3.

4 Inorganic and inorganic compounds nanomaterials

Cadmium selenide (CdSe), an important II–VI semicon-
ductor material, has been one of the most extensively stud-
ied semiconductor systems in nanoscale form over the last
20 years due to the specific photoelectric properties and
potential use in optoelectronics, luminescent materials,
lasing materials, and biomedical imaging [98].

Scheme 9 Mechanism for the pH-responsive self-assembly of MCP

nanoparticles [97].

Scheme 10 Mechanism for the temperature-responsive self-assembly of

MCP nanoparticles [97].
404 Li W, et al. Sci China Tech Sci February (2012) Vol.55 No.2
In ref. [99], CdSe nanostructures with urchin-like shape an important semiconductor material, CuS has attracted much
were successfully synthesized in two types of microemul- attention due to not only its excellent electrical, opti- cal
sion solutions (water content w=13.5), which were prepared properties but also its potential applications in optical
by adding equivalent volume of Na2SeSO3 or Cd[(NH3)4]2+ recording material [105], sensors [106], solar cell [107], and
solution drop by drop to an n-octane/cetyl trimethyl ammo- catalysts [108] and so on. CuS hollow spheres have been
nium bromide (CTAB)/1-butanol system. The X-ray pow- der synthesized using microemulsion templates.
diffraction pattern of the product showed that it was pure In ref. [109], CuS hollow spheres have been successfully
CdSe in zinc blende structure rather than thermody- namically synthesized through a facile microemulsion-template-in-
favored wurtzite structure. It was found that nu- merous one- terfacial-reaction route using copper naphthenate as metal
dimensional CdSe nanorods radiated from the center of the precursor and thioacetamide as the source of S2. In this
agglomerate to form urchin-like nanostructures and grow way, hollow spheres could be obtained directly since the
along the (111) crystal planes. Figure 33 showed the TEM reaction of two reactants respectively dissolved in two dif-
images of the CdSe nanoparticle. The photolumi- nescence ferent phases of an O/W microemulsion only occurs at the oil/
spectrum of the urchin-like nanostructures indi- cated that water interface. Therefore, it is a key for forming hol- low
there was a blue-shift as compared with that of the bulk spheres to optimize the interfacial reaction rate by con-
CdSe. Additionally, these interesting urchin-like trolling reaction conditions. Furthermore, the size of the
nanostructures showed an increased specific surface area. hollow spheres can be tailored by changing the content of
This study provides a simple method to prepare urchin-like oil phase. In this study, the average diameter of the CuS
CdSe nanostructures on large scale, which may broad their hollow spheres can be adjusted from 110 to 280 nm by
practical applications. changing the content of oil phase from 0.5 mL to 1.5 mL. In
Hollow spheres have received considerable attention re- addition, the reaction temperature is a very important factor
cently because of diverse applications, including catalysis for forming CuS hollow spheres and the appropriate reac- tion
[100], drug delivery [101], electric magnetic absorption temperature is about 50°C. Figure 34 showed the TEM images
[102], chemical sensors[103], structural materials [104]. As of the samples prepared at 50°C. A schematic illustration of
the formation mechanism of the CuS is shown in Scheme 11.

Figure 32 TEM images of (a) magnetic chitosan oligosaccharide pluronic

(MCP) nanoparticles and (b) chitosan-coated magnetic nanoparticles [97].
Figure 34 TEM images of the samples prepared at 50°C with different
oil phase contents: (a) 0.5 mL, and (b) 1.5 mL [109].

Figure 33 (a) Low magnification FE-SEM image of the product prepared

at 120°C for 12 h (w=13.5); (b) FE-SEM image of an individual urchin-like Scheme 11 Schematic illustration of the formation of the CuS hollow
CdSe nanostructure; (c) FE-SEM image of a spherical structure; and (d) spheres [109].
EDS spectrum of the spherical structure [99].
 Li W, et al. Sci China Tech Sci February (2012) Vol.55 No.2 405
Semiconductor nanocrystals are of great interests for the TEM, HRTEM image, and SAED of CdS nanoparticles.
both fundamental research and industrial development. This The results confirmed that both ethylenediamine and ultra-
is due to their unique size-dependent optical and electronic sound played important roles in the formation of the final
properties and their exciting utilization in the field of light- nanostructure. Scheme 12 illustrated the proposed model for
emitting diode [110], electrochemical cells, laser [111], hy- the formation of CdS nanoparticle.
drogen producing catalyst [112], biological label [113]. Middle-phase microemulsions (MPMs) are multi-phase
They are usually prepared in the liquid reaction system at high equilibrium systems comprising the microemulsions and
temperatures for several hours. These methods are ei- ther residual water or residual oil, i.e., a lower-phase oil in water
expensive, explosive, moisture sensitive or extreme toxic, (O/W, Winsor I) microemulsion with excess oil upper-phase
energy consuming. In most cases, the particles are formed by or an upper-phase water in oil (W/O, Winsor II) microe-
arresting precipitation of reaction precursors of the reverse mulsion with excess water lower-phase or MPMs with bi-
W/Omicroemulsions under certain conditions [114]. It is continuous water and oil are called BC (Winsor III)
worth mentioning that microemulsions and ul- trasound microemulsion.
irradiation are two synthetic methods for na- nosized sulfides In ref. [118], middle-phase microemulsions (MPMs) in two
that have been studied intensively and have aroused more and systems of a cationic surfactant, tetradecyltrimethyl-
more attention [115]. ammonium bromide (TTABr)/n-butanol/isooctane/ Na2CO3
Ghows et al. [116] reported that cadmium sulfide or CaCl2 and an anionic surfactant, sodium dodecyl sulfate
nanoparticles with a hexagonal phase (~10 nm) were pre- (SDS)/n-butanol/ iso-octane/Na2CO3 or CaCl2, were used to
pared at a relatively low temperature (70°C). This synthesis synthesize nanostructured calcium carbonates. MPMs pro-
was carried out shortly (30 min) through a new microemul- vide a simple and versatile reaction medium, i.e., up- per-
sion (O/W) induced by ultrasound without surfactant. Ul- phase W/O, BC, and O/W structured equilibrium mi-
trasound can provide an excess energy for new interface croemulsions to be used for synthesizing hierarchically
formation and obtain emulsions even in the absence of sur- structured CaCO3 on the nanometer scale. On the basis of
factants. This technique avoids some problems that nor- the investigations on the phase behavior of the MPMs, the
mally exist in conventional microemulsion synthesis such as hierarchically structured calcium carbonates with dendrites,
the presence of different additives and calcinations. In addi- ellipsoids, square-schistose cubes, and spheres were synthe-
tion, it was possible to tune the particle size, the band gap, and sized through the MPM-based routes (Figure 36).
the phases of CdS nanoparticles by changing the vari- ables This work was to develop a method to synthesize nano-
such as ultrasonic irradiation time, intensity, precursor, and meter-scale inorganic particles, open alternative pathways
ratio of the components. It was also found that the syn- to synthesize complex superstructures of inorganic materials,
thesized nanoparticles had a bandedge emission at about and construct the correlation between the morphologies of
460 nm with a blue-shift to a higher energy which is due to CaCO3 and the structures of microreactor media.
the typical quantum confinement effects. Figure 35 showed Particles with well-defined pore morphology are essen-
tial for many areas of modern technology. Potential applica-
tions include catalysis [119] and electrocatalysis [120],
chromatography [121], and drug delivery [122]. Precise
control over the pore size and shape is crucial for the

Figure 35 (a) TEM, (b) HRTEM image, and (c) SAED of CdS nanopar- Figure 36 SEM images of CaCO3 synthesized from the upper-phase
ticles [117]. equilibrium W/O microemulsions of the TTABr system [118].
406 Li W, et al. Sci China Tech Sci February (2012) Vol.55 No.2

Scheme 12 Proposed model for the formation of CdS nanoparticle [117].

successful performance of the particles. It allows for opti- Scheme 13 showed the sketch of liquid silica precursor
mization of fluid transport in a catalyst, determines the mo- emulsion system. Figure 37 showed the TEM of the parti-
lecular release of solute by a drug delivery vehicle, or de- cles.
fines the size selectivity in chromatography. Zhang et al. [124] investigated the effect of ultrasound on
Ref. [123] showed that hierarchically bimodal porous
structures could be obtained by templating silica micropar-
ticles with a specially designed surfactant micelle/micro-
emulsion mixture. Tuning the phase state by adjusting the
surfactant composition and concentration allows for the
controlled design of a system where microemulsion droplets
coexist with smaller surfactant micellar structures. The mi-
croemulsion droplet and micellar dimensions determine the
two types of pore sizes. They also demonstrate the fabrica- Scheme 13 Sketch of liquid silica precursor emulsion system. (a) Aque-
tion of carbon and carbon/platinum replicas of the silica ous silica precursor emulsion drops (light gray) in hexadecane oil (dark
microspheres using a “lost-wax” approach. Such particles gray). Microemulsion droplets form and occupy the internal drop volume
have great potential for the design of electrocatalysts for (small dark gray circles). (b) Single aqueous silica precursor drop. CTAB
is above the CMC, forming micelles (red) in addition to microemulsion
fuel cells, chromatography separations, and other applica- droplets (dark gray). (c) Oil/water interface with adsorbing surfactants
tions. from the two immiscible phases [123].

Figure 37 Characterization of templated carbon particles and templated carbon particles decorated with platinum nanoparticles. (a) SEM image of carbon
particle surface; (b) TEM image of the carbon particle cross section showing the internal structure; (c) TEM of the templated carbon particle decorated with
platinum nanoparticles; (d) TEM of the cross section of templated carbon particle decorated with platinum nanoparticles showing the internal structure and
dispersion of the platinum nanoparticles; (e) TEM of the templated carbon particle decorated with platinum nanoparticles at higher magnification [123].
 Li W, et al. Sci China Tech Sci February (2012) Vol.55 No.2 407
the microenvironment of sodium bis(2-ethylhexyl) sulfosuc- zeolites template from a mixture of small organic ammo-
cinate (AOT) reverse micelles in isooctane. It showed that the nium salts and mesoscale cationic polymers. The route in-
micellar shape transformed from spherical to ellipsoidal with volves a one-step hydrothermal synthesis, and the templated
ultrasound. On the basis of these investigations, ZnS nano- mixture is homogeneously dispersed in the synthetic gel. In
rods and nanofibers were synthesized in the reverse micelles their work, hierarchical mesoporous Beta zeolite (Beta-H)
by the ultrasound-induced method (Figure 38). was crystallized in the presence of TEAOH and a mesoscale
A possible mechanism for ultrasound-induced formation cationic polymer, polydiallyldimethylammonium chloride
of nanorods and nanofibers in reverse micelles was dis- (PDADMAC). Low-magnification scanning electron mi-
cussed (Scheme 14). It revealed that ultrasound resulted in croscopy (SEM) images of the calcined sample of Beta-H
reaggregation of the reverse micelles and thus enlarged the are shown in Figures 39(a) and 39(b). The presence of hier-
water core of the micelles. Spherical ZnS nanoparticles can archical mesoporosity in the Beta-H sample is attributed to
also transform into nanorods and nanofibers in the reverse the use of the molecular and aggregated cationic polymer
micelles with the aid of ultrasound, and their length can be PDADMAC. The molecular weight of the cationic polymer
controlled by ultrasound time. lies in the range 1 × 105–1 × 106, and its size is estimated to
Xiao et al. [125] demonstrated a facile, controllable, and be 5–40 nm, which is in good agreement with the dimen- sions
universal route for the synthesis of hierarchical mesoporous of the mesopores obtained from high-resolution (HR) TEM
studies (Figure 39(d)). The cationic polymers could
effectively interact with negatively charged inorganic silica
species in alkaline media, resulting in the hierarchical
mesoporosity. The addition of a greater amount of cationic
polymer to the synthetic gel yields Beta zeolite with larger
mesoporosity, indicating the controllable mesoporosity of
the zeolite sample. These novel zeolites exhibit excellent
catalytic properties compared with conventional zeolites.
After that, Liu et al. [126] reported that ordered hexago-
nal mesoporous silica materials with additional disordered
large-mesopore networks (DL-SBA-15s) had been prepared
by one-pot process using urea as a producer of gas. The result
showed that DL-SBA-15s not only had ordered
2D hexagonal mesopores (about 10 nm), but also had an-
other disordered large-mesopore network (about 20 nm)
interconnected with hexagonal mesoporous channels,
which were confirmed by nitrogen isotherms (Figure 40).
The ordered hexagonal mesopores were templated by

Figure 38 TEM photographs of ZnS particles with different ultrasound

times (t). (a) t = 0 h; (b) t = 0.5 h; (c) t = 2 h; (d) t = 4 h [124].

Figure 39 Electron microscopy images of calcined Beta-H: (a), (b) SEM

images at low and high magnification, respectively (the separation between
Scheme 14 Proposed mechanisms for the ultrasound-induced formation each marker represents 5 mm and 100 nm, respectively); (c), (d) TEM
of nanorods and nanofibers in AOT microemulsion [124]. images at low and high magnification, respectively [125].
408 Li W, et al. Sci China Tech Sci February
(2012) Vol.55 No.2

Scheme 15 Proposed mechanism on synthesis of DL-

SBA-15 samples
[
1
2
6
]
.

Figure 40 SEM images of DL-SBA-15-85 in (a) low

magnification, (b) high magnification of area A and (c) high
magnification, and (d) schematic drawing of the
interconnected pore channels in area B [126].

polymer surfactant micelle, and disordered large-

meso- pores were formed by gaseous expansion
due to the de- composition of urea added in the
silica gel. The proposed mechanism on synthesis
of DL-SBA-15 samples was il- lustrated in
Scheme 15.