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21st Century Nanoscience – A Handbook
21st Century Nanoscience – A Handbook: Nanophysics Sourcebook (Volume One)
21st Century Nanoscience – A Handbook: Design Strategies for Synthesis and Fabrication (Volume Two)
21st Century Nanoscience – A Handbook: Advanced Analytic Methods and Instrumentation (Volume Three)
21st Century Nanoscience – A Handbook: Low-Dimensional Materials and Morphologies (Volume Four)
21st Century Nanoscience – A Handbook: Exotic Nanostructures and Quantum Systems (Volume Five)
21st Century Nanoscience – A Handbook: Nanophotonics, Nanoelectronics, and Nanoplasmonics (Volume Six)
21st Century Nanoscience – A Handbook: Bioinspired Systems and Methods (Volume Seven)
21st Century Nanoscience – A Handbook: Nanopharmaceuticals, Nanomedicine, and Food Nanoscience (Volume Eight)
21st Century Nanoscience – A Handbook: Public Policy, Education, and Global Trends (Volume Ten)
21st Century Nanoscience – A Handbook
Design Strategies for Synthesis and Fabrication (Volume Two)
Edited by
Klaus D. Sattler
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Editor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii
Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
1 Large-Scale Colloidal Synthesis of Nanoparticles Vladimir Lesnyak . . . . . . . . . . . . . . . . 1-1
2 Plasma Synthesis of Nanomaterials Antaryami Mohanta and Raj K. Thareja . . . . . . . . . 2-1
3 Plant-Mediated Synthesis of Nanoparticles Alireza Ebrahiminezhad, Seyedeh-Masoumeh
Taghizadeh, Saeed Taghizadeh, Younes Ghasemi, Aydin Berenjian, and Mostafa Seifan . . . . 3-1
4 Cellulosic Nanomaterials Subrata Mondal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-1
5 Upconversion Nanoparticles: Design Strategies for Their Synthesis and Fabrication of Their
Surface Chemistry Karan Malhotra, Muhammad Shahrukh, Hifza Najib, and
Ulrich J. Krull . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-1
6 Microwave-Hydrothermal Synthesis of Perovskite Oxide Nanomaterials Weiren Xia,
Yao Lu, and Xinhua Zhu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-1
7 Gram-Scale Synthesis of Graphene Quantum Dots Xiluan Wang . . . . . . . . . . . . . . . . . 7-1
8 Electrocatalytic Optically Modulated Green Prepared Nanoparticles Xolile Fuku and
Mmalewane Modibedi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-1
9 Carbon Nanotube Products from the Floating Catalyst Method Hai M. Duong and
Thang Q. Tran . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9-1
10 Gold Nanoparticles by Green Chemistry Rakesh Kumar Sharma, Sneha Yadav, and
Sriparna Dutta . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10-1
11 Self-assembly of Amphiphilic Molecules Domenico Lombardo, Maria Teresa Caccamo,
and Pietro Calandra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11-1
12 Pre-programmed Self-assembly Carlos I. Mendoza and Daniel Salgado-Blanco . . . . . . . . . 12-1
13 Survey of Nanomaterials Synthesis, Fabrication, and Growth Xuefeng Song, Kai Tao,
Shuai Wang, Xiaofeng Zhao, and Jijin Xu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13-1
14 Inkjet Printing of Catalytic Materials Petros G. Savva and Costas N. Costa . . . . . . . . . . 14-1
15 Calix-Assisted Fabrication of Metal Nanoparticles: Applications and Theoretical Insights
Anita R. Kongor, Manthan K. Panchal, Vinod K. Jain, and Mohd Athar . . . . . . . . . . . . . 15-1
16 Biofabrication of Graphene Oxide Nanosheets Badal Kumar Mandal . . . . . . . . . . . . . . . 16-1
17 Radio Frequency Magnetron-Sputtered Germanium Nanoislands: Comprehensive
Investigations of Growth Parameters Alireza Samavati and Ahmad Fauzi Ismail . . . . . . . 17-1
18 Active Scanning Probes in Nanostructure Fabrication Ivo W. Rangelow and
Matias Holz . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18-1
19 Nanoscale Electrocrystallization: Eco-Friendly and Site-Selective Nanofabrication
of Organic Nanocrystals Based on Electrochemistry Hiroyuki Hasegawa . . . . . . . . . . . . . 19-1
20 Bio-Inspired Graphene-Derived Membranes Enlai Gao, Xiangzheng Jia, Han Shui, and
Ruishan Li . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20-1
21 Nanoscale Shape Control Zhaohui Wu and Wei Wu . . . . . . . . . . . . . . . . . . . . . . . . . . 21-1
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I-1
Editor
Klaus D. Sattler pursued his undergraduate and master’s carbon nanocones. His current work focuses on novel nano-
courses at the University of Karlsruhe in Germany. He materials and solar photocatalysis with nanoparticles for the
received his PhD under the guidance of Professors G. Busch purification of water. He is the editor of the sister refer-
and H.C. Siegmann at the Swiss Federal Institute of Tech- ences, Carbon Nanomaterials Sourcebook (2016) and Silicon
nology (ETH) in Zurich. For three years was a Heisenberg Nanomaterials Sourcebook (2017), as well as Fundamen-
fellow at the University of California, Berkeley, where he tals of Picoscience (2014). Among his many other accom-
initiated the first studies with a scanning tunneling micro- plishments, Dr. Sattler was awarded the prestigious Walter
scope of atomic clusters on surfaces. Dr. Sattler accepted a Schottky Prize from the German Physical Society in 1983.
position as professor of physics at the University of Hawaii, At the University of Hawaii, he teaches courses in general
Honolulu, in 1988. In 1994, his group produced the first physics, solid state physics, and quantum mechanics.
Contributors
1.1 Introduction
Over the last few decades, research on nanoparticles (NPs)
has been an intensively developing area of science inspired
by a fascinating endeavor of understanding the behavior
of a solid when its physical dimensions decrease to only a
few hundreds/thousands of atoms. In this size regime, the
quantum mechanical coupling of the constituent atoms gives
rise to new interesting physical phenomena. Over the years,
intensive efforts by many research groups around the world FIGURE 1.1 (a) A common setup for hot-injection synthesis
have made it possible to reach an outstanding level of control of semiconductor NPs. (b) Calculated atomic structure of a 5 nm
of these quantum mechanical properties by tuning the size, sized PbS NP capped with oleic acid (Zherebetskyy et al., 2014).
shape, structure, and composition of many different types (c) LaMer diagram depicting the concentration variation during
of materials at the nanoscale. Furthermore, the small size the nucleation and growth of NPs (Xia et al., 2009). (Reproduced
of NPs, combined with their large surface-to-volume ratio, with permission from AAAS and Wiley VCH Verlag GmbH & Co.)
make them valuable contenders for several applications
in many different fields, for instance, in (opto)electronics, controlled to produce monodisperse NPs. There is a very
sensor technologies, photovoltaics, nanophotonics, catal- narrow window of variability of parameters for the NP prop-
ysis, and medicine (Choi et al., 2015; Kagan et al., 2016; erties to remain practically the same from batch to batch.
Kovalenko et al., 2015; Medintz et al., 2005; Michalet This has led to the major road block in making nanomate-
et al., 2005; Panthani & Korgel, 2012; Pelaz et al., 2012; rials available to solve real issues and to be used to their full
Sapsford et al., 2013; Talapin et al., 2010; Yang et al., potential – the lack of large-scale production techniques.
2016). Ligand-capped NPs, i.e., particles made of an inor- Among various nanomaterials, colloidal semiconductor
ganic core and an organic shell of stabilizing ligands (surfac- NPs (otherwise known as quantum dots, QDs), primarily
tants) (Figure 1.1b), are particularly suitable candidates for made of metal chalcogenide compounds, have been the
low-cost processing, as they can be employed in the form most studied objects. QDs exhibit extremely attractive
of liquid solutions, e.g., as inks in printed electronics or optical features, such as widely tunable absorption spectra
in the form of composites with biomolecules in biomedical extending over a broad wavelength range, high photolumi-
applications. nescence (PL) quantum yields (QYs), narrow PL spectral
Compared to a large body of fundamental research that bandwidth, and high thermal and photochemical stability.
has been devoted to nanomaterials over the years, in part Above all, the possibility to tune their optical features
fueled by the hype on nanoscience and nanotechnology, by varying their size, shape, and composition by simple
the number of applications that have made their way into chemical methods induced the development of more refined
consumer products has been relatively small so far. To a approaches, resulting in the NPs with widely varied sizes and
large extent, this is due to one simple reason – making NPs shapes, easily accessible from well-consolidated solution-
in large amounts is still difficult. For example, the reaction phase synthetic schemes. Furthermore, many types of QDs
conditions of the colloidal synthesis have to be carefully have already been commercialized, and several applications
1-1
1-2 Design Strategies for Synthesis and Fabrication
have been developed. One of the latest and most fascinating Section 1.3, although in order to make them truly large scale,
examples is a line-up of Samsung QLED TVs, in which QDs a continuous, uninterrupted supply of precursors should be
are employed as color converters. Recently added members further developed.
to the list of fluorescent QDs are represented by methylam- Taking into account the abovementioned need for
monium (or cesium) lead halide perovskite NPs. Perovskites upscaling the colloidal synthesis of various NPs, in this
have attracted intensive interest over the last several years chapter, the main methods of the large-scale production of
due to their unique properties that make them appealing for NPs developed up to date are summarized, beginning with
applications in photovoltaics, optoelectronics, and lighting simplest one-batch reactions, which are widely used in a
(Akkerman et al., 2018; Kovalenko et al., 2017). Initially common laboratory practice, followed by more sophisticated
evolved as thin films and bulk single crystals, they have soon approaches based on the continuous production of nanoma-
been developed in the nanocrystal form too, featured by terials in flow reactors, such as microfluidic and spinning disc
their strong fluorescence (especially the APbX3 compounds, reactors. Prior to overviewing these synthetic approaches,
with A = methylammonium, formamidinium, or Cs, X = the main features of the colloidal synthesis of NPs will be
Cl, Br, or I) (Bai et al., 2016; González-Carrero et al., introduced.
2016; González-Carrero et al., 2015; Protesescu et al., 2015).
In addition to QDs, many companies all over the world
1.1.1 Basics of the Colloidal Synthesis of
have commercialized the production of noble metal and
Nanoparticles
magnetic NPs, having in view their great perspective in
biomedical applications, in particular, in biosensing (noble Solution-based colloidal synthesis has emerged as a sepa-
metal NPs), magnetic resonance imaging (MRI), and hyper- rate branch of synthetic chemistry due to the flexibility
thermia (magnetic NPs), as well as catalysis. in preparing NPs of a broad range of materials and due
In designing a lab-scale synthesis route to NPs, one to excellent control over their sizes and shapes, in addi-
focuses on a desired composition with well-defined crystal tion to employing a relatively simple experimental equip-
phase and stability in common solvents, through a process ment. Typical setup for the so-called hot-injection synthesis
which can be carried out in a moderately equipped chem- (discussed in more detail in Section 1.2.2) is presented
ical laboratory, and in quantities sufficient for their charac- in Figure 1.1a. High-quality materials can be produced
terization and, in some cases, for the fabrication of a few by this method at surprisingly low cost. In the colloidal
prototype devices. The know-how accumulated so far will synthesis, suitable molecular precursors (mainly inorganic
provide directions for the future work and will help to iden- salts or organometallic compounds) are reacted in a liquid
tify materials that could be explored more extensively, with medium in the presence of stabilizing agents (also known as
a synthesis process that can be industrially scalable. There capping ligands). Chemical reactions between the precur-
have been many reports on the colloidal synthesis of various sors release reactive species, called monomers which are
NPs based on relatively simple, generalized, inexpensive responsible for the further nucleation and the growth of
methods and employing nontoxic reagents. Many of these NPs (Kim et al., 2013; Klimov, 2004; Kwon et al., 2007;
methods have been claimed to be easily scalable to prepare Lee et al., 2016; Rogach, 2008; Schmid, 2010; Yang et al.,
at least grams of products. When seen from an industrial 2015). A general synthetic strategy involves several consecu-
perspective, the fabrication requirements are unfortunately tive steps: (i) nucleation, when a critical concentration of the
not much promising, as they involve high temperatures, or active monomer species in the reaction mixture is reached;
the use of vacuum and inert atmosphere as typical reaction (ii) growth, when the formed nuclei do not dissolve back
conditions. Therefore, scaling-up of successful lab protocols into monomeric units but instead keep attracting monomers
to an industrial level is often not straightforward, and there from the solution phase and further enlarge in size; (iii)
is still a strong demand for simpler and inexpensive methods arresting the growth – quenching the reaction and separa-
for large-scale production of high-quality NPs. tion of the particles from the reaction mixture, when the
It is quite difficult to define exact minimal space-time desired size/composition has been achieved; and (iv) post-
production yields in the synthesis of colloidal NPs, after synthetic treatments, if necessary. It is important to tempo-
which a system can be considered as a large-scale production rally separate nucleation and growth in order to achieve a
unit. It is mainly due to unspecified times and capabilities of narrow size distribution of the NPs (Murray et al., 1993;
the post-synthetic treatment of NPs, especially their purifi- Park et al., 2007; Thanh et al., 2014). This is generally
cation, which is an unavoidable step of the whole process and achieved by tuning the rate at which the monomer species
which is highly time-consuming. Obviously, different mate- are released from corresponding precursors. The chemical
rials require different processing and thus different times. reactions which produce these monomer species can be, e.g.,
Therefore, focusing solely on the reaction, a system with the decomposition of molecular precursors (in the case of
a throughput of at least 1 g/h would be evaluated as QDs), the hydrolysis of salts with subsequent oxidation (for
capable of large-scale production. This, however, is a very metal oxide NPs), or the reduction of metal ions (in the
rough estimation which should not be considered literally. synthesis of noble metal NPs) (Park et al., 2007).
Also, important is the potential for upscaling which is quite The pioneering work by LaMer and Dinegar defines the
obvious in the case of flow syntheses, which are discussed in synthesis parameters for obtaining monodisperse colloidal
Large-Scale Colloidal Synthesis 1-3
1.12 g of ultrathin Bi2 Te3 nanoplates with thickness of 1–3 and temperatures, either above or below their critical point,
nm was obtained upon reacting bismuth dodecanethiolate to increase the solubility of solid precursors and to speed
and tri-n-octylphosphine-tellurium complex (TOP-Te) in up reactions among them in a sealed vessel. Using this
the presence of OlAm (Figure 1.3e) (Son et al., 2012). After method, highly crystalline hydrophilic and hydrophobic
being sintered into nanostructured bulk pellets, this mate- magnetic 20 nm Fe3 O4 NPs exhibiting a room temper-
rial exhibited excellent thermoelectric properties. ature magnetization as high as 84 emu/g were synthe-
Based on the setup used in the aqueous synthesis of sized (Kolen’ko et al., 2014). A single reaction gave 86%
CdTe QDs introduced by Gaponik et al. (2002) and in (1.4 g) or 68% (0.9 g) yield of hydrophilic and hydrophobic
the organometallic synthesis of InP QDs developed in the magnetite nanocrystals, respectively. These NPs not only
Reiss group (Li et al., 2008), Miao et al. established a demonstrated super-paramagnetic behavior with notably
hot-bubbling synthesis of monodisperse cadmium phosphide high saturation magnetization, but also exhibited excellent
NPs (Figure 1.3f) using ex situ produced phosphine, which performance in magnetic hyperthermia. Another example of
yielded gram-scale amounts (Miao et al., 2012). In this potentially up-scalable process is the synthesis of Bi2 S3 and
method, PH3 gas, generated by the reaction between Ca3 P2 Sb2 S3 nanorods from single-source precursors under air at
powder and H2 SO4 , was bubbled through a hot solution of relatively low reaction temperatures (Lou et al., 2007).
Cd-oleate in ODE, which afterwards was kept at a desired Microwave irradiation methodology has been explored
temperature (from 80◦ C to 250◦ C). Size-controlling parame- to synthesize various NPs, such as lanthanide orthophos-
ters in this synthesis were the reaction time and the temper- phate nanorods (Patra et al., 2005); InGaP, InP, and
ature: an increase of either parameter led to the growth of CdSe NPs (Gerbec et al., 2005); rods and wires of ZnS,
Cd6 P7 NPs. ZnSe, CdS, and CdSe (Panda et al., 2006); as well as rare
By employing the heat-up method, it is possible to earth oxide (M2 O3 , M = Pr, Nd, Sm, Eu, Gd, Tb, Dy),
synthesize more complex metal chalcogenide NPs, composed nanorods and nanoplates (Panda et al., 2007). Most of
of three (ternary compounds) or even four (quaternary) them used conventional/cooking microwave ovens, making
different elements, in gram-scale amounts. Thus, monodis- the process rapid and simple, without the need of inert
perse 3–8 nm sized CIS pyramidal nanocrystals, which are a atmosphere or high pressure. The more uniform heating
promising material for solar harvesting and lighting applica- provided by microwave irradiation eliminates issues linked
tions, were synthesized with 80%–90% reaction yield (2.3 g to thermal gradients, making this method promising for
in one batch) by Zhong et al. by heating a mixture of copper preparing large quantities of various nanomaterials. Also,
iodide, indium acetate, dodecanethiol (DDT), OlAc, and much higher heating rates than with conventional heating
ODE at 200◦ C for 2 h (Zhong et al., 2010). In another report, can be achieved, which therefore provide an additional
wurtzite CIS NPs were obtained by a one-pot reaction of means of tuning reactivity. Apparently, further upscaling of
copper nitrate, indium nitrate, and DDT, with >80% yield this synthesis to industrial amounts requires its implemen-
(Lu et al., 2011). The size and the shape of these NPs were tation in a continuous reaction mode by coupling, e.g., with
controlled by varying the Cu/In ratio and by introducing microfluidic systems which are described in Section 1.3.1.
additional ligands, such as OlAm and OlAc (Figure 1.3g,h).
For instance, uniform nanorods were formed starting from a
Cu/In feed ratio of 2:1 with the assistance of both DDT and 1.2.2 Hot-Injection Method
OlAc. They were demonstrated to assemble into large-scale The intensive development of the hot-injection method for
superlattices on substrates by a solvent evaporation method. the colloidal synthesis of NPs was ignited by a pioneering
One more promising material for photovoltaic applications work of Murray, Norris, and Bawendi on the synthesis of
is represented by more complex quaternary CZTS NPs. monodisperse CdS, CdSe, and CdTe QDs (Murray et al.,
Chesman et al. reported a non-injection synthesis of this 1993). On one hand, this approach provides an excel-
material that delivered multi-gram yields (Chesman et al., lent control over the size, shape, and composition of NPs,
2013; van Embden et al., 2014). Their approach provides including complex alloyed and heterostructures. On the
a precise control of the metal composition of the particles other, its successful scale-up is challenged by significantly
(Cu/Zn/Sn ratio), through the selective use of a binary retarded heat and mass transport when large volumes of
sulfur precursor-ligand in the reaction mixture, which decou- reaction mixtures are involved. Nevertheless, there have
ples the nucleation and the growth stages. Heating zinc ethyl been reports on a large-scale hot-injection production of
xanthate, CuI, and SnCl4 × 5H2 O in a mixture of DDT and different materials, such as metallic Fe (Yang et al., 2007)
OlAm (1/3) to 250◦ C, and then maintaining this tempera- and Cu (Lee et al., 2008), Cu2 O (Park et al., 2009), as
ture for additional 30 min under a nitrogen flow resulted in well as various metal sulfide NPs (Zhang et al., 2012).
tetrahedral CZTS nanocrystals (Figure 1.3i) with approxi- For example, a fast injection of Fe(CO)5 into a mixture
mately 80% yield. of kerosene and OlAm at 180◦ C yielded ∼2 g of 3–12
nm Fe NPs (Yang et al., 2007). The particle size was
Solvothermal and Microwave Irradiation Syntheses
controlled by varying the reaction time, the molar ratio
The solvothermal (with hydrothermal as a particular case of OlAm to Fe(CO)5 , and the Fe(CO)5 concentration in
of it) approach utilizes solvents under elevated pressures kerosene. Another example of metal particles prepared in
1-6 Design Strategies for Synthesis and Fabrication
large quantities by the hot-injection is represented by copper as a ligand in an open-air synthesis to produce 9.6 g of
nanocrystals (Lee et al., 2008). Approximately 50 g of Cu CdSe QDs, thus effectively avoiding the commonly used
NPs was obtained in one batch by the rapid injection of 1 L in this process expensive solvents and toxic, air-sensitive
of a 1 M solution of copper sulfate in ethylene glycol into organic phosphines (Liu et al., 2008). A fast method with
a mixture of sodium hypophosphite (as a reducing agent) minimum cost and effort to prepare core/shell QDs was
and polyvinylpyrrolidone (PVP) (used as a stabilizer) in developed by successive injections of precursors in one pot,
4 L of ethylene glycol at 90◦ C under ambient atmosphere. according to the synthetic scheme displayed in Figure 1.4b,
The size of these copper NPs was controlled between 30 yielding 0.2 kg of CdSe/ZnSe QDs, which were easily puri-
and 65 nm by varying the reaction time, temperature, and fied and redispersed in various organic solvents (Kim & Lee,
CuSO4 /PVP ratio. Thus produced NP colloids were further 2006).
processed via ink-jet printing into metallic copper patterns The hot-injection technique has been used by several
on polyimide substrates. After a relatively low-temperature groups to obtain high-quality NPs of various materials and
sintering process, the final patterns had low electrical resis- compositions, but translating this to a large-scale synthesis
tivity (≥3.6 µΩ cm, or ≥2.2 times the resistivity of bulk is not straightforward as the step of injecting a large quan-
copper). tity of a precursor/reactant in a short time, while regu-
More efforts have been devoted to the large-scale hot- lating the precise reaction temperature of a large volume,
injection synthesis of various metal chalcogenide NPs. A is indeed a challenge. The group of Reiss solved this issue
general approach to the gram-scale production (more than by using a peristaltic pump and a mechanical stirrer in a
30 g in a single reaction) of monodisperse metal sulfide 2 L batch reactor (see Figure 1.4c) (Protière et al., 2011).
(Cu2 S, CdS, SnS, ZnS, MnS, Ag2 S, and Bi2 S3 ) NPs was They demonstrated an efficient approach to optimize the
developed by the group of Robinson, who employed for synthesis and prepare differently sized CdSe QDs by design-
the first time (NH4 )2 S as a sulfur precursor (Zhang et al., of-experiment method. The lab-scale synthesis yielded 100–
2012). This method enabled high reaction yields (≥87%) 200 mg, and when the reaction was scaled up by a factor
at moderate reaction temperatures, due to the high reac- of 20 using a 2 L batch reactor with mechanical stirring,
tivity of (NH4 )2 S. The size tuning of the NPs was achieved 2–3 g of CdSe QDs was obtained, without sacrificing the
by varying reaction temperature, time, and precursor ratios. narrow size distribution and the reaction yield. Further-
Du et al. (2012) synthesized ultrathin nanosheets of different more, using the same setup, the authors synthesized ∼1.3 g
metal sulfides in gram scales with ∼100% yield, starting of CdSe/CdS/ZnS core/shell/shell QDs, which exhibited an
from their respective metal chlorides: 1.4 g of 1.3 nm thick excellent photoluminescence quantum yield (PLQY) of up
CuS nanosheets (reaction scheme is presented in Figure to 81%. Yarema et al. proposed an ingenious solution to
1.4a), 1.3 g of ZnS, 1.6 g of Bi2 S3 , and 1.7 g of Sb2 S3 speed up the injection of a large volume of a precursor
nanowires (sub-2 nm diameter) were obtained from a single from an addition funnel by applying mild underpressure
batch. According to this scheme, first, a lamellar complex (1–10 mbars) to the flask reactor (Yarema et al., 2017).
CuCl(octylamine(OctAm), OlAm)x is formed by the reac- Using this method, they successfully upscaled synthetic
tion of corresponding compounds at 130◦ C, which then acts protocols for Sn, PbS, CsPbBr3 , and Cu3 In5 Se9 NPs by 1−2
as a soft template for the nucleation and growth of ultra- orders of magnitude to obtain tens of grams of the prod-
thin CuS nanosheets after the addition of S powder. A ucts per synthesis maintaining their high quality. This work
similar lamellar soft template, CdCl2 (OctAm, OlAm)2 , was shows that fast addition of large injection volumes does not
employed by the Hyeon group for the large-scale synthesis intrinsically limit upscaling of hot-injection-based colloidal
of CdSe and CdTe nanosheets as thin as 1.4 nm (Son et al., syntheses.
2009): about 4 g of single-layered CdSe nanosheets were As Cd-containing compounds are considered to be toxic,
prepared by reacting Se-powder dispersed in OctAm/OlAm alternatives have been sought. An example is a large-scale
mixture with CdCl2 (OctAm, OlAm)2 complex, followed by synthesis of InPZnS alloy QDs, which yielded ∼3 g of
mild sonication in chloroform. the product (after the work-up process) at lab scale (see
Another important family of NPs is the cadmium chalco- Figure 1.4d) (Kim et al., 2012). In this method, a phos-
genides (CdS, CdSe, and CdTe), whose large-scale hot- phorous precursor (a solution of tris(trimethylsilyl) phos-
injection synthesis became feasible after the introduction phine (TMS3 P) in ODE) was slowly added to the hot
by Peng and Peng of CdO as a Cd-precursor replacing mixture (210◦ C) of metal precursors. Such slow addition
dimethyl cadmium Cd(CH3 )2 (extremely toxic, pyrophoric, appears to be more favorable for a potential industrial
expensive, unstable at room temperature, and explosive at production of the material than a rapid injection. There-
elevated temperatures compound) (Peng & Peng, 2000). after, ZnS-rich shell was grown by adding zinc acetate and
They demonstrated the synthesis of about 0.7 g of CdTe DDT followed by heating at 230◦ C for 5 h to improve
NPs in a single lab-scale reaction. In another report, a the PLQY of the QDs and their stability. The emis-
gram-scale synthesis of red-emitting CdSe QDs (using stan- sion of these InPZnS alloy/ZnS core/shell QDs could be
dard air-free techniques) was developed (Zhong et al., 2006). precisely and reproducibly tuned by controlling the ratio
In the logic of further simplifying the synthesis condi- of DDT/palmitic acid employed as a sulfur-source and
tions, Liu et al. used diesel fuel as a solvent and OlAc ligands.
Large-Scale Colloidal Synthesis 1-7
FIGURE 1.4 Examples of large-scale hot-injection syntheses of different materials. (a) Scheme of the synthesis of CuS nanosheets
with corresponding electron microscopy images (Du et al., 2012). (b) Scheme of successive injection of precursors in one pot for preparing
CdSe/ZnSe core/shell QDs with a photo of corresponding NP colloid and TEM images of core CdSe and core/shell CdSe/CdS QDs (Kim &
Lee, 2006). (c, from left to right) Experimental setup used for the gram-scale synthesis of CdSe QDs; CdSe/CdS/ZnS core/shell/shell
QDs in the 2 L reactor at the final stage of the synthesis; purification using a glass filter column retaining the precipitated QDs, while
the solvent and by-products are collected in the round-bottom flask below; corresponding TEM images (Protière et al., 2011). (d)
Experimental setup for the synthesis of InPZnS alloy QDs, absorption and emission spectra of alloyed InPZnS/ZnS core/shell QDs,
photo of different QD colloids under UV light, and photo demonstrating the amount of the final product in a single reaction (Kim et al.,
2012). (Reproduced with permission from Wiley VCH Verlag GmbH & Co, Nature Publishing Group, Springer, and American Chemical
Society.)
1.3 Continuous and Multiphase reactors. Although the main body of work on the contin-
Flow Synthesis uous flow synthesis of NPs has been done on micro-
scopic flow capillary-based reactors, there are few reports
Continuous flow processes are performed in two main on large-scale synthesis using simpler macroscopic tubular
types of reactors: tubular and spinning disc (or tube) reactors.
1-8 Design Strategies for Synthesis and Fabrication
FIGURE 1.5 Examples of flow reactors for the synthesis of NPs. FIGURE 1.6 Scheme of a typical micro-flow chemical synthesis
(a) Scheme of the setup for the synthesis of CZTS NPs (Shavel platform depicting reagent pumps, mixing chips, immobilized
et al., 2012). (b) Setup for chemical aerosol flow synthesis of CdS, reagent containing columns, flow reactor coils, and analytical (e.g.
CdSe, and CdTe QDs. Inset: a photo of nebulized mist produced spectrometers) and work-up units (in-line evaporators) (Myers
by the ultrasonic fountain (Didenko & Suslick, 2005). (Reproduced et al., 2014). (Reproduced with permission from Wiley VCH Verlag
with permission from the American Chemical Society.) GmbH & Co.)
Large-Scale Colloidal Synthesis 1-9
sample coils (B and C) are used to feed the precursors In a next step, in-line heating (such as oil bath shown in
at proper temperatures, which can be achieved also by Figure 1.7b,c) was introduced. This helped to solve the long-
microwave heating. The precursor streams can be mixed at standing problem of inhomogeneity in mixing and tempera-
the T-piece (D) or in an in-line glass static mixer chip (F). ture control in large-scale reactors. For example, CdSe QDs
Since most of the time the reaction has to run by constant were prepared at 230◦ C–300◦ C from a mixture of TOP-Se
supply of reagents, such provision can be made through and Cd(CH3 COO)2 in stearic acid, and trioctylphosphine
cartridges packed with immobilized materials (G), which oxide (TOPO) loaded into a glass syringe and connected
may be recycled periodically during breaks in the contin- to a glass capillary, one section of which was heated in
uous flow process. The choice of the tubing is based on the an oil bath (Nakamura et al., 2002). Continuous produc-
temperature, pressure, and the nature of the liquid flowing tion was demonstrated, and narrow size distribution of the
through. The materials for this range from polyfluoroac- NPs was achieved using a 200 µm thin capillary. In 2002,
etate to polytetrafluoroethylene (Teflon), steel, Hastelloy, a significant step forward was made by the de Mello group
and others. The reactor coil (H) needs to be carefully in the synthesis of CdS NPs employing a continuous flow
designed, since in this part of the flow system, almost all the micromixer, where the inlets containing the reactants were
“action” takes place. Consequently, the coil should be manu- split into separate multichannel streams before they were
factured of unreactive material to withstand a wide range of brought in contact for mixing (Edel et al., 2002). Later,
temperatures, pressures, and different flow rates. The pres- in 2004, the same group reported the synthesis of CdSe
sure can be adjusted through in-line back-pressure regula- NPs through the direct reaction of Se and Cd(CH3 COO)2
tors (I). The entire system is monitored through a network dissolved in a TOPO-TOP mixture, coupled with an in-
of webcams (J) and in-line monitoring equipment (K; such line analysis system that enabled real-time monitoring of
as various spectrometers), which are computer-controlled the quality of the obtained material (Krishnadasan et al.,
and might be regulated remotely through the internet (L). 2004). This was a major step forward to designing intelligent
The work-up unit (M) at the end of the system leads feedback-driven NPs production. Likewise, OlAc/OlAm
to the final product collection. In the reactor, converging stabilized InP nanocrystals were obtained in a microflu-
streams of fluids flow in parallel but without turbulence, idic reactor by in-line recording of their PL spectra
resulting in diffusion controlled mixing of compounds at (Nightingale & de Mello, 2009). As in the case of single
the congregating fluid-interface, enabling a rapid trans- batch reactions, the use of single-source precursors simplifies
port of heat and mass. Additionally, the high surface-to- the hardware and facilitates the control of the NP synthesis
volume ratio of miniaturized channels and reactor coils in a microfluidic setup. An example of this strategy is the
often results in a dramatic enhancement in throughput synthesis of CdS, CdSe, CdSe/CdS core/shell, and CdSeS
and yields, as compared to a corresponding batch synthesis alloy QDs from Cd(S2 CNMen Hex)2 and Cd(Se2 Pi Pr2 )2
(Reyes et al., 2002). The flow systems are valuable for dissolved in OlAm (Abdelhady et al., 2011).
conducting reactions involving harsh conditions, such as Another breakthrough was made by the Weller group
superheated solvents, owing to a better control and more when they developed a continuous flow system that mimics
safety in comparison with the conventional methods. Simi- the hot-injection method to produce fluorescent CdSe QDs
larly, toxic precursors and side products are confined in with optional shell-coating (CdS, ZnS, or CdS/ZnS double
the system and can be removed and disposed continuously, shell) (Ness et al., 2012). The interchangeable components
thus avoiding a pile-up of large amounts of toxic mate- of the reactor made it possible to obtain the QDs of any
rials. desired configuration. In this system, nucleation and growth
Different groups have designed their own reactors with steps were separated in time and in space in two different
in-line heating, based on the requirements for the synthesis. parts of the system. Moreover, the reactor was able to
Microfluidic production of Au, Ag, Co, Cu, SiO2 , TiO2 , CdS, withstand temperatures as high as 320◦ C, typical to hot-
CdSe, CdSe/ZnS, and CdSe/CdS core/shell NPs has been injection synthesis. Recently, high-temperature continuous
reported. Some of the setups developed are illustrated in flow synthesis of core/shell CdS/ZnS and CdSeS/ZnS as
Figure 1.7. An early report on the flow synthesis of colloidal well as core/shell/shell CdSe/CdS/ZnS QDs was success-
CdS NPs in an aqueous media was published in 1992 by fully realized in rather millifluidic than microfluidic regime
Fischer and Giersig (1992). In their method, two water solu- (in a stainless steel coil with an inner diameter of 2.2 mm)
tions (Cd(ClO4 )2 with sodium polyphosphate and NaSH (Naughton et al., 2015). A simple design of the reactor
with polyphosphate) were pumped into a mixing chamber allowed the authors to exclude preheating or in-line mixing
in conjunction with a chromatographic column to obtain and to achieve high flow rates of ∼10 mL/min. Moreover,
NPs, which further passed through the in-line detector for a high PLQYs of 50%–60% for the obtained QDs were demon-
rapid recording of their absorption spectra. One of the initial strated.
reasons why flow reactors gained interest as a NP synthesis In recent years, the use of capillary-based droplet reac-
technique was that the existing at that time methods were tors has become more popular due to a series of issues with
time-consuming and unsuitable for large-scale production, continuous flow reactors. One of them is the spread of resi-
as the NP samples were polydisperse and required repeti- dence times due to the viscous drag at the channel walls,
tive size-selection to obtain a desired particle size. leading to different fluid velocities in the flow. Another one
1-10 Design Strategies for Synthesis and Fabrication
FIGURE 1.7 Examples of the microfluidic reactor systems. (a, left) Setup for the synthesis of anisotropic Au NPs: aqueous solutions
of Au3+ , Ag+ , and CTAB (R1), ascorbic acid (R2), and Au seed NPs (S) are separately fed through individual inlets into one arm
of the T-junction. Silicone oil, as the continuous liquid, is fed to the perpendicular arm. (a, right, top) Reagents get in contact at
the T-junction, being dispensed into small picoliter droplets. The oil forms a thin lubricating layer around the droplets preventing
contact between growing NPs and the microchannel walls. (a, right, bottom) Stereomicroscopy images of flow patterns observed in the
microchannel under different flow conditions (Duraiswamy & Khan, 2009). (b, left) Setup for the synthesis of CdSe NPs comprising
droplet generator, heated oil-bath, and in-line optical detector with a close-up of a droplet generation stage. (b, right) Dynamic phase
diagram for ODE droplets in perfluoropolyether (PFPE), indicating the flow rate of the carrier and reagent phases with the marker
shape denoting the aspect ratio of the resultant droplets (Nightingale et al., 2011). (c, left) A multichannel reactor for the synthesis of
CdSe, CdTe, and alloyed CdSeTe NPs. (c, right) Photographs of the corresponding NP colloids under UV illumination and of 54.4 g of
purified CdTe NP powder from 9 h production run (Nightingale et al., 2013). (d, left) Schematic of a dual-stage continuous flow reactor
for the synthesis of PbS QDs from Pb-oleate in ODE (precursor A) and bis(trimethylsilyl) sulfide (TMS) in ODE (precursor B). (d, right)
Absorbance and PL spectra of PbS QDs synthesized with a single-stage flow approach compared to batch synthesis and dual-stage flow
setup (Pan et al., 2013).
(Continued)
Large-Scale Colloidal Synthesis 1-11
FIGURE 1.7 (CONTINUED) (e, top left) Setup integrated with online absorbance and PL detection for the synthesis and real-
time characterization of CsPbX3 perovskite NPs, which allows for precise tuning of the chemical payload of the formed droplets by
continuously varying the ratio between the lead and cesium sources (R1) and the ratio between halides (R2). (e, bottom left) Image
of the generated droplets after exiting the heating zone, showing bright PL of CsPbX3 NPs under UV excitation. (e, right) Online PL
spectra of CsPbX3 NPs (X: Cl, Br, I, and Cl/Br and Br/I mixed halide systems) (Lignos et al., 2016). (Reproduced with permission
from Wiley VCH Verlag GmbH & Co, the Royal Society of Chemistry, and American Chemical Society.)
is the deposition of NPs on the reactor’s walls, eventually (Pan et al., 2013). The flow rate in this setup was typically
leading to reactor fouling. Instead, in capillary-based droplet in the range of 1–3 mL/min, the nucleation temperature was
reactors, droplets are generated commonly by mixing a varied in the range of 80◦ C–150◦ C, while the growth temper-
precursor solution with an immiscible liquid acting as a ature was set between 50◦ C and 100◦ C. The authors demon-
carrier fluid. For example, an aqueous solution containing strated that the solar cell fabricated from these QDs had a
precursors and metal NP seeds was mixed with silicone oil performance equivalent to that made from batch synthe-
(Figure 1.7a) (Duraiswamy & Khan, 2009). In the other sized particles, and was superior to the conventional single-
case, the solvent of the droplet phase was ODE, and the stage flow-synthesis product. In-line real-time monitoring of
carrier fluid was a perfluorinated polyether used to synthe- the near-infrared PL spectra enabled a rapid optimization
size Ag, TiO2 , and CdSe NPs (Figure 1.7b) (Nightingale of reaction conditions resulted in high-quality PbS QDs,
et al., 2011). This capillary-based process was also extended emitting in the range of 765–1600 nm with QYs of up to
to prepare dextran-coated superparamagnetic iron oxide 28%, as well as PbSe QDs with PL ranging from 860 to
NPs in water, which were small, stable, and highly crys- 1600 nm (Lignos et al., 2014). The thus-produced QDs were
talline, with narrow size distribution (Kumar et al., 2012). successfully used in the fabrication of Schottky solar cells,
The same group also developed a multichannel (five-channel exhibiting 3.4% power conversion efficiency.
prototype) droplet reactor for the production of CdSe, Recently developed and already booming cesium lead
CdTe and alloyed CdSeTe QDs (Figure 1.7c) (Nightingale halide perovskite CsPbX3 nanocrystals were synthesized
et al., 2013). In particular, by using this system the authors on a microfluidic platform by the groups of deMello and
demonstrated large-scale production of CdTe QDs (54.4 g Kovalenko (Figure 1.7e) (Lignos et al., 2016). Apart from
from a 9 h production run) at a rate of 145 g/day. its great potential for a large-scale and reproducible produc-
Mixing fluid and gas streams was demonstrated to tion of these nanomaterials having bright and tunable PL,
generate segmented flow where droplets of liquid were microfluidic system in combination with in-line PL and
chopped by gas bubbles inside the capillary. This method absorption measurements allows the rigorous and rapid
was successfully employed for the continuous synthesis of mapping of the reaction parameters, including molar ratios
Pt and Pd nanostructures of varied morphologies (Sebastian of precursors, reaction temperatures, and reaction times.
et al., 2016). In this approach, O2 , CO, or N2 were used The rapid screening is especially important in this system,
to chop both aqueous and non-aqueous fluids containing since it has an extremely fast reaction kinetics, which
reactants and ligands. This enabled tuning the reduction is very difficult to monitor using a corresponding batch
kinetics and controlling the size and the shape of the NPs. approach. This in turn translates into enormous savings in
In addition to the droplet generation, separation of the reagent usage and screening times. Another recent example
nucleation and the growth steps by introduction of a dual- of a complex synthesis realized on a microfluidic platform
temperature stage was used in the synthesis of PbS QDs with the aid of in-line monitoring of the optical proper-
developed by the Sargent group on a commercially available ties is a scalable production of core/shell CuInS2 /ZnS NPs
continuous flow reactor, FlowSyn Multi-X, (Figure 1.7d) (Yashina et al., 2016). This in-line detection enabled a rapid
1-12 Design Strategies for Synthesis and Fabrication
assessment of optimal reaction parameters which resulted in transport rates within thin films and hence tuning the NP
the formation of NPs with high PLQYs of up to 55%, emit- size and size distribution (Chin et al., 2008).
ting in the range of 580–760 nm, within a few seconds. In Two designs of the SDPs have been reported so far. The
this method ZnS-single-source precursor was injected into first one is relatively straightforward, with the reagents
droplets containing CuInS2 NP cores without their purifica- fed to the spinning disc, where they form a thin film and
tion. interact, yielding the product which is taken away to the
collection point at the bottom (Figure 1.8a) (Iyer et al.,
2007). In the second type, also known as a high-gravity
1.3.2 Spinning Disc and Rotating Tube
process, the disc is placed vertically so that the product
Reactors
easily drops out of the reactor chamber (Figure 1.8b). Two
Spinning disc and rotating tube reactors (also called proces- operation modes can be employed in these reactors: a contin-
sors, SDP and RTP, respectively) are considered as a uous mode (Tai et al., 2009a) or a recycle mode (Tai et al.,
scalable, continuous, and high-throughput method for NPs 2009b), when the collected product is fed back to the disc.
synthesis (Chen et al., 2014). Basically, an SDP consists Using the first type of design, Ag NPs of different sizes were
of a rotating disc with speed control and feeding jets that synthesized from silver nitrate, ascorbic acid, and soluble
supply reactants to the disc, as shown in Figure 1.8a. The starch as a stabilizing agent (as its biocompatibility is favor-
disc can be rotated at high speeds to obtain thin fluid films able for biomedical application) in water at room tempera-
(1–200 µm) resulting in a high area-to-volume ratio. These ture (Iyer et al., 2007). The tunability in particle size from
thin films are divided into two zones: (i) the injection point 5 to 200 nm was achieved by varying the disc speed and the
where the reagents hit the disc to form a pool in its center, concentration of the reactants. ZnO NPs were synthesized
and (ii) the acceleration and synchronized flow area, where using two feed solutions: zinc nitrate hexahydrate and PVP
the fluid film initially experiences an increase in radial flow in ethanol, and a base in ethanol (Hartlieb et al., 2007). In
velocity and then the liquid is rotating close to the disc this method, size control was realized by raising the disc
velocity. The shear forces and viscous drag between the temperature up to 80◦ C, although this also increased the
moving fluid layer and the disc surface create turbulence and polydispersity of the NPs. For superparamagnetic Fe3 O4
ripples, thus giving rise to highly efficient mixing within the NPs to be used in various applications such as MRI, targeted
thin fluid film that ensures extremely short reaction resi- drug delivery, magnetic separation, and others, the size
dence times and enables impulse heating and immediate has to be less than 20 nm. A continuous synthesis by
subsequent cooling. Controlling the levels of mixing asso- SDP delivered Fe3 O4 NPs in the range of 5–10 nm, with
ciated with the waves offers the possibility of governing the narrow size distribution, characterized by remarkably high
FIGURE 1.8 (a, top) Schematic representation of an SDP (Iyer et al., 2007). (a, bottom) Hydrodynamics of the fluid flow over a
spinning disc surface (Chin et al., 2008). (b) High-gravity SDP system (Tai et al., 2009a). (c) Continuous flow synthesis of Au nanorods
using an RTP serially with a narrow channel processor (NCP) (Bullen et al., 2011). (Reproduced with permission from the Royal Society
of Chemistry, Wiley VCH Verlag GmbH & Co, and American Chemical Society.)
Large-Scale Colloidal Synthesis 1-13
saturation magnetizations (Chin et al., 2008). For the first by turning the synthesis into a continuous mode employing
time, ammonia gas was used as a base blown on a thin film tubular or spinning disc reactors. Especially attractive is
of aqueous iron salt on a disc. the application of microfluidic systems, which benefit from
By using the second type of the design in the recycle a better control owing to a small amount of reaction mixture
mode, Ag NPs of ≥10 nm were synthesized at room temper- processed at a time, and reduced hazard potential. At the
ature by a green chemistry approach (Tai et al., 2008), in same time, this small reaction volume can be disadvanta-
which two aqueous solutions, AgNO3 with starch and NaOH geous, as it significantly decreases throughput of the system.
with glucose (as a reducer), were fed into the center of the Here, a further development is needed to adopt microfluidic
rotating disc (1000–4000 rpm) to form thin film and subse- reactors to scale up amounts of NPs produced to meet indus-
quently reacted, yielding the NPs. Recycle mode ensured NP trial demands.
yield of >56%, as the residence time on the disc was short As a general trend in the large-scale production of NPs,
and sometimes, one run was insufficient to reach an efficient one can define the use of low-cost precursors, low-energy
conversion of reagents. This approach was further extended consumption, as well as simple and environment-friendly
to synthesize Ag NPs of <10 nm in size by replacing starch processes. As discussed in this chapter, modern synthetic
with PVP, where the reaction yield was improved up to 85% protocols, even by upscaling, ensure high quality and narrow
by increasing the recycling time (Tai et al., 2009b). They size distribution of NPs, which has a special importance
also exploited this synthesis in continuous mode in order to for the QDs with bright and narrow fluorescence engaged
increase the production rate and found that the yield was in various light-emitting applications. This allows one to
higher in the recycle mode (Tai et al., 2009a). Furthermore, eliminate additional post-synthetic treatment processes,
using the same setup, spherical- and disc-shaped magnesium such as size selection of the particles. However, such common
hydroxide NPs were synthesized (Tai et al., 2007). steps, as the separation and the purification of the as-
RTPs are related to SDPs in generating thin films with prepared NPs, are typically performed using batch princi-
turbulent flow, with an advantage of an extended residence ples rather than continuous ones. Such steps, involving the
time of the liquid in the reactor. While in SDPs, this time is coagulation of NPs in reaction mixture, with their precipi-
less than a second for a 10 cm disc, in RDPs, the residence tation by centrifugation followed by repetitive washing, are
time can be controlled up to a minute depending on the size presently not optimized or automated. This means that
of the tube, flow rates, and viscosity of the liquid (Bullen there is still plenty of room for improving the whole effi-
et al., 2011). In an RTP, the centrifugal force generates ciency of the process, as, e.g., these steps too could be
dynamic thin films as the liquid moves along the rotating executed in a continuous mode. Here, regeneration and recy-
tube. Figure 1.8c presents an example of such reactor cling of organic solvents/ligands used in the synthesis should
coupled with a narrow channel processor (NCP) which were lead to a significant reduction of the processes and mate-
used for the continuous seedless synthesis of Au nanorods rials costs, as solvents/ligands constitute a main part of the
(Bullen et al., 2011). The RTP employed in this work was reaction mixture in the colloidal synthesis. This is the area
6 cm in diameter and 30 cm in length, and its rotation rate where a valuable contribution from the chemical and process
was set at 1000 rpm resulting in an average film thickness of engineers is highly demanded.
ca. 300 µm at a residence time of 30 s. The authors used two For further advancing the large-scale production of NPs,
feed solutions: HAuCl4 /cetyltrimethylammonium bromide one would need efficient coupling of the synthesis and
(CTAB)/acetylacetonate and AgNO3 /CTAB/carbonate the post-synthetic treatment units with a high-throughput
buffer. During the processing, Au NPs formed in the RTP analytical systems for in-line characterization and control
were fed into the NCP for the further growth of the Au of the processes and products. Directly related to this is
nanorods. the development of a user-friendly advanced software which
would allow controlling all the production stages from one
operator center. Therefore, to turn NPs to industrial and
1.4 Conclusions and Outlook commercial lines, coordinated efforts from a wide range
of specialists including synthetic and analytical chemists,
In this chapter, the main methods for the colloidal synthesis
chemical, process and automatization engineers, physicists,
of various NPs that have demonstrated large-scale produc-
managers, etc. are highly required.
tion capabilities are summarized. Among the one-batch
modes, the heat-up approach seems to be the most suit-
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Procter and Gamble Company.
MU9153.
Professional Films, Inc.
LP43667.
Professional Selling Institute, Inc.
MP25567 - MP25576.
Profiles in literature.
MP25827 - MP25848.
MP25923.
Profiles of achievement.
MP25673.
Program for management achievement.
MP25690 - MP25699.
Programming in a VS environment.
MP25583.
MP25737.
Progressive Broadcasting Foundation.
MP26012 - MP26015.
Promised land, troubled land.
MP25540.
Prospecting the million dollar year.
MP25569.
Psychology today film.
MP26000.
MP26001.
MP26002.
Public Communication Foundation for North Texas, Dallas.
MP25808.
Public Media, Inc.
MP25760.
Public Media, Inc. Visual Education Centre.
MP25508.
Public relations, this means you.
MP26046.
Pursuit driving, Defensive driving 4.
MP25758.
Pyramids.
LP43902.
Q
Quadrant films, Ltd.
LP43740.
Quality, a constant search.
LP43695.
Queen is crowned.
LF185.
Queen’s diamonds.
LF190.
Quick cuts.
MU9162.