germany, 1991; Vol. 2, pp 158−179.
filtration Membranes with Poly(2-hydroxyethyl methacrylate) Grafted (62) Pratsinis, S. E. OverviewNanoparticulate Dry (Flame)
Silica Nanoparticles as Additive. J. Membr. Sci. 2014, 451, 157−168. Synthesis & Application. In Technical Proceedings of the 2006
(43) Wu, H.; Mansouri, J.; Chen, V. Silica Nanoparticles as Carriers NSTI Nanotechnology Conference and Trade Show, Boston, MA,
of Antifouling Ligands for PVDF Ultrafiltration Membranes. J. Membr. May 7−11, 2006; NSTI-Nanotech: Austin, TX, 2006; Vol. 1, pp 301−
Sci. 2013, 433, 135−151. 307.
(44) Huang, J.; Zhang, K.; Wang, K.; Xie, Z.; Ladewig, B.; Wang, H. (63) Strobel, R.; Pratsinis, S. E. Flame Aerosol Synthesis of Smart
Fabrication of Polyethersulfone-Mesoporous Silica Nanocomposite Nanostructure Materials. J. Mater. Chem. 2007, 17, 4743−4756.

8906 DOI: 10.1021/[Link].6b01839

Ind. Eng. Chem. Res. 2016, 55, 8891−8913
Industrial & Engineering Chemistry Research Review

(64) Flagan, R. C.; Mori, Y. Generation of Particle by Reaction. In (87) Moreland, C. Handbook of Fillers and Reinforcements for Plastics;
Powder Technology Handbook, 3; Masuda, H., Higashitani, K., Yoshida, Van Nostrand Reinhold: New York, 1978.
H., Eds.; CRC Press: Boca Raton, 2006; pp 413−418. (88) Becuwe, M.; Danjou, P.-E.; Cazier, F.; Woisel, P.; Delattre, F.
(65) Ulrich, G. D. Special Report. Chem. Eng. News 1984, 62, 22−29. Immobilization of Fluorescent Chemosensor on Pyrogenic Silica: A
(66) Klopfer, H. Verfahren zum Reinigen von hochdispersen Oxyden Promising Device for Gaseous Detection. J. Colloid Interface Sci. 2015,
von Metallen bzw. Metalloiden. D.E. Patent 762,723 C, July 28, 1952. 450, 62−67.
(67) White, L. J.; Duffy, G. J. Staff-Industry Collaborative Report (89) Al-Hussaini, A. S.; Zoromba, M.; Sh; El-Ghamaz, N. A. In Situ
Vapor-Phase Production of Colloidal Silica. Ind. Eng. Chem. 1959, 51, Polymerization and Characterization of Aniline and o-Anthranilic Acid
232−238. Copolymer/Pyrogenic Silica Nanocomposites. Polym.-Plast. Technol.
(68) Evonik Industries. Basic Characteristics of AEROSIL Fumed Eng. 2013, 52, 1089−1096.
Silica; Technical Bulletin Fine Particles 11 [Online]. [Link] (90) Zhang, H.; Zhang, H.; Tang, L.; Zhou, L.; Eger, C.; Zhang, Z.
[Link]/sites/lists/IM/Documents/TB-11-Basic-Characteristics- Comparative Study on the Optical, Surface Mechanical and Wear
[Link] (accessed July 26, 2016). Resistant Properties of Transparent Coatings Filled with Pyrogenic
(69) Cabot Corporation. General Guide: CAB-O-SIL Fumed Silica Colloidal Silica Nanoparticles. Compos. Sci. Technol. 2011, 71, 471−
and SpectrAl Fumed Alumina [Online], Cabot Corporation: MA, 479.
2011. [Link] (91) Becuwe, M.; Cazier, F.; Delattre, F.; Landy, D.; Ruellan, S.;
[Link] (accessed Mar 22, 2016). Woisel, P. Internal Structure Investigation of Pyrogenic Modified Silica
(70) Wacker Chemical Corporation. There’s More to It than You by Fluorescent Labeling. Colloids Surf., A 2011, 384, 248−253.
Think HDK- Pyrogenic Silica [Online], Waker Chemie AG: Münich, (92) Hewitt, N. Compounding Precipitated Silica in Elastomers: Theory
2009. [Link] and Practice; William Andrew: Norwich, 2007.
6174_EN.pdf (accessed Mar 22, 2016). (93) Mihaly, M.; Lacatusu, I.; Olteanu, N. L.; Meghea, A. A
(71) Boldridge, D. Morphological Characterization of Fumed Silica Systematic Methodology to Design Silica Templates: Silica Micro-
Aggregates. Aerosol Sci. Technol. 2010, 44, 182−186. emulsion Formulation and Nanodroplet Type and Size Estimation. C.
(72) Leblanc, J. L. Filled Polymers: Science and Industrial Applications; R. Chim. 2014, 17, 342−351.
CRC Press: Boca Raton, 2010. (94) Canton, G.; Riccò, R.; Marinello, F.; Carmignato, S.; Enrichi, F.
(73) Taikum, O.; Friehmelt, R.; Scholz, M. The Last 100 Years of Modified Stöber Synthesis of Highly Luminescent Dye-Doped Silica
Fumed Silica in Rubber Reinforcement. Rubber World 2010, 242, 35− Nanoparticles. J. Nanopart. Res. 2011, 13, 4349−4356.
44. (95) Filipović, R.; Obrenović, Z.; Stijepović, I.; Nikolić, L. M.; Srdić,
(74) Pratsinis, S. E. Flame Aerosol Synthesis of Ceramic Powders. V. V. Synthesis of Mesoporous Silica Particles with Controlled Pore
Prog. Energy Combust. Sci. 1998, 24, 197−219.
Structure. Ceram. Int. 2009, 35, 3347−3353.
(75) Vansant, E. F.; van der Voort, P.; Vrancken, K. C.
(96) Betancor, L.; Luckarift, H. R. Bioinspired Enzyme Encapsulation
Characterization and Chemical Modification of the Silica Surface;
for Biocatalysis. Trends Biotechnol. 2008, 26, 566−572.
Elsevier Science B.V.: Amsterdam, 1995.
(97) Abarkan, I.; Doussineau, T.; Smaïhi, M. Tailored Macro/
(76) Hurd, A. J.; Flower, W. L. In Situ Growth and Structure of
Microstructural Properties of Colloidal Silica Nanoparticles via
Fractal Silica Aggregates in a Flame. J. Colloid Interface Sci. 1987, 122,
Microemulsion Preparation. Polyhedron 2006, 25, 1763−1770.
178−192.
(98) Dingsøyr, E.; Christy, A. A. Effect of Reaction Variables on the
(77) Xiao, Y.; Wang, Y.; Luo, G.; Bai, S. Using Hydrolysis of Silicon
Formation of Silica Particles by Hydrolysis of Tetraethyl Orthosilicate
Tetrachloride to Prepare Highly Dispersed Precipitated Nanosilica.
Chem. Eng. J. 2016, 283, 1−8. Using Sodium Hydroxide as a Basic Catalyst. Prog. Colloid Polym. Sci.
(78) Park, H. K.; Park, K. Y. Vapor-Phase Synthesis of Uniform Silica 2001, 116, 67−73.
Spheres through Two-Stage Hydrolysis of SiCl4. Mater. Res. Bull. 2008, (99) Sierra, L.; Lopez, B.; Guth, J. L. Preparation of Mesoporous
43, 2833−2839. Silica Particles with Controlled Morphology from Sodium Silica
(79) Isobe, H.; Kaneko, K. Porous Silica Particles Prepared from Solutions and a Non-Ionic Surfactant at pH Values between 2 and 6.
Silicon Tetrachloride Using Ultrasonic Spray Method. J. Colloid Microporous Mesoporous Mater. 2000, 39, 519−527.
Interface Sci. 1999, 212, 234−241. (100) Matsoukas, T.; Gulari, E. Dynamics of Growth of Silica
(80) Yan, F.; Jiang, J.; Chen, X.; Tian, S.; Li, K. Synthesis and Particles from Ammonia-Catalyzed Hydrolysis of Tetra-ethyl-orthosi-
Characterization of Silica Nanoparticles Preparing by Low-Temper- licate. J. Colloid Interface Sci. 1988, 124, 252−261.
ature Vapor-Phase Hydrolysis of SiCl4. Ind. Eng. Chem. Res. 2014, 53, (101) Bazula, P. A.; Arnal, P. M.; Galeano, C.; Zibrowius, B.;
11884−11890. Schmidt, W.; Schüth, F. Highly microporous monodisperse silica
(81) Moreno, Y. P.; Cardoso, M. B.; Ferrão, M. F.; Moncada, E. A.; spheres synthesized by the Stöber process. Microporous Mesoporous
dos Santos, J. H. Z. Effect of SiCl4 on the Preparation of Mater. 2014, 200, 317−325.
Functionalized Mixed-Structure Silica from Monodisperse sol-gel silica (102) Bogush, G. H.; Tracy, M. A.; Zukoski, C. F. Preparation of
nanoparticles. Chem. Eng. J. 2016, 292, 233−245. Monodisperse Silica Particles: Control of Size and Fraction. J. Non-
(82) Teoh, W. Y.; Amal, R.; Mädler, L. Flame Spray Pyrolysis: An Cryst. Solids 1988, 104, 95−106.
Enabling Technology for Nanoparticles Design and Fabrication. (103) van Helden, A. K.; Jansen, J. W.; Vrij, A. Preparation and
Nanoscale 2010, 2, 1324−1347. Characterization of Spherical Monodisperse Silica Dispersions in
(83) Brunner, S.; Wakili, K. G. Hints for an Additional Aging Factor Nonaqueous Solvents. J. Colloid Interface Sci. 1981, 81, 354−368.
Regarding the Thermal Performance of Vacuum Insulation Panels with (104) Stöber, W.; Fink, A.; Bohn, E. Controlled Growth of
Pyrogenic Silica Core. Vacuum 2014, 100, 4−6. Mondisperse Silica Spheres in the Micron Size Range. J. Colloid
(84) Diao, S.; Zhang, S.; Yang, Z.; Feng, S.; Zhang, C.; Wang, Z.; Interface Sci. 1968, 26, 62−69.
Wang, G. Effect of Tetraphenylphenyl-Modified Fumed Silica on (105) Chang, C. L.; Fogler, H. S. Kinetics of Silica Particle Formation
Silicone Rubber Radiation Resistance. J. Appl. Polym. Sci. 2011, 120, in Non-Ionic W/O Microemulsions from TEOS. AIChE J. 1996, 42,
2440−2447. 3153−3163.
(85) Prasertsri, S.; Rattanasom, N. Fumed and Precipitated Silica (106) PPG Industries. PPG to increase precipitated silica production
Reinforced Natural Rubber Composites Prepared from Latex System: capacity in North America [Online]. Pittsburgh, PA, February 7, 2016.
Mechanical and Dynamic Properties. Polym. Test. 2012, 31, 593−603. [Link]
(86) Wagner, E.; Brünner, H. Aerosil, Herstellung, Eigenschaften und North-America-precipitated-silica/ (accessed Mar 22, 2016).
Verhalten in Organischen Flüssigkeiten. Angew. Chem. 1960, 72, 744− (107) Brazil & Germany: Evonik − precipitated silicaFocus Pigm.
750. 2015, No. 2015 (7), 5.10.1016/[Link].2015.07.022

8907 DOI: 10.1021/[Link].6b01839

Ind. Eng. Chem. Res. 2016, 55, 8891−8913
Industrial & Engineering Chemistry Research Review

(108) Evonik Completes US Precipitated Silica Expansion, Adds (129) Liu, Q.; Zhang, Y.; Xu, H. Properties of Vulcanized Rubber
Capacity in Japan. Addit. Polym., No. 2014 (11), 8−9.10.1016/S0306- Nanocomposites Filled with Nanokaolin and Precipitated Silica. Appl.
3747(14)70173-3 Clay Sci. 2008, 442, 232−237.
(109) Evonik to build new precipitated silica plant in Brazil and (130) Jesionowski, T.; Krysztafkiewicz, A. Influence of Silane
silanes labs in GermanyAddit. Polym. 2014, 2014 (9), 6−7.10.1016/ Coupling Agents on Surface Properties of Precipitated Silicas. Appl.
S0306-3747(14)70137-X Surf. Sci. 2001, 172, 18−32.
(110) Huber Engineered Materials. Huber’s Expansion of Its (131) Quang, D. V.; Dindi, A.; Rayer, A. V.; Hadri, N. E.; Abdulkadir,
Precipitated Silica Plant in India on Track for Completion in 2012. A.; Abu-Zahra, M. R. M. Impregnation of Amines onto Porous
Atlanta, GA, March 12, 2012. [Link] Precipitated Silica for CO2 Capture. Energy Procedia 2014, 63, 2122−
(accessed March 22, 2016). 2128.
(111) Okel, T. A.. Microporous Precipitated Silica. U.S. Patent (132) Goeppert, A.; Meth, S.; Prakash, G. K. S.; Olah, G. A.
8,114,935 B2, February 14, 2012. Nanostructured Silica as a Support for Regenerable High-Capacity
(112) Shapiro, I.; Kolthoff, I. M. Studies on Aging of Precipitates and Organoamine-Based CO2 Sorbents. Energy Environ. Sci. 2010, 3,
Coprecipitation. XXXIII. The Thermal Aging of Imperfect Barium 1949−1960.
Sulphate. J. Phys. Chem. 1940, 44, 921−935. (133) Quang, D. V.; Sarawade, P. B.; Hilonga, A.; Park, S. D.; Kim, J.-
(113) Sierra, L.; Guth, J. L. Synthesis of Mesoporous Silica with K.; Kim, H. T. Facile Route for Preparation of Silver Nanoparticle-
Tunable Pore Size from Sodium Silicate Solutions and a Polyethylene Coated Precipitated Silica. Appl. Surf. Sci. 2011, 257, 4250−4256.
Oxide Surfactant. Microporous Mesoporous Mater. 1999, 27, 243−253. (134) Zhang, T.; Wang, Y.; Luo, G.; Bai, S. Effects of Precipitation
(114) Brinkmann, U.; Ettlinger, M.; Kernerm, D.; Schmoll, R. and Drying Processes on the Synthesis of Silica Materials with a Large-
Synthetic Amorphous Silicas. In Colloidal Silica Fundamentals and Pore-Volume and Narrow-Pore-Diameter Distribution. Ind. Eng. Chem.
Applications; Bergna, H. E., Roberts, W. O., Eds.; CRC Press: Boca Res. 2016, 55, 3579−3587.
Raton, 2006; pp 575−588. (135) Miyake, Y.; Hanaeda, M.; Asada, M. Separation of Organic
(115) Esch, H.; Kuhlmann, R.; Neumueller, M.; Otto, K.; Rausch, R. Compounds by Spherical Mesoporous Silica Prepared from W/O
Process for the Production of Precipitated Silica. U.S. Patent 5,484,581 Microemulsions of Tetrabutoxysilane. Ind. Eng. Chem. Res. 2007, 46,
A, January 16, 1996. 8152−8157.
(116) Chevallier, Y.; Prat, E. Precipitated Silica. U.S. Patent 6,335,396 (136) Aubert, T.; Grasset, F.; Mornet, S.; Duguet, E.; Cador, O.;
B1, January 1, 2002. Cordier, S.; Molard, Y.; Demange, V.; Mortier, M.; Haneda, H.
(117) Stenzel, O.; Uhrlandt, S.; Luginsland, H. D.; Weheier, A. Functional Silica Nanoparticles Synthesized by Water-in-Oil Micro-
Highly Dispersible Precipitated Silica with a High Surface Area. U.S. emulsion Processes. J. Colloid Interface Sci. 2010, 341, 201−208.
Patent 20,060,137,575 A1, December 8, 2009. (137) Nakahara, Y.; Motohashi, K.; Tanaka, Y.; Miyata, K.
(118) Donnet, J. B.; Vrisakis, G.; Coudurier, M.; Baudru, B. Processes Preparation of the Spherical Silica Particles and Their Properties.
for the Manufacturing of Precipitated Silica. U.S. Patent 4,243,428 A, Shikizai Kyokaishi 1978, 51, 521−527.
(138) Yamauchi, H.; Ishikawa, T.; Kondo, S. Surface Characterization
January 6, 1981.
(119) Hagar, W. J.; Gallis, K. W. Continuous Silica Production of Ultramicro Spherical Particles of Silica Prepared by W/O
Microemulsion Method. Colloids Surf. 1989, 37, 71−80.
Process and Silica Product Prepared from Same. U.S. Patent
(139) Arriagada, F. J.; Osseo-Asare, K. Synthesis of Nanosize Silica in
20,110,206,746 A1, August 25, 2011.
a Non-Ionic Water-in-Oil Microemulsion Effects of the Water/
(120) Idrus, S. S.; Ismail, H.; Palaniandy, S. Study of the Effect of
Surfactant Molar Ratio and Ammonia Concentration. J. Colloid
Different Shapes of Ultrafine Silica as Fillers in Natural Rubber
Interface Sci. 1999, 211, 210−220.
Compounds. Polym. Test. 2011, 30, 251−259.
(140) Arriagada, F. J.; Osseo-Asare, K. Controlled Hydrolysis of
(121) Pattanawanidchai, S.; Loykulnant, S.; Sae-oui, P.; Maneevas,
Tetraethoxysilane in a Non-Ionic Water-in-Oil Microemulsion: A
N.; Sirisinha, C. Development of Eco-Friendly Coupling Agent for
Statistical Model of Silica Nucleation. Colloids Surf., A 1999, 154, 311−
Precipitated Silica Filled Natural Rubber Compounds. Polym. Test.
326.
2014, 34, 58−63. (141) Osseo-Asare, K.; Arriagada, F. J. Growth Kinetics of Nanosized
(122) Sun, Z.; Bai, C.; Zheng, S.; Yang, X.; Frost, R. L. A Silica in a Non-Ionic Water-in-Oil Microemulsion: A Reverse Micellar
Comparative Study of Different Porous Silica Minerals Supported Pseudophase Reaction Model. J. Colloid Interface Sci. 1999, 218, 69−
TiO2 Catalysts. Appl. Catal., A 2013, 458, 103−110. 76.
(123) Kim, J. K.; Park, J. K.; Kim, H. K. Synthesis and (142) Arriagada, F. J.; Osseo-Asare, K. Phase and Dispersion Stability
Characterization of Nanoporous Silica Support for Enzyme Immobi- Effects in the Synthesis of Silica Nanoparticles in a Non-Ionic Reverse
lization. Colloids Surf., A 2004, 241, 113−117. Microemulsion. Colloids Surf. 1992, 69, 105−115.
(124) Müller, A. K.; Ruppel, J.; Drexel, C. P.; Zimmermann, I. (143) Osseo-Asare, K.; Arriagada, F. J. Preparation of SiO2
Precipitated Silica as Flow Regulator. Eur. J. Pharm. Sci. 2008, 34, Nanoparticles in a Non-Ionic Reverse Micellar System. Colloids Surf.
303−308. 1990, 50, 321−339.
(125) Faramawy, S.; El-Naggar, A. Y.; El-Fadly, A. M.; El-Sabagh, S. (144) Arriagada, F. J.; Osseo-Asare, K. Synthesis of Nanosize Silica in
M.; Ibrahim, A. A. Silica, Alumina and Aluminosilicates as Solid Aerosol OT Reserve Microemulsions. J. Colloid Interface Sci. 1995,
Stationary Phases in Gas Chromatography. Arab. J. Chem. [Online 170, 8−17.
access]. DOI: 10.1016/[Link].2011.08.015. Published Online: August (145) Esquena, J.; Tadros, T. F.; Kostarelos, K.; Solans, C.
27, 2011. URL: [Link]/science/article/pii/ Preparation of Narrow Size Distribution Silica Particles using
S1878535211002280 (accessed July 25, 2016). Microemulsions. Langmuir 1997, 13, 6400−6406.
(126) Zhang, Q.; Liu, Q.; Zhang, Y.; Cheng, H.; Lu, Y. Silane-Grafted (146) Kawaguchi, T.; Ono, K. Spherical Silica Gels Precipitated from
Silica-Covered Kaolinite as Filler of Styrene Butadiene Rubber. Appl. Acid Catalyzed TEOS Solutions. J. Non-Cryst. Solids 1990, 121, 383−
Clay Sci. 2012, 65−66, 134−138. 388.
(127) Schaefer, D. W.; Kohls, D.; Feinblum, E. Morphology of (147) Chattopadhyay, P.; Gupta, R. B. Supercritical CO2-Based
Highly Dispersing Precipitated Silica: Impact of Drying and Formation of Silica Nanoparticles Using Water-in-Oil Microemulsions.
Sonication. J. Inorg. Organomet. Polym. Mater. 2012, 22, 617−623. Ind. Eng. Chem. Res. 2003, 42, 465−472.
(128) Zhang, Y.; Liu, Q.; Zhang, Q.; Lu, Y. Gas Barrier Properties of (148) Guo, L.; Zhao, X.; Zhang, R.; Chen, C.; Chen, J.; Chen, A.; Liu,
Natural Rubber/Kaolin Composites Prepared by Melt Blending. Appl. X.; Hou, Z. Mesoporous Spherical Silica Encapsulating Pd Nano-
Clay Sci. 2010, 50, 255−259. particles Prepared by CO2-Induced Microemulsion and Catalytic

8908 DOI: 10.1021/[Link].6b01839

Ind. Eng. Chem. Res. 2016, 55, 8891−8913
Industrial & Engineering Chemistry Research Review

Application in Suzuki Coupling Reaction. J. Supercrit. Fluids 2016, 107, (168) Lian, J.; Xu, Y.; Lin, M.; Chan, Y. Aqueous-Phase Reactions on
715−722. Hollow Silica-Encapsulated Semiconductor Nanoheterostructures. J.
(149) Thakur, R.; Gupta, R. B. Supercritical CO2 Based Silica Am. Chem. Soc. 2012, 134, 8754−8757.
Coating of Gold Nanoparticles Using Water-in-Oil Microemulsion. (169) Jiang, F.; Fu, Y.; Zhu, Y.; Tang, Z.; Sheng, P. Fabrication of
Ind. Eng. Chem. Res. 2005, 44, 3086−3090. Iron Oxide/Silica Core-Shell Nanoparticles and Their Magnetic
(150) Wang, W.; Cao, L.; Wang, J.; Zhao, J.; Wu, X.; Hao, Y. Characteristics. J. Alloys Compd. 2012, 543, 43−48.
Characterization and Adsorptive Properties of Poly(1-vinylimidazole)/ (170) Wang, Z.; Zong, S.; Chen, H.; Wu, H.; Cui, Y. Silica Coated
Silica Nanocomposites Synthesized in Supercritical Carbon Dioxide. e- Gold Nanoaggregates Prepared by Reverse Microemulsion Method:
Polym. 2015, 15, 245−254. Dual Mode Probes for Multiplex Immunoassay Using SERS and
(151) Liu, L.; Yue, S.; Zhang, Y.; Qin, R.; Liu, L.; Zhang, D.; Sun, R.; Fluorescence. Talanta 2011, 86, 170−177.
Chen, L. One-Pot Reverse Microemulsion Synthesis of Core-Shell (171) Chung, S. H.; Lee, D. W.; Kim, M. S.; Lee, K. Y. The Synthesis
Structured YVO4:Eu3+@SiO2 Nanocomposites. Opt. Mater. 2015, 39, of Silica and Silica-Ceria, Core-Shell Nanoparticles in a Water-in-Oil
207−210. (W/O) Microemulsion Composed of Heptane and Water with the
(152) Nooney, R.; O’Connell, C.; Roy, S.; Boland, K.; Keegan, G.; Binary Surfactants AOT and NP-5. J. Colloid Interface Sci. 2011, 355,
Kelleher, S.; Daniels, S.; McDonagh, C. Synthesis and Characterisation 70−75.
(172) Zhang, J.; Liu, Z.; Han, B.; Li, Z.; Yang, G.; Li, J.; Chen, J.
of Far-Red Fluorescent Cyanine Dye Doped Silica Nanoparticles
Preparation of Silica and TiO2-SiO2 Core-Shell Nanoparticles in
Using a Modified Microemulsion Method for Application in Bioassays.
Water-in-Oil Microemulsion Using Compressed CO2 as Reactant and
Sens. Actuators, B 2015, 221, 470−479. Antisolvent. J. Supercrit. Fluids 2006, 36, 194−201.
(153) Ren, Y.; Zhao, Y.; Zhang, Y.; Tang, W.; Xin, X.; Shen, J.; Wang, (173) Grasset, F.; Marchand, R.; Marie, A. M.; Fauchadour, D.;
L. Facile Synthesis of Au@SiO2 Core-Shell Nanoparticles with Fajardie, F. Synthesis of CeO2@SiO2 Core-Shell Nanoparticles by
Multiple Au Nanodots by a Reverse Microemulsion (Water-in-Oil) Water-in-Oil Microemulsion. Preparation of Functional Thin Firm. J.
Method. Colloids Surf., A 2015, 486, 14−20. Colloid Interface Sci. 2006, 299, 726−732.
(154) Finnie, K. S.; Bartlett, J. R.; Barbé, C. J. A.; Kong, L. Formation (174) van Blaaderen, A.; Kentgens, A. P. M. Particle Morphology and
of Silica Nanoparticles in Microemulsions. Langmuir 2007, 23, 3017− Chemical Microstructure of Colloidal Silica Spheres Made from
3024. Alkoxysilanes. J. Non-Cryst. Solids 1992, 149, 161−178.
(155) Reetz, M. T.; Zonta, A.; Simpelkamp, J. Efficient Immobiliza- (175) Plumeré, N.; Ruff, A.; Speiser, B.; Feldmann, V.; Mayer, H. A.
tion of Lipases by Entrapment in Hydrophobic Sol-Gel Materials. Stöber Silica Particles as Basis for Redox Modifications: Particle Shape,
Biotechnol. Bioeng. 1996, 49, 527−534. Size, Polydispersity and Porosity. J. Colloid Interface Sci. 2012, 368,
(156) Zhao, M.; Zheng, L.; Li, N.; Yu, L. Fabrication of Hollow Silica 208−219.
Spheres in an Ionic Liquid Microemulsion. Mater. Lett. 2008, 62, (176) Ibrahim, I. A. M.; Zikry, A. F. F.; Sharaf, M. A. Preparation of
4591−4593. Spherical Silica Nanoparticles: Stöber Silica. J. Am. Sci. 2010, 6, 985−
(157) Bao, Y.; Shi, C.; Wang, T.; Li, X.; Ma, J. Recent Progress in 989.
Hollow Silica: Template Synthesis, Morphologies and Applications. (177) Wang, X.-D.; Shen, Z.-X.; Sang, T.; Cheng, X.-B.; Li, M.-F.;
Microporous Mesoporous Mater. 2016, 227, 121−136. Chen, L.-Y.; Wang, Z.-S. Preparation of Spherical Silica Particles by
(158) Lin, C.-H.; Chang, J.-H.; Yeh, Y.-Q.; Wu, S.-H.; Liu, Y.-H.; Stöber Process with High Concentration of Tetra-ethyl-orthosilicate. J.
Mou, C.-Y. Formation of Hollow Silica Nanospheres by Reverse Colloid Interface Sci. 2010, 341, 23−29.
Microemulsion. Nanoscale 2015, 7, 9614−9626. (178) Takeda, Y.; Komori, Y.; Yoshitake, H. Direct Stöber Synthesis
(159) Lv, X.; Zhang, L.; Xing, F.; Lin, H. Controlled Synthesis of of Monodisperse Silica Particles Functionalized with Mercapto-, Vinyl-
Monodispersed Mesoporous Silica Nanoparticles: Particle Size Tuning and Aminopropylsilanes in Alcohol-Water Mixed Solvents. Colloids
and Formation Mechanism Investigation. Microporous Mesoporous Surf., A 2013, 422, 68−74.
Mater. 2016, 225, 238−244. (179) Lee, Y.-G.; Park, J.-H.; Oh, C.; Oh, S.-G.; Kim, Y. C.
(160) Ma, K.; Werner-Zwanziger, U.; Zwanziger, J.; Wiesner, U. Preparation of Highly Monodisperse Hybrid Silica Spheres Using a
Controlling Growth of Ultrasmall Sub-10 nm Fluorescent Mesoporous One-Step Sol-Gel Reaction in Aqueous Solution. Langmuir 2007, 23,
Silica Nanoparticles. Chem. Mater. 2013, 25, 677−691. 10875−10878.
(161) Lu, F.; Wu, S.-H.; Hung, Y.; Mou, C.-Y. Size Effect on Cell (180) Barrera, E. G.; Livotto, P. R.; dos Santos, J. H. Z. Hybrid Silica
Uptake in Well-Suspended, Uniform Mesoporous Silica Nanoparticles. Bearing Different Organosilanes Produced by the Modified Stöber
Small 2009, 5, 1408−1413. Method. Powder Technol. 2016, 301, 486−492.
(162) Kobler, J.; Möller, K.; Bein, T. Colloidal Suspensions of (181) Bai, A.; Song, H.; He, G.; Li, Q.; Yang, C.; Tang, L.; Yu, Y.
Functionalized Mesoporous Silica Nanoparticles. ACS Nano 2008, 2, Facile Synthesis of Core-Shell Structured ZrO2@SiO2 Via a Modified
Stöber Method. Ceram. Int. 2016, 42, 7583−7592.
791−799.
(182) Ashik, U. P. M.; Wan Daud, W. M. A. Stabilization of Ni, Fe,
(163) Möller, K.; Kobler, J.; Bein, T. Colloidal Suspensions of
and Co Nanoparticles Through Modified Stöber Method to Obtain
Nanometer-Sized Mesoporous Silica. Adv. Funct. Mater. 2007, 17,
Excellent Catalytic Performance: Preparation, Characterization, and
605−612. Catalytic Activity for Methane Decomposition. J. Taiwan Inst. Chem.
(164) Miyake, Y.; Yumoto, T.; Kitamura, H.; Sugimoto, T. Eng. 2016, 61, 247−260.
Solubilization of Organic Compounds into As-Synthesized Spherical (183) Hyde, E. D. E.; Moreno-Atanasio, R.; Millner, P.; Neville, F.
Mesoporous Silica. Phys. Chem. Chem. Phys. 2002, 4, 2680−2684. Surface Charge Control Through the Reversible Adsorption of a
(165) Huo, Q.; Feng, J.; Schüth, F.; Stucky, G. D. Preparation of Biomimetic Polymer on Silica Particles. J. Phys. Chem. B 2015, 119,
Hard Mesoporous Silica Spheres. Chem. Mater. 1997, 9, 14−17. 1726−1735.
(166) Nooney, R.; O’Connell, C.; Roy, S.; Boland, K.; Keegan, G.; (184) Neville, F.; Dixon, L.; Hyde, E. D. E. R. A Comparison Study
Kelleher, S.; Daniels, S.; McDonagh, C. Synthesis and Characterisation of Hydrophobic Silica Particles Synthesis. Adv. Powder Technol., in
of Far-Red Fluorescent Cyanine Dye Doped Silica Nanoparticles press, DOI: 201610.1016/[Link].2016.07.007.
Using a Modified Microemulsion Method for Application in Bioassays. (185) Mine, E.; Yamada, A.; Kobayashi, Y.; Konno, M.; Liz-Marzán,
Sens. Actuators, B 2015, 221, 470−479. L. M. Direct Coating of Gold Nanoparticles with Silica by Seeded
(167) Fernandes, M. T. C.; Garcia, R. B. R.; Leite, C. A. P.; Kawachi, Polymerization Technique. J. Colloid Interface Sci. 2003, 264, 385−390.
E. Y. The Competing Effect of Ammonia in the Synthesis of Iron (186) Kobayashi, Y.; Katakami, H.; Mine, E.; Nagao, D.; Konno, M.;
Oxide/Silica Nanoparticles in Microemulsion/Sol-Gel System. Colloids Liz-Marzán, L. M. Silica Coating of Silver Nanoparticles Using a
Surf., A 2013, 422, 136−142. Modified Stöber Method. J. Colloid Interface Sci. 2005, 283, 392−396.

8909 DOI: 10.1021/[Link].6b01839

Ind. Eng. Chem. Res. 2016, 55, 8891−8913
Industrial & Engineering Chemistry Research Review

(187) Khan, S. A.; Günther, A.; Schmidt, M. A.; Jensen, K. F. Diatom Silica Revealed by Atomic Force Microscopy. J. Microsc. 2009,
Microfluidic Synthesis of Colloidal Silica. Langmuir 2004, 20, 8604− 235, 172−187.
8611. (210) Hildebrand, M.; Kim, S.; Shi, D.; Scott, K.; Subramaniam, S.
(188) Simpson, T. L. The Cell Biology of Sponges.; Springer-Verlag: 3D Imaging of Diatoms with Ion-Abrasion Scanning Electron
New York, 1984. Microscopy. J. Struct. Biol. 2009, 166, 316−328.
(189) Morse, D. E. Silicon Biotechnology: Harnessing Biological (211) Kröger, N.; Poulsen, N. Diatoms − From Cell Wall Biogenesis
Silica Production to Construct New Materials. Trends Biotechnol. 1999, to Nanotechnology. Annu. Rev. Genet. 2008, 42, 83−107.
17, 230−232. (212) Sumper, M. A Phase Separation Model for the Nanopatterning
(190) Sumper, M.; Brunner, E. Learning from Diatoms: Nature’s of Diatom Biosilica. Science 2002, 295, 2430−2433.
Tools for the Production of Nanostructured Silica. Adv. Funct. Mater. (213) Knecht, M. R.; Sewell, S. L.; Wright, D. W. Size Control of
2006, 16, 17−26. Dendrimer-Templated Silica. Langmuir 2005, 21, 2058−2061.
(191) Wang, Q.; Yu, J.; Zheng, J.; Liu, D.; Jiang, F.; Zhang, X.; Li, W. (214) Lutz, K.; Gröger, C.; Sumper, M.; Brunner, E. Biomimetic
Morphology-Controlled Synthesis of Silica Materials Template by Self- Silica Formation: Analysis of the Phosphate-Induced Self-Assembly of
Assembled Short Amphiphilic Peptides. RSC Adv. 2013, 3, 15955− Polyamines. Phys. Chem. Chem. Phys. 2005, 7, 2812−2815.
15965. (215) Hedrich, R.; Machill, S.; Brunner, E. Biomineralization in
(192) Scheffel, A.; Poulsen, N.; Shian, S.; Kröger, N. Nanopatterned Diatoms − Phosphorylated Saccharides Are Part of Stephanopryxis
Protein Microrings from a Diatom that Direct Silica Morphogenesis. turris Biosilica. Carbohydr. Res. 2013, 365, 52−60.
Proc. Natl. Acad. Sci. U. S. A. 2011, 108, 3175−3180. (216) Belton, D. J.; Patwardhan, S. V.; Annenkov, V. V.;
(193) Richthammer, P.; Börmel, M.; Brunner, E.; van Pée, K.-H. Danilovtseva, E. N.; Perry, C. C. From Biosilication to Tailored
Biomineralization in Diatoms: The Role of Silacidins. ChemBioChem Materials: Optimizing Hydrophobic Domains and Resistance to
2011, 12, 1362−1366. Protonation of Polyamines. Proc. Natl. Acad. Sci. U. S. A. 2008, 105,
(194) Brunner, E.; Richthammer, P.; Ehrlich, H.; Paasch, S.; Simon, 5963−5968.
P.; Ueberlein, S.; van Pée, K. H. Chitin-Based Organic Networks: An (217) Bernecker, A.; Wieneke, R.; Riedel, R.; Seibt, M.; Geyer, A.;
Intergral Part of Cell Wall Biosilica in the Diatom Thalassiosira Steinem, C. Tailored Synthesis Polyamines for Controlled Biomimetic
pseudonana. Angew. Chem., Int. Ed. 2009, 48, 9724−9727. Silica Formation. J. Am. Chem. Soc. 2010, 132, 1023−1031.
(195) Durkin, C. A.; Mock, T.; Armbrust, E. V. Chitin in Diatom and (218) Sumper, M. Biomimetic Patterning of Silica by Long-Chain
Its Association with Cell Wall. Eukaryotic Cell 2009, 8, 1038−1050. Polyamines. Angew. Chem., Int. Ed. 2004, 43, 2251−2254.
(196) Wenzl, S.; Hett, R.; Richthammer, P.; Sumper, M. Silacidins: (219) Wang, S.; Cai, Q.; Du, M.; Xue, J.; Xu, H. Synthesis of 1D
Highly Acidic Phosphopeptides from Diatom Shells Assist in Silica Silica Nanostructurues with Controllable Sizes Based on Short Anionic
Precipitation In Vitro. Angew. Chem., Int. Ed. 2008, 47, 1729−1732. Peptide Self-Assembly. J. Phys. Chem. B 2015, 119, 12059−12065.
(197) Kröger, N. Prescribing Diatom Morphology: Toward Genetic (220) Wallace, A. F.; DeYoreo, J. J.; Dove, P. M. Kinetics of Silica
Engineering of Biological Nanomaterials. Curr. Opin. Chem. Biol. 2007, Nucleation on Carboxyl- and Amine-Terminated Surfaces: Insights for
11, 662−669. Biomineralisation. J. Am. Chem. Soc. 2009, 131, 5244−5250.
(198) Perry, C. C.; Belton, D.; Shafran, K. Studies of Biosilicas; (221) Pamirsky, I. E.; Golokhvast, K. S. Silaffin of Diatoms: From
Structural Aspects, Chemical Principles, Model Studies and the Future.
Applied Biotechnology to Biomedicine. Mar. Drugs 2013, 11, 3155−
Prog. Mol. Subcell. Biol. 2003, 33, 269−299.
3167.
(199) Poulsen, N.; Sumper, M.; Kröger, N. Biosilica Formation in
(222) Sumper, M.; Kröger, N. Silica Formation in Diatoms: The
Diatoms: Characterization of Native Siliaffin-2 and Its Role in Silica
Function of Long-Chain Polyamines and Silaffins. J. Mater. Chem.
Morphologenesis. Proc. Natl. Acad. Sci. U. S. A. 2003, 100, 12075−
2004, 14, 2059−2065.
12080.
(223) Lechner, C. C.; Becker, C. F. W. Exploring the Effect of Native
(200) Poulsen, N.; Kröger, N. Silica Morphogenesis by Alternative
and Artificial Peptide Modifications on Silaffin Induced Silica
Processing of Silaffins in the Diatom Thalassiosira Pseudonana. J. Biol.
Chem. 2004, 279, 42993−42999. Precipitation. Chem. Sci. 2012, 3, 3500−3504.
(201) Sumper, M.; Lorenz, S.; Brunner, E. Biomimetic Control of (224) Spinde, K.; Kammer, M.; Freyer, K.; Ehrlich, H.; Vournakis, J.
Size in the Polyamine-Directed Formation of Silica Nanosphere. N.; Brunner, E. Biomimetic Silication of Fibrous Chitin from Diatoms.
Angew. Chem., Int. Ed. 2003, 42, 5192−5195. Chem. Mater. 2011, 23, 2973−2978.
(202) Kröger, N.; Lorenz, S.; Brunner, E.; Sumper, M. Self-Assembly (225) Shimizu, K.; Cha, J.; Stucky, G. D.; Morse, D. E. Silicatein α:
of Highly Phosphorylated Silaffins and Their Function in Biosilica Cathepsin L-like Protein in Sponge Biosilica. Proc. Natl. Acad. Sci. U. S.
Morphogenesis. Science 2002, 298, 584−586. A. 1998, 95, 6234−6238.
(203) Kröger, N.; Deutzmann, R.; Sumper, M. Silica-Precipitating (226) Werner, P.; Blumtritt, H.; Zlotnikov, I.; Graff, A.; Dauphin, Y.;
Peptides from Diatoms: The Chemical Structure of Silaffin-1A from Fratzl, P. Electron Microscopy Analyses of the Bio-Silica Basal Spicule
Cylindrotheca Fusiformis. J. Biol. Chem. 2001, 276, 26066−26070. from the Monorhaphis chuni Sponge. J. Struct. Biol. 2015, 191, 165−
(204) Kröger, N.; Deutzmann, R.; Bergsdorf, C.; Sumper, M. Species- 174.
Specific Polyamines from Diatoms Control Silica Morphology. Proc. (227) Wang, X.; Schröder, H. C.; Brandt, D.; Wiens, M.; Lieberwirth,
Natl. Acad. Sci. U. S. A. 2000, 97, 14133−14138. I.; Glasser, G.; Schloβmacher, U.; Wang, S.; Müller, W. E. G. Sponge
(205) Kröger, N.; Deutzmann, R.; Sumper, M. Polycationic Peptides Biosilica Formation Involves Syneresis Following Polycondensation In
from Diatom Biosilica that Direct Silica Nanosphere Formation. Vivo. ChemBioChem 2011, 12, 2316−2324.
Science 1999, 286 (5442), 1129−1132. (228) Matsunaga, S.; Sakai, R.; Jimbo, M.; Kamiya, H. Long-Chain
(206) Wang, X.; Schröder, H. C.; Wang, K.; Kaandorp, J. A.; Müller, Polyamines (LCPAs) form Marine Sponge: Possible Implication in
W. E. G. Genetic, Biological and Structural Hierarchies During Sponge Spicule Formation. ChemBioChem 2007, 8, 1729−1735.
Spicule Formation: From Soft Sol-Gels to Solid 3D Silica Composite (229) Müller, W. E. G.; Wang, X.; Kropf, K.; Boreiko, A.;
Structures. Soft Matter 2012, 8, 9501−9518. Schloβmacher, U.; Brandt, D.; Schröder, H. C.; Wiens, M. Silicatein
(207) Lopez, P. J.; Desclés, J.; Allen, A. E.; Bowler, C. Prospects in Expression in the hexactinellid Crateromorpha meyeri: The Lead Marker
Diatom Research. Curr. Opin. Biotechnol. 2005, 16, 180−186. Gene Restricted to Siliceous Sponges. Cell Tissue Res. 2008, 333, 339−
(208) Poulsen, N.; Scheffel, A.; Sheppard, V. C.; Chesley, P. M.; 351.
Kröger, N. Pentalysine Clusters Mediate Silica Targeting of Silaffins in (230) Belikov, S. I.; Kaluzhnaya, O. V.; Schöder, H. C.; Krasko, A.;
Thalassiosira pseudonana. J. Biol. Chem. 2013, 288, 20100−20109. Müller, I. M.; Müller, W. E. G. Expression of Silicatein in Spicules from
(209) Hildebrand, M.; Holton, G.; Joy, D. C.; Doktycz, M. J.; Allison, the Baikalian Sponge Lubomiroskia baicalensis. Cell Biol. Int. 2005, 29,
D. P. Diverse and Conserved Nano- and Mesoscale Structures of 943−951.

8910 DOI: 10.1021/[Link].6b01839

Ind. Eng. Chem. Res. 2016, 55, 8891−8913
Industrial & Engineering Chemistry Research Review

(231) Funayama, N.; Nakatsukasa, M.; Kuraku, S.; Takechi, K.; Dohi, (248) Wieneke, R.; Bernecker, A.; Riedel, R.; Sumper, M.; Steinem,
M.; Iwabe, N.; Miyata, T.; Agata, K. Isolation of Ef silicatein and Ef C.; Geyer, A. Silica Precipitation with Synthetic Silaffin Peptides. Org.
lectin as Molecular Markers Sclerocytes and Cells Involved in Innate Biomol. Chem. 2011, 9, 5482−5486.
Immunity in the Freshwater Sponge Ephydatia f luviatilis. Zool. Sci. (249) Tomczak, M. M.; Glawe, D. D.; Drummy, L. F.; Lawrence, C.
2005, 22, 1113−1122. G.; Stone, M. O.; Perry, C. C.; Pochan, D. J.; Deming, T. J.; Naik, R. R.
(232) Pozzolini, M.; Sturla, L.; Cerrano, C.; Bavestrello, G.; Polypeptide-Templated Synthesis of Hexagonal Silica Platelets. J. Am.
Camardella, L.; Parodi, A. M.; Raheli, F.; Benatti, U.; Müller, W. E. Chem. Soc. 2005, 127, 12577−12582.
G.; Giovine, M. Molecular Cloning of Silicatein Gene from Marine (250) McKenna, B. J.; Birkedal, H.; Bartl, M. H.; Deming, T. J.;
Sponge Petrosia f iciformis (Porifera, Demospongiae) and Development Stucky, G. D. Micrometer-Sized Spherical Assemblies of Polypeptides
of Primmorphs as a Model for Biosilication Studies. Mar. Biotechnol. and Small Molecules by Acid-Base Chemistry. Angew. Chem. 2004,
2004, 6, 594−603. 116, 5770−5773.
(233) Krasko, A.; Lorenz, B.; Batel, R.; Schröder, H. C.; Müller, I. M.; (251) Patwardhan, S. V.; Maheshwari, R.; Mukherjee, N.; Kiick, K. L.;
Müller, W. E. G. Expression of Silicatein and Collagen Genes in the Clarson, S. J. Conformation and Assembly of Polypeptide Scaffolds in
Marine Sponge Suberites domuncula is Controlled by Silicate and Templating the Synthesis of Silica: An Example of a Polylysine
Myotrophin. Eur. J. Biochem. 2000, 267, 4878−4887. Macromolecular “Switch. Biomacromolecules 2006, 7, 491−497.
(234) Cha, J. N.; Shimizu, K.; Zhou, Y.; Christiansen, S. C.; Chmelka, (252) Patwardhan, S. V.; Mukherjee, N.; Steinitz-Kannan, M.;
B. F.; Stucky, G. D.; Morse, D. E. Silicatein Filaments and Subunits Clarson, S. J. Bioinspired Synthesis of New Silica Structures. Chem.
from a Marine Sponge Direct the Polymerization of Silica and Commun. 2003, 10, 1122−1123.
Silicones. Proc. Natl. Acad. Sci. U. S. A. 1999, 96, 361−365. (253) Patwardhan, S. V.; Mukherjee, N.; Clarson, S. J. The Use of
(235) Schröder, H. C.; Wiens, M.; Schloβmacher, U.; Brandt, D.; Poly-L-Lysine to Form Novel Silica Morphologies and the Role of
Müller, W. E. G. Silicatein-Mediated Polycondensation of Orthosilicic Polypeptides in Biosilication. J. Inorg. Organomet. Polym. 2002, 11,
Acid: Modelling of a Catalytic Mechanism Involving Ring Formation. 195−198.
Silicon 2012, 4, 33−38. (254) Coradin, T.; Durupthy, O.; Livage, J. Interactions of Amino-
(236) Müller, W. E. G.; Boreiko, A.; Schloβmacher, U.; Wang, X.; Containing Peptides with Sodium Silicate and Colloidal Silica: A
Tahir, M. N.; Tremel, W.; Brandt, D.; Kaandorp, J. A.; Schröder, H. C. Biomimetic Approach of Silicification. Langmuir 2002, 18, 2331−2336.
Fractal-Related Assembly of the Axial Filament in the Demosponge (255) Coradin, T.; Roux, C.; Livage, J. Biomimetic Self-Activated
Suberites domuncula: Relevance to Biomineralization and the Formation of Multiscale Porous Silica in the Presence of Arginine-
Formation of Biogenic Silica. Biomaterials 2007, 28, 4501−4511. Based Surfactants. J. Mater. Chem. 2002, 12, 1242−1244.
(237) Schloβmacher, U.; Wiens, M.; Schröder, H. C.; Wang, X.; (256) Han, W.; MacEwan, S. R.; Chilkoti, A.; Lopez, G. P. Bio-
Jochum, K. P.; Müller, W. E. G. Silintaphin-1 − Interaction with inspired Synthesis of Hybrid Silica Nanoparticles Templated from
Silicatein During Structure-Guiding Bio-Silica Formation. FEBS J. Elastin-like Polypeptide Micelles. Nanoscale 2015, 7, 12038−12044.
2011, 278, 1145−1155. (257) Jan, J.-S.; Lee, S.; Carr, C. S.; Shantz, D. F. Biomimetic
(238) Müller, W. E. G.; Link, T.; Schröder, H. C.; Korzhev, M.; Synthesis of Inorganic Nanospheres. Chem. Mater. 2005, 17, 4310−
Neufurth, M.; Brandt, D.; Wang, X. Dissection of the Structure- 4317.
Forming Activity from the Structure-Guiding Activity of Silicatein: A (258) Li, X.; Yang, T.; Gao, Q.; Yuan, J.; Cheng, S. Biomimetic
Biomimetic Molecular Approach to Print Optical Fibers. J. Mater. Synthesis of Copolymer-Silica Nanoparticles with Tunable Composi-
Chem. B 2014, 2, 5368−5377. tions and Surface Properties. J. Colloid Interface Sci. 2009, 338, 99−
(239) Zhou, Y.; Shimizu, K.; Cha, J. N.; Stucky, G. D.; Morse, D. E. 104.
Efficient Catalysis of Polysiloxane Synthesis by Silicatein α Requires (259) Yuan, J. J.; Zhu, P. X.; Fukazawa, N.; Jin, R. H. Synthesis of
Specific Hydroxyl and Imidazole Functionalities. Angew. Chem., Int. Ed. Nanofiber-Based Silica Networks Mediated by Organized Poly-
1999, 38, 779−782. (ethyleneimine): Structure, Properties, and Mechanism. Adv. Funct.
(240) Neville, F.; Broderick, M. J. F.; Gibson, T.; Millner, P. A. Mater. 2006, 16, 2205−2212.
Fabrication and Activity of Silicate Nanoparticles and Nanosilicate- (260) Jin, R. H.; Yuan, J. J. Poly(ethyleneimine) Aggregates Pre-
Entrapped Enzymes Using Polyethyleneimine as a Biomimetic Organized by Media Modulation. Macromol. Chem. Phys. 2005, 206,
Polymer. Langmuir 2011, 27, 279−285. 2160−2170.
(241) Rodriguez, F.; Glawe, D. D.; Naik, R. R.; Hallinan, K. P.; Stone, (261) Yuan, J. J.; Jin, R. H. Multiply Shaped Silica Mediated by
M. O. Study of the Chemical and Physical Influences Upon In Vitro Aggregates of Linear Poly(ethyleneimine). Adv. Mater. 2005, 17, 885−
Peptide-Mediated Silica Formation. Biomacromolecules 2004, 5, 261− 888.
265. (262) Brunner, E.; Lutz, K.; Sumper, M. Biomimetic Synthesis of
(242) Knecht, M. R.; Wright, D. W. Functional Analysis of the Silica Nanospheres Depends on the Aggregation and Phase Separation
Biomimetic Silica Precipitating Activity of the R5 Peptide from of Polyamines in Aqueous Solution. Phys. Chem. Chem. Phys. 2004, 6,
Cylindrotheca f usiformis. Chem. Commun. 2003, 2003, 3038−3039. 854−857.
(243) Naik, R. R.; Whitlock, P. W.; Rodriguez, F.; Brott, L. L.; Glawe, (263) Patwardhan, S. V.; Mukherjee, N.; Clarson, S. J. The Use of
D. D.; Clarson, S. J.; Stone, M. O. Controlled Formation of Biosilica Poly-L-Lysine to Form Novel Silica Morphologies and the Role of
Structures In Vitro. Chem. Commun. 2003, 9, 238−239. Polypeptides in Biosilication. J. Inorg. Organomet. Polym. 2001, 11,
(244) Patwardhan, S. V.; Mukherjee, N.; Clarson, S. J. Silication and 193−198.
Biosilication. Silicon Chem. 2002, 1, 207−214. (264) Patwardhan, S. V.; Mukherjee, N.; Clarson, S. J. Effect of
(245) Brott, L. L.; Naik, R. R.; Pikas, D. J.; Kirkpatrick, S. M.; Process Parameters on the Polymer Mediated Synthesis of Silica at
Tomlin, D. W.; Whitlock, P. W.; Clarson, S. J.; Stone, M. O. Ultrafast Neutral pH. Silicon Chem. 2002, 1, 47−55.
Holographic Nanopatterning of Biocatalytically Formed Silica. Nature (265) Patwardhan, S. V.; Mukherjee, N.; Clarson, S. J. Formation of
2001, 413, 291−293. Fiber-like Amorphous Silica Structures by Externally Applied Shear. J.
(246) Hu, J.-J.; Hsieh, Y.-H.; Jan, J.-S. Polyelectrolyte Complex-Silica Inorg. Organomet. Polym. 2001, 11, 117−121.
Hybrid Colloidal Particles Decorated with Different Polyelectrolytes. J. (266) Noll, F.; Sumper, M.; Hampp, N. Nanostructure of Diatom
Colloid Interface Sci. 2015, 438, 94−101. Silica Surfaces and of Biomimetic Analogues. Nano Lett. 2002, 2, 91−
(247) Wang, S.; Xue, J.; Zhao, Y.; Du, M.; Deng, L.; Xu, H.; Lu, J. R. 95.
Controlled Silica Deposition on Self-Assembled Peptide Nanostruc- (267) Knecht, M. R.; Wright, D. W. Amine-Terminated Dendrimers
tures via Varying Molecular Structures of Short Amphiphilic Peptides. as Biomimetic Templates for Silica Nanosphere Formation. Langmuir
Soft Matter 2014, 10, 7623−7629. 2004, 20, 4728−2732.

8911 DOI: 10.1021/[Link].6b01839

Ind. Eng. Chem. Res. 2016, 55, 8891−8913
Industrial & Engineering Chemistry Research Review

(268) Neville, F.; Murphy, T.; Wanless, E. J. The Formation of (289) Chen, G.; Shan, R.; Li, S.; Shi, J. A Biomimetic Silicification
Polyethyleneimine-Trimethoxymethylsilane Organic-Inorganic Hybrid Approach to Synthesize CaO-SiO2 Catalyst for the Transesterification
Particles. Colloids Surf., A 2013, 431, 42−50. of Palm Oil into Biodiesel. Fuel 2015, 153, 48−55.
(269) Cha, J. N.; Stucky, G. D.; Morse, D. E.; Deming, T. J. (290) Li, J.; Xu, L.; Yang, B.; Bao, Z.; Pan, W.; Li, S. Biomimetic
Biomimetic Synthesis of Order Silica Structures Mediated by Block Synthesized Chiral Mesoporous Silica: Structures and Controlled
Copolypeptides. Nature 2000, 403, 289−292. Release Functions as Drug Carriers. Mater. Sci. Eng., C 2015, 55, 367−
(270) Ki, M. R.; Jang, E. K.; Pack, S. P. Hypothetical Cathepsin-like 372.
Protein from Nematostella vectensis and Its Silicatein-like Cathepsin (291) Cui, J.; Feng, Y.; Yue, S.; Zhao, Y.; Li, L.; Liu, R.; Lin, T.
Mutant for Biosilica Production. Process Biochem. 2014, 49, 95−101. Magnetic Mesoporous Enzyme-Silica Composites with High Activity
(271) Song, X.; Jiang, Z.; Li, L.; Wu, H. Immobilization of β- and Enhanced Stability. J. Chem. Technol. Biotechnol. 2016, 91, 1905−
Glucuronidase in Lysozyme-Induced Biosilica Particles to Improve Its 1913.
Stability. Front. Chem. Sci. Eng. 2014, 8, 353−361. (292) Kawachi, Y.; Kugimiya, S.; Nakamura, H.; Kato, K. Enzyme
(272) Neville, F.; Seyfaee, A. Real-Time Monitoring of in Situ Encapsulation in Silica Gel Prepared by Polylysine and Its Catalytic
Polyethyleneimine-Silica Particle Formation. Langmuir 2013, 29, Activity. Appl. Surf. Sci. 2014, 314, 64−70.
14681−14690. (293) Zhu, Y.; Jiang, Y.; Gao, J.; Zhou, L.; He, Y.; Jia, F.
(273) Yang, S. H. Biomimetic Silica Nanostructures on the Surface, Immobilization of Glucose Oxidase in Liposome-Templated Biomi-
Controlled by Polyvalent Counteranions. Solid State Sci. 2013, 23, 1− metic Silica Particles. Chin. J. Catal. 2013, 34, 741−750.
7. (294) Kuan, I.-C.; Lee, C.-C.; Tsai, B.-H.; Lee, S.-L.; Lee, W.-T.; Yu,
(274) Yi, J.; Jang, H. S.; Lee, J. S.; Park, W. I. Bioinspired C.-Y. Optimizing the Production of Biodiesel Using Lipase Entrapped
Morphologenesis of Highly Intricate and Symmetric Silica Nanostruc- in Biomimetic Silica. Energies 2013, 6, 2052−2064.
tures. Nano Lett. 2012, 12, 3743−3748. (295) Sheppard, V. C.; Scheffel, A.; Poulsen, N.; Kröger, N. Live
(275) Pires, J.; Fernandes, A. C.; Avo, R. Bio-Inspired Synthesis of Diatom Silica Immobilization of Multimeric and Redox-Active
Mesoporous Silicas Using Large Molecular Weight Poly-L-Lysine at Enzymes. Appl. Environ. Microbiol. 2012, 78, 211−218.
Neutral pH. J. Mater. Sci. 2014, 49, 6087−6092. (296) Lai, J.-K.; Chuang, T.–H.; Jan, J.-S.; Wang, S. S.-S. Efficient and
(276) Yu, J.; Wang, Q.; Zhang, X. Effects of External Force Fields on Stable Enzyme Immobilization in a Block Copolypeptide Vesicle-
Peptide Self-Assembly and Biomimetic Silica Synthesis. Appl. Surf. Sci. Templated Biomimetic Silica Support. Colloids Surf., B 2010, 80, 51−
2014, 311, 799−807. 58.
(277) Huang, Z.; Yao, Y.; Che, S. Design of Amphiphilic Peptide (297) Kuan, I.-C.; Wu, J.-C.; Lee, S.-L.; Tsai, C.-W.; Chuang, C.-A.;
Geometry towards Biomimetic Self-Assembly of Chiral Mesoporous Yu, C.-Y. Stabilization of D-Amino Acid Oxidase from Rhodosporidium
Silica. Chem. - Eur. J. 2014, 20, 3273−3276. toruloides by Encapsulation in Polyallylamine-Mediated Biomimetic
(278) Shi, J.-Y.; Yao, G.-T.; Fu, S.-Q. Two-Dimensional Silica Sieve Silica. Biochem. Eng. J. 2010, 49, 408−413.
(298) Marner, W. D.; Shaikh, A. S.; Muller, S. J. Enzyme
Plates Mimicking the Diatom Valve. Chem. - Eur. J. 2013, 19, 8073−
Immobilization via Silaffin-Mediated Autoencapsulation in a Biosilica
8077.
Support. Biotechnol. Prog. 2009, 25, 417−423.
(279) Yuan, J.-J.; Jin, R.-H. Temporally and Spatially Controlled
(299) Poulsen, N.; Berne, C.; Spain, J.; Krö ger, N. Silica
Silicification for Self-Generating Polymer@Silica Hybrid Nanotube on
Immobilization of an Enzyme Through Genetic Engineering of the
Substrates with Tunable Film Nanostructure. J. Mater. Chem. 2012, 22,
Diatom Thalassiosira pseudonana. Angew. Chem., Int. Ed. 2007, 46,
5080−5088.
1843−1846.
(280) Pouget, E.; Dujardin, E.; Cavalier, A.; Moreac, A.; Valéry, C.;
(300) Jin, R. H.; Yuan, J. J. One-Pot and Rapid Synthesis of
Marchi-Artzner, V.; Weiss, T.; Renault, A.; Paternostre, M.; Artzner, F. Uniformed Silica Spheres via Mediation of Linear Poly-
Hierarchical Architectures by Synergy Between Dynamic Template (ethyleneimine)s and Dyes. Polym. J. 2007, 39, 822−827.
Self-Assembly and Biomineralization. Nat. Mater. 2007, 6, 434−439. (301) Müller, C.; Kraushaar, K.; Doebbe, A.; Mussgnug, J. H.; Kruse,
(281) Zhu, Y.; Fang, Y.; Borchardt, L.; Kaskel, S. PEGylated Hollow O.; Kroke, E.; Patel, A. V. Synthesis of Transparent Aminosilane-
Mesoporous Silica Nanoparticles as Potential Drug Delivery Vehicles. Derived Silica Based Networks for Entrapment of Sensitive Materials.
Microporous Mesoporous Mater. 2011, 141, 199−206. Chem. Commun. 2013, 49, 10163−10165.
(282) Tan, S. Y.; Ang, C. Y.; Li, P.; Yap, Q. M.; Zhao, Y. Drug (302) Forsyth, C.; Yip, T. W. S.; Patwardhan, S. V. CO 2
Encapsulation and Release by Mesoporous Silica Nanoparticles: The Sequestration by Enzyme Immobilized onto Bioinspired Silica.
Effect of Surface Functional Groups. Chem. - Eur. J. 2014, 20, 11276− Chem. Commun. 2013, 49, 3191−3193.
11282. (303) Luckarift, H. R.; Dickerson, M. B.; Sandhage, K. H.; Spain, J. C.
(283) Shiomi, T.; Tsunoda, T.; Kawai, A.; Mizukami, F.; Sakaguchi, Rapid, Room-Temperature Synthesis of Antibacterial Bionanocompo-
K. Biomimetic Synthesis of Lysozyme − Silica Hybrid Hollow Particles sites of Lysozyme with Amorphous Silica or Titania. Small 2006, 2,
Using Sonochemical Treatment: Influence of pH and Lysozyme 640−643.
Concentration on Morphology. Chem. Mater. 2007, 19, 4486−4493. (304) Hamade, R.; Okahata, Y.; Yamamori, N. Glucoxide Derivatives
(284) Shiomi, T.; Tsunoda, T.; Kawai, A.; Chiku, H.; Mizukami, F.; for Enzyme Modification, Lipid-Coated Enzymes, Method of
Sakaguchi, K. Chem. Commun. 2005, 2005 (42), 5325−5327. Producing such Enzymes and Antifouling Paint Composition. U.S.
(285) Luckarift, H.; Spain, J. C.; Naik, R. R.; Stone, M. O. Enzyme Patent 5,770,188 A, June 23, 1998.
Immobilization in a Biomimetic Silica Support. Nat. Biotechnol. 2004, (305) Kolesar, G. B.; Siddiqui, W. H.; Geil, R. G.; Malczewski, R. M.;
22, 211−213. Hobbs, E. J. Subchronic Inhalation Toxicity of Tetramethoxysilane in
(286) Gill, I.; Ballesteros, A. Bioencapsulation within Synthetic Rats. Toxicol. Sci. 1989, 13, 285−295.
Polymers (Part 1): Sol-Gel Encapsulated Biologicals. Trends Biotechnol. (306) Seyfaee, A.; Hyde, E. D. E. R.; Aubin, J.; Moreno-Atanasio, R.;
2000, 18, 282−296. Neville, F. Investigation of Polymeric Nuclei and Their Role in
(287) Gill, I.; Ballesteros, A. Encapsulation of Biologicals within Biomimetic Silication: Effect of Physical Conditions [Online]. In
Silicate, Siloxane and Hybrid Sol-Gel Polymers: An Efficient and Proceedings of Asia Pacific Conference of Chemical Engineering
Generic Approach. J. Am. Chem. Soc. 1998, 120, 8587−8598. Congress 2015: APCChE 2015, incorporating CHEMECA 2015,
(288) Jo, B. H.; Seo, J. H.; Yang, Y. J.; Baek, K.; Choi, Y. S.; Pack, S. Melbourne, Australia, September 27−October 1, 2015; Engineers
P.; Oh, S. H.; Cha, H. J. Bioinspired Silica Nanocomposite with Australia: Melbourne, 2015; pp 2081−2092.
Autoencapsulated Carbonic Anhydrase as a Robust Biocatalyst for (307) Seyfaee, A.; Neville, F.; Moreno-Atanasio, R. Experimental
CO2 Sequestration. ACS Catal. 2014, 4, 4332−4340. Results and Theoretical Modeling of the Growth Kinetics of

8912 DOI: 10.1021/[Link].6b01839

Ind. Eng. Chem. Res. 2016, 55, 8891−8913
Industrial & Engineering Chemistry Research Review

Polyamine-Derived Silica Particles. Ind. Eng. Chem. Res. 2015, 54, (329) Randolph, A. D.; Larson, M. A. Theory of Particulate Processes;
2466−2475. Academic Press: New York, 1971.
(308) Seyfaee, A.; Moreno-Atanasio, R.; Neville, F. High-Resolution (330) Smoluchowski, M. Drei Vorträge über Diffusion, Brownsche
Analysis of the Influence of Reactant Concentration on Nucleation Molekularbewegung und Koagulation von Kolloidteilchen. Phys. Zeit.
Time and Growth of Polyethyleneimine-Trimethoxymethylsilane 1916, 2, 530−594.
Particles. Colloid Polym. Sci. 2014, 292, 2673−2685.
(309) He, P.; Greenway, G.; Haswell, S. J. Microfluidic Synthesis of
Silica Nanoparticles Using Polyethylenimine Polymers. Chem. Eng. J.
2011, 167, 694−699.
(310) Coradin, T.; Coupé, A.; Livage, J. Interactions of Bovine Serum
Albumin and Lysozyme with Sodium Silicate Solutions. Colloids Surf.,
B 2003, 29, 189−196.
(311) Annenkov, V. V.; Pal’shin, V. A.; Verkhozina, O. N.; Larina, L.
I.; Danilovtseva, E. N. Composite Nanoparticles: A New Way to
Siliceous Materials and a Model of Biosilica Synthesis. Mater. Chem.
Phys. 2015, 165, 227−234.
(312) Zhao, S.; Xu, D.; Ma, H.; Sun, Z.; Guan, J. Controllable
Preparation and Formation Mechanism of Monodispersed Silica
Particles with Binary Sizes. J. Colloid Interface Sci. 2012, 388, 40−46.
(313) Nozawa, K.; Gailhanou, H.; Raison, L.; Panizza, P.; Ushiki, H.;
Sellier, E.; Delville, J. P.; Delville, M. H. Smart Control of
Monodisperse Stöber Silica Particles: Effect of Reactant Addition
Rate on Growth Process. Langmuir 2005, 21, 1516−1523.
(314) Nagao, D.; Satoh, T.; Konno, M. A. Generalized Model for
Describing Particle Formation in the Synthesis of Monodisperse Oxide
Particles Based on the Hydrolysis and Condensation of Tetraethyl
Orthosilicate. J. Colloid Interface Sci. 2000, 232, 102−110.
(315) Giesche, H. Synthesis of Monodispersed Silica Powders I.
Particle Properties and Reaction Kinetics. J. Eur. Ceram. Soc. 1994, 14,
189−204.
(316) van Blaaderen, A.; van Geest, J.; Vrij, A. Monodisperse
Colloidal Silica Spheres from Tetraalkoxysilanes: Particle Formation
and Growth Mechanism. J. Colloid Interface Sci. 1992, 154, 481−501.
(317) Bailey, J. K.; Mecartney, M. L. Formation of Colloidal Silica
Particles from Alkoxides. Colloids Surf. 1992, 63, 151−161.
(318) Bogush, G. H.; Zukoski, C. F. Studies of the Kinetics of the
Precipitation of Uniform Silica Particles through the Hydrolysis and
Condensation of Silicon Alkoxides. J. Colloid Interface Sci. 1991, 142,
1−18.
(319) Bogush, G. H.; Zukoski, C. F. Uniform Silica Particle
Precipitation: An Aggregative Growth Model. J. Colloid Interface Sci.
1991, 142, 19−34.
(320) Harris, M. T.; Brunson, R. R.; Byers, H. The Base-Catalyzed
Hydrolysis and Condensation Reactions of Dilute and Concentrated
TEOS Solutions. J. Non-Cryst. Solids 1990, 121, 397−403.
(321) Matsoukas, T.; Gulari, E. Monomer-Addition Growth with a
Slow Initiation Step: A Growth Model for Silica Particles from
Alkoxides. J. Colloid Interface Sci. 1989, 132, 13−21.
(322) LaMer, V. K.; Dinegar, R. H. Theory, Production and
Mechanism of Formation of Monodispersed Hydrosols. J. Am. Chem.
Soc. 1950, 72, 4847−4854.
(323) Stockmayer, J. Theory of Molecular Size Distribution and Gel
Formation in Branched-Chain Polymers. J. Chem. Phys. 1943, 11, 45−
55.
(324) Flory, P. J. Principals of Polymer Chemistry; Cornell Univ. Press:
Ithaca, NY, 1953.
(325) Flory, P. J. Molecular Size Distribution in Linear Condensation
Polymers. Molecular Size Distribution in Linear Condensation
Polymers. J. Am. Chem. Soc. 1936, 58, 1877−1885.
(326) Klemperer, W. K.; Ramamurthi, S. D. Molecular Growth
Pathways in Silica Sol-Gel Polymerization. MRS Online Proc. Libr.
1988, 121, 1−13.
(327) Zhao, S.; Xu, D.; Ma, H.; Sun, Z.; Guan, J. Controllable
Preparation and Formation Mechanism of Monodispersed Silica
Particles with Binary Sizes. J. Colloid Interface Sci. 2012, 388, 40−46.
(328) Fleming, B. A. Kinetics of Reaction between Silicic Acid and
Amorphous Silica Surfaces in NaCl Solutions. J. Colloid Interface Sci.
1986, 110, 40−64.

8913 DOI: 10.1021/[Link].6b01839

Ind. Eng. Chem. Res. 2016, 55, 8891−8913