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Journal of the Taiwan Institute of Chemical Engineers

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Recent progress in the synthesis of inorganic particulate materials

using microfluidics
Kyoung-Ku Kang, Byungjin Lee, Chang-Soo Lee∗
Department of Chemical Engineering and Applied Chemistry, Chungnam National University, 99 Daehak-ro, Yuseong-gu, Daejeon 34134, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Microfluidic systems have unique advantages originating from the miniaturization of real chemical pro-
Received 1 February 2018 cesses. On this basis, the synthesis of inorganic materials, including micro- and nanomaterials, can be
Revised 28 July 2018
used to develop useful features, such as a uniform particle size distribution, morphology control, online
Accepted 13 August 2018
monitoring, etc. In this review, we introduce and discuss the recent progress in the preparation of in-
Available online xxx
organic materials, mainly microfluidics systems. Furthermore, utilizing microfluidic devices, we present
Keywords: the basic principles and representative shape of microfluidic systems. In addition, the synthesis of var-
Microreaction technology ious inorganic material particles using microfluidic systems, such as metal nanoparticles, metal oxide
Microfluidics nanoparticles, semiconductor nanoparticles, organic-inorganic hybrid particles, surface functionalized par-
Microreactor ticles, core-shell particles, and traditional porous materials, is introduced. Finally, we propose the future
Inorganic particulate materials prospects of microfluidics in the synthesis of noble inorganic materials.
Nanoparticle
© 2018 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Inorganic functionalized nanoparticles

1. Introduction physicochemical properties, such as composition, surface nature,

Over the last decade, the area of particulate material synthe-
sis has evolved rapidly due to the development of analysis and
synthesis technologies. The development of synthesis methods
and processes has also contributed greatly to the development of
materials research. Among these, microfluidics, including microre-
actors, has become one of the most widely used tools in material
synthesis because of its advantages, such as producing monodis-
perse droplets, consuming small amounts of reagents, facilitating
rapid reactions due to the high surface area-to-volume ratio, and
the independent control characteristics. The polymeric and inor-
ganic materials prepared by microfluidics have also been used as
functional materials in various fields. Furthermore, these polymeric
and inorganic materials as functional materials have also been
widely applied to the fields of medicine [1], biology [2], chemistry
[3,4], physics [5,6], electricity [7,8], electronics, nanotechnology
[1,3,7,9,10], biotechnology [2,11], clean and reusable energy [9],
photonic materials [12], micro-objects [13–16], consumer and
personal care products [3], particle-based display technologies
[8,17], field-responsive rheological fluids [10,18], therapeutics [1],
tissue engineering scaffolds [2,11], high-performance composite
filler materials [10,13], and food additives [15,19].
In general, the functions of particulate materials, includ-
ing polymers and inorganics, are strongly affected by their
∗
Corresponding author. .
E-mail address: rhadum@cnu.ac.kr (C.-S. Lee).
morphology, particle size, and uniformity. These are also important
determinants of application possibilities and achievements [16].
Therefore, it is desirable to use a well-defined synthesis system,
which is precisely controlled, to ensure stable, controlled and
predictable results in application fields. For these reasons, a deep
understanding of the entire synthesis system is necessary. In par-
ticular, it will be necessary to develop new functional materials.
However, it is difficult to control the synthesis conditions, such
as uniformity of mixing and the reaction temperature, when the
particulate materials are synthesized using conventional chemical
reactors [20–27]. The reaction condition tolerances can influence
the physicochemical properties of prepared materials, such as
the molecular weight, morphology, size and crystallinity of the
synthesized materials. Therefore, various synthesis systems have
been studied to improve the difficulties of these conventional
synthesis systems [28,29]. Microfluidics, in comparison with con-
ventional chemical reactors, offers precise control of the overall
reaction conditions, and these unique advantages originate from
the miniaturization of chemical synthesis systems [30,31].
Furthermore, microfluidics can be combined with real-time
analysis and feedback control to instantly adjust the synthesis
conditions. In particular, in the case of droplets, it can be directly
used as a microreactor for chemical and biochemical reactions.
This can provide the greatest advantages in designing and syn-
thesizing functional particles, especially inorganic particles, using
microfluidic devices, and these advantages can present a new
paradigm in material synthesis. The purpose of this article is

https://doi.org/10.1016/j.jtice.2018.08.027
1876-1070/© 2018 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article as: K.-K. Kang et al., Recent progress in the synthesis of inorganic particulate materials using microfluidics, Journal
of the Taiwan Institute of Chemical Engineers (2018), https://doi.org/10.1016/j.jtice.2018.08.027
JID: JTICE
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2 K.-K. Kang et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2018) 1–18
Fig. 1. Representative formation mechanisms of inorganic particles. (C) is reprinted with permission from ref [32]. Copyright 2015. The Royal Society of Chemistry.
to review the recent advances in inorganic particulate materials
that take advantage of and profit from microfluidics. First, the
principle of the formation phenomena of inorganic particles and
the microfluidic reactor will be briefly introduced. Next, the rep-
resentative inorganic materials synthesized by using microfluidic
systems and the unique features of synthesized inorganic materi-
als will be explained. Finally, a perspective on future microfluidic
device developments will be provided.
2. Design factors for the synthesis of inorganic materials using
microfluidics
2.1. Basic mechanism for the formation of inorganic particles
The synthesis of inorganic particles can be performed through
a number of physicochemical processes. In general, commercial
inorganic particulate materials have been synthesized by a ’top-
down’ method, which breaks down bulk materials into smaller
units, or the gas phase synthesis method. In contrast, the syn-
thesis of inorganic particles through chemical synthesis pathways
is referred to as the ’bottom-up’ method. Chemical synthesis
methods, such as the sol-gel method and reduction method, easily
obtain particles having a small and uniform size and shape. Fig. 1
schematically shows the representative formation mechanisms of
inorganic particles. Before discussing the synthesis of inorganic
particles using microfluidics, this section will give an overview
of some theories about the nucleation and growth of inorganic
particles in a solution.
2.1.1. LaMer model
The LaMer model has been reported through the study of the
synthesis of sulfur sols from the decomposition of sodium thiosul-
fate, and the formation of particles has been classified into two
stages: nucleation and growth [33,34]. The first step, nucleation,
forms free sulfur in the thiosulfate, and the second involves the
formation of sulfur sol in the solution. Fig. 1 shows a diagram of
the LaMer model in which the concentration of the monomer is
Please cite this article as: K.-K. Kang et al., Recent progress in the synthesis of inorganic particulate materials using microfluidics, Journal
of the Taiwan Institute of Chemical Engineers (2018), https://doi.org/10.1016/j.jtice.2018.08.027
[m5G;November 12, 2018;11:33]
schematically shown as a function of time [35]. The mechanism
proposed by LaMer divides the nucleation and growth process into
three parts. The concentration of the free monomer in the solu-
tion increases sharply in the initial reaction stage. After this, the
monomer undergoes a "burst-nucleation" in which the concentra-
tion of the free monomer in the solution is significantly reduced.
Since the concentration of the monomer is low, nucleation hardly
occurs at this stage. In the next stage, the growth of the nuclei pro-
gresses under the diffusion control of the monomer in the solution.
2.1.2. Ostwald ripening and digestive ripening
Since Ostwald Ripening was first published in 1900 [36] and
this involving relocation and fields applications in emulsion sci-
ence [37–39], materials science [40], and chemical engineering
[41]. In particular, it is utilized as an effective strategy for im-
proving the uniformity of inorganic nanoparticles [41,42]. During
the Ostwald ripening, the growth of nuclei is attributed from the
solubility changes of nanoparticles depending on the size of the
particles, which can be explained by the Gibbs-Thomson relation
[43]. Due to the high solubility and surface energy of small parti-
cles in solution, re-dissolution and further growth of the particles
are proceeded. Finally, the size of particle prepared becomes more
uniform. The most typical example of the Ostwald ripening is
sol-gel process using a base catalyst and silicone alkoxide as a
silica source, which produce uniform silica particles [44,45]. The
silica precursor is hydrolyzed by a sol-gel catalyst at the beginning
of sol-gel process and then the hydrolyzed silica precursor is
polymerized and transformed to nuclei. The resulting nuclei grow
into silica nanoparticles with wide size distribution. Next, the
silica nanoparticles becomes more uniform through aging process.
These unique properties have recently been widely used in the
synthesis of various inorganic nanoparticles [46–48].
Both Ostwald ripening and digestive ripening, the growth
of particles occurs thermodynamically in the most stable state
through re-dissolution and regrowth, and the particle size be-
comes uniform through this process. However, the digestive
ripening is the opposite of Ostwald ripening [49]. In general, the
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synthesis of nanoparticles using digestive ripening method pro-
ceeds three steps: (1) breaking the polydispersed large particles
into small particles through the addition of ligand, (2) removing
by-products from the mixture containing nanoparticles, and (3)
forming the monodispersed nanoparticles through the heating
the mixture containing nanoparticles stabilized by ligand. The
preparation of gold nanoparticles is one of the most representative
materials initially synthesized through digestive ripening method,
and the synthesized gold nanoparticles have a significantly high
monodispersity [50–52].
2.1.3. Finke–Watzky two step mechanism
The Finke–Watzky two step mechanism is a process in which
nucleation and growth occur simultaneously [53]. This mechanism
consists of nucleation that is continuous but slow during auto-
catalytic surface growth, which is not governed by the diffusion
of the precursor monomer. This process was found through the
reduction of transition metal salts by hydrogen, which was studied
through the reduction process of cyclohexene. However, this is
not clearly demonstrated and can only be confirmed by kinetic
fitting at present. Although this nucleation and growth mechanism
also differs from the former reported traditional mechanism,
it is known that the critical particle size produced follows the
traditional mechanism.
2.1.4. Coalescence and oriented attachment
Coalescence and oriented attachment are quite similar on the
agglomerated surface of particles. The grain boundaries of the
particles in contact and the orientations of the crystal lattices of
the particles are considerably different. In the case of coalescence,
there is no particular tendency toward crystal orientation [54].
On the other hand, for the oriented attachment crystal plane, the
continuous crystal structure of the crystal lattice’s interconnected
nanoparticles is exactly aligned [55,56]. These examples have
been verified through electron microscopic analysis of generated
particles [57–59]. Interestingly, when the nanoparticles are inter-
connected by oriented attachment, the nanoparticles rotate and
contact until the directions of the two crystal domains of the crys-
tal lattices exactly match. The particles are oriented and attached,
and the remaining empty space is filled in a very short time. Un-
usual movements, such as particle jumping, are observed to make
contact between particles at this time. Such a jump phenomenon
due to the attraction between particles is generally explained by
the Coulomb force. However, the polarization of anisotropic parti-
cles and van der Waals interaction cannot be completely excluded.
2.2. Dimensionless number
The characteristics of fluids are of considerable importance in
the synthesis of inorganic materials using microfluidic devices. A
fluid is a continuous, unshaped material that tends to move freely
from one molecule to another and take the form of a container
without a specific shape. In general, the movement of the fluid
in the microfluidic channel is determined by the characteristics
of the fluid and the microchannel. To obtain well-defined droplets
in droplet-based microfluidic systems, the dripping and jetting
flow regions must be predicted. Furthermore, this prediction must
be performed for the synthesis of an inorganic material using a
microfluidic fluid in which two or more fluids are mixed with
each other to control the chemical composition and physical state.
By predicting the flow pattern of the fluid flowing through the
microfluidic channel, it is possible to generate and stabilize flow
patterns in the microfluidic device. Therefore, this prediction is
important in determining the success of the synthesis of functional
materials using microfluidics. Prediction of flow patterns is possi-
ble using the physical properties of the fluid flowing through the
Please cite this article as: K.-K. Kang et al., Recent progress in the synthesis of inorganic particulate materials using microfluidics, Journal
of the Taiwan Institute of Chemical Engineers (2018), https://doi.org/10.1016/j.jtice.2018.08.027
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3
microfluidic channel and the dimensionless number calculated by
combining these properties [35,60–62]. Therefore, understanding
flow patterns in microfluidics is the first step in the design of a
microfluidic system for the synthesis of inorganic materials.
Table 1 shows the microfluidics-related dimensionless numbers.
These dimensionless numbers describe the competition between
various forces, such as buoyancy, gravity, inertia, viscosity and
interfacial forces. The Grashof number (buoyancy for viscous
forces), Bond numbers (gravity for interfacial forces) and Reynolds
numbers (inertia for viscous forces) are accumulated to the third,
second and first forces of the flow dimensions, respectively. There-
fore, the importance of force action on a fluid varies dramatically
from conventional batch scales (macroscales) to microscales. As
the synthesis systems are miniaturized to microscale in microflu-
idics, buoyancy, gravity and inertia become less important, while
viscous and interfacial forces become more visible and predomi-
nant. In other words, interfacial tension is especially noticeable in
the geometry- and size-miniaturized microfluidic system.
2.2.1. Reynold number (Re)
The Reynolds number (Re), which reflects the relative im-
portance of an inertial force compared to the viscous force, is
defined by the characteristic velocity U, where DH is the hydraulic
diameter of the microchannel, μ is the viscosity of the fluid, and
ρ is the density of the fluid. In the case of the most microfluidics
including droplet-based microfluidics, Re is less than 1 because the
channel size is on the micrometer scale. In detail, the Re usually
ranges between 10−6 and 10 in microfluidic flows. Therefore, the
fluids flowed through the microchannel show the laminar flow
patterns and the viscous force is dominant over the fluid inertia.
ρ U DH
Re =
μ
2.2.2. Capillary number (Ca)
The capillary number (Ca), is the most commonly used dimen-
sionless number, which is the ratio of viscous stress to capillary
pressure. Ca is defined by using the interfacial tension and viscos-
ity and is determined by the viscosity of the fluid (μ), characteristic
velocity (U) and interfacial tension (γ ). In the case of microfluidic,
the Ca of microchannels is usually ranges between 10−3 and 10
and the inertial stress does not directly depend on the length of
the device. However, when the device length is reduced, viscous
stress and capillary pressure increase, whereas the gravitational ef-
fect is decreased. At this situation, when the microchannel length
is sufficiently small, the viscous and capillary forces strongly affect
fluids, and these effect can change the flow patterns of fluid [63–
65]. In addition, Re is rarely used in the interfacial slows associated
with droplet formation using microfluidic devices, and Ca is used
more because the interfacial tension between two fluids is more
important parameters in droplet generation [66]. Therefore, these
also indicate that Ca is an important dimensionless number that
can define and present the microflow in a microchannel.
μU
Ca =
γ
2.2.3. Weber number (We)
Fluid inertia is negligible for most microfluidic flows. However,
during co-flowing with a high flow velocity, jetting and other flow
pattern formations, such as droplet vicinity and bubble pinch-off,
increase. In this case, the inertial and capillary forces have dom-
inant roles compared to the viscous stresses, and the Webber
number can become an important dimensionless number [60,67].
The Weber number (We) is defined by the relative importance of
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Table 1
Important dimensionless numbers in microfluidics.
Dimensionless number Definition
Inertial f orce
Reynolds number (Re) V iscous f orce
V iscous f orce
Capillary number (Ca) sur f ace tension
Gravity
Bond number (Bo) Inertial f orce
Buoyancy
Grachof number (Gr) V iscous f orce
Weber number (We) Relative importance of the fluid inertia on surface tension
U: characteristic velocity; DH : is the hydraulic diameter of the microchannel; μ: viscosity of the fluid; ρ :
density of the fluid; g: standard acceleration of free fall; β : coefficient of thermal expansion.
inertia and the capillary pressure, where d is the characteristic
diameter of the fluid. We is also considered to be a significant
number when the inertial and capillary forces have dominant roles
compared to the viscous stresses, such as the formation of jetting
during co-flowing with a high flow rate. We is less than 1 for most
microfluidics.
ρ DH U 2
W e = Re · Ca =
γ phase improves the stability of the droplets. Well-defined spherical
2.3. Two-phase flow microfluidics
The microfluidic synthesis of inorganic particles provides strong
advantage in controlling reaction conditions such as rapid mix-
ing, heat exchange rate, and short residence time compared to
conventional batch synthesis [30]. In microfludic system, most of
inorganic particles are synthesized using single or multiple fluids,
and the phase of the precursor of the inorganic particles becomes
an important consideration in determining the type of these fluids
[68]. In the case of single-phase microfluidics for the synthesis of
inorganic particles, the mixture of reactant is generally a liquid
phase and continuously flows in microchannels under the precisely
controlled reaction conditions. When the preparation of inorganic
particles is carried out using single microchannel including mul-
tiple inlets, the flow pattern of fluids is laminar and the mixing
of each components proceeds by simple diffusion at interface of
individual fluid. A multi-phase microfluidic system is a mixture
of two or more fluids that are normally immiscible [67]. When
immiscible two fluids are introduced through different inlets, one
fluid is segmented by immiscible another fluid. The fluid segments
or droplets can be used to convert the inherently two-dimensional
flows to three-dimensional chaotic flows under suitable conditions.
For example, as a segment fluid traverses a microchannel, the flow
inside each segment fluid alternates between two flow patterns
with crossing streamlines. This flow pattern induces chaotic ad-
vection and rapid mixing. The basic principle can be also applied
to mix liquid segments separated by gas bubbles [26].
Inevitable issue is the precise understanding and elaborate
control of flow pattern of fluid flowing in a microchannel with
considering formation mechanism of inorganic particles. Except
for single phase flow including single and multiple fluids, droplet
formation can be considered as the first step in the microfluidic
synthesis. Many different techniques have been developed to pro-
duce droplets [26,60,66]. In the majority of techniques, the flow
field causes the interface between the two fluids to deform, lead-
ing to a growth of interfacial instabilities. In general, the disperse
phase is introduced into a microchannel by a pressure-driven flow,
while the continuous fluid of the second immiscible fluid is driven
independently. These two phases meet at a junction, where the
local flow field, determined by the geometry of the junction and
the flow rates of the two fluids, deforms the interface. Eventually
droplets pinch off from the dispersed phase finger by a free surface
instability. Generally, three types of microfluidic geometries are
Please cite this article as: K.-K. Kang et al., Recent progress in the synthesis of inorganic particulate materials using microfluidics, Journal
of the Taiwan Institute of Chemical Engineers (2018), https://doi.org/10.1016/j.jtice.2018.08.027
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Equations
ρ U DH
μ
μU
γ
gd 2
γ
D3H ρ 2 gβ T
μ2
Re · Ca = ρ DγH U
2
utilized for generating droplets such as T-junctions, flow-focusing,
and co-flowing as shown in Fig. 2.
According to the previous report, the well-defined droplet
formation systems are similar to the emulsion systems of oil and
water [69,70]. Depending on the nature of the channel surface,
the dispersed phase is commonly an aqueous phase containing
a small amount of emulsifier, and the continuous phase is an
oil-like phase as a counterpart. The emulsifier in the dispersed
droplets are generated under the specific flow patterns formed
within the channels of a microfluidic device. In addition, these
flow patterns are dominated by the flow rate and the physical
properties of the fluids. The most representative flow patterns
are dripping, jetting and co-flow, which represent unique flow
profiles. The spherical droplets addressed in this article are mainly
generated by the dripping flow pattern, but some of them are
generated in the jetting flow pattern, depending on the design and
structure of the microfluidic devices. In previous reports, studies
addressed the formation mechanism from the dripping to the
co-flow pattern regime in microfluidic devices [60,62,63,66,71–74].
In 2013, Nune et al. summarized and reported on the formation
of the dripping, transition, jetting and co-flow patterns and their
mechanisms based on the results of numerous simulations and
experiments [67].
2.3.1. T-junction
A schematic illustration of the operating condition of the T-
junction is shown in Fig. 1A. The dispersed phase is fed to the side
channel, and the continuous phase is injected into the main chan-
nel. The T-junction device was first reported by Thorsen et al. to
produce a monodisperse water droplet in oil as a continuous phase
[75]. Since this report, T-junction and similar forms of microflu-
idics have been widely used due to their simplicity and ability to
produce monodisperse droplets. Studies on the geometric changes
of T-junctions have continued and been reported recently. In fact,
it is difficult to achieve the requirement for various application
with the channel structure of T-junction [76,77]. In considering the
droplet of viscosity and density that flows from a T-junction with
two equal arms of the same width and height, the droplet pro-
duced is too large to remain spherical inside the channel and has
a length l0 times larger than the width of the channel generally.
Thus, T-junction geometric structure limits in forming a perfect
spherical particle. Therefore, geometric changes to T-junctions have
recently been studied and reported [63,64,78,79]. The effect of
junction angle on the mechanism of droplet formation and droplet
size are investigated in previous studies [63,64]. The numerical
and experimental results indicate that the active area for droplet
formation generally increases with the decrease of junction angle.
Many studies suggested that a junction angle of around 60° was
predicted as the most efficient angle and the droplets were formed
in a wide range of capillary number only if junction angle was
equal to 90°. In addition, the droplet size decreases as junction
angle increases, and it decreases more quickly when the junc-
tion angle is less than 60°. Prior to approaching the equilibrium
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Table 2
Inorganic particulate materials synthesized via microfluidic systems.

Functionalmaterials Materials Formation Microfluidic platform Precursor Reducing agent,Stabilizer,Catalyst Size Reference

Metal nanoparticles Au Nanoparticle Continuous flow HAuCl4 Ascorbic acid 5–50 nm 147

ARTICLE IN PRESS
Au, Ag Nanoparticle Continuous flow HAuCl4 ,AgNO3 NaBH4 4–7 nm 148
Au, Ag Nanosphere to nanorod Continuous flow HAuCl4 ,AgNO3 NaBH4 Appox.30 – 60 nm 149
Au Nanocube Continuous flow HAuCl4 NaBH4 53–75 nm 150
Pt Nanoparticle Continuous flow H2 PtCl6 Ethylene glycol 1–4 nm 151
Pd Nanoparticle Continuous flow PdCl2 LiBH(C2 H5 )3 ∼ 3 nm 152
Pd Nanoparticle Continuous flow Pd(OAc)2 Oleylamine ∼ 1 nm 153
Au Nanoparticle Segmented flow(T-junction) AgNO3 NaBH4 3–7 nm 154, 155
Cu Nanoparticle Segmented flow(Co-flowing) CuSO4 NaBH4 2–5 nm 156
Cu Nanoparticle Continuous flow CuCl2 LiBH(C2 H5 )3 ∼ 8.9 nm 157
Ni Nanoparticle Continuous flow NiCl2 N2 H4 ∼ 80 nm 158
Quantum Dots CdSe Nanoparticle Continuous flow Cd(CH3 COO)2 ,TOP-Se – 2–4.5 nm 168
CdSe Nanoparticle Continuous flow Cadmium oleate,TOP-Se – 1.5–2.7 nm 169
CdSe Nanoparticle Segmented flow(Co-flowing) Cadmium oleate,TOP-Se – 2–10 nm 170
CdSe Nanoparticle Segmented flow(Flow focusing) Cadmium oxide,TOP-Se – ∼ 3.4 nm 171
CdSe/ZnS,CdTe/ZnS Nanoparticle Continuous flow Cadmium oleate,TOP-Se – 1.5–3.2 nm 172, 173
ZnSe Core-Shell nanoparticle Continuous flow ZnSe crystal,PEI – 4 – 6 nm (NPs),50 – 80 nm (Core-shell) 174
Metal oxide TiO2 Nanoparticle Continuous flow Titanium tetraisopropoxide H2 O <3 nm 184
TiO2 Nanoparticle Continuous flow Titanium tetraisopropoxide H2 O 25.9 × 3 nm(L × D) 185
Fe2 O3 Spinel nanoparticle Segmented flow(Co-flowing) FeCl2 •4H2 O,FeCl3 •6H2 O Ammonium hydroxide ∼ 4 nm 186
γ -Fe2 O3 /silica Core-shell nanoparticle Continuous flow γ -Fe2 O3 –COOH,TEOS Ammonia ∼ 50 nm 80
Porous inorganic SiO2 Mesoporousnanoparticle Segmented flow(Vibrating orifice) TEOS HCl 5–10 μm 188
SiO2 Mesoporousnanoparticle Segmented flow (Flow focusing) TEOS HCl 15–35 μm 189
SiO2 Mesoporousnanoparticle Segmented flow (Flow focusing) TEOS HCl ∼ 30 μm 190

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Fig. 2. Schematic of a representative microfluidic device. (A) T-junction microfluidic device, (B) flow focusing microfluidics device, and (C) coflowing microfluidic device. Qd
is the dispersion phase velocity, and Qc is the continuous phase velocity.
state, there is always a periodic deviation in the relative distance
between droplets when junction angle is not equal to 90°. This
phenomenon is common to be encountered in an experiment
on cross-junction devices, however, a double T-junction devices
are highly recommended for alternating droplet formation with
uniform distance between droplets. This can avoid the merging
droplets when they are moving from T-junctions to reservoir.
Materials with multiple ingredients or multiple reaction pro-
cesses are often produced through generation of the droplets by
co-encapsulating different reagents at the same time by merging
individually generated droplets to precisely control the reaction
volume of each reactant, such as iron oxide and CdS [80,81].
Various types of multiple junctions have been proposed to meet
this need. Various modified T-junctions, such as the K-junction
and V-junction, have been developed to control the size, com-
position, and generation frequency, required for biochemical
analysis [78,82–84]. In addition, for several special applications, T-
junction microfluidics have also recently been applied in designing
microvalves and microactuators [85,86].
When droplets are generated using this T-junction microflu-
idics, three distinguishable flow regimes, squeezing, dripping or
jetting, can be observed, depending on the physical parameters of
the fluids. The emergence of each flow pattern is closely related
to the capillary number (Ca) and the difference of the flow rate
between the two fluids flowing through the channel. At low Ca
(<10−2 ) values, the shear forces are not sufficient to distort the
disperse phase, resulting in confined fluidic environments formed
by blocking the channel through the growth of the disperse phase.
In this state, the disperse phase increases its pressure, while a thin
film of the continuous phase between the disperse phase and the
wall of the device is generated at the T-junction. This squeezes
the disperse phase, eventually breaking up the disperse phase into
droplets. This type of pressure-dominated formation of droplets is
known as “squeezing” .
Above a relatively higher Ca (>10−2 ) value, the continuous
phase strongly affects the dispersed phase at the junction, caus-
ing it to separate into droplets. This shear-driven formation of
droplets is referred to as “dripping” . In this regime, the sizes of
the droplets can be controlled by Ca and the ratio of the flow
rates between the continuous phase (Qc ) and disperse phase
(Qd ) [87,88]. For example, Garstecki et al. demonstrated that the
droplet size formed at low Ca values mainly depends on the flow
ratio of the disperse phase and the continuous phase (Qd /Qc ) [88].
The typical size of droplets formed at low Ca values is larger
than the size of the microchannels, while at relatively higher
Ca values, the size of the droplets is affected by the local shear
stress, forming droplets smaller than the size of the microchannel.
At even higher Ca (>10−1 ) values, jetting or co-flowing occurs
[89–91]. For example, Gupta et al. demonstrated that jetting and
Please cite this article as: K.-K. Kang et al., Recent progress in the synthesis of inorganic particulate materials using microfluidics, Journal
of the Taiwan Institute of Chemical Engineers (2018), https://doi.org/10.1016/j.jtice.2018.08.027
[m5G;November 12, 2018;11:33]
stable co-flowing were generated as Ca increased from 0.1 to 0.3
within the given dimensions of the T-junction microfluidic devices
[90]. In addition, Guillot and Colin showed that stable co-flowing
developed as the flow rate of the disperse phase overcame that of
the continuous phase, and the critical values of the flow rate were
decreased by increasing the viscosity of the disperse phase [89,92].
2.3.2. Flow-focusing
The flow-focusing approach was first introduced by Anna et al.
[93]. It is also one of the most general methods used to study the
fluidic evolution from the dripping to jetting regime by manipu-
lating the physical parameters of the fluids [63,65,94–103]. In this
method, two immiscible fluids, comprising a continuous phase and
a disperse phase, are introduced into each inlet. The two fluids are
flow-focused into a small orifice, as shown in Fig. 2B. In this fluidic
state, the continuous phase causes a symmetrical shear force that
affects the disperse phase, resulting in an elongated fluidic state.
The elongation-dominated velocity field of the continuous phase
consistently stretches the disperse phase into a thin jet, finally
breaking up the thread into droplets. For example, Liu and Zhang
reported that the dripping-to-jetting transition is controlled by
increasing the ratio of the fluids (Qd /Qc ) from 0.6 to 3 at a given
Ca (0.004). Humphry et al. revealed that the boundary condition
between stable and unstable co-flowing occurred at Qd /Qc ࣌ 0.58.
In addition, the size of the droplets was controlled by simply
varying Ca and the ratio of the flow rates [63,104,105).
2.3.3. Co-flowing
The co-flowing method is a simple approach to form droplets
that was first utilized by Umbanhowar et al. at the macroscale, and
several other researchers have also brought it to the microscale
[71–73,106–112]. Co-flowing microfluidic devices are generally
composed of a set of concentric capillaries, inner and outer cap-
illaries in a coaxial direction. The continuous phase and dispersed
phase are individually injected through each capillary, forming a
parallel flow, as shown in Fig. 2C. In this state, the disperse phase
becomes unstable due to interfacial tension, minimizing the inter-
facial area, which is known as Rayleigh-Plateau instability [113].
This results in the breakup of the disperse phase into droplets. For
example, Utada et al. demonstrated that when each flow rate is
low, droplets are formed at the tip of the inner capillary, which
is known as dripping. When the ratio of the flow rates (Qc /Qd )
is increased, the size of the droplets decreases. When the size of
the droplets is approximately the size of the tips, the fluids en-
ter the jetting regime, which eventually becomes unstable due to
the Rayleigh-Plateau instability. This result eventually leads to the
formation of droplets at the tip of the extended jet. In this state,
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increasing the fluid velocity is favorable, enabling the formation of
stable jetting. In contrast, absolute stability [114–118] is dominant
at low Ca values, leading to disturbances in the fluid velocity. These
results allowed the fluids to separate into droplets [119]. The capil-
lary number (Ca) and ratio of the flow rates are major parameters
for controlling the dripping regime and the jetting regime.
3. Microfluidic approaches for the synthesis of inorganic
materials
In general, inorganic materials (particles) have various physic-
ochemical properties depending on their crystallinity, shape, and
size. In particular, nanometer-sized particles exhibit significantly
different properties from bulk materials of the same composi-
tion. In the conventional synthesis of inorganic particles, uniform
mixing and temperature control must occur during synthesis to
produce uniform nuclei; thereafter, the generated nuclei form in-
organic particles through redissolution and growth, depending on
their size [68,120–123]. The sizes and shapes of the nanoparticles
are also influenced by the concentration of precursors, additives,
reaction temperature and time, and solvent selection [124–126].
When the prepared inorganic particle reaches the desired size and
shape, the synthesis process is terminated by quenching thermally.
In other words, the synthesis of uniform monodisperse inorganic
particles involves many factors that require precise control over
the entire synthesis process. Therefore, to control this property of
inorganic particles, which depends on the change in morphology,
a synthesis technique that minimizes the differences within the
synthesized particles is essential [127–132]. However, the dis-
advantages of conventional inorganic particle synthesis include
variations in the initial concentrations of reagents and difficult
control of mixing and temperature during synthesis, which leads
to interparticle variations in the sizes and shapes. From this point
of view, the synthesis of inorganic particles using microfluidics
can provide the ability to solve these difficulties by performing
nucleation and growth steps in a continuous flow process and
controlling the injection, mixing, and temperature profile. The dif-
ficulties of synthesizing inorganic particles remain because there
are large differences between the polymerization of the hydro-
carbons and the synthesis of the inorganic substances. In general,
inorganic synthesis uses inorganic precursors and, in many cases,
involves complicated formation reactions. Furthermore, much of
the formation of inorganic particles occurs at a high temperature,
and the phase change before and after the formation reaction is
abrupt. To make matters worse, the synthesized inorganic particles
are highly influenced by intermediates and byproducts, which
are produced in the formation reactions. The overall formation
mechanism is difficult to understand in detail. Due to these com-
plexities, there are only a relatively small number of studies on
the synthesis of inorganic materials using microfluidics.
As mentioned above, the high mixing efficiency and temper-
ature control and other process conditions must be considered
as the most important parameters in the synthesis of inorganic
materials using microfluidics. For this reason, the synthesis of in-
organic particulate materials using microfluidics will be discussed
differently from that of the prior polymeric particles. In other
words, in this section, the types of inorganic materials synthesized
using a microfluidic or similar system will be introduced and
discussed without focusing on the principle of droplet generation,
rheological viewpoint, and formation mechanism.
3.1. Metal nanoparticles
Metal nanoparticles are interesting materials because of their
broad range of applications [133–142]. Metal nanoparticles, such
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[m5G;November 12, 2018;11:33]
7
as gold, silver, platinum and palladium, are interesting materials
because of their size- and shape-dependent properties [135].
However, they are difficult to prepare with the desired size distri-
butions because they tend to aggregate and precipitate to lower
the surface free energy. The structure of the synthesized particles
is also a factor that has a great effect on the physical properties of
the nanoparticles and is important for synthesis studies. Therefore,
heat and mass control are very important for the formation of
metal particles. In the view point of these, microfluidics can
provide a useful control tool for synthesis conditions due to the
fast heat and mass transfer rate induced by the small and short
dimensions.
Recently, Au nanoparticles have received much attention
because their application fields have increased dramatically [143–
146]. The synthesis and modification of Au nanoparticles have also
been studied by many researchers. Fig. 3 shows the representative
synthesis of Au nanoparticles using a microfluidic system. The
synthesis of Au nanoparticles in microfluidics was performed with
a Au salt (HAuCl4 ) and reducing agents under various conditions
[147]. The prepared Au nanoparticles had a size of 5–50 nm, and
the particle size distribution was uniform compared with the
bulk synthesis. Au and silver nanoparticles between 4 and 7 nm
were also prepared by the reduction of Au and Ag salt solutions
with reducing agents in a microfluidic mixer containing eight
split and recombine microfluidic units at room temperature [148].
Boleininger et al. reported the synthesis of Au and silver nanorods
[149]. This method can produce fine-tuned particle shapes from
spheres to rod structures. Au and silver nanorods were fabricated
using PVC and PEEK capillary tubes. The shape of the particles is
controlled and reproduced by continuous flow synthesis through
on-line optical monitoring. This study shows the possibility of
synthesizing metal particles with a non-spherical shape using a
soft template through a microfluidic device.
Recently, Theile and co-workers reported the synthesis of
non-spherical Au nanoparticles using Dean flow induced microflu-
idic devices [150]. The synthesis of the particles was carried out
through a three multi-step synthesis. The first two steps, seed
formation and growth, were performed in the microfluidic device.
The additional particle growth process was performed by using
the resulting intermediated product recovered from the microflu-
idic device. The Dean flow induced by the microfluidic device
caused the rapid mixing of the reactants, and the non-spherical
Au nanoparticles produced had a cubic shape. The size of the
synthesized cubic nanosized Au nanoparticles could be controlled
by controlling the process conditions of each stage of the multi-
step synthesis process. In addition, the advantages of microfluidics
were fully exploited in the synthesis, and the consumption of
materials could be reduced by 95%.
Fig. 4 shows a microfluidic device and prepared novel metal
nanoparticles. Pt-nanoparticles can be prepared continuously by
the polyol process using microfluidic devices [151]. Dispersed
colloidal Pt-nanoparticles with mean particle sizes between 1
and 4 nm were prepared continuously in microstructured devices
using ethylene glycol as the solvent and reducing agent and
H2 PtCl6 as the metal precursor. Nanoparticle formation occurs in
the microchannel in short time intervals, and conversion of the
Pt salt can be adjusted by the residence time and temperature.
Therefore, the formation process of Pt nanoparticles could be split
into two different steps, i.e., nucleation and particle growth, and
these sequential processes were carried out in the micromixer and
micro residence time module. Through the microfluidic device,
it was confirmed that the factor affecting nucleation and parti-
cle growth of Pt was pH (NaOH concentration). Nucleation was
dominant at a high pH, and particle growth was dominant at a
low pH. In addition, particle synthesis can be separated using a
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8 K.-K. Kang et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2018) 1–18

Fig. 3. Synthesis of metal nanoparticles with various microfluidic devices and microreactors. (A) Schematic drawing of a microfluidic device and synthesized Au nanoparticles
[147]. Reproduced with permission from Wagner and Köhler [147]. Nano Letters; published by the American Chemical Society, 2005. (B) Microfluidic device arrangement for
the flow-through process for the synthesis of Au nanoparticles and synthesized Au nanoparticles [148]. Reproduced with permission from Wagner et al. [148]. Chem. Eng. J.;
published by Elsevier, 2008. (C) Microfluidic device arrangement for the synthesis of Ag nanoparticles and synthesized Ag nanoparticles [148]. Reproduced with permission
from Wagner et al. [148]. Chem. Eng. J.; published by Elsevier, 2008. (D) A schematic diagram of the synthesis of multi-stage Au nanoparticles (nanocubes) using Dean flow
induced microfluidic devices (DFM) and the synthesized Au nanocubes [150]. Reproduced with permission from Theile et al. [150]. Lab Chip; published by the Royal Society
of Chemistry, 2017.

microfluidic device, and a more uniform size of Pt nanoparticles
can be obtained.
A continuous flow polymeric microreactor, fabricated using
negative photoresist SU-8 on a 10 × 10 cm PEEK (polyetherether-
ketone) substrate by standard UV lithography, was utilized to
synthesize palladium nanoparticles [152]. The palladium metal
solution was prepared by dissolving PdCl2 in THF. Lithium hy-
drotriethylborate (LiBH(C2 H5 )3 ) was used as a reducing agent, and
3-(N,N-dimethyldodecylammonia)-propanesulfonate was used as a
stabilizer. The reducing agent and stabilizer were dissolved in THF.
The metal solution and the mixed solution of the reducing agent
and the stabilizer were introduced into the microfluidic device,
respectively. These two solutions were mixed in a 4-way mixer
in the microfluidic device. The Pd nanoparticles prepared in the
microfluidic device have a narrower size distribution compared
with those obtained by conventional batch synthesis.
Furthermore, Karim et al. studied the synthesis of 1 nm sized
Pd nanoparticles using SAXS (small angle X-ray scattering) and
XAFS (X-ray absorption fine structure) on microfluidic devices
[153]. The microfluidic device, which was equipped with SAXS and
XAFS, allows a time resolution ranging from milliseconds to sev-
eral minutes, with a residence time of over an hour. The synthesis
of Pd nanoparticles was investigated in the presence of oleylamine
and trioctylphosphine ligands. The SAXS analysis results indicated
that the nucleation of Pd nanoparticles progressed slowly in both
ligands. Particle growth is initially autocatalytic and proceeds fairly

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K.-K. Kang et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2018) 1–18 9

Fig. 4. Synthesis of Pt and Pd nanoparticles with various microfluidic devices and microreactors. (A) Optical images of a microfluidic device for the preparation of Pt
nanoparticles and synthesized Pt nanoparticles [151]. Reproduced with permission from Baumgard et al. [151]. Chem. Eng. J.; published by Elsevier, 2013. (B) Schematic
illustration of an overall microfluidic system and proposed mechanism for the preparation of ligand uncapped Pd nanoparticles and synthesized Pd nanoparticles [153].
Reproduced with permission from Karim et al. [153]. Phy. Chem. Chem. Phys.; published by the Royal Society of Chemistry, 2015.

quickly. On the other hand, despite a large amount of unreacted
Pd precursor remaining, the particle growth dramatically slowed
down, and the particle size reached a certain level during the
formation of the nanoparticles. According to the XAFS analysis, the
Pd-P coordination increase, which originated from the coordina-
tion between trioctylphosphine and the Pd nanoparticle, coincided
with the decrease in the growth rate. The combination of the
online analysis tools and microfluidics also provided unique and
important experimental results, which indicate that the nucleation
of Pd nanoparticles and the growth of particles are strongly influ-
enced by the interaction with the ligands. This study shows that if
the nanoparticles induce a strong interaction between the ligands,
it is possible to produce very small metal nanoparticles near the
1 nm size. This study demonstrates that microfluidic devices have
advantages in the study of nanoparticle synthesis.
Fig. 5 shows the preparation of Ag nanoparticles using a
microfluidic device under various process conditions. Liu et
al. demonstrated the biosynthesis of silver nanoparticles using

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10 K.-K. Kang et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2018) 1–18

Fig. 5. Synthesis of silver nanoparticles in microfluidics. (A) Schematic illustration of a microfluidic system for the synthesis of Ag nanoparticles and the analysis results of
Ag nanoparticles synthesized by using various flow rates [154]. Reproduced with permission from Liu et al. [154], Chem. Eng. J; published by Elsevier 2012. (B) Schematic
illustration of a microfluidic system for the synthesis of Ag nanoparticles and the analysis results under various flow rates [155]. Reproduced with permission form Xu et al.
[155], Chem. Eng. Process.; published by Elsevier 2016.

modified T-junction microfluidics and the effect of flow rates
and mixing efficiency in tuning the silver nanoparticle size [154].
They used Cacumen Platycladi extract as a formation agent for Ag
nanoparticles. The size of the nanoparticles could be controlled
by controlling the inlet flow rate and reaction time. The size of
the Ag nanoparticles was strongly influenced by the inlet flow
rate, and when the inlet flow increased, the average size of the
Ag nanoparticles decreased. The inlet flow rates varied from 200
to 600 μL/min, and the average sizes of the Ag nanoparticles at
flow rates of 20 0, 30 0, 40 0, 50 0, and 60 0 μL/min were (3.5 ± 0.9),
(4.2 ± 0.9), (7.2 ± 2.0), (5.2 ± 2.3) and (3.0 ± 0.5) nm, respectively.
In summary, the average size of the Ag nanoparticle was found
to increase and then decrease with the increase in flow rate.
Synthesis of silver nanoparticles was performed by Xu et al. using
a microfluidic device in which two T-junctions were connected
continuously [155]. In the microfluidic device used for silver
nanoparticles, the Ag precursor (AgNO3 ) and the reducing agent
NaBH4 met at one T-junction. At the second T-junction, both fluids
formed droplets, and this fluid was mixed in the droplet. The
resulting silver nanoparticles were stabilized by EDTA (ethylenedi-
aminetetraacetic acid). The silver particles were changed by molar
ratios of NaBH4 and AgNO3 . The particle size also changed as the
flow rate varied. As a result, as the molar ratios of NaBH4 and
AgNO3 decreased and as the flow rate increased, the size of the
silver nanoparticles increased. This shows that the formation of
nanoparticles is easily controlled by using a microfluidic device.
Furthermore, this also shows that microfluidics can be useful tools
for the synthesis of nanoparticles at the same time.
Ke et al. reported a successful continuous-flow production
process of copper (Cu) nanoparticles with particle sizes of 2–5 nm
[156]. Fig. 6A shows the microfluidic device and the prepared Cu
nanoparticles. The Cu precursor was aqueous copper sulfate, and
the reducing agent was aqueous NaBH4 . The microfluidic device
was similar to the co-flowing type and consisted of an inner tube
and an outer tube. The formation reaction using two aqueous
solutions was carried out in the annular microchannel between

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Fig. 6. Preparation of Cu and Ni metal nanoparticles in microfluidics. (A) Structure and principle of TMR (tube-in-tube microchannel reactor) and an HRTEM image of Cu
nanoparticles [156]. Reproduced with permission form Ke et al. [156], J. Nanosci. Nanotechnol.; published by American Scientific Punishers 2011. (B) TEM analysis results and
particle size distributions of Cu nanoparticles prepared using the microfluidic system of ref. 128 [157]. Reproduced with permission from Song et al. [157], J. Phys. Chem.
B; published by the American Chemical Society, 2005. (C) Schematic diagrams of a microfluidic system and Ni nanoparticles synthesized by it at 70 °C for 3.9 min [158].
Reproduced with permission form Zeng et al. (158), Chem. Eng. J.; published by Elsevier, 2012.

the two tubes. The characterization results of the Cu nanoparticles
obtained in the batch process using the TEM, XRD and UV/vis
techniques were compared with those achieved in the microfluidic
synthesis process. Due to the improved micromixing effect of mi-
crofluidic reactors, the Cu nanoparticles have a more uniform and
smaller size. In addition, the stability of the microfluidic reactor
was also improved, enabling the production of several liters per
minute.
Song and his coworkers also synthesized Cu in a similar
manner to their previous report [152,157]. The copper metal
precursors were prepared by dissolving CuCl2 in THF, and the
same compounds, lithium hydrotriethylborate (LiBH(C2 H5 )3 ) and
3-(N,N-dimethyldodecylammonia)-propanesulfonate, used in their
previous report were used as a mixture solution of the reduc-
ing agent and the stabilizer. Prior to the synthesis of the Cu
nanoparticles in the microfluidic devices, sulfobetaine-stabilized
Cu nanoparticles were analyzed by X-ray absorption near-edge
structure (XANES) spectroscopy, UV–vis spectroscopy and reaction
calorimetry. According to these results, it was found that the
stability of Cu(I) complexes are sensitive to the concentration of
the sulfobetaine stabilizer and the rate of addition of the reducing
agent, and the resulting complexes of Cu(I) and sulfobetaine stabi-
lizers formed mainly linear complexation. Based on this, they were
applied to the synthesis of Cu nanoparticles using microfluidic
devices. Compared with the Cu nanoparticles synthesized by the
conventional batch synthesis process, the obtained Cu nanoparti-
cles were less than half the size, and the particle size uniformity
was also improved to a considerably high level, as shown in
Fig. 6B. The resulting copper particles had an fcc structure and
improved chemical stability, enabling relatively stable maintenance
of the reduced metal state without oxidation in air.
Zeng et al. reported the synthesis of nickel nanoparticles, which
was carried out in a vapor-liquid segmented microfluidic device
[158]. Fig. 6C shows a schematic illustration of the microfluidic
system and TEM images of the prepared Ni nanoparticles. This
vapor-liquid segmented microfluidic device could prevent clogging
of the microchannel by the generated nickel particles, and the
nickel nanoparticles could be continuously synthesized. The aver-
age diameter and particle size distribution were strongly affected
by the experimental parameters. An increase in the reaction
temperature caused decreases in the particle size and particle
size distribution of the nickel nanoparticles. The addition of a
surfactant (cetyltrimethylammonium bromide) also reduced the
average particle size and particle size distribution. Consequently,
Zeng et al. proposed that this method has potential to synthesize
other types of nanoparticles in microfluidics. Various types of
metal nanoparticles, such as cobalt and core shell, including metal
nanoparticles obtained using such a microfluidic device, have been

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Fig. 7. Various microfluidic (microreaction) systems for the preparation of QDs. (A) Schematic diagram of a capillary microreaction system for the preparation of CdSe
nanoparticles [168]. Reproduced with permission from Nakamura et al. [168]. Chem. Commun.; published by the Royal Society of Chemistry, 2002. (B) A capillary microreactor
with an inline convective mixer for CdSe nanoparticles [168]. Reproduced with permission from Yen et al. [169]. Adv. Mater.; published by Wiley InterScience, 2003. (C)
Channel design with a droplet jet injector [170]. (Refer to the references for details of the reactor.) Reproduced with permission from Chan et al. [171]. J. Am. Chem. Soc.;
published by the American Chemical Society, 2005. (D) Continuous-flow synthesis of QDs functionalized with OA and TOP in a multistep microfluidic system (OA: oleic acid;
TOP: tri-n-octylphosphine) [171]. Reproduced with permission from Kikkeri et al. [172]. Angew. Chem. Int. Ed.; published by Wiley InterScience, 2010.

reported [152,159–161]. Further studies have been reported on the
synthesis of multi-metal particles in more complex forms, such as
core-shell metal particles.
3.2. Quantum dot nanoparticles
Semiconductor nanoparticles, well-known as quantum dots
(QDs), formed of binary compounds such as CdSe, CdS, and
ZnS, have tunable adjustable physicochemical properties, such as
optical, electronic and surface properties [162,163]. These physic-
ochemical properties have been revealed to be closely related to
their shape and size. Due to these unique properties, QDs are
widely used for electronics optics, solar cells, and fluorescence
analysis in biotechnology. Therefore, many researchers have at-
tempted to prepare nanoparticles with well-defined sizes and
desired structures [164–167]. The conventional synthesis of QDs
is performed using a batch type reactor under high temperature.
It is difficult to precisely control the synthesis condition in the
batch reactor, and microfluidics have thus been proposed as an
alternative approach for the preparation method of QDs to control
the synthesis conditions using the advantages of microfluidics.
Research on the synthesis of QDs utilizing the advantages of
microfluidics has often been reported. In this section, we will
discuss the synthesis of CdSe, which is the most typical QD.
Fig. 7 shows the representative reports of QD synthesis. Naka-
mura et al. studied the synthesis of QDs using continuous capillary
microfluidic devices, which were fabricated by using a silica glass
capillary [168]. CdSe nanoparticle synthesis was carried out from
230 to 300 °C in an oil bath under different residence times, which
was determined by the volumetric rates and the dimensions of
the capillary tube. Yen et al. also studied a microcapillary flow
reactor for the preparation of a size series of colloidal CdSe
nanoparticles [169]. To prepare QDs in microfluidic devices at a
high temperature, the synthesis process was carried out using a
high boiling point solvent system. The particle size of the prepared
CdSe nanoparticles was controlled by the concentration of Se pre-
cursors, which can produce high-quality CdSe nanocrystals with
sizes corresponding to a wide spectral range. Yen and co-workers
also reported the synthesis of CdSe using a continuous capillary
microfluidic device, which could produce segmented droplets
using nitrogen gas [170]. These concepts led to an improvement of
the mixing efficiency of the segmented liquid droplets containing
the synthesis mixture of inorganic precursors and solvents, and the
process time decreased. Droplet-based microfluidics was applied to
the preparation of CdSe nanoparticles [171]. Using an octadecene
droplet containing Cd and Se precursors, the synthesis process was
carried out at a high temperature (240–300 °C), and the prepared
CdSe nanoparticles were investigated by spectroscopic analysis
and TEM. High-quality CdSe nanoparticles could be reproduced
consistently. This study shows that it is possible to synthesize
inorganic materials under precisely controlled conditions through
encapsulation of droplets at a high temperature. Kikkeri et al.
studied surface functionalized CdSe and CdTe nanoparticles using
multistep single-phase microfluidics. The prepared QDs were func-
tionalized with carbohydrate and carboxylic acid and had emission
properties at 480–598 nm [172].

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Fig. 8. Preparation of functionalized QDs and a microreaction system equipped with special equipment. (A) Schematic diagram of a continuous flow reaction system for
the preparation of carbohydrate-functionalized QDs and TEM images of QDs and functionalized QDs [173]. Reproduced with permission from Laurino et al. [173]. Nature
Protocols; published by Springer Nature, 2011. (B) Schematic diagram of the FPLAM (femtosecond pulsed laser ablation) system in a capillary reactor [174]. Reproduced with
permission from Yang et al. [174]. Applied Surface Science; published by Elsevier, 2017.

Laurino et al. demonstrated the synthesis protocol for car-
bohydrate and dihydrolipoic acid (DHLA)-coated CdSe/ZnS and
CdTe/ZnS nanoparticles in continuous microfluidics, as shown in
Fig. 8A [173]. They used the three steps of the microfluidic system,
operating at three different temperatures for the synthesis of
mannose-, galactose- or DHLA-functionalized QDs. The CdSe and
CdTe nanoparticles were prepared in the first step of synthesis.
The physical properties of the QDs are controlled by adjusting the
residence time and reaction temperature. In the second step of
the synthesis, ZnS doping was carried out at a substantially lower
temperature than the temperature for the QD growth in the batch
reactor. The trioctylphosphine/oleic acid ligand was replaced with
either carbohydrate PEG-thiol species or DHLA at 60 °C during the
third synthesis step. This proposed synthesis process can provide
the synthesis of useful materials for biotechnology. Recently,
Yang et al. proposed the FLAM (femtosecond laser ablation in
microfluidics) process for the synthesis of photoluminescent ZnSe
nanoparticles [174]. The FLAM equipment is shown in Fig. 8B. ZnSe
quantum dots (4–6 nm) were synthesized, and hyperbranched PEI
(polyethyleneimine) was used as the coated layer. These aqueous
nanosized micelles consisting of quantum dots showed a bright
green light emission centered at approximately 500 nm under
excitation of 365 nm ultraviolet light. Furthermore, this synthesis
process could also provide a non-toxic QD synthesis process. In
addition to the studies on the synthesis of CdSe nanoparticles us-
ing microfluidics, various studies on ZnS, CdS, other QD materials,
surface modified QDs, and microfluidic devices combined with
other devices have been reported. [81,175–183]
3.3. Metal oxide nanoparticles
Metal oxides with many useful physicochemical properties are
among the most synthesized materials to date. They are also used
as a raw material in various industrial fields because their char-
acteristics vary according to the type of metal. In addition, due to
these various characteristics, they are still being studied as a basic
material in various research fields, including synthesis research. In
particular, the study of metal oxide nanoparticles is of great value.
The synthesis of metal oxide particles using microfluidic de-
vices is also proceeding in various ways. Fig. 9 shows the synthesis
of TiO2 nanoparticles in microfluidic systems. Wang et al. demon-
strated the synthesis of TiO2 using a Y-shaped microfluidic device
[184]. The two immiscible fluids are not mixed with each other in
the channel and maintain a stable interface. The interface between
the solvents maintains the velocity of the solvent and the fluid. A
TiO2 particle of less than 10 nm is generated continuously at the
interface, with great advantages in terms of particle size control
and measurement. This synthesis also has the advantage that no
additional stabilizers or additives are required. Another method
for synthesizing TiO2 using trace fluids was reported by Cottam
and coworkers [185]. The synthesis process was carried out using
oleic acid, titanium tetraisopropoxide and trimethylamine N-oxide
dehydrate solution in a Y-shaped microfluidic device that induced
rapid mixing. The TiO2 production rate is 10 times faster than that
in the batch reactor due to the improvement of mixing efficiency.
In addition, the TiO2 produced has a well-developed 1D shape and
a high aspect ratio.
Fig. 10A shows the droplet-based microfluidic device for the
synthesis of iron oxide nanoparticles. Frenz et al. first reported
the synthesis of spinel magnetic iron oxide nanoparticles using
a microfluidic device [80]. They coupled two spatially separated
droplets into one droplet using in-line electro-coalescence. The
individual droplets contained each reactant and induced a reaction
through the fusion of droplets. The fusion between these two
droplets led to a high mixing rate, and the mixing time was
extremely reduced. In addition, a 99.99% yield of the fusion of
droplets was achieved by controlling the operating conditions of
the microfluidic device. Additionally, iron oxide nanoparticles were
synthesized using this coupling of droplets. Due to the mixing
rate improvement, smaller particles were able to be synthesized,
and the iron oxide nanoparticles had a narrower particle size
distribution. Recently, the single-phase multistep synthesis of
magneto-fluorescent nanoparticles was implemented by perform-
ing sequential reactions in separated microfluidic devices, as
shown in Fig. 10B [186]. The multi-step synthesis of magneto-
fluorescent core-shell γ -Fe2 O3 /silica nanoparticles consists of
three successive steps. First, (3-aminopropyl) -triethoxysilane
(APTES) is grafted onto γ -Fe2 O3 grains. Next, rhodamine B isoth-
iocyanate (RITC) -labeled APTES and tetraethyl orthosilicate (TEOS)
are mixed. Finally, the nanoparticles are encapsulated by the

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14 K.-K. Kang et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2018) 1–18

Fig. 9. (A) Schematic illustration of the microfluidic device for the synthesis of TiO2 nanoparticles [184]. (B) Optical microscopic image of the interface between the or-
ganic solvent (cyclohexane) and water in the microchannel [184]. Reproduced with permission from Wang et al. [184]. Chem. Commun.; published by the Royal Society of
Chemistry, 2002. (C) Co-flowing type microfluidic device for the synthesis of TiO2 nanoparticles [185]. (D) TEM image of the synthesized TiO2 nanoparticles in a microfluidic
device [185]. Reproduced with permission from Cottam et al. [185]. Lab. Chip; published by the Royal Society of Chemistry, 2007.

Fig. 10. (A) Droplet pairing module and fusion module for iron oxide nanoparticle synthesis [80]. Reproduced with permission from Frenz et al. [80]. Angew. Chem. Int. Ed.;
published by Wiley InterScience, 2008. (B) Continuous multistep preparation of magneto-fluorescent core-shell γ -Fe2 O3 /silica nanoparticles in microfluidic devices [186].
Reproduced with permission from Abou-Hassan et al. [186]. Angew. Chem. Int. Ed.; published by Wiley InterScience, 2009.

fluorescent polysiloxane layer through hydrolysis and condensation
of the silica precursor with ammonia. The particles synthesized
in the microfluidic reactor had almost the same shape and size as
the particles synthesized in the bulk and were synthesized rapidly.
3.4. Spherical porous inorganic particles
Silica is the most abundant material on the planet and has
also been given much attention in various research fields. For
these reasons, many synthesis methods for producing silica with
uniform size and shape have been developed. One of these, the
Stöber method, is based on sol-gel chemistry and is a conventional
approach for the synthesis of spherical silica nanoparticles. The
synthesis method involves hydrolysis and condensation of silicon
alkoxides in alcohol with ammonium hydroxide as a catalyst and
produces prepared monodisperse silica spheres of predetermined
sizes in the range 0.05–2 μm [187]. Since this method was re-
ported, it is still widely used as a synthetic method for silica
nanoparticles. However, silica has several limitations in applica-
tion, and the most serious one is due to the morphology of silica

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of the Taiwan Institute of Chemical Engineers (2018), https://doi.org/10.1016/j.jtice.2018.08.027
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K.-K. Kang et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2018) 1–18
Fig. 11. Synthesis of spherical inorganic functional materials using droplet-based
microfluidics. (A) SEM image and (B) TEM image of representative spherical meso-
porous materials synthesized by VOAG (vibrating orifice aerosol generator) [188].
Reproduced with permission from Rama Rao et al. [188], Advanced Materials; pub-
lished by John Wiley and Sons, 2002. (C) Schematic illustration of a microfluidic
device for synthesis of spherical mesoporous particles, and (D) representative SEM
image of the synthesized spherical mesoporous particle [189]. Reproduced with per-
mission from Lee et al. [189], Advanced Materials; published by John Wiley and
Sons, 2008. (E) Optical microscopy image of droplets of the silica precursor solu-
tion emulsified in a flow-focusing microfluidic device in hexadecane, and (F) the
TEM image of prepared spherical mesoporous particles [190]. Reproduced with per-
mission from Carrol et al. [190], Langmuir; published by the American Chemical
Society, 2008.
prepared by the Stöber method. Subsequently, new functional
silica-based materials have been developed and synthesized in
terms of improvement in functionality. Mesoporous materials are
one of the most representative silica-based functional materials.
However, it is difficult to control the shape of mesoporous par-
ticles because of the complexity of the formation mechanism of
mesoporous materials. Therefore, studies using microfluidics for
the synthesis of mesoporous materials with spherical uniform
shapes and sizes have been carried out. Fig. 11 shows the repre-
sentative synthesis of mesoporous materials using droplet-based
microfluidic systems.
Synthesis of mesoporous materials using droplet-based mi-
crofluidics was reported by Rama Rao et al. [188]. The particles
were synthesized using VOAG (vibrating orifice aerosol generator),
which is slightly different from the well-known conventional
droplet-based microfluidic devices. VOAG has a micrometer-sized
orifice for droplet production, but the resulting droplet is ejected
into a gas phase and solidified into particles. Synthesis of spher-
ical mesoporous particles of 5 to 10 μm in size were produced
by droplets generated from VOAG, and the synthesis proceeded
rapidly within a few seconds. The size and geometry of the
microfluidic channels flanking the surface and the composition
parameters, such as the flow rate and oil type of the precursor
solution and the oil, were changed and easily controlled. In addi-
Please cite this article as: K.-K. Kang et al., Recent progress in the synthesis of inorganic particulate materials using microfluidics, Journal
of the Taiwan Institute of Chemical Engineers (2018), https://doi.org/10.1016/j.jtice.2018.08.027
[m5G;November 12, 2018;11:33]
15
tion, the synthesis process is expandable and can be continuously
produced under appropriate conditions. The synthesis of meso-
porous materials synthesized by flow-focusing type microfluidic
devices has been reported. Lee et al. reported the synthesis of
monodisperse ordered mesoporous silica microspheres using a
droplet-based microfluidic device in the form of a flow-focusing
channel, called one-step in situ synthesis [189]. This method
combines rapid solvent diffusion-induced self-assembly within the
microfluidic channel after the creation of uniform droplets in a
uniform microfluidic channel. Carroll and co-workers also synthe-
sized spherical mesoporous materials using droplets generated by
flow-focusing microfluidic devices [190]. The solvent was diffused
and discharged from the droplet, and the process was conducted
in such a manner as to induce concentration of the interfacial ac-
tive agent and micellar growth. The synthesized materials were of
two types, individually separated particles and interconnected par-
ticles, both of which had well-developed mesoporous pores. Both
methods have shown that the size of mesoporous silica particles
can be systematically controlled by controlling the fluid conditions.
4. Conclusion and outlook
In this review, the results of studies on the synthesis of in-
organic materials were discussed, which were performed using
various microfluidic devices. According to this survey, we can
obtain the following conclusions. Microfluidics can be a useful
platform for the synthesis of inorganic materials. Furthermore,
using microfluidic devices in the synthesis of inorganic materi-
als, it was found not only that fine particles of well-controlled
physicochemical properties could be synthesized, which were
difficult to obtain by the conventional synthesis method, but also
that functional fine particles with new physicochemical properties
could be synthesized. The most distinctive features were in the
properties of materials made using microfluidics devices. Various
inorganic particles prepared using the microfluidic devices can
exhibit better properties than particles prepared through conven-
tional methods. In addition, these unique features can be applied
to a wide variety of applications, and it is believed that this
could provide a platform for a strong raw material for research
in the fields of medicine, optics, and electronics, including basic
science research. Consequently, although the synthesis of inorganic
materials using microfluidic devices is still in the research stage, if
research on microfluidic devices with new structures and shapes
continues, it will be a very important platform for the discovery
of new inorganic materials for various applications.
Acknowledgments
This work is supported by the Space Core Technology Pro-
gram (NRF-2013M1A3A3A02042262), the Basic Core Technology
Development Program for the Oceans and the Polar Regions
(NRF-2015M1A5A1037054), and Global Research Laboratory (NRF-
2015K1A1A2033054) through the National Research Foundation of
Korea (NRF) funded by the Ministry of Science, ICT (Information
and Communication Technologies).
References
[1] Nagarwal RC, Kant S, Singh PN, Maiti P, Pandit JK. Polymeric nanoparticu-
late system: a potential approach for ocular drug delivery. J Control Release
2009;136:2–13.
[2] Velasco D, Tumarkin E, Kumacheva E. Microfluidic encapsulation of cells in
polymer microgels. Small 2012;8:1633–42.
[3] Pardeike J, Hommoss A, Muller RH. Lipid nanoparticles (SLN, NLC) in cosmetic
and pharmaceutical dermal products. Int J Pharm 2009;366:170–84.
[4] Watts P, Haswell SJ. Microfluidic combinatorial chemistry. Curr Opin Chem
Biol 2003;7:380–7.
[5] Wyss HM, Franke T, Mele E, Weitz DA. Capillary micromechanics: measuring
the elasticity of microscopic soft objects. Soft Matter 2010;6:4550–5.
JID: JTICE
ARTICLE IN PRESS
16 K.-K. Kang et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2018) 1–18
[6] Kleinberger RM, Burke NAD, Dalnoki-Veress K, Stöver HDH. Systematic study
of alginate-based microcapsules by micropipette aspiration and confocal flu-
orescence microscopy. Mater Sci Eng C 2013;33:4295–304.
[7] Wood V, Panzer MJ, Caruge JM, Halpert JE, Bawendi MG, Bulovic V. Air-stable
operation of transparent, colloidal quantum dot based LEDs with a unipolar
device architecture. Nano Lett 2010;10:24–9.
[8] Comiskey B, Albert JD, Yoshizawa H, Jacobson J. An electrophoretic ink for
all-printed reflective electronic displays. Nature 1998;394:253–5.
[9] Rhodes R, Asghar S, Krakow R, Horie M, Wang ZJ, Turner ML, et al. Hybrid
polymer solar cells: from the role colloid science could play in bringing de-
ployment closer to a study of factors affecting the stability of non-aqueous
ZnO dispersions. Colloid Surface A 2009;343:50–6.
[10] Grosse C, Delgado AV. Dielectric dispersion in aqueous colloidal systems. Curr
Opin Colloid In 2010;15:145–59.
[11] Chung BG, Lee KH, Khademhosseini A, Lee SH. Microfluidic fabrication of mi-
croengineered hydrogels and their application in tissue engineering. Lab Chip
2012;12:45–59.
[12] Kim SH, Lee SY, Yang SM, Yi GR. Self-assembled colloidal structures for pho-
tonics. Npg Asia Mater 2011;3:25–33.
[13] Thangawng AL, Howell PB, Spillmann CM, Naciri J, Ligler FS. UV polymeriza-
tion of hydrodynamically shaped fibers. Lab Chip 2011;11:1157–60.
[14] Sacanna S, Pine DJ. Shape-anisotropic colloids: Building blocks for complex
assemblies. Curr Opin Colloid In 2011;16:96–105.
[15] Gouin S. Microencapsulation: industrial appraisal of existing technologies and
trends. Trends Food Sci Tech 2004;15:330–47.
[16] De La Vega JC, Elischer P, Schneider T, Hafeli UO. Uniform polymer mi-
crospheres: monodispersity criteria, methods of formation and applications.
Nanomedicine-Uk 2013;8:265–85.
[17] Oh SW, Kim CW, Cha HJ, Pal U, Kang YS. Encapsulated-dye all-organic
charged colored ink nanoparticles for electrophoretic image display. Adv
Mater 2009;21:4987–91.
[18] Stanway R. Smart fluids: current and future developments. Mater Sci
Tech-Lond 2004;20:931–9.
[19] Neethirajan S, Kobayashi I, Nakajima M, Wu D, Nandagopal S, Lin F.
Microfluidics for food, agriculture and biosystems industries. Lab Chip
2011;11:1574–86.
[20] Kawakatsu T, Kikuchi Y, Nakajima M. Regular-sized cell creation in mi-
crochannel emulsification by visual microprocessing method. J Am Oil Chem
Soc 1997;74:317–21.
[21] Nakashima T, Shimizu M, Kukizaki M. Particle control of emulsion by
membrane emulsification and its applications. Adv Drug Deliver Rev
20 0 0;45:47–56.
[22] Nakashima T, Shimizu M, Kukizaki M. Membrane emulsification by microp-
orous glass. Key Eng Mater 1992;61–62:513–16.
[23] Ganan-Calvo AM. Generation of steady liquid microthreads and micron-sized
monodisperse sprays in gas streams. Phys Rev Lett 1998;80:285–8.
[24] Mason TG, Bibette J. Shear rupturing of droplets in complex fluids. Langmuir
1997;13:4600–13.
[25] Perrin P. Amphiphilic copolymers: a new route to prepare ordered monodis-
perse emulsions. Langmuir 1998;14:5977–9.
[26] Song H, Chen DL, Ismagilov RF. Reactions in droplets in microflulidic chan-
nels. Angew Chem Int Edit 2006;45:7336–56.
[27] Theberge AB, Courtois F, Schaerli Y, Fischlechner M, Abell C, Hollfelder F,
Huck WTS. Microdroplets in microfluidics: an evolving platform for discov-
eries in chemistry and biology. Angew Chem Int Edit 2010;49:5846–68.
[28] Swihart MT. Vapor-phase synthesis of nanoparticles. Curr Opin Colloid In
2003;8:127–33.
[29] Aymonier C, Loppinet-Serani A, Reverón H, Garrabos Y, Cansell F. Re-
view of supercritical fluids in inorganic materials science. J Supercrit Fluid
2006;38:242–51.
[30] Whitesides GM. The origins and the future of microfluidics. Nature
2006;442:368–73.
[31] Stone HA, Stroock AD, Ajdari A. Engineering flows in small devices: microflu-
idics toward a lab-on-a-chip. Annu Rev Fluid Mech 2004;36:381–411.
[32] Stein B, Zopes D, Schmudde M, Schneider R, Mohsen A, Goroncy C, et al. Ki-
netics of aggregation and growth processes of PEG-stabilised mono-and mul-
tivalent gold nanoparticles in highly concentrated halide solutions. Faraday
Discuss 2015;181:85–102.
[33] Mer VKL. Nucleation in phase transitions. Ind Eng Chem 1952;44:1270–7.
[34] LaMer VK, Dinegar RH. Theory, production and mechanism of formation of
monodispersed hydrosols. J Am Chem Soc 1950;72:4847–54.
[35] Hyeon T Chemical synthesis of magnetic nanoparticles. Chem Commun
2003:927–34.
[36] Ostwald W. Über die vermeintliche Isomerie des roten und gelben Queck-
silberoxyds und die Oberflächenspannung fester Körper. Zeitschrift für
physikalische Chemie 1900;34:495–503.
[37] Taylor P. Ostwald ripening in emulsions. Adv Colloid Interface Sci
1998;75:107–63.
[38] Kabalnov A. Ostwald Ripening and Related Phenomena. J Dispersion Sci Tech-
nol 2001;22:1–12.
[39] Huang Z, Su M, Yang Q, Li Z, Chen S, Li Y, et al. A general patterning approach
by manipulating the evolution of two-dimensional liquid foams. Nat Commun
2017;8:14110.
[40] Ratke L, Voorhees PW. Growth and coarsening: ostwald ripening in material
processing. Springer Science & Business Media; 2013.
Please cite this article as: K.-K. Kang et al., Recent progress in the synthesis of inorganic particulate materials using microfluidics, Journal
of the Taiwan Institute of Chemical Engineers (2018), https://doi.org/10.1016/j.jtice.2018.08.027
[m5G;November 12, 2018;11:33]
[41] Hyde ED, Seyfaee A, Neville F, Moreno-Atanasio R. Colloidal silica particle
synthesis and future industrial manufacturing pathways: a review. Ind Eng
Chem Res 2016;55:8891–913.
[42] Voorhees PW. The theory of Ostwald ripening. J Stat Phys 1985;38:231–52.
[43] Yu WW, Qu L, Guo W, Peng X. Experimental determination of the extinction
coefficient of CdTe, CdSe, and CdS nanocrystals. Chem Mat 2003;15:2854–60.
[44] Iler RK. The chemistry of silica 1979. New York: J. Wiley and Sons; 1979.
[45] Brinker CJ, Scherer GW. Sol-gel science: the physics and chemistry of sol-gel
processing. Academic Press; 2013.
[46] Yang HG, Zeng HC. Preparation of hollow anatase TiO2 nanospheres via Ost-
wald ripening. J Phys Chem B 2004;108:3492–5.
[47] Yec CC, Zeng HC. Synthesis of complex nanomaterials via ostwald ripening. J
Mater Chem A 2014;2:4843–51.
[48] Zhang Z, Wang Z, He S, Wang C, Jin M, Yin Y. Redox reaction induced ost-
wald ripening for size-and shape-focusing of palladium nanocrystals. Chem
Sci 2015;6:5197–203.
[49] Irzhak V. Digestive ripening of nanoparticles. Russ J Phys Chem A
2017;91:1502–6.
[50] Prasad B, Stoeva SI, Sorensen CM, Klabunde KJ. Digestive ripening of
thiolated gold nanoparticles: the effect of alkyl chain length. Langmuir
2002;18:7515–20.
[51] Stoeva S, Klabunde KJ, Sorensen CM, Dragieva I. Gram-scale synthesis of
monodisperse gold colloids by the solvated metal atom dispersion method
and digestive ripening and their organization into two-and three-dimensional
structures. J Am Chem Soc 2002;124:2305–11.
[52] Lin X, Wang G, Sorensen C, Klabunde K. Formation and dissolution of
gold nanocrystal superlattices in a colloidal solution. J Phys Chem B
1999;103:5488–92.
[53] Watzky MA, Finke RG. Nanocluster size-control and “Magic Number” inves-
tigations. experimental tests of the “Living-metal polymer” concept and of
mechanism-based size-control predictions leading to the syntheses of irid-
ium (0) nanoclusters centering about four sequential magic numbers. Chem
Mat 1997;9:3083–95.
[54] Zheng H, Smith RK, Jun Y-w, Kisielowski C, Dahmen U, Alivisatos AP. Ob-
servation of single colloidal platinum nanocrystal growth trajectories. Science
2009;324:1309–12.
[55] Niederberger M, Cölfen H. Oriented attachment and mesocrystals: non-clas-
sical crystallization mechanisms based on nanoparticle assembly. Phys Chem
Chem Phys 2006;8:3271–87.
[56] Li D, Nielsen MH, Lee JR, Frandsen C, Banfield JF, De Yoreo JJ. Direction-spe-
cific interactions control crystal growth by oriented attachment. Science
2012;336:1014–18.
[57] Banfield JF, Welch SA, Zhang H, Ebert TT, Penn RL. Aggregation-based crys-
tal growth and microstructure development in natural iron oxyhydroxide
biomineralization products. Science 20 0 0;289:751–4.
[58] Penn RL, Banfield JF. Morphology development and crystal growth in
nanocrystalline aggregates under hydrothermal conditions: insights from ti-
tania. Geochim Cosmochim Acta 1999;63:1549–57.
[59] van Huis MA, Kunneman LT, Overgaag K, Xu Q, Pandraud G, Zandbergen HW,
et al. Low-temperature nanocrystal unification through rotations and re-
laxations probed by in situ transmission electron microscopy. Nano Lett
2008;8:3959–63.
[60] Christopher GF, Anna SL. Microfluidic methods for generating continuous
droplet streams. J Phys D Appl Phys 2007;40. R319–RR36.
[61] Squires TM, Quake SR. Microfluidics: Fluid physics at the nanoliter scale. Rev
Mod Phys 2005;77:977–1026.
[62] Zhao CX, Middelberg APJ. Two-phase microfluidic flows. Chem Eng Sci
2011;66:1394–411.
[63] Abate AR, Poitzsch A, Hwang Y, Lee J, Czerwinska J, Weitz DA. Impact
of inlet channel geometry on microfluidic drop formation. Phys Rev E
2009;80:026310–14.
[64] Ménétrier-Deremble L, Tabeling P. Droplet breakup in microfluidic junctions
of arbitrary angles. Phys Rev E 2006;74:035303.
[65] Anna SL, Mayer HC. Microscale tipstreaming in a microfluidic flow focusing
device. Phys Fluids 2006;18:121512–21.
[66] Seemann R, Brinkmann M, Pfohl T, Herminghaus S. Droplet based microflu-
idics. Rep Prog Phys 2012;75:016601–42.
[67] Nunes JK, Tsai SSH, Wan J, Stone HA. Dripping and jetting in microfluidic
multiphase flows applied to particle and fibre synthesis. J Phys D Appl Phys
2013;46:114002–21.
[68] Cushing BL, Kolesnichenko VL, O’Connor CJ. Recent advances in
the liquid-phase syntheses of inorganic nanoparticles. Chem Rev
2004;104:3893–946.
[69] Bibette J, Calderon FL, Poulin P. Emulsions: basic principles. Rep Prog Phys
1999;62:969–1033.
[70] Roach LS, Song H, Ismagilov RF. Controlling nonspecific protein adsorption in
a plug-based microfluidic system by controlling interfacial chemistry using
fluorous-phase surfactants. Anal Chem 2005;77:785–96.
[71] Utada AS, Fernandez-Nieves A, Stone HA, Weitz DA. Dripping to jetting tran-
sitions in coflowing liquid streams. Phys Rev Lett 2007;99:094502–5.
[72] Guillot P, Colin A, Ajdari A. Stability of a jet in confined pressure-driven
biphasic flows at low Reynolds number in various geometries. Phys Rev E
2008;78:016307–19.
[73] Herrada MA, Ganan-Calvo AM, Guillot P. Spatiotemporal instability of a con-
fined capillary jet. Phys Rev E 2008;78:046312–18.
JID: JTICE
ARTICLE IN PRESS
K.-K. Kang et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2018) 1–18
[74] Gu H, Duits MHG, Mugele F. Droplets formation and merging in two-phase
flow microfluidics. Int J Mol Sci 2011;12:2572–97.
[75] Thorsen T, Roberts RW, Arnold FH, Quake SR. Dynamic pattern formation in
a vesicle-generating microfluidic device. Phys Rev Lett 2001;86:4163–6.
[76] Link DR, Anna SL, Weitz DA, Stone HA. Geometrically mediated breakup of
drops in microfluidic devices. Phys Rev Lett 2004;92:054503.
[77] Jullien M-C, Tsang Mui Ching M-J, Cohen C, Menetrier L, Tabeling P. Droplet
breakup in microfluidic T-junctions at small capillary numbers. Phys Fluids
20 09;21:0720 01.
[78] Lin R, Fisher JS, Simon MG, Lee AP. Novel on-demand droplet generation for
selective fluid sample extraction. Biomicrofluidics 2012;6:024103.
[79] Abate AR, Weitz DA. Air-bubble-triggered drop formation in microfluidics. Lab
Chip 2011;11:1713–16.
[80] Frenz L, El Harrak A, Pauly M, Bégin-Colin S, Griffiths AD, Baret JC.
Droplet-based microreactors for the synthesis of magnetic iron oxide
nanoparticles. Angew Chem Int Edit 2008;47:6817–20.
[81] Hung L-H, Choi KM, Tseng W-Y, Tan Y-C, Shea KJ, Lee AP. Alternating droplet
generation and controlled dynamic droplet fusion in microfluidic device for
CdS nanoparticle synthesis. Lab Chip 2006;6:174–8.
[82] Rhee M, Liu P, Meagher RJ, Light YK, Singh AK. Versatile on-demand droplet
generation for controlled encapsulation. Biomicrofluidics 2014;8:034112.
[83] Ding Y, i Solvas XC. “V-junction”: a novel structure for high-speed generation
of bespoke droplet flows. Analyst 2015;140:414–21.
[84] Tangen U, Sharma A, Wagler P, McCaskill JS. On demand nanoliter-scale mi-
crofluidic droplet generation, injection, and mixing using a passive microflu-
idic device. Biomicrofluidics 2015;9:014119.
[85] Wang L, Zhang Y, Cheng L. Magic microfluidic T-junctions: valving and bub-
bling. Chaos Solitons Fractals 2009;39:1530–7.
[86] Khoshmanesh K, Almansouri A, Albloushi H, Yi P, Soffe R, Kalantar-Zadeh K.
A multi-functional bubble-based microfluidic system. Sci Rep 2015;5:9942.
[87] van Steijn V, Kleijn CR, Kreutzer MT. Flows around confined bubbles and their
importance in triggering pinch-off. Phys Rev Lett 2009;103:214501–4.
[88] Garstecki P, Fuerstman MJ, Stone HA, Whitesides GM. Formation of droplets
and bubbles in a microfluidic T-junction - scaling and mechanism of
break-up. Lab Chip 2006;6:437–46.
[89] Guillot P, Colin A. Stability of parallel flows in a microchannel after a T junc-
tion. Phys Rev E 2005;72:066301–4.
[90] Gupta A, Murshed SMS, Kumar R. Droplet formation and stability of flows in
a microfluidic T-junction. Appl Phys Lett 2009;94:164107.
[91] Gupta A, Kumar R. Flow regime transition at high capillary numbers in a
microfluidic T-junction: Viscosity contrast and geometry effect. Phys Fluids
2010;22:122001–11.
[92] Tice JD, Lyon AD, Ismagilov RF. Effects of viscosity on droplet formation and
mixing in microfluidic channels. Anal Chim Acta 2004;507:73–7.
[93] Anna SL, Bontoux N, Stone HA. Formation of dispersions using "flow focusing"
in microchannels. Appl Phys Lett 2003;82:364–6.
[94] Cubaud T, Mason TG. Capillary threads and viscous droplets in square mi-
crochannels. Phys Fluids 2008;20:053302–13.
[95] Yobas L, Martens S, Ong WL, Ranganathan N. High-performance flow-focusing
geometry for spontaneous generation of monodispersed droplets. Lab Chip
2006;6:1073–9.
[96] Humphry KJ, Ajdari A, Fernandez-Nieves A, Stone HA, Weitz DA. Suppres-
sion of instabilities in multiphase flow by geometric confinement. Phys Rev
E 2009;79:056310–14.
[97] Berthier J, Le Vot S, Tiquet P, David N, Lauro D, Benhamou PY, et al. Highly
viscous fluids in pressure actuated flow focusing devices. Sensor Actuat a–
Phys 2010;158:140–8.
[98] Funfschilling D, Debas H, Li HZ, Mason TG. Flow-field dynamics during
droplet formation by dripping in hydrodynamic-focusing microfluidics. Phys
Rev E 2009;80:015301–4.
[99] Lapierre F, Wu N, Zhu Y. Influence of flow rate on the droplet genera-
tion process in a microfluidic chip. In: Proceedings of the smart nano-micro
materials and devices: international society for optics and photonics; 2011.
p. 82040H–82046H.
[100] Lee W, Walker LM, Anna SL. Impact of viscosity ratio on the dynamics of
droplet breakup in a microfluidic flow focusing device. AIP Publishing; 2008.
THE XV INTERNATIONAL CONGRESS ON RHEOLOGY: The Society of Rheology
80th Annual Meeting p. 994–6.
[101] Lee W, Walker LM, Anna SL. Role of geometry and fluid properties in
droplet and thread formation processes in planar flow focusing. Phys Fluids
2009;21:032103–16.
[102] Ong WL, Hua JS, Zhang BL, Teo TY, Zhuo JL, Nguyen NT, et al. Experimental
and computational analysis of droplet formation in a high-performance flow–
focusing geometry. Sensor Actuat a-Phys 2007;138:203–12.
[103] Peng L, Yang M, Guo SS, Liu W, Zhao XZ. The effect of interfacial tension on
droplet formation in flow-focusing microfluidic device. Biomed Microdevices
2011;13:559–64.
[104] Garstecki P, Stone HA, Whitesides GM. Mechanism for flow-rate controlled
breakup in confined geometries: a route to monodisperse emulsions. Phys
Rev Lett 2005;94:164501–4.
[105] Nie ZH, Seo MS, Xu SQ, Lewis PC, Mok M, Kumacheva E, et al. Emulsification
in a microfluidic flow-focusing device: effect of the viscosities of the liquids.
Microfluid Nanofluid 2008;5:585–94.
[106] Umbanhowar PB, Prasad V, Weitz DA. Monodisperse emulsion generation via
drop break off in a coflowing stream. Langmuir 20 0 0;16:347–51.
Please cite this article as: K.-K. Kang et al., Recent progress in the synthesis of inorganic particulate materials using microfluidics, Journal
of the Taiwan Institute of Chemical Engineers (2018), https://doi.org/10.1016/j.jtice.2018.08.027
[m5G;November 12, 2018;11:33]
17
[107] Cramer C, Fischer P, Windhab EJ. Drop formation in a co-flowing ambient
fluid. Chem Eng Sci 2004;59:3045–58.
[108] Jeong WJ, Kim JY, Choo J, Lee EK, Han CS, Beebe DJ, et al. Continuous fab-
rication of biocatalyst immobilized microparticles using photopolymerization
and immiscible liquids in microfluidic systems. Langmuir 2005;21:3738–41.
[109] Utada AS, Fernandez-Nieves A, Gordillo JM, Weitz DA. Absolute instability of
a liquid jet in a coflowing stream. Phys Rev Lett 20 08;10 0:014502–5.
[110] Guillot P, Colin A, Utada AS, Ajdari A. Stability of a jet in confined
pressure-driven biphasic flows at low Reynolds numbers. Phys Rev Lett
2007;99:104502–5.
[111] Castro-Hernandez E, Gundabala V, Fernandez-Nieves A, Gordillo JM. Scaling
the drop size in coflow experiments. New J Phys 2009;11:075021–38.
[112] Cordero ML, Gallaire F, Baroud CN. Quantitative analysis of the dripping and
jetting regimes in co-flowing capillary jets. Phys Fluids 2011;23:094111–19.
[113] Rayleigh L. XVI. On the instability of a cylinder of viscous liquid under capil-
lary force. The London, Edinburgh, and Dublin Philosophical Magazine and J
Sci 1892;34:145–54.
[114] Leib S, Goldstein M. Convective and absolute instability of a viscous liquid jet.
Phys Fluids 1986;29:952–4.
[115] Vansaarloos W. Front propagation into unstable states .2. Linear ver-
sus nonlinear marginal stability and rate of convergence. Phys Rev A
1989;39:6367–90.
[116] Vansaarloos W. Front propagation into unstable states - marginal stability as
a dynamical mechanism for velocity selection. Phys Rev A 1988;37:211–29.
[117] Huerre P, Monkewitz PA. Local and global instabilities in spatially developing
flows. Annu Rev Fluid Mech 1990;22:473–537.
[118] Chomaz JM. Global instabilities in spatially developing flows: non-normality
and nonlinearity. Annu Rev Fluid Mech 2005;37:357–92.
[119] Guillot P, Ajdari A, Goyon J, Joanicot M, Colin A. Droplets and jets in microflu-
idic devices. C R Chim 2009;12:247–57.
[120] Mullin JW. Crystallization. Butterworth-Heinemann; 2001.
[121] Kumar S, Nann T. Shape control of II–VI semiconductor nanomaterials. Small
2006;2:316–29.
[122] Burda C, Chen X, Narayanan R, El-Sayed MA. Chemistry and properties of
nanocrystals of different shapes. Chem Rev 2005;105:1025–102.
[123] Peng X. Mechanisms for the shape-control and shape-evolution of colloidal
semiconductor nanocrystals. Adv Mater 2003;15:459–63.
[124] Nair PS, Fritz KP, Scholes GD. Evolutionary shape control during colloidal
quantum-dot growth. Small 2007;3:481–7.
[125] Kumar S, Jones M, Lo SS, Scholes GD. Nanorod heterostructures showing pho-
toinduced charge separation. Small 2007;3:1633–9.
[126] Peng ZA, Peng X. Mechanisms of the shape evolution of CdSe nanocrystals. J
Am Chem Soc 2001;123:1389–95.
[127] Murray C, Norris DJ, Bawendi MG. Synthesis and characterization of nearly
monodisperse CdE (E= sulfur, selenium, tellurium) semiconductor nanocrys-
tallites. J Am Chem Soc 1993;115:8706–15.
[128] Hu J, Li L-s, Yang W, Manna L, Wang L-w, Alivisatos AP. Linearly
polarized emission from colloidal semiconductor quantum rods. Science
2001;292:2060–3.
[129] Gur I, Fromer NA, Chen C-P, Kanaras AG, Alivisatos AP. Hybrid solar cells with
prescribed nanoscale morphologies based on hyperbranched semiconductor
nanocrystals. Nano Lett 2007;7:409–14.
[130] Yu WW, Wang YA, Peng X. Formation and stability of size-, shape-, and struc-
ture-controlled CdTe nanocrystals: ligand effects on monomers and nanocrys-
tals. Chem Mat 20 03;15:430 0–8.
[131] Murray CB, Kagan C, Bawendi M. Synthesis and characterization of monodis-
perse nanocrystals and close-packed nanocrystal assemblies. Annu Rev Mater
Sci 20 0 0;30:545–610.
[132] Yin Y, Alivisatos AP. Colloidal nanocrystal synthesis and the organic–inorganic
interface. Nature 2005;437:664–70.
[133] Daniel L, Fedlheim CAF. Metal nanoparticles: synthesis, characterization, and
applications. CRC Press; 2001.
[134] Murphy C, Sau T, Gole A, Orendorff C, Gao J, Gou L, et al. Anisotropic metal
nanoparticles: Synthesis, assembly, and optical applications. J Phys Chem B
2005;109:13857–70.
[135] Yguerabide J, Yguerabide EE. Light-scattering submicroscopic particles as
highly fluorescent analogs and their use as tracer labels in clinical and
biological applications: II. Experimental Characterization. Anal Biochem
1998;262:157–76.
[136] Jain PK, Huang X, El-Sayed IH, El-Sayed MA. Review of some interesting sur-
face plasmon resonance-enhanced properties of noble metal nanoparticles
and their applications to biosystems. Plasmonics 2007;2:107–18.
[137] Pelton M, Aizpurua J, Bryant G. Metal-nanoparticle plasmonics. Laser Photon
Rev 2008;2:136–59.
[138] Eustis S, El-Sayed MA. Why gold nanoparticles are more precious than pretty
gold: noble metal surface plasmon resonance and its enhancement of the ra-
diative and nonradiative properties of nanocrystals of different shapes. Chem
Soc Rev 2006;35:209–17.
[139] Tolaymat TM, El Badawy AM, Genaidy A, Scheckel KG, Luxton TP,
Suidan M. An evidence-based environmental perspective of manufactured
silver nanoparticle in syntheses and applications: a systematic review
and critical appraisal of peer-reviewed scientific papers. Sci Total Environ
2010;408:999–1006.
[140] Kelly KL, Coronado E, Zhao LL, Schatz GC. The optical properties of metal
nanoparticles: the influence of size, shape, and dielectric environment. J Phys
Chem B 2003;107:668–77.
JID: JTICE
ARTICLE IN PRESS
18 K.-K. Kang et al. / Journal of the Taiwan Institute of Chemical Engineers 000 (2018) 1–18
[141] Welch CM, Compton RG. The use of nanoparticles in electroanalysis: a review.
Anal Bioanal Chem 2006;384:601–19.
[142] Yan N, Xiao C, Kou Y. Transition metal nanoparticle catalysis in green sol-
vents. Coord Chem Rev 2010;254:1179–218.
[143] Daniel M-C, Astruc D. Gold nanoparticles: assembly, supramolecular chem-
istry, quantum-size-related properties, and applications toward biology, catal-
ysis, and nanotechnology. Chem Rev 2004;104:293–346.
[144] Link S, El-Sayed MA. Shape and size dependence of radiative, non-radia-
tive and photothermal properties of gold nanocrystals. Ind Rev Phys Chem
20 0 0;19:409–53.
[145] Mohamed MB, Volkov V, Link S, El-Sayed MA. Thelightning’gold nanorods:
fluorescence enhancement of over a million compared to the gold metal.
Chem Phys Lett 20 0 0;317:517–23.
[146] Sönnichsen C, Franzl T, Wilk T, von Plessen G, Feldmann J, Wilson O,
et al. Drastic reduction of plasmon damping in gold nanorods. Phys Rev Lett
2002;88:077402.
[147] Wagner J, Köhler J. Continuous synthesis of gold nanoparticles in a microre-
actor. Nano Lett 2005;5:685–91.
[148] Wagner J, Tshikhudo T, Koehler J. Microfluidic generation of metal nanoparti-
cles by borohydride reduction. Chem Eng J 2008;135. S104–S1S9.
[149] Boleininger J, Kurz A, Reuss V, Sönnichsen C. Microfluidic continuous flow
synthesis of rod-shaped gold and silver nanocrystals. Phys Chem Chem Phys
2006;8:3824–7.
[150] Thiele M, Knauer A, Malsch D, Csaki A, Henkel T, Kohler JM, et al. Combi-
nation of microfluidic high-throughput production and parameter screening
for efficient shaping of gold nanocubes using Dean-flow mixing. Lab Chip
2017;17:1487–95.
[151] Baumgard J, Vogt A-M, Kragl U, Jähnisch K, Steinfeldt N. Application of mi-
crostructured devices for continuous synthesis of tailored platinum nanopar-
ticles. Chem Eng J 2013;227:137–44.
[152] Song Y, Kumar CSSR, Hormes J. Synthesis of palladium nanoparticles us-
ing a continuous flow polymeric micro reactor. J Nanosci Nanotechnol
2004;4:788–93.
[153] Karim AM, Al Hasan N, Ivanov S, Siefert S, Kelly RT, Hallfors NG, et al. Synthe-
sis of 1 nm Pd nanoparticles in a microfluidic reactor: insights from in situ
X-ray absorption fine structure spectroscopy and small-angle X-ray scattering.
J Phys Chem C 2015;119:13257–67.
[154] Liu H, Huang J, Sun D, Lin L, Lin W, Li J, et al. Microfluidic biosynthesis of
silver nanoparticles: effect of process parameters on size distribution. Chem
Eng J 2012;209:568–76.
[155] Xu L, Peng JH, Yan M, Zhang D, Shen AQ. Droplet synthesis of silver nanopar-
ticles by a microfluidic device. Chem Eng Process 2016;102:186–93.
[156] Ke T, Zeng XF, Wang JX, Le Y, Chu GW, Chen JF, et al. Microfluidic synthesis
of monodisperse Cu nanoparticles in aqueous solution. J Nanosci Nanotechnol
2011;11:5154–8.
[157] Song YJ, Doomes EE, Prindle J, Tittsworth R, Hormes J, Kumar C. Investigations
into sulfobetaine-stabilized cu nanoparticle formation: Toward development
of a microfluidic synthesis. J Phys Chem B 2005;109:9330–8.
[158] Zeng C, Wang C, Wang F, Zhang Y, Zhang L. A novel vapor–liquid segmented
flow based on solvent partial vaporization in microstructured reactor for con-
tinuous synthesis of nickel nanoparticles. Chem Eng J 2012;204:48–53.
[159] Song Y, Modrow H, Henry LL, Saw CK, Doomes E, Palshin V, et al. Microfluidic
synthesis of cobalt nanoparticles. Chem Mat 2006;18:2817–27.
[160] Song Y, Zhang T, Yang W, Albin S, Henry LL. Fine crystal structure transition
of cobalt nanoparticles formed in a microfluidic reactor. Cryst Growth Des
2008;8:3766–72.
[161] Knauer A, Thete A, Li S, Romanus H, Csaki A, Fritzsche W, et al. Au/Ag/Au
double shell nanoparticles with narrow size distribution obtained by contin-
uous micro segmented flow synthesis. Chem Eng J 2011;166:1164–9.
[162] Moras JD, Strandberg B, Suc D, Wilson K. Semiconductor clusters, nanocrys-
tals, and quantum dots. Science 1996;271:933.
[163] Hines MA, Guyot-Sionnest P. Synthesis and characterization of strongly lumi-
nescing ZnS-capped CdSe nanocrystals. J Phys Chem 1996;100:468–71.
[164] Murray CB, Kagan CR, Bawendi MG. Synthesis and characterization of
monodisperse nanocrystals and close-packed nanocrystal assemblies. Annu
Rev Mater Sci 20 0 0;30:545–610.
[165] Lee J, Yang J, Kwon SG, Hyeon T. Nonclassical nucleation and growth of inor-
ganic nanoparticles. Nat Rev Mater 2016;1:16034.
[166] Samarth N. Quantum materials discovery from a synthesis perspective. Nat
Mater 2017;16:1068.
Please cite this article as: K.-K. Kang et al., Recent progress in the synthesis of inorganic particulate materials using microfluidics, Journal
of the Taiwan Institute of Chemical Engineers (2018), https://doi.org/10.1016/j.jtice.2018.08.027
[m5G;November 12, 2018;11:33]
[167] Pu Y, Cai F, Wang D, Wang J-X, Chen J-F. Colloidal synthesis of semiconduc-
tor quantum dots toward large-scale production: a review. Ind Eng Chem Res
2018;57:1790–802.
[168] Nakamura H, Yamaguchi Y, Miyazaki M, Maeda H, Uehara M, Mulvaney P
Preparation of CdSe nanocrystals in a micro-flow-reactor. Chem Commun
2002:2844–5.
[169] Yen BK, Stott NE, Jensen KF, Bawendi MG. A continuous-flow microcapillary
reactor for the preparation of a size series of CdSe nanocrystals. Adv Mater
2003;15:1858–62.
[170] Yen BK, Günther A, Schmidt MA, Jensen KF, Bawendi MG. A microfabricated
gas–liquid segmented flow reactor for high-temperature synthesis: the case
of CdSe quantum dots. Angew Chem 2005;117:5583–7.
[171] Chan EM, Alivisatos AP, Mathies RA. High-temperature microfluidic syn-
thesis of CdSe nanocrystals in nanoliter droplets. J Am Chem Soc
2005;127:13854–61.
[172] Kikkeri R, Laurino P, Odedra A, Seeberger PH. Synthesis of carbohy-
drate-functionalized quantum dots in microreactors. Angew Chem Int Edit
2010;49:2054–7.
[173] Laurino P, Kikkeri R, Seeberger PH. Continuous-flow reactor-based synthe-
sis of carbohydrate and dihydrolipoic acid-capped quantum dots. Nat Protoc
2011;6:1209–20.
[174] Yang C, Feng G, Dai S, Wang S, Li G, Zhang H, et al. Femtosecond pulsed
laser ablation in microfluidics for synthesis of photoluminescent ZnSe quan-
tum dots. Appl Surf Sci 2017;414:205–11.
[175] Edel JB, Fortt R Microfluidic routes to the controlled production of nanoparti-
cles. Chem Commun 2002:1136–7.
[176] Krishnadasan S, Tovilla J, Vilar R. On-line analysis of CdSe nanoparticle
formation in a continuous flow chip-based microreactor. J Mater Chem
2004;14:2655–60.
[177] Luan W, Yang H, Fan N, Tu S-T. Synthesis of efficiently green lumines-
cent CdSe/ZnS nanocrystals via microfluidic reaction. Nanoscale Res Lett
2008;3:134.
[178] Marre S, Park J, Rempel J, Guan J, Bawendi MG, Jensen KF. Supercritical con-
tinuous-microflow synthesis of narrow size distribution quantum dots. Adv
Mater 2008;20:4830–4.
[179] Singh A, Limaye M, Singh S, Lalla NP, Malek CK, Kulkarni S. A facile and fast
approach for the synthesis of doped nanoparticles using a microfluidic device.
Nanotechnology 2008;19:245613.
[180] Wang C-W, Oskooei A, Sinton D, Moffitt MG. Controlled self-assembly of
quantum dot− block copolymer colloids in multiphase microfluidic reactors.
Langmuir 2010;26:716–23.
[181] Nightingale AM, de Mello J. Controlled synthesis of III–V quantum dots in
microfluidic reactors. ChemPhysChem 2009;10:2612–14.
[182] Uehara M, Nakamura H, Maeda H. Preparation of ZnS/CdSe/ZnS quantum
dot quantum well by using a microfluidic reactor. J Nanosci Nanotechnol
2009;9:577–83.
[183] Wan Z, Luan W, Tu S-t. Size controlled synthesis of blue emitting core/shell
nanocrystals via microreaction. J Phys Chem C 2010;115:1569–75.
[184] Wang H, Nakamura H, Uehara M, Miyazaki M, Maeda H Preparation of tita-
nia particles utilizing the insoluble phase interface in a microchannel reactor.
Chem Commun 2002:1462–3.
[185] Cottam BF, Krishnadasan S, Shaffer MS. Accelerated synthesis of titanium ox-
ide nanostructures using microfluidic chips. Lab Chip 2007;7:167–9.
[186] Abou-Hassan A, Bazzi R, Cabuil V. Multistep continuous-flow microsynthesis
of magnetic and fluorescent γ -Fe2 O3 @ SiO2 Core/Shell nanoparticles. Angew
Chem Int Edit 2009;48:7180–3.
[187] Stöber W, Fink A, Bohn E. Controlled growth of monodisperse silica spheres
in the micron size range. J Colloid Interface Sci 1968;26:62–9.
[188] Rama Rao G, López GP, Bravo J, Pham H, Datye AK, Xu H, Ward TL. Monodis-
perse mesoporous silica microspheres formed by wvaporation-induced self
assembly of surfactant templates in aerosols. Adv Mater 2002;14:1301–4.
[189] Lee I, Yoo Y, Cheng Z, Jeong HK. Generation of monodisperse mesoporous
silica microspheres with controllable size and surface morphology in a mi-
crofluidic device. Adv Funct Mater 2008;18:4014–21.
[190] Carroll NJ, Rathod SB, Derbins E, Mendez S, Weitz DA, Petsev DN.
Droplet-based microfluidics for emulsion and solvent evaporation synthesis
of monodisperse mesoporous silica microspheres. Langmuir 2008;24:658–61.