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Composite Nanoparticles
Composite Nanoparticles
Composite Nanoparticles
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Composite Nanoparticles
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Guangsheng Luo Le Du
Tsinghua University Beijing University of Chemical Technology
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Tsinghua University
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Overview
Cross-References
In the past two decades, composite nanoparticles
▶ Finite Volume and Finite Difference Methods have attracted great attention for their special and
for Modeling and Simulation multiple properties. The synthesis of composite
▶ Meshless Methods nanoparticles has not been confined to simply
integration of some categories with special
effects. The structure has become much more
complex, and the scale of composite has been
Composite Nanoparticles reduced to less than 1–20 nm, which can be
referred to as quantum dots. According to the
Guangsheng Luo, Le Du, Yunjun Wang and structural features, composite nanoparticles can
Kai Wang be mainly grouped into three categories: simple
The State Key Laboratory of Chemical hybrid, core/shell structured composite
Engineering, Department of Chemical nanoparticles, and multifunctional quantum
Engineering, Tsinghua University, Beijing, dots, as shown in Fig. 1.
China Synthesizing nanoparticle with core/shell
structure is a way to combine multiple function-
alities on nanocomposites. Core/shell
Synonyms nanomaterials are generally composed of the
core in the center and the coated shell outside,
Core/shell nanoparticles; Multifunctional which are structured by a variety of materials,
nanocomposite; Quantum dot-quantum well including polymers, inorganics, and metals [1].
(QDQW nanoparticles) Most of the synthesis strategies are based on
C 454 Composite Nanoparticles
Composite Nanoparticles, Fig. 1 Schematic representation for the basic structures of composite nanoparticles: (a)
simple hybrid (10–100 nm); (b) core/shell structured (10–100 nm); (c) multifunctional quantum dots (1–20 nm)
chemical incorporation, such as fluorescent or structure formed, the quantum yield can be
photoreactive organic dye molecule cross-linked increased up to about 50–70 %. Furthermore,
shell or surface coating on a nanoparticle core. the extinction coefficient has been increased by
The earlier core/shell nanoparticle architectures multiple manyfold, and a strong fluorescence
were synthesized mainly for the basic research, emission has been formed. For instance, more
such as optical tracer diffusion measurements current research on quantum dots is mainly
and optimized preparation of homogeneous based on CdX (X = S, Se, Te).
nanoparticle–polymer composites. Recently, the The strategies for composite nanoparticles can
focus in core/shell nanoparticle design has shifted be divided into vapor phase method, precipitation,
to more complex nanoscopic core/shell architec- sol–gel, self-assembly, magnetron sputtering, and
tures and multiple functionalities. The core/shell laser synthesis. Among these methods, precipita-
structure has exhibited the potential scientific and tion has been paid much attention for the low-cost
medical benefits for optical, electrical, magnetic, process and facility to industrialization. The syn-
and catalytic applications. Especially the interest thesis of nanoparticles typically involves three
in multifunctional biocompatible nanoscopic stages: nucleation, growth, and agglomeration.
core/shell systems has promoted the combination Especially synthesizing composite nanoparticles
of supramolecular surface chemistry and nano- with efficient functionality, specific morphology
particle synthesis. and small size, homogeneous reaction environ-
Semiconductor nanocrystals can be referred to ment, and ultrafast mixing is obviously essential.
as quantum dots; the nanoparticles are composed Thus, the decrease of linear dimension of the
of Group II–VI or III–V elements. Since the device and the increase of temperature and con-
1970s, quantum dots have been applied to the centration gradients are of great importance. Since
electronic and optical material field due to their the 1990s, microfluidics has become one of the
unique optical properties [2]. With the prepara- best options to create an effective and homoge-
tion of quantum dot technology developed, quan- neous mixing environment for nanoparticle prep-
tum dots have been more and more widely aration. Microfluidic devices can provide precise
applied to biological research. Quantum dots control on mixing scale, contact area, residence
behave differently from bulk solids due to the time, and reaction temperature [3]. Owing to these
reduced size and quantum-confinement effects advantages, microfluidics has been applied to syn-
that are responsible for their remarkably attrac- thesize particles with novel morphologies and spe-
tive properties. The size of the quantum dots has cial properties.
great influence on its light absorption and emis-
sion characteristics. Quantum dot particles with
a single component are susceptible to the impu- Basic Methodology
rities and lattice defects, and the traditional syn-
thesis generally obtains low fluorescence Precipitations are by far the most widely used
quantum yield. But with another semiconductor strategies for synthesizing composite
material coated, which means after the core/shell nanoparticles in both bulk solutions and
Composite Nanoparticles 455 C
C
Composite Nanoparticles, Fig. 2 Schematic representation for the basic structures and operation mode of different
microfluidic devices: (a) fast mixing flow; (b) segmented microfluidic; (c) steady laminar flow
microfluidics. Generally, two or more reactants Generally microfluidic devices for synthesizing
are employed in the reactions and the products composite nanoparticles can be mainly grouped
with low solubility precipitate, which are the into four categories: fast mixing flow, segmented
required composite nanoparticles. During the microfluidic, steady laminar flow, and multistep
precipitation process, nucleation, growth, and reactions (can be combined by the three afore-
agglomeration occur simultaneously in bulk sys- mentioned devices). The basic structures and
tems due to the difficulties of isolating these operation mode are shown in Fig. 2. These dif-
processes independently – not to mention the ferent strategies are reviewed in this section.
complex nanocomposites via multistep reactions.
Microfluidics employs millimeter or submillime- Synthesis of Nanoparticles by Fast Mixing
ter scale fabricated devices by microtechnology Flow
and precision engineering, which exhibits precise Synthesis of nanoparticles with fast mixing flow
control and homogeneous reaction environment. is by far the most widely utilized tunable strategy
Compared with bulk reactions, microfluidics in microfluidics, because a variety of reactions
exhibits relatively outstanding advantages of can be carried out in a homogeneous liquid phase.
controllability and precise operation as follows: Fast mixing flow has exhibited the potential use
first of all, the intrinsic small scale of micro- due to its high level of controllability. Generally
devices efficiently utilizes some expensive or the flows are sprayed and interdigitated in the
toxic chemicals with hardly any waste or pollu- outer space, so that efficient mixing is achieved
tion in the process. Secondly, the large surface in the mixer and there is no fouling in the reactant
area to volume ratio of micro-devices can provide inlet. Thus, the monodispersity of particles was
enhanced heat and mass transfer performance significantly improved.
compared with traditional reactors. Thirdly, coat- However, the strategies for synthesizing com-
ing or growing process for some composite posite nanoparticles usually tend to be too com-
nanoparticles can be easily accomplished in plex to be carried out via simply fast mixing. The
micro-devices due to the massively reduced char- design of microfluidic device requires higher
acteristic time and utilization of diffusion for the accuracy, such as position of the mixing and
transport process. Moreover, precise control is of size of the microchannel for multiple reactants’
great importance for preparing monodispersed contact, and also the length of channel for suffi-
nanoparticles via multistep processes. cient compound or growing.
Microfluidic devices provide potential for accu- For instance, Nightingale et al. [2] developed
rately operating, such as combining different a continuous in situ synthesis of ZnSe/ZnS core/
reactions, cross-linking, coating, growing, and shell quantum dots in a microfluidic reaction
purification in one or more simple microchips. system. Once the precursors were mixed, the
In a word, microfluidic devices keep offering mixture solution was moved to the heating zone
potential opportunities for exploring and devel- for the further nucleation and growth of core and
oping novel nanoparticle synthesis routes. shell of quantum dots. The continuous flow
C 456 Composite Nanoparticles
microfluidic reaction systems have exhibited mixing conditions, they were able to control the
effectively and alternatively due to precise con- size of the liposome molds that encapsulated the
trollability of reaction conditions. gel precursor. The microfluidic approach can be
As well known, enhancing mixing and customized for the synthesis of a wide variety of
suppressing fouling are key factors for continu- soft nanoparticles that are currently prepared via
ous fast mixing flow. Thus, the strategies usually bulk methods.
require low concentration, relatively high flow Laminar flow microfluidic devices have
rate and separation of reaction from microstruc- exhibited some advantages such as simplicity
tures. Single-phase flow exhibits a variety of and high flexibility for operating, and also ease
advantages, such as controllable operation and for manufacture. But some serious problems still
high-throughput and facile separation. However, remain, including frequent blockage of the chan-
limitations still remain in synthesizing multiple nel and fouling on the channel surface with
functional composite nanoparticles only using a relatively high product polydispersity. Further-
fast mixing flow. Because mostly, both mass more, the laminar flow leads to a broad residence-
transfer and growth of nanoparticles need time distribution, which causes the generation of
multistep, it is difficult to control the mixing large particles and wide particle size distributions.
conditions and the residence time. Thus, the Thus, the design and manufacture of microfluidic
selection of reactants and the design of devices when utilizing steady laminar flow must
microfluidic devices when utilizing fast mixing be carried out with great caution. And sometimes,
flow must be handled with great caution. enhancing the mixing performance in laminar flow
microfluidic devices is an extremely important
Controllable Coating/Growing with Steady objective especially in the initial stage of synthe-
Laminar Flow sizing composite nanoparticles.
Owing to the simple geometries of microfluidic
devices, fluid behavior is primarily influenced by Synthesis of Nanoparticles via Segmented
viscosity rather than inertia, which results in lam- Flow Microfluidic Devices
inar flow. Thus, diffusion is effective for moving Segmented flow is based on multiphase flows in
and mixing reactants on the micrometer to milli- microfluidics, which have been applied in nano-
meter length scales in laminar flow. The mixing particle preparation. One strategy is processing
process only by diffusion in microfluidic systems without interphase mass transfer, which means
is slow, which goes against fast nucleation for a continuous phase flow is introduced to form
nanoparticles. However, the hydrodynamic flow downstream a non-coalescing train of droplets/
in microchannels can be fairly directed and bubbles to overcome blockage or fouling of chan-
highly symmetric. Compared to macroscale nels and control the residence time in the micro-
tubes in which flow regimes are always turbulent, device. Especially for the highly uniform com-
it is beneficial to synthesize composite posite nanoparticles, this strategy can provide
nanoparticles needing growth or coating process. relatively precise control over the synthesis. Gen-
With reactants mixing and reacting under erally, the reactants are introduced into the main
diffusion-based laminar flow, reaction time, tem- channel, and droplets/bubbles are formed by
perature, diffusion rate, and reactant concentra- a strong shearing force of the continuous phase.
tions are the typical control parameters for the The inert phase is usually used to control the
synthesis of composite nanomaterials. subsequent step and isolate the reactants from
Coaxial flow microchannel is one of the most the channel. This strategy prevents not only clog-
widely used laminar flow microchannels. For ging by introducing an inert phase but also
instance, Hong et al. [4] used microfluidic hydro- intense advection within the reactants droplets.
dynamic focusing to control the convective–- Another strategy is processing with interphase
diffusive mixing of two miscible nanoparticle mass transfer, which means two or more fluid
precursor solutions. By varying microfluidic phases are involved in the reaction. By adjusting
Composite Nanoparticles 457 C
concentrations of the different phases and flow the possibility of carrying out further online mod-
rates, droplets/bubbles with different shapes and ifications of the silica surface and online detection
sizes are generated. In this situation, mass transfer has been demonstrated.
and chemical reaction can significantly influence In a continuous flow system, reactions are
the interfacial tension and flow patterns. For performed at steady state, which makes it possi-
multiphase flow, appropriate microfluidics can ble to achieve better control and reproducibility.
facilitate the synthesis of composite nanoparticles Furthermore, the ability to manipulate reactant C
with complex structures and special functions. concentrations in both space and time also pro-
Chang et al. [5] utilized microtubes to gener- vides a high level of reaction control than that of
ate micro-segmented flow. Upon surface modifi- bulk stirred reactors. The spatial and temporal
cation, the prepared nanoparticles were mixed controls of chemical reactions in microfluidic
with a monomer and emulsified into uniform devices are useful to control and alter chemical
droplets in a capillary-based microfluidic device. reactivity according to the preliminary design.
The microchannel-based reactor offered reliable And usually multistep synthesis can produce par-
control over the nanocomposite products by pre- ticles with fairly complex shapes and functional-
cisely adjusting the interfacial tension. ities. However, the coalescence between
The gas–liquid-based segmented flow offers droplets, the stability of flows after several
easy separation of gas from liquid, but still suffers times of mixing, and the controllability of the
from clogging since the composite nanoparticles fluid by multistep still remain to be improved.
produced may contact the channel wall. In con-
trast, the liquid–liquid segmented flow approach
encapsulates the reactants in liquid droplets to Key Research Findings
avoid contacting with channel walls. Further-
more, the droplets or plugs can be precisely con- As described above, the controllability and mass
trolled and delivered in microfluidic reactors. transfer performance provided by microfluidics
Segmented flow has been intensively investi- are well suited for the synthesis and modification
gated in recent years, and more functionalized of composite nanoparticles. Microfluidic envi-
composite nanoparticles such as magnetic ronments have huge potential for the precise
nanoparticles, quantum dots, or drugs have been aggregation or encapsulation of composite
successfully synthesized. nanoparticles to produce higher-order and accu-
rate structures with multifunctional properties.
Multistep Continuous Synthesis According to the structural features, composite
Generally, the complex structure and morphol- nanoparticles can be mainly grouped into three
ogy of composite nanoparticles are difficult to be categories: simple hybrid, core/shell structured
obtained by single step. Thus, a multistep contin- composite nanoparticles, and multifunctional
uous synthesis in a microfluidic device is quantum dots. Novel research findings on these
expected to provide qualified functional products different categories are reviewed in this section.
with improved controllability for complicated
reactions. The process is carried out by precisely Relatively Simple Hybrid Composite
combining all of the three strategies as mentioned Nanoparticles
before. The synthesis of hybrid nanostructured materials
Hassan et al. [6] synthesized magnetic and fluo- has become a major interdisciplinary area of
rescent core/shell g-Fe2O3@silica nanoparticles as research over recent decades. Hybrid composite
a model for demonstrating the practicability of the nanoparticles with relatively simple structure are
multistep microchemical synthesis. The choice of the most adjustably synthesized materials in
this system was motivated by numerous applica- microfluidics. Generally, just an appropriate reac-
tions of these core/shell nanoparticles in the bio- tants ratio, proper time for mixing and mass trans-
medical field and the need for scale-up. Moreover, fer, and relatively precise operation can synthesize
C 458 Composite Nanoparticles
nanoparticles, more extensive studies should be 5. Chang Z, Li S, Bouquey M, Kraus I, Serra CA,
carried on, which include: Koehler JM (2010) Continuous-microflow synthesis
of multiscale materials based on polymer microparti-
1. It is highly required to design new composite cles/inorganic nanoparticles composites. Zographou,
nanoparticles with new structures, different Athens
morphologies, or special components for 6. Abou-Hassan A, Bazzi R, Cabuil V (2009) Multistep
extensive applications. continuous-flow microsynthesis of magnetic and fluo-
rescent gamma-Fe2O3@SiO2 core/shell nanoparticles.
2. Simple devices and green synthesis technolo- Angew Chem Int Ed 48(39):7180–7183
gies should be developed to provide more 7. Lan WJ, Li SW, Xu JH, Luo GS (2012) A one-step
precise control abilities at nanoscale and microfluidic approach for controllable preparation of
microscale to meet high demands from nanoparticle-coated patchy microparticles.
Microfluid Nanofluid 13(3):491–498
increasingly complex composite nanoparticles 8. Zhao CX, He L, Qiao SZ, Middelberg APJ (2011)
with multifunction. Nanoparticle synthesis in microreactors. Chem Eng
3. Fundamental principles and CFD simulation Sci 66(7):1463–1479
of multiphase microflows remain to be further 9. Gomez L, Arruebo M, Sebastian V, Gutierrez L,
Santamaria J (2012) Facile synthesis of SiO2-Au
investigated. nanoshells in a three-stage microfluidic system.
4. Scaling up strategies of microfluidic processes J Mater Chem 22(40):21420–21425
should be exploited to realize large-scale 10. Nightingale AM, de Mello JC (2009) Controlled syn-
production of composite nanoparticles for thesis of III–V quantum dots in microfluidic reactors.
Chemphyschem 10(15):2612–2614
industrial applications.
Considering the rapid development in
microfluidic technology, the controllable prepa-
ration of composite nanoparticles with
microfluidics will obtain another breakthrough Compression Ratio
with developments of novel approaches of the
micro-dispersion and new microfluidic theories. Definition
We certainly will see more and more applications
of highly sophisticated systems in the very near In a ▶ positive displacement pump, a moving
future. boundary changes the volume of a pump cham-
ber. The compression ratio is the ratio of the
difference between the maximum and minimum
Acknowledgement We gratefully acknowledge the sup- volume (also called the stroke volume), and the
port of the National Natural Science Foundation of China
minimum volume (or dead volume).
(21036002) and the National Basic Research Program of
China (2012CBA01203) on this work.
Cross-References
References ▶ Dead Volume
1. Hung LH, Lee AP (2007) Microfluidic devices for the
▶ Electrostatic Valves
synthesis of nanoparticles and biomaterials. J Med ▶ Magnetic Pumps
Biol Eng 27(1):1–6 ▶ Membrane Actuation for Micropumps
2. Nightingale AM, de Mello JC (2010) Microscale syn- ▶ Microactuators
thesis of quantum dots. J Mater Chem
▶ Peristaltic Pumps
20(39):8454–8463
3. Luo GS, Du L, Wang YJ, Lu YC, Xu JH ▶ Piezoelectric Valves
(2011) Controllable preparation of particles with ▶ Pneumatic Valves
microfluidics. Particuology 9(6):545–558 ▶ Positive Displacement Pump
4. Hong JS, Stavis SM, Lacerda SHD, Locascio LE,
Raghavan SR, Gaitan M (2010) Microfluidic
▶ Stroke Volume
directed self-assembly of liposome-hydrogel hybrid ▶ Thermomechanical Valves
nanoparticles. Langmuir 26(13):11581–11588 ▶ Thermopneumatic Valve