From Formation Mechanisms To Synthetic Methods Toward Shape-Controlled Oxide NP (2013)

Nanoscale
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From formation mechanisms to synthetic methods

toward shape-controlled oxide nanoparticles
Cite this: Nanoscale, 2013, 5, 9455
Thanh-Dinh Nguyen*
Metal oxide nanomaterials have been intensively pursued for modern science and nanotechnology.
Control over the size and shape of the oxide nanoparticles enables tunability of their unique properties
sought for many useful applications. This review presents a comprehensive overview of the recent
advances in the shape-controlled synthesis of colloidal oxide nanoparticles. We introduce the size- and
shape-dependent properties of the oxide nanoparticles along with their potential applications and
subsequent descriptions of the kinetic regime concepts of the formation of the monodisperse
nanocolloids. Variations of the experimental conditions including capping molecules, precursor
monomer concentration, and reaction temperature/aging have been explored to control the shape of
the oxide nanoparticles in wet-chemistry syntheses. The different capping molecule-assisted synthetic
methods of the hydro-solvothermal route, the two-phase route, heating-up thermolysis, and reverse
Received 11th April 2013
Accepted 17th July 2013
micelle are presented as a collection of clear examples of the regular oxide nanoparticles. We also
discuss the advantages and obstacles of the synthetic methods that have proven to be controllable and
DOI: 10.1039/c3nr01810e
reproducible. The author concludes this review with valuable portraits on working hypotheses for the
www.rsc.org/nanoscale shape-controlled oxide nanoparticle synthesis.
1 Introduction large diversity of oxide nanocompounds with intriguing geom-

etries and unique electronic structures that could give rise to
Inorganic nanoparticles of the characteristic length from 1 to new optical, magnetic, and catalytic properties.3,5 The oxide
100 nm possess the best electronic and transport properties of nanoparticles have been used as fundamental building blocks
both bulk materials and molecules resulting from the surface to fabricate nanohybrids that could offer the inspiration for the
states and quantum connement effects.1 As a broad family of design of new materials.6–9 The future application options for
functional materials, metal oxide nanomaterials play an oxide-based nanomaterials would appear to be endless. In the
important role in many areas of nanotechnology.2–4 Metal emerging eld of nanotechnology, the oxide nanomaterials are
elements react with enriched oxygen reactants to generate a used in the commercial construction and design of catalysts,
nanoelectronics, optics, sensors, solar cells, piezoelectric
devices, etc.10–12 These materials have also opened up new
Department of Chemical Engineering, Laval University, Quebec G1V 0A6, Canada.
opportunities for the development of optical sensors, imaging-
E-mail: thanh-dinh.nguyen.1@ulaval.ca
guided therapy, and drug delivery agents as the magnetic
properties of iron oxide nanoparticles provide diagnostic
advantages in biomedicine.13–17
Thanh-Dinh Nguyen completed
The goal of preparing oxide nanostructures is to create new
his BS (2003) and MS (2006)
properties with respect to those of bulk species. The oxide
degrees in chemistry from Hue
nanoparticles can exhibit unique physicochemical properties
University, Vietnam. He moved to
originating from their limited size and a high density of their
Laval University, Canada in
corner or edge surface sites associated with the shape effect.18–21
2007, where he studied with Prof.
These features of oxide nanomaterials are determined by a set
Trong-On Do and completed his
of physical parameters, such as size, shape, composition,
PhD degree in 2011 in chemical
structure, and surface chemistry.22,23 The interest in oxide
engineering. His research inter-
nanoparticles stems from the fact that the tunable new prop-
ests are focused on the shape-
erties acquired at the nanoscale length could be drastically
controlled synthesis of uniform,
altered in the size and shape changes.24 The bounding facets of
monodisperse oxide nano-
the oxide nanocrystal, the number of step edges and kink sites,
particles and dependent catalytic
and the high specic surface area can dictate unique surface
properties.
This journal is ª The Royal Society of Chemistry 2013 Nanoscale, 2013, 5, 9455–9482 | 9455
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chemistries. From the fundamental scientic viewpoints, the growth.34 The organic molecule-capped oxide nanoparticles
synthesis of uniform oxide nanoparticles with size and shape could act as intermediate seeds to grow up into elongated
control is very important to characterize their dependent nanoparticles by oriented attachment of the crystal facets with
properties. In principle, one could ne-tune the particle prop- high surface energy.35,36 Otherwise, the formation of intrinsic
erties by controlling any one of the reaction parameters, but the anisotropic nanoparticles is found to be highly kinetically
scope of the change is highly sensitive to the specic parame- driven, which could occur far away from the thermodynamic
ters. The most important requirement in the synthesis of oxide equilibrium, and is overdriven by high precursor monomer
nanomaterials is the good controllability of the size and shape, concentration.37
while maintaining the uniformity of the monodisperse nano- Being small could make the surface of an oxide nanoparticle
particles.25 Otherwise, to fully exploit the potential of the oxide unstable due to the high surface energy and the large surface
nanoparticles with desired properties through the under- curvature. Thus, it is necessary to develop protection methods
standing of the relationship between morphology and reaction to chemically stabilize the naked oxide nanoparticles against
parameters, it is essential that they be synthesized with precise degradation during or aer synthesis. Capping molecule-assis-
size and shape control. On the other hand, the costs required ted synthesis has become a powerful tool for manipulating the
for preparing oxide nanomaterials are limiting factors for uniform shape of the monodisperse oxide nanoparticles.24,38,39
scalable production. The production of large quantities of Different capping molecule-based methods including solvo-
uniformly sized oxide nanoparticles will become critical for the hydrothermal treatment, thermolysis, and reverse micelle have
realization of nanoscale devices and converting them into demonstrated success in the superior shape and size control for
commercial products. exploring their unique nanomaterial properties. The selective
Much progress in the synthesis of colloidal oxide nano- adsorption of the capping molecules on the nanoparticle
particles over the past ten years has been pursued for a nano- surfaces allows for controlling the growth of the desired parti-
technological revolution in many useful applications.26–29 The cles.34,40 This protocol was rst developed for the synthesis of
synthetic procedures for metal oxide nanoparticles in colloidal the metal and metal oxide nanoparticles,38,41 the capping
solution have evolved gradually from 1950s onward since Far- molecule-stabilized synthesis has been extended to the diverse
aday's pioneering work on gold sols more than 150 years ago.30 nanoheterostructures.42 In the capping molecule-assisted
The particle growth was described by the growth model of synthesis, the choice of appropriate capping molecules is
LaMer reported in 1950s.31 The central aspect of LaMer's model crucial for controlling the nucleation and growth kinetics in
is that the formation of the seeds rst occurs by increasing the manipulating the size and shape of the nanostructures. By
precursor monomer concentration in the bulk solution to a varying the nature and concentration of the capping molecules,
supersaturation level. The monomers continuously aggregate it has proven to be possible to tune the shape, the size, and the
on the seeds leading to a depletion of the monomer concen- properties of the nanoparticles.22,43 These methods comprise
tration to generate nanoparticles. The size focusing of the capping with organic molecules or coating with a thin layer of
colloidal particles occurs in the burst nucleation and controlled polymer or silica whichever is preferred.44 It is known that an
growth under high supersaturation conditions. Binding of the unavoidable problem relevant to the oxide nanoparticles is their
coordinating molecules to the oxide seeds retards the particle intrinsic instability over longer periods of time. Such small
formation and keeps the supersaturation level high enough for particles tend to form agglomerates to relieve the surface energy
a while. The coordinating molecules bound on the particle associated with a high surface area-to-volume ratio, which could
surface endow them with a good colloidal stabilization in the lead to a loss of their unique properties. The capping of the
reaction solvents. surface with the organic molecules not only stabilizes the oxide
The nucleation and growth kinetics of the seeds play a major nanoparticles, but could also be used for the surface function-
role in determining the morphology of the oxide nanoparticles. alization to be compatible with applied environments. The
A real understanding of formation mechanisms of the uniform, capping molecules play critical roles in reducing the surface
monodisperse oxide nanoparticles is a demanding task for one activity of the uniform particle building blocks to self-assemble
to manipulate predictive phases and morphology manners.32,33 into ordered close-packed nanoarrays on substrates that offer
In the wet-chemical synthesis, the control of the kinetic regimes unforeseen intrinsic physical properties for multipurpose
and thermodynamic growth is a key factor to be able to yield the applications.8
uniform, monodisperse oxide nanoparticles. Within the Reviews are essential for keeping up with the current state of
regimes, the formation of the oxide nanoparticles could be by the research of interest in academic elds. This review aims to
Ostwald ripening with the growth of larger crystals occurring at focus on the classic oxide types with special emphasis on two
the expense of smaller particles.34 The growth of the nuclei has a aspects: the formation kinetics and the synthetic chemistry of
tendency to form low-energy particles, so the supply of suffi- capping molecule-assisted methods toward shape-controlled
cient energy to the reaction solution usually leads to the oxide nanoparticles. As we proceed, we will discuss the effects of
formation of sphere-shaped particles rather than other shaped surface and electronic properties of the oxide nanoparticles with
ones. Selective and nonselective binding of the capping mole- different sizes and shapes on the reaction performances. To give
cules to different crystal facets of the growing nanoparticles a more complete understanding of the formation of oxide
could result in controlling the morphology because of the nanoparticles, we described the oxide particle formation in detail
possibility of breaking the limitations of the dynamic crystal that is governed by kinetic (e.g., reactant concentration, reaction
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rate, solubility, diffusion) and thermodynamic (e.g., temperature, ratio. In other studies, the nanoscale connements of charge
surface passivation) parameters. This may be useful for readers carriers in the oxide particles include their size-dependent
who would have an overall view of the controlled growth mech- bandgaps, resulting in the tunability of the optical spectroscopy
anisms. We presented the possibility of effective capping mole- in the case of semiconducting particles48 and super-
cule-assisted methods for diverse uniform, monodisperse oxide paramagnetism in the case of magnetic particles,14 just as for
nanoparticle colloids. Besides discussing the synthetic advan- the semiconductors with smaller diameter possessing a
tages, we also mentioned the barriers to each method that were bandgap of higher energy, which exhibit a blue shi in the
overcome by materials researchers in order to advance their optical wavelength with respect to the corresponding bulk
promise for nanotechnology. species.48 This led to an increase of the energy of the excited
carriers in the semiconductor nanoparticles providing higher-
2 Interesting size and shape tunable energy excitons that enable better photocatalytic degradation of
properties absorbed organics and conversion of sunlight into electrical
energy.49–51 The dependence of photocatalytic hydrogen
Successful nanomaterial-enabled applications require oxide production on the size of the deposited particles and the
nanoparticles with well-dened geometries in order to predict structural phase of the nanosupports is shown in Fig. 1a and b.
their properties. Oxide nanoparticles have tunable nanoscale Murdoch et al.45 demonstrated that the photocatalytic hydrogen
properties as a result of their controlled size and shape. The production from ethanol over Au/TiO2 anatase is two orders of
precise control of their structural morphologies could provide magnitude higher than that over Au/TiO2 rutile. The Au/TiO2
one with a facile strategy to tailor the surface structure depen- anatase exhibited an enhanced catalytic rate with an increase in
dent properties of the oxide nanomaterials. This allows us to the Au particle size from 3 to 12 nm (up to 4 wt% Au) and a
integrate them into a new platform response with potential uses decreased reaction rate when increasing the size of the Au
in many possible applications. The largest activity in this eld at particles to 16 nm (up to 8 wt% Au). Kim et al.46 demonstrated
this time has been in the controlled synthesis of novel oxide that magnetic properties of g-Fe2O3 nanoparticles are strongly
nanoparticles of different sizes and new shapes. dependent on their particle size. Fig. 1c and d show eld-
The size effects constitute a fascinating aspect of oxide dependent magnetization curves of 1.5, 2.2, 3, and 12 nm-sized
nanomaterials. When the size of an oxide particle decreases to a g-Fe2O3 nanoparticles. The temperature-dependent magneti-
nanometer regime, the associated properties are increasingly zation measurement shows that the blocking temperatures of
governed by considerations of an increased surface area to the 12, 3, and 2.2 nm-sized g-Fe2O3 particles were found to be
volume ratio and quantum connement effects. The increasing 197, 8, and <5 K, respectively. The coercivity and remanence of
surface area-to-volume ratio leads to an increase in the domi- extremely small-sized g-Fe2O3 particles (<4 nm) were negligible
nance of the surface atoms of the oxide nanoparticle over those in at 5 K compared to conventional superparamagnetic nano-
its interior. The size quantization refers to the change in the particles. The dramatically decreased magnetization of the
energy level structures of the oxide nanoparticles when the extremely small-sized g-Fe2O3 particles can be attributed to
building unit size drops below a certain size. This size tuned from their small particle volume of a signicant shrinkage of the
~100 nm to a single nanometer associated with the Bohr diam- magnetic core. The room-temperature magnetic properties of
eter of the material. The electronic structure could be altered these materials are necessary for developing a magnetic reso-
from the continuous electronic bands to the discrete or quan- nance imaging (MRI) technique in clinical diagnosis applica-
tized electronic levels that could give rise to the dependent tions. These demonstrations distinctly imply that optimizing
properties. The effect of the reducing size of the oxide nano- the size of the oxide nanoparticles would produce surface-active
particles is associated with localized electrons and defects that materials with enhanced reaction performance.
are the most signicant contributions to the evolution of the The capping molecule-assisted methods of synthesizing the
surface structure dependent properties of these nite systems. oxide nanomaterials have also shown that in addition to size,
The effective percentage of the surface atoms is a function of the the nanostructure's shape can also profoundly affect their
particle diameter with an increase in the number of the surface physicochemical properties. The particle shape is strongly
atoms along with a decrease in the particle size. The number of related to the surface atomic structure, which could be deter-
atoms at the surface and the limited number of atoms within the mined by the adsorption of the reactant molecules, surface
lattice are considered to be defect sites relative to unsaturated transfer between electrons, and reactant molecules. The surface
ions. Thus, increasing the effective percentage of the surface atomic arrangement and coordination could be tuned along
atoms could result in improving the reaction performance of the with the orientation of the crystal facets. With the continuing
nanoparticles (e.g. high reactive/selective catalysts). decrease in the particle size, the surface area-to-volume ratio
Some early reports demonstrated the exciting size-depen- increases dramatically and the shape could impart its own
dent optical property of Au cluster solutions similar to Au sols, inuence on the surface structure. The high energy facets
which originates from the self-assembly of the Aun clusters with usually exhibit preferable activities due to the unsaturated
atom shells in a cubic close-packed arrangement with an coordination atoms, atomic steps and ledges. The concept of
enhanced stability.47 The result of this self-assembly includes an shape-dependent nanocatalysis was found in the various oxide
appearance of the unique properties in the electronic structure nanomaterials. Optimizing the nanocatalyst morphology has
of the Au nanomaterials with a high surface area-to-volume become a prolic area of investigation, where the materials
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Fig. 1 The size effect of the oxide nanoparticles on the reaction performance. Photocatalytic hydrogen production depending on the size of the deposited Au particles
and the structural phase of the TiO2 nanosupports: (a) electron microscopy image of 2 wt% Au/TiO2 anatase photocatalysts. (b) Hydrogen photo-production over the
Au/TiO2 anatase and rutile as a function of Au loading. Reproduced with permission from ref. 45, copyright 2011 Nature Publishing Group. (c) Field-dependent
magnetization curves at 300 K for the different sized g-Fe2O3 nanoparticles. (d) Description of the spin canting effect in the different sized g-Fe2O3 nanoparticles with a
core–shell structure. Reproduced with permission from ref. 46, copyright 2011 American Chemical Society.
Fig. 2 The shape effect of the oxide nanoparticles on the reaction performance. (a) Hydrogen production rate as a function of the percentage of the exposed active
facets of NaOH-treated TiO2 nanocrystals loaded 1.0 wt% Pt under solar illumination in methanol–water. Reproduced with permission from ref. 52, copyright 2012
American Chemical Society. (b) CO conversion over the CeO2 nanocrystals with cubic and truncated octahedron shapes. Reproduced with permission from ref. 53,
copyright 2012 The Royal Society of Chemistry. (c) Comparative oxygen storage capacity of the CeO2 nanocrystals with cubic {100} facets and the irregularly shaped
CeO2 powders. (d) TEM images of the CeO2 nanocubes and irregularly shaped CeO2 powders. Reproduced with permission from ref. 54, copyright 2011 American
Chemical Society.
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researchers can rationally control the oxide nanoparticle shape homogeneous nucleation, heterogeneous nucleation, and
and surface morphology. Fig. 2a shows that the hydrogen secondary nucleation. The homogeneous nucleation occurs due
production rate is a function of the percentage of the exposed to the driving force of thermodynamics because the supersat-
active facets of the TiO2 nanocrystals. Gordon et al.52 demon- urated solution is unstable in energy.59 To gain uniform oxide
strated that NaOH-treated TiO2 nanocrystals with high nanoparticles, the supersaturation high enough for the bulk
percentages of exposed active {101} facets exhibit an enhanced solution should be maintained to guarantee that the nucleation
photocatalytic activity of the hydrogen generation from meth- of the oxide seeds occurs in a short period under reaction-
anol. Yang et al.55 revealed that exposed {001} facets of truncated controlled conditions, aer which the system should enter a
octahedral TiO2 nanoparticles are more reactive than {101} diffusion-controlled regime without subsequent nucleation,
facets for the dissociative adsorption of the reactant molecules. where the growth is eventually restricted by the rate of the long-
Wang et al.53 reported that CeO2 nanocubes exposed with {100} distance reactant transport.
facets show higher CO catalytic activity than truncated octahe- Most materials researchers have assumed that the oxide
dral CeO2 nanocrystals enclosed by six {100} and eight {111} nanoparticle growth proceeded by a mechanism analogous to
facets. As shown in Fig. 2b, the catalytic activity of the {100} the formation of monodisperse sulfur colloids in ethanol
facets is better than the {111} facets because the ceria nano- solution previously postulated by LaMer.31 This model revealed
cubes may contain more coordinatively unsaturated cerium that the oxide nanoparticles are generated from a process of the
atoms and more active adsorption of dissociated oxygen species burst nucleation and growth by monomer addition, and these
on the highly exposed reactive {100} facets. This result is two stages are temporally distinct.60 The concentration of the
comparable with our recent report on the CO catalytic activity seeds steadily increases with the reaction time when the
over hybrid Cu/CeO2 nanocatalysts.56 The surface properties of precursors are decomposed into monomers by heating; the
the CeO2 nanoparticles play a fundamental role in enhancing formation of colloidal oxide nanoparticles comprises three
the catalytic activity, particularly the pattern of the oxygen periods. In the rst period, the monomers that are generated at
vacancies originating from the redox processes involving the the cost of the precursors begin to aggregate into nuclei by self-
Ce4+/Ce3+ pair allows the effective oxygen adsorption and acti- nucleation when increasing the monomer concentration in the
vation for the CO conversion.57,58 This concept was studied by bulk solution to a supersaturation level. The nucleation reaction
Zhang et al.54 on the low-temperature oxygen storage capacity is retarded because of the high chemical potential of the
(OSC) of CeO2 nanocrystals with cubic facets. Fig. 2c and d show nucleus. In the second period, the monomers continuously
that the OSC of {100}-closed CeO2 nanocubes was nearly 2.6 aggregate on the pre-existing nuclei, which leads to a gradual
orders of magnitude greater than the OSC of irregular CeO2 decrease of the monomer concentration. The fast nucleation of
particles at 400 C even with their smaller surface area. These the oxide particles occurs resulting in an abrupt increase in the
demonstrations indicate that the crystallographic orientation of particle number concentration. The monomers are rapidly
the facet surfaces, the number of the kink sites associated with consumed to form the particles, so that the monomer concen-
corners and edges, and the high surface areas of the oxide tration is kept below the critical level and further nucleation is
nanomaterials all play signicant roles in the chemical reactivity. suppressed. In the last period, with a continuous supply of the
From the viewpoints of the most interesting size and shape monomers via ongoing precursor decomposition, the nuclei
tunable properties of the oxide nanomaterials according to their grow up into the nanoparticles of increasingly larger size until
practical applications, the exploration of the controlled an equilibrium state is reached between the monomers on the
manners of the particle shapes in the synthesis would be particle solid surface and the monomers in the bulk solution.61
necessary. To give an insight for readers, we present the kinetic Within the regimes, the monomers dissolve from the smaller
regime concepts and exible shape control ways of the forma- particles and precipitate on the larger particles (referred to as
tion of colloidal oxide nanoparticles in Sections 3 and 4. Ostwald ripening), suggesting that the monomers in the bulk
solution are likely exhausted in the later part of the third stage.
3 Kinetic regime concepts
The wet-chemistry synthesis of oxide nanomaterials would 3.1 Homogeneous nucleation
become rapid when a skillful combination of theoretical In the wet-solution synthesis of colloidal oxide nanoparticles,
concepts and experimental approaches is performed, which either dehydration or decomposition of the precursor mole-
could predict the crystal structure formation from rst princi- cules in the bulk solution rst generates monomers that
ples and monomer modeling techniques. A comprehensive subsequently nucleate to clusters (seeds) in the supersaturated
understanding of the precipitation could help one to improve solution followed by aggregation into larger secondary oxide
the engineering of the growth of the oxide nanoparticles to particles. The thermodynamic driving force for the formation of
desired size and shape. Unlike a bulk material, the kinetic and a new phase is the supersaturation of the bulk solution. The
thermodynamic considerations for the nanoparticle formation nucleation increases when the concentration of the growth
are complicated by the high surface-area-to-volume ratio of units falls below a minimum supersaturation level.62,63 The
particles in this size regime. It is generally accepted that the nucleation involves the formation of a solid phase and the
precipitation consists of a nucleation step followed by particle creation of a surface. The nucleation reaction can be regarded
growth stages. The nucleation process is oen composed of as a phase transition of the monomers (M) from the bulk
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" #
solution to a particle phase. Then, the reaction rate of the dN 16pg3 Vm 2
nucleation can be written in the Arrhenius form: ¼ A exp (7)

dt 3k3 T 3 NA 2 ðlnSÞ2
dN DGN
¼ A exp (1) where NA is the Avogadro's number.

dt kT
This equation indicates that the high monomer concentration
where N, A, k, T, DGN are the number of nuclei, the pre-expo- and low critical energy barrier favor the formation of a large
nential factor, the Boltzmann constant, reaction temperature, and number of the nuclei. The nucleation rate increases strongly with
the overall free energy of the nucleation, respectively. The driving decreasing the surface energy and increasing the supersaturation
force of the crystallization is the change of the chemical potential and decreases to zero when the precursor monomer concentra-
and thus, the free enthalpy of the crystallization reaction: tion has equilibrated with the oxide nuclei in the bulk solution.
From the expression of the nucleation's equations, we could
ms mL ¼ Dm ¼ kT ln S (2) propose that for obtaining colloidal oxide nanoparticles with
uniform size distribution, the best condition is the formation of
where ms and mL are the respective chemical potentials of the
all of the nuclei at the same reaction time, giving rise to the same
solid and the dissolved phase. Dm: the change in the chemical
cluster size. To achieve this condition, a sharp nucleation in a
potential during the phase transformation of a liquid phase
very short period of time is expected, where the concentration of
with the chemical potential mL into a new solid phase with the
the monomer growth is increased abruptly to a high supersatu-
chemical potential ms. When the nucleus of the radius r forms
ration and then is quickly depleted below the minimum
from the homogeneous solution, the free energy (DG) change
concentration for the nucleation. Below this critical level, further
due to the nucleation that the new surface with new volume is
nucleation is suppressed, so that no more new nuclei form.
created can be expressed by:
Under this condition, the resulting nuclei dispersed in the bulk
4 solution continue to grow until the monomer concentration
DG ¼ nðmS mL Þ þ Ag ¼ 4pr2 g þ pr3 DGV (3)
3 reduces to the equilibrium concentration, which is referred to as
where n, A, g are the number of moles in the nucleus, the the subsequent growth of the nuclei.
surface area, the surface free energy per unit volume of the
crystal, respectively. DGV is expressed as the difference between 3.2 Subsequent growth of nuclei
the free energy of the monomers in the particle and solution: The size distribution of the oxide nanoparticles is strongly
dependent on the subsequent growth of the nuclei. The nuclei
RTðln Co ln CÞ RT ln S
DGV ¼ ¼ (4) growth involves multi-step diffusion–adsorption and growth
Vm Vm
processes, such as diffusion of the monomers from the bulk
where Vm is the molar volume of the monomers in the crystal. C solution to the growth surface, the adsorption of the monomers
is the monomer concentration in the solution, and Co is the onto the growth surface, and surface growth through irrevers-
equilibrium monomer concentration in the crystal. S is super- ible incorporation of the monomers onto the solid surface.64
saturation and dened as the ratio C/Co. S represents the Thus, the size distribution of the initial nuclei may increase or
driving force for the nucleation and growth reactions. decrease depending on the kinetics of the subsequent growth.
In the homogeneous solution, the nucleation is accompa- The formation of uniformly sized nanoparticles can be achieved
nied by the formation of an interface between solution and the if the growth process is appropriately controlled.
particle at the cost of an increase in the free energy. The There are typically two processes occurring in the growth of
monomers in a particle have a smaller free energy than that in the crystal particle in the solution. The rst is the transport of
the bulk solution if the solution is supersaturated. The number the monomers from the bulk solution onto the particle surface
of nuclei with particle radius (r) formed is dependent on the and the second is the reaction of the monomers on the surface.
supersaturation level, which is considered as the rate of their The description of the rst process begins with Fick's law of
formation. It can be seen from eqn (4) that a large saturation diffusion:
ratio S implies a small critical nuclei size. Hence rc is the
dC
minimum radius of the nucleus that existed in the bulk solu- J ¼ D (8)
dt
tion. The value of rc can be found by using dDG/dr ¼ 0 at r ¼ rc:
where J and D are the monomer ux and the diffusion constant,
2g
rc ¼ (5) respectively. Let x be the radial distance from the center of the
DGV
particle. The monomer concentration is Cs at the surface of the
Inserting this relation into eqn (3) and (4), we obtain the particle (x ¼ r) and the bulk concentration is Cb. Consider a
expression for DGN. spherical surface of radius x whose center is identical to that of
the nanoparticle. From eqn (8), the diffusion rate of the
16pg3 16pg3 Vm 2 monomers, dM/dt, through this surface is
DGN ¼ ¼ (6)
3ðDGV Þ2 3ðRT ln SÞ2 dM dC
¼ JA ¼ 4px2 D (9)
Finally, by inserting eqn (6) into eqn (1), the nucleation rate dt dx
equation is obtained.
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In the steady state, dM/dt is constant at any x. Aer dividing lower kd. The equations for kp and kd reecting the change of the
both sides by x2, the equation can be integrated from r to r + d activation energy according to the chemical potential of the
and from Cs to Cb for le and right-hand sides, respectively. particle are
Then, for r d, we have

Dm
kp ¼ kpo exp a (19)
dM RT
¼ 4pDrðCs Cb Þ (10)
dt
Dm
The increasing rate of the particle volume is equal to the kd ¼ kdo exp ð1 aÞ (20)
RT
monomer supply rate. In equation form, this can be expressed
as: In these equations a is the transfer coefficient of the
monomer precursors and inserting eqn (18) into eqn (19) and
dM 4pr2 dr
¼ (11) (20) yields:
dt Vm dt

2gVm
Equating (10) and (11), we get kp ¼ kpo exp a (21)
rRT
dr Vm D
¼ ðCb Cs Þ (12)
dt r 2gVm
kd ¼ kdo exp ð1 aÞ (22)
rRT
To modify eqn (12), we need an expression of Cs as a function
of r. This can be obtained by considering the second process of Putting together eqn (12), (17), (21) and (22), we have a
the particle growth. On the particle surface, the precipitation general growth rate equation:
and dissolution reactions occur simultaneously with the
dr* S expð1=r* Þ
monomer (MS) in the solution and in the particle (MC): ¼ (23)
ds r* þ K expða=r* Þ
kp
nM S ) * mMnC (13) The feature of this growth rate function is very important for
kd understanding the size distribution control mechanism. The
where kp and kd are the reaction rate constants for the precipi- growth occurs until the nuclei derived from the precursor
tation and dissolution, respectively. Their reaction rates are monomer concentration has equilibrated with the oxide particles.
expressed as follows: Aer the nucleation and growth, the particle size can be changed
dM C by aging processes, during which the total amount of the solid
¼ 4pr2 kp Cs (14) material remains constant. The main aging processes for the
dt
evolution of the particles are proposed by Ostwald ripening and
dM S coarsening that is described by the Gibbs–Thomson equation:
¼ 4pr2 kd (15)
dt
2gVm
cr ¼ cr¼N exp (24)
Note that the precipitation is assumed to be a rst-order RTr
reaction of Cs, while the dissolution is independent of it. To
obtain the expression for Cs, we utilize the relation between dM/ Eqn (24) denes the number of the critical nuclei created per
dt, dMC/dt, and dMS/dt. unit volume-time in the given monomer solution because the
solubility of the particles of this size equals exactly the mono-
dM dM S dM C
¼ (16) mer concentration in the bulk solution. Any particles smaller
dt dt dt
than this critical size could have higher solubility and thus
By inserting eqn (10), (13) and (15) into this equation, we get could be unstable in the solution. Conversely, larger particles
eqn (17) for Cs. possess low solubility and are stable under the given conditions.
The equilibrium shape (Gibbs–Wulff theory) of a particle is one
DCb þ kd r
Cs ¼ (17) that minimizes the surface energy for a given enclosed
D þ kp r
volume.66 If the surface energy is isotropic, the equilibrium
The relation between the chemical potential of a particle and shape will be spherical as the sphere has a minimum surface
its radius is known as the Gibbs–Thomson relation.65 Let moC and area. When the supersaturation level is low, the broadening of
mC(r) be the chemical potentials of the bulk crystal and a particle the size distribution occurs mainly via the Ostwald ripening
with radius r, respectively. Then, their difference Dm is process. In this process, a considerable number of the smaller
particles dissolve and the larger particles grow by receiving the
2gVm
Dm ¼ (18) monomers from the dissolving particles.
r
The diffusion-limited growth is desired for the formation of
That is, the smaller particle has a higher chemical potential. the monosized nanoparticles. A exible way to control this
The smallest particle has the highest chemical potential and the diffusion is the introduction of diffusion barriers, such as
precipitation reaction faces a higher energy barrier than the organic ligands adsorbed on the surface of a growing particle,
dissolution reaction. The increase of r results in a higher kp and offering a powerful tool for the particle shape control. The oxide
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nanoparticles are small and are not thermodynamically stable strongly to the particle surface is not suitable, as it would not
for crystal growth. As capped by the surface protecting mole- allow particle growth, whereas a weakly coordinating molecule
cules, the oxide nanoparticle dispersions are stable if the would yield either large particles or aggregates. The capping
interaction between the capping groups and the solvent is molecules used must be mobile enough to provide access for the
favorable. The particle growth rates are in turn exponentially addition of the monomer units, while preventing the particle
correlated with the crystal surface energy and the anisotropic aggregation. The capping agents must be stable at high reaction
nanoparticle growth could result by enhancing or reducing the temperatures (100–400 C) required for the growth. The selec-
surface energy by capping agent adhesion. There are also other tive molecular interaction between capping agents and crystal
ways to manipulate the particle growth, namely, the monomer facets oen generate anisotropic shaped oxide nanoparticles. The
concentration is kept extremely low and the diffusion distance growth is limited on the crystal facet where binding is strong and
should be very large resulting in a limiting diffusion. The use of promoted on the crystal facet where binding is weak. The capping
the reaction solvents having a high viscosity also gives the agents commonly used for the synthesis of colloidal oxide nano-
limiting diffusion of the precursor monomers. particles are fatty acids, alkyl amines, amino acids, tri-
Despite recent attempts to understand the nucleation and octylphosphine oxide, and block copolymers.34
crystal growth in the bulk solution, the general description of The advantage of the capping molecule-assisted methods is
these processes still remains elusive for the oxide nano- that they could synthesize uniform, monodisperse oxide nano-
materials, which makes the prediction of the crystal shape and particles with shape control. To control the particle growth, the
structure at a more substantial level and on a wider scale arising surface energies must be changed by adjusting the nature and
from a specic reaction difficult. The detailed description of the concentration of the capping molecules. The surface energy of
nucleation and growth of the oxide nuclei in this section allows the oxide particles could be varied from the signicant growth
the design of effective synthetic methods toward the shape- rate differences between crystallographic directions, since the
controlled oxide nanomaterials. growth rate is exponentially proportional to the surface energy.
Through the surface interactions, the modulation of the surface
energies of the different crystallographic facets by using a
4 Shape control surface selective surfactant is a key parameter for the shape
There have been recent reviews in the literature which focus on control. The capping agents were composed of a coordinating
the reaction parameters affecting the size and shape of the head group and a long alkyl chain which adsorb onto the
capping molecule-assisted synthesis and thereby their role in surfaces of the growing oxide nanoparticles. This provides a
governing the size and shape of the synthesized product. It is to dynamic organic capping layer which renders the oxide nano-
be noted that there are no simple rules that decide the particles highly stable in solution and also mediates their
morphology of the synthesized product. However, the particle growth, offering a good control of the particle size and shape.
growth that typically occurs aer the nucleation of the precursor The growth of the oxide nanoparticles upon selective binding
monomers in the bulk solution is also inuenced by other of the surfactant to specic crystal facets is a general method to
reaction parameters including capping molecules, reaction control the particle shape in the colloidal synthesis. A one-
temperature/aging, and precursor concentration. A full under- dimensional shape evolution of anatase TiO2 nanoparticles is a
standing of the inuences of these reaction parameters on the clear example for examining the surface-energy effect reported by
colloidal synthesis could allow for tuning the unique properties Jun et al.67 A selective lauric acid surfactant and a nonselective
of the oxide nanoparticles through morphology changes. In the trioctylphosphine oxide surfactant were used for the synthesis of
following sections of the review, we have concentrated on ex- the TiO2 particles. The evolution of the TiO2 particles from bullet
ible shape-controlled ways of oxide particle synthesis that are and diamond to rod and branched shapes when changing the
governed by major factors including capping molecules, reac- ratio of the nonselective and surface selective surfactants
tion temperature/aging, and precursor concentration. employed was observed. The TiO2 anatases with a tetragonal
structure nucleated to truncated octagonal-bipyramid seeds with
exposed eight equivalent {101} facets and two-equivalent {001}
4.1 Surface capping and selective adsorbates facets. The signicant difference of the intrinsic surface energy
The growth of oxide particles in the solution phase oen has a induced the formation of bullet- and diamond-shaped nano-
strong tendency to aggregate into irregularly larger particles to particles arising from the shrinking of the {001} facets and the
relieve their high surface free energy. To address this short- complete elimination of the {001} facets at one or two ends of the
coming, the capping molecules, that are added to the bulk solu- truncated octahedral bipyramid seeds. As the lauric acid mole-
tion dynamically adsorb onto the surface of the growing particles cules were involved as selective capping molecules in the
to reduce their surface tension during synthetic reaction. The synthetic reaction, lauric acid selectively bound to the {001} facets
capping molecules selectively adsorb onto specic crystal facets, and reduced the growth rate along the [001] direction. Under the
which allow control of the particle shape at the crystallographic reduced growth rate along the [001] direction, which was close to
level. The interplay between dissolution and selective adsorption 2.7 times that of the 101 direction, the monomers continuously
is oen a result of the formation of the uniform, monodisperse grew further on both the {001} and {101} facets of the truncated
oxide nanoparticles. The choice of the capping molecules varies octahedral bipyramid seeds. This resulted in the progressive
from case to case: an organic ligand molecule that binds too elongation along the [001] direction, while preserving the surface
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area of the {001} facets. Further retardation of the growth rate nanoparticles have different polyhedron, plate, and disk
along the [001] direction at a higher concentration of lauric acid shapes. The sterically diffusive kinetics concerning the alkyl
induced the formation of branched nanorods, which resulted in chain length of the capping molecules play a crucial role in the
the growth from the equivalent {101} facets of the truncated elongated control of the oxide nanoparticles. Similar growth
octahedral bipyramid seeds. These observations indicated that patterns were observed in W18O49, Mn3O4, and TiO2 nano-
the shape evolution of the anisotropic TiO2 nanoparticles is structures.70 The W18O49 particles had a monoclinic structure
controlled by the relative facet energy. The surface energy varia- with the highest atom packing density of {010} facets. As
tion by crystallographically selective adhesion of the surfactant expected by the surface energy trend, W18O49 nanorods elon-
molecules is a powerful tool for tailoring the particle shape even gated along the [010] direction were formed by the thermal
in the case of the metal oxides. reaction of tungsten chloride with an oleic acid–oleylamine
The selective binding and nonbinding of the capping mole- mixture, whereas Mn3O4 and TiO2 rods synthesized using cor-
cules to the different crystal facets of the growing nanocrystal responding MnCl2 and TiCl2 precursors were obtained by
can offer a way to control the product's morphology. The binary unidirectional growth along the [001] direction.
capping molecules selectively adsorb on different crystallo- The shape control was also reported by Nguyen et al.71
graphic facets, resulting in the shape control of the oxide through selective adsorption of oleylamine and nonselective
nanocrystals. Fig. 3 shows a facile approach of using binary adsorption of oleic acid on SmVO4 nanoparticles. When oleyl-
oleic acid–oleylamine as a decisive structure-directing agent for amine was used alone, SmVO4 nanospheres of 17 nm in
the synthesis of the monodisperse NaLa(MoO4)2:Eu3+ bipyr- diameter were obtained. The use of the oleic acid instead of
amid-shaped nanocrystals reported by Bu et al.68 The use of only oleylamine, however, formed hexagonal-like nanoparticles,
oleic acid yielded a mixture of spherical particles and rods, while maintaining their particle size. A more interesting
while the product was found to be irregular clusters in the prospective application of surface selective surfactants would be
presence of only oleylamine. In contrast to both above cases, the to nely tune the growth rate of the facets to follow the resulting
use of a binary oleic acid and oleylamine with an equimolar shape evolution process. Thus, progressive addition of a selec-
ratio yielded monodisperse NaLa(MoO4)2 particles with tive surfactant should yield a sequence of shapes as a result of
uniform tetragonal bipyramid shape. The authors proposed eliminating highest energy facets during crystal growth. The
that the formation of the well-dened tetragonal bipyramid elongation of 6-aminohexanoic acid (AHA)-capped MnWO4
shape is a result of the preferential adsorption of deprotonated nanoparticles from bar to rod shapes with increasing the AHA
oleic acid on {101} and {001} facets of the NaLa(MoO4)2:Eu3+ concentration from 0.031 to 0.610 M was also reported by
nanocrystals. This selective capping led to a change in the Nguyen et al.72 The analyzed results suggest that {021} facets of
surface energy of the crystal facets and facilitated the growing the MnWO4 nanocrystals were selectively adsorbed and stabi-
rate of the exposed {101} facets. Si et al.69 demonstrated that lized by the AHA molecules, while {100} facets were uncovered.
oleic acid bound more strongly than oleylamine to the surface The mixed oxide crystals grew anisotropically along the 100
atoms of rare earth oxide nanoparticles due to its higher oxo- direction due to their higher surface energies resulting in the
philicity. Because of the selective adsorption of the oleic acid nanorod product. Because AHA adsorbed only on the {021}
ligands on certain cubic facets during particle growth, the oxide facets, the nanorods with high aspect ratios formed at the high
AHA concentration could be associated with the oriented
attachment of the primary particles predominantly during
synthesis. It was also found that an increase of the alkyl chain
length of the amino acid capping agents led to a change in the
shape of the MnWO4 nanocrystals from anisotropic bar into
isotropic sphere/hexagon. This is also consistent with our
previous report on the synthesis of vanadium oxide nano-
particles, in which the longer alkyl chain lengths generated
smaller particles owing to the slower nucleation and growth
rate.73
To stabilize the nuclei and larger oxide nanoparticles against
aggregation by repulsive force for the controlled growth, the
coating of silica and polymer layers on the oxide particle surface
has also been achieved. The coated oxide nanostructures
retained their original physical properties, the resulting oxide
nanocomposites show multifunctional properties. This surface
modied method is a powerful paradigm for fabricating anti-
body-conjugated nanohybrids for multifunctional theranostic
applications.9,13,74,75 These capping molecules play several
Fig. 3 A schematic illustration of a binary oleic acid–oleylamine cooperative-
controlled crystallization mechanism for the formation of monodisperse tetrag-
different roles in the nanoparticle synthesis. The organic
onal bipyramid NaLa(MoO4)2 nanocrystals. Reproduced with permission from ref. ligand-capped oxide nanoparticle colloids could function as
68, copyright 2009 American Chemical Society. ideal building blocks for the self-assembly of periodic
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superlattice structures.6,76 The role of the capping agents is to diffusion controlled model of the CdSe growth. This model had
make the uniform, small sized capped oxide particles like well- been applied for explaining the shape evolution mechanism of
dened molecules to arrange in the orientational order for self- the anisotropic oxide nanoparticles upon increasing the
assembly.77 The organized structures of these capped oxide precursor monomer concentration in the synthesis solution.
nanoparticles in multi-dimensional superlattices could have Fig. 4 shows SmVO4 nanoparticles elongated from dot to wire
collective physical properties different from the individual shapes with an increase in the metal complex precursor
particles resulting from coupling of the particles. These concentration reported by Nguyen et al.71 During the synthetic
assembled superlattices would enable the generation of prom- reaction, the monomer concentration dropped to a level lower
ising materials for the design of optoelectronic devices.78–80 than that required for a given shape. At a low monomer
concentration (0.065 M), isotropic SmVO4 nanoparticles grew
toward the lowest chemical potential environment, giving only
4.2 Shape evolution nanocores. When the synthesis was carried out at a median
The mechanism of the oxide nanoparticle evolution is ratio- monomer concentration (0.130 M), mixed rod- and core-shaped
nalized within the framework of the kinetic and thermody- SmVO4 nanoparticles were formed, resulting from the isotropic
namic arguments providing complementary descriptions of the growth in a three-dimensional growth stage. The anisotropic
anisotropic particle regime realized in the present colloidal growth along the [200] direction of the SmVO4 nanorods
system.34 A balance established between kinetic and thermo- occurred at a higher monomer concentration (0.260 M) in favor
dynamic growth regimes plays a key role in determining the size of the formation of nanowires. This shape evolution is strongly
and shape of the oxide nanoparticles. In the extremely small associated with an increase in the chemical potential in the
size range, the relative chemical potential is sensitive to the bulk solution as well as the dominant oriented attachment for
nuclei conguration associated with the particle growth and the the nanowire formation. Our experimental result is consistent
oxide nuclei generally grow into the nanoparticles with lowest with Peng's report,37 who gured out three stages for the shape
energy shape. The isotropic growth of the oxide nanoparticles evolution of a rod-shaped nanoparticle when the precursor
(e.g., thermodynamically stable spherical shape) with lowest monomer concentration decreases. When the monomer
overall surface energy is preferred under the thermodynamic concentration was low, the reaction system reached an equi-
growth regime, which is characterized by sufficient supply of librium by dissolution and regrowth of the monomers from the
the thermal energy and low monomer concentration. The highest energy facet to other facets, resulting in the formation
particle synthesis carried out using the high monomer of the nanospheres. A median diffusion concentration induced
concentrations generally resulted in the anisotropic growth a directional growth of the nanoparticles. Due to the differences
along a specic direction with low activation energy barriers in the chemical potential between different particle facets, the
under the nonequilibrium kinetic growth regime. The growth monomers existed on the nanoparticles moved in an intra-
rate has been shown to be an important factor in controlling the particle manner to convert from the nanorods to nanodots.
shape of the oxide nanoparticles. Thus, the presence of the During the one-dimensional growth stage, the monomers with
surface-selective surfactants may hinder the oriented attach- high concentration highly diffused into a diffusion layer, which
ment during growth and the anisotropic shaped nanoparticles promotes the preferential one-dimensional growth of the
could be obtained through addition of the monomers onto the monomers on the highest energy facet.
high energy surface. Other materials researchers also achieved the controlled
The highly kinetically driven process for the formation of the growth by changing the reactant concentration responsive to
inorganic nanoparticles was proposed by Peng37 through a the shape evolution of the oxide nanoparticles. For example,
Fig. 4 Effect of the precursor monomer concentration in the bulk solution on the shape evolution from nanocores to nanowires. TEM images of SmVO4 nanoparticles
synthesized using the different precursor concentrations while keeping the Sm/V molar ratio ¼ 1 (C ¼ [samarium(oleate)3] ¼ [vanadate(tetraoctylammonium)3]): (a)
C ¼ 0.065 M, 3 nm nanocores, (b) C ¼ 0.130 M, a mixture of 3 nm nanocores and 3 nm 10–50 nm nanorods, (c) C ¼ 0.195 M, 3 nm 200 nm nanowires. Reproduced
with permission from ref. 71, copyright 2009 American Chemical Society.
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Buonsanti et al.81 synthesized TiO2 nanocrystals via sequential active centers with the movement of the atoms to the lattice.
thermal activation of the aminolysis and pyrolysis of TiCl4 The active centers are the corners, edges, or twists of the growth
precursors in an oleic acid–oleylamine–1-octadecene mixture surface. The nucleation of a new layer could start from the
via a multi-injection reactant delivery technique. By varying the surface nucleation of an island (active center) on the facets,
amount of an equimolar TiCl4–oleic acid from 2 to 20 mmol, the which grows further by attachment of the additional atoms/ions
shape evolution of the diameter and the length sizes was ach- to the corners, edges, or twists of the new layer until the crystal
ieved in 3–10 and 30–200 nm intervals, respectively, which surface is completed. However, the growth of a surface is rarely
transcribed into nanorods with the aspect ratio spanning from perfect, and a number of defective crystals exist in the form of
3 to 20. Recently, Buonsanti et al.82 also reported the shape vacancies or screw dislocations on the crystal surface. The
evolution of hyperbranched TiO2 nanocrystals through addi- adsorbed atoms could not be static and are able to detach into
tions of extra TiCl4 and oleic acid reactants to a hot reaction the bulk solution even at the thermodynamic equilibrium.
mixture containing the preformed TiO2 branched nanocrystals. These different growth conditions could lead to deviations from
The rapid evolution of delicate cross-shaped TiO2 nanocrystals the equilibrium morphology for a crystal.86
was observed when the synthetic reaction was carried out using Under the equilibrium conditions, the shape of the single
a TiCl4 : oleic acid molar ratio of 1 : 4 at 320 C. The oriented crystals is related to the intrinsic structure of the unit cell and the
assembly of tight-packed nanorod arms into fanning-out crystal shape can reect the unit-cell replication and amplica-
bundles of the TiO2 nanocrystals occurred at 280 C at a tion. However, the crystal morphology oen varies signicantly
TiCl4 : oleic acid molar ratio of 1 : 2. The synthesis performed at from the shape of the unit cell. As proposed in the early last
240 C at a TiCl4 : oleic acid molar ratio of 1 : 1 produced highly century by Wulff,87,88 the changes of the diverse crystal shapes are
split bunch-shaped TiO2 branched nanocrystals. The authors dependent on the external growth environment. Wulff's rule is
assumed that the anisotropic evolutions of the TiO2 nano- expressed by the equation giAi ¼ Fs where gi, Ai, Fs are the surface
crystals upon alternating additions of extra TiCl4 and oleic acid energy, the surface area, and the surface free energy, respectively.
reactants are determined by a limited diffusion step of the This rule describes the inuence of changing the surface energy
monomer uxes involved in the oriented attachment growth. of the facets on the shape of the crystals. If this could be done in a
Cozzoli et al.83 revealed the shape evolution of Fe3O4 nano- facet selective way, the equilibrium shape of a crystal could be
particles from dot to tripod proportional to the Fe(CO)5 tuned in a dened and predictable way.
concentration injected into the preformed seed solution. Yang According to the Wulff construction model, each facet of the
et al.84 studied the shape evolution of ZnO nanoparticles crystal is described by its free surface and interfacial energy and
induced by selectively doping Mg clusters on the facets of the the formation of the crystal shape results from minimizing
preformed seeds. The relative concentration of the dopant these energies for a certain volume. This model is valid only at
precursors in the ZnO supports is important for the selective the thermal equilibrium, so that the resulting shape is an
growth of the Mg clusters at the ZnO particle's facets. The shape equilibrium one of the crystal. The proposed pseudo Wulff
evolution of the Mg-dopped ZnO particles from tetrapod to wire construction is based on the fact that the driving factor is not
was observed when increasing the dopant magnesium stearate the equilibrium surface, but the growth rate of each facet is
concentration. determined by kinetics. The normal distance from the crystal
facets to the crystal center was proportional to the corre-
sponding growth velocity rather than the surface and interfacial
4.3 Crystal rearrangement energy. Generally speaking, the growth rate of a crystal facet is
Temperature is the most common reaction parameter used to directly related to its surface energy if the growth mechanism
control the reaction kinetics of the oxide nanoparticle forma- acts on each facet in the same manner. The high-surface-energy
tion upon heat treatment. A low temperature is applied for facets will grow quickly to reduce the surface area or disappear
hydro-solvothermal precipitation reactions, while higher completely upon crystal growth in the nal shape, while the
temperature is required for thermal decomposition reactions. facets with low surface energies will grow slowly and dominate
The synthetic reaction of the oxide nanoparticles is dependent the nal shape. This behavior could be predicted by Wulff's
on the nature of the reaction as well as the diffusion of the rule. The equilibrium shape of a single crystal is dened by its
precursor monomers from the bulk to the nuclei surface. The minimum surface free energy, which could be calculated from
diffusion coefficient of the monomers increases with increasing the sum of the surface energy and surface area of all of the
the temperature, while the product concentration depends on exposed facets of a product.
the chemical potential of the monomers employed. Some studies have applied the Wulff facet theory in the oxide
According to the classical crystallization theory,85 the at particle synthesis to explain the shape transformation upon
facets of a crystal grow via layer-by-layer adsorption of solute adjusting the reaction temperature. Fig. 5 shows the shape
atoms on the existing crystal facets. When an atom approaches transformation of Mn3O4 nanoparticles along with increasing the
the crystal surface from the bulk solution, it is not immediately temperature. Zhao et al.89 synthesized Mn3O4 nanocrystals using
integrated into the crystal lattice but could migrate on the manganese(II) stearate precursors in a two-phase water–toluene
crystal surface. These atoms form the so-called adsorption layer system. When increasing the reaction temperature from 120 to
with a relative thickness of 1 nm. The atoms migrating on the 150 and 180 C, the shape of the Mn3O4 nanoparticles trans-
crystal surface could be integrated into the crystal lattice at formed from the sphere into quasi-sphere and cube. According to
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Fig. 5 Effect of the reaction temperature on the shape transformation. TEM images of Mn3O4 nanoparticles synthesized at different temperatures: (a and b) 120 C,
nanocubes; (c and d) 150 C, quasi-nanospheres; (e and f) 180 C, nanospheres. Reproduced with permission from ref. 89, copyright 2008 Wiley-VCH.
the Wulff facet theory, the crystal growth occurred rapidly on the On the other hand, the shape transformation of Co3O4
high-free-energy facets, and the anisotropic growth of the Mn3O4 nanocubes into nanospheres prepared by a two-phase method
nanocubes occurred at relatively low temperature in the early by varying the reaction time from 12 to 24 h was also reported by
stages. The growth rate of the nanoparticles became higher at Nguyen and Do.92 It was observed that in the early stages, the
relatively high temperature, so that the intraparticle movement of Co3O4 nanocubes enclosed by six {100}, {010}, {001} crystal
the atoms from the high-energy facets (corner and tips) to other facets are generated in the anisotropic growth of {111} facets of
facets (side facets) occurred at high temperatures. This monomer the cuboctahedral clusters. The cubic shape eventually trans-
movement led to the shape transformation of the nanocubes into forms into the stable sphere when extending the reaction time.
nanospheres. Sui et al.90 elucidated that the reaction temperature This resulted from moving the monomers from the {111} facets
was responsible for the shape-controlled synthesis of polyvinyl to the {100} ones in intraparticles owing to the difference in
pyrrolidone-capped Cu2O nanoparticles. A transformation of the chemical potentials between different facets of the Co3O4
Cu2O particles from truncated octahedron into equiaxial shapes nanocrystals. Fan and Ng93 observed that the growth of Cu2O
occurred when increasing the reaction temperature from 70 to nanoparticles appears to shi into the thermodynamic regime
100 C. The authors proposed that increasing the reaction upon reaction aging and the thermodynamically stable octa-
temperature enhances the reaction leading to an increase of the hedral shape is obtained. The formation of spherical Cu2O
diffusion rate. Nguyen et al.91 presented a capping molecule- nanoclusters was dominant at 30 min, which grew up into
assisted solvothermal method for the decomposition of mixed hexagonal nanoplates aer 90 min. The reaction aging period of
oxide rare earth oleate and vanadate tetraoctylammonium 3 days resulted in a transformation of the triangular nanoplates
bromide complexes and the subsequent combination of co- into octahedral nanocrystals. Regarding this concept, Bu et al.68
precursor monomers in oleylamine–toluene to form mixed rare also revealed the reaction time-dependent morphological
earth (Ce, Sm) orthovanadate nanoparticles. The size of the mixed evolution of NaLa(MoO4)2 tetragonal bipyramid nanocrystals.
oxide particles can be controlled by the synthesis temperature. When the reaction time was prolonged from 1 to 6 h, the
Cubic-shaped SmVO4 and round-shaped CeVO4 nanoparticles NaLa(MoO4)2 tetragonal bipyramid nanocrystals exhibited more
with an average diameter of 15 nm were found at 150 C. When uniformity. When the reaction lasted as long as 12 h, the
the synthesis temperature increased to 180 C for 16 h, both bipyramid nanocrystals grew bigger and became polydisperse
uniform SmVO4 and CeVO4 nanospheres were observed, while via Ostwald ripening. These observations on the reaction
maintaining their particle diameter. Nguyen et al.72 also temperature and time effects indicate that the minimization
reported the transformation of cube into spherical shaped 6- of the overall surface energy was achieved preferentially by
aminohexanoic acid-capped MnWO4 nanocrystals when dissolution and regrowth of the precursor monomers during
increasing the hydrothermal reaction temperature from 180 to Ostwald ripening rather than by interparticular aggregation
220 C. processes.
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4.4 Oriented attachment and coarsening this trend. The truncated diamond-shaped anatase TiO2 nano-
particles have three different {001}, {010}, {101} crystal facets
The investigation of the growth and coarsening mechanisms in
with the surface energy of the {001} facet higher than those of
the nanometer range is fundamental to the understanding of
the other facets. When there is a sufficient thermal energy in the

the formation of the anisotropic oxide nanostructures.94 The
reaction system, the removal of the high-energy facets is ther-
nanoparticle growth in the bulk solution typically involves the
modynamically favorable. Thus, the fusion of the diamond-
fast nucleation of primary particles and the subsequent growth
shaped nanoparticles along the [001] direction was facilitated
by two primary mechanisms of coarsening and aggregation.
Coarsening, also known as the Ostwald ripening process, is a by oriented attachment, giving a necklace-shaped nanoparticle.
mechanism driven by the fact that the chemical potential of an Penn and Baneld97 considered the primary nanoparticles as
molecules to prove the kinetic model for the oriented attach-
oxide particle increases with a decrease in the particle size. This
ment mechanism. The two primary particles collided at the
process is described by the Gibbs–Thompson equation as
interface to irreversibly generate a two-dimensional structure
expressed in Section 3.2. This classical crystal coarsening is
with compatible orientation, whereby the kinetics of the
described in terms of the growth of large particles at the
particle–particle coalescence in the colloidal suspension may be
expense of smaller particles. Otherwise, the studies on the
interpreted as shown in Fig. 6b and eqn (25). The rate of the
coarsening behavior and morphology evolution of the oxide
nanoparticles generated upon heat treatment would provide the oriented attachment is kinetically second order in the concen-
formulation of a second mechanism of the crystal growth. The tration of the primary nanoparticles and describes the sponta-
neous self-organization of the adjacent particles with a common
oriented attachment mechanism describes the spontaneous
crystallographic orientation.
self-organization of adjacent oxide particles, so that they share
the common crystallographic orientation followed by joining of ½Po
P þ P/P P dðP PÞ=dt ¼ kðPÞ2 ½P ¼ (25)
these particles at a planar interface. The primary particles 1 þ 2k½Po t
attach to each other at their high-energy facets; they crystallo-
graphically fuse and eliminate these facets to form a secondary The surface-stabilized oxide nanoparticles, acting as
anisotropic particle.95 building blocks, can spontaneously self-assemble into ordered
The attachment between particles occurs at the high energy nanostructures, a process which is usually controlled by altering
facets, allowing the elimination of the surfaces at which the the surface properties of the nanoparticles using organic
crystals join. The intermediate steps may be related to the yield coating layers. The organic ligand with high nanoparticle
of the effective collisions or to the agglomeration and realign- binding affinities can promote an oriented-assembly, driven by
ment processes. This interpretation has been used by some the interaction between surface-adsorbed ligands instead of
researchers aiming to gain a more thorough understanding of between the particles themselves. Fig. 7 shows the oriented
the growth behavior in the colloidal suspensions. The concept attachment of a-Fe2O3 nanocrystals to moniliforme shaped
of the oriented attachment was rst demonstrated by Baneld straight-chains. Meng et al.98 synthesized uniform coalescent
and Penn96 in the hydrolytic synthesis of TiO2 nanoparticles. moniliforme shaped a-Fe2O3 straight nanochains derived from
Fig. 6a illustrates this reaction that is shown by a high-resolu- self-assembled primary polyhedron particles. The metastable
tion transmission image of two TiO2 nanoparticles coalesced in oleic acid–oleylamine-capped a-Fe2O3 polyhedron particles
emerged from the bulk solution under a kinetic growth regime
at an early stage. The metastability of the colloidal particles can
be controlled not only by the reaction conditions, but also by the
Fig. 6 The oriented attachment mechanism of the oxide nanoparticles. (a)

HRTEM image of TiO2 nanoparticles showing the crystal growth of the single
crystal anatases through attachment interfaces under hydrothermal conditions. Fig. 7 The oriented attachment of a-Fe2O3 nanoparticles into moniliforme-
Reproduced with permission from ref. 96, copyright 2008 Elsevier. (b) The shaped straight-chains. (a) SEM image of moniliforme-shaped a-Fe2O3 nano-
oriented collision for the coalescence of two particles, where [P] is the concen- structures, insets of the SEM are TEM images showing two nanochains abutting
tration of primary particles (particles/volume) and k is the reaction constant and each other side by side of truncated hexagonal bipyramid units. (b) A schematic
the line represents the chemical bonds between two oriented primary particles. illustration of the formation mechanism of the moniliforme shaped straight-
Assuming that the reaction occurs in a single step, [P] is defined in terms of the chains of the a-Fe2O3 nanoparticles. Reproduced with permission from ref. 98,
initial concentration [P]o by eqn (25). copyright 2010 American Chemical Society.
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inuence of the capping selective adhesion. Through the aging is an important concept involving the particle-based crystalli-
process, the polyhedron particles attached to each other at high- zation pathways. The growth of the oxide nanoparticles can
energy {001} facets to form a-Fe2O3 straight nanochains. This occur by the total surface energy minimization, where the
coalescence occurred when two particles approached each other crystal morphologies cannot be nucleated via a classical ion/
closely and are attracted to each other by van der Waals forces. molecule-based crystallization. The oriented attachment
During aging, the assembled particles rearranged to exhibit a process can be inuenced by formation of the anisotropic
low-energy conguration represented by the coherent particle– particles that occurs preferentially on the high energy facets.
particle interface. This led to the growth of a linear chain of the This minimization can be achieved by tailoring highly aniso-
particles that fused end-to-end along the longitudinal axis. The tropic nanoparticles in favor of low-energy facets.
organic capping molecules, acting as controlled aggregation
agents, can bind tightly to the crystal facets and restrain their
growth while restricting others.
5 Synthesis and design of colloidal oxide
Another interesting example of the oriented attachment was
nanomaterials
observed in the synthesis of MnO multipods reported by Zitoun The synthesis of the oxide nanoparticles with controlled shapes,
et al.99 The MnO multipods were prepared using the non- potential materials with directional- and shape-dependent
hydrolytic sol–gel reaction of a Mn–oleate–oleic acid–trioctyl- properties, is an important goal of advanced materials chem-
amine mixture. The growth of these MnO multipods was istry. The oxide nanomaterials have been synthesized using
proposed by the two-step mechanism involving the nucleation solid-state methods over the past centuries. The features of this
of truncated octahedra and the subsequent oriented attach- route are applicable for large-scale industrial production in
ment of these particles into nanopods. Similar observations for some specic cases. Nevertheless, the solid-state synthesis
the oriented attachment mechanism were reported later by typically produces particle aggregates resulting from the
other materials researchers. Polleux et al.100 reported that the uncontrolled nucleation and growth processes and also
oriented attachment of the individual anatase nanoparticles requires high-temperature annealing. To address this short-
into a pearl necklace structure is a result of the water-promoted coming, new wet-chemistry methods have been developed over
desorption of the organic ligand from {001} facets of the the past decades and have opened up a nanoscale oxide revo-
building blocks together with dissociative adsorption of water lution for accessing the innovative potential of nanotechnology.
on these crystal facets. The anisotropic self-assemblies of TiO2 The development of the wet-chemistry synthetic routes allows
and SnO2 nanoparticles into chain-like nanostructures with the for manipulating the homogenous nucleation occurring under
aid of the block copolymer in the aqueous media were reported the same conditions, likely giving rise to the nucleus with
by Wang et al.101 Ribeiro et al.102 also used this kinetic model to similar size. These nuclei subsequently grow with the same rate,
propose the oriented attachment growth in the dispersed resulting in uniform oxide nanoparticles. In this section, we
nanoparticles. The authors considered the growth behavior in explicitly focus on the wet-chemistry methods including the
colloidal SnO2 suspensions, where the SnO2 particles with hydro-solvothermal route, the two-phase route, thermolysis,
similar crystallographic orientations have the same trend of the and reverse micelle that have been used to well control the size
coalescence. Zhang et al.103 gured out the inuence of the and shape of the monodisperse oxide nanocrystals. Taking
chain length of the alkylamine capping molecules on the advantages of the oxide particle colloids over the conventional
oriented assembly of Tb-doped Y2O3 nanoparticles from sphere materials, which are also used as exible building blocks for
to rod shapes. Nguyen et al.104 revealed that the synthesis of further design and surface modication of the new functional
Sm2O3 nanorods consists of two steps of growth. The formation composites and periodically self-assembled lms, the author
of the oxide nanoparticles rst occurred at relatively low expects that these uniformly sized oxide nanoparticles with
temperature (120–140 C) by Ostwald ripening followed by the different shapes and their derivatives will nd important
oriented attachment of these nanoparticles at higher tempera- applications in many areas including catalysis, optical sensing,
ture (160–200 C) to produce nanorods. Douglas et al.105 biomedicine, and energy conversion technology.
demonstrated the growth of lanthanide oxide nanoribbons via
the oriented attachment of individual nanoparticles derived
from the solvothermal decomposition of lanthanide oleates in 5.1 Hydro-solvothermal route
an oleic acid–oleylamine–dioctyl ether mixture. The electron Hydrothermal processing, where the aqueous solution and
microscopy observations gave evidence of the self-assembly vapor react with the solid precursors at high temperature and
process composed of three stages. The rst stage is the pressure, is a well-known process in mineralogy for the forma-
production of the individual nanoparticles that sequentially tion of minerals.106,107 Taking advantage of the high reactivity of
assembled into a polycrystalline chain to reduce the free surface the metal salts and complexes at the elevated temperatures and
energy. The nal recrystallization of the individual nano- pressures, the inorganic nanomaterials are conveniently
particles into the polycrystalline oxide chains occurred as a prepared at temperatures considerably lower than in the solid-
result of the formation of longer, aligned, more uniform oxide state reactions. The simple method for the generation of the
nanoparticles. metal oxide nanoparticles is based on the forced hydrolysis of
These observations of the new crystal growth of the oxide metallic salt mixtures. During hydrothermal treatment, poly-
nanoparticles suggest that the oriented attachment mechanism valent metal cations rst hydrolyze in the form of polymeric
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hydroxides and subsequent deprotonation of coordinated water faster growth rates, which could be changed by addition of the
molecules to form metal oxide monomers over reaction time. capping molecules through selective capping on the certain
The metal oxide monomers, generated by accelerating with crystal surfaces.
increasing temperature, serve as intermediates in the precipi- There has been tremendous progress in this route for pro-
tation (growth) of the metal oxide particles during aging on the cessing oxide nanomaterials.107 Fig. 8 shows a straightforward
reaction time. In a sealed vessel, there is an increase of the shape-controlled route employed by Nguyen et al.112 for the
autogenous pressure resulting from heating, thus the reaction synthesis of erbium-compound micro- and nano-structures of
solvent could be brought to temperature above its boiling point. Er(OH)3, ErOOH, Er2O3 from the hydrothermal reaction of
The basic aqueous media could shi the equilibrium toward the erbium nitrate in a decanoic acid–ethanol–aqueous basic
formation of metal hydroxides. The concentration of the alkali mixture. The synthetic reactions occurred in a water–ethanol
reactants is oen kept in excess relative to the metal salt mixture, a “one polar phase” system at a relatively low
concentration to ensure the precipitation of all of the metal ions temperature of #180 C. The decanoic acid-capped products
present in the bulk mixture. Water, ethanol, and ethylene glycol were precipitated at the bottom of a bomb reactor instead of
solvents at the elevated temperatures play important roles in the becoming dispersed in the toluene phase as described in a
precursor material transformation.108 following two-phase route. By only tuning the temperature of
It becomes obvious that the hydrolysis reaction should the reaction system, monoclinic ErOOH and cubic Er2O3 phases
proceed rapidly and produce an abrupt supersaturation to can be obtained. The various particle sizes in the range of
ensure a burst of the nucleation, resulting in the formation of a thousands to tens of nanometers and different shapes can be
large number of small nuclei and eventually leading to the controlled by varying the synthetic conditions including the
formation of small particles. However, the high growth rate of concentration of decanoic acid and erbium precursors and the
the oxide monomers in high-polarity solvents oen results in water volume. This hydrothermal method has also been
the formation of large sized oxide particle aggregates. To extended to synthesize mixed metal oxide nanoparticles. For
address this problem for controlling the shape and mono- example, Nguyen et al.113,114 synthesized uniform MnWO4
dispersity of the oxide particles, the addition of the capping nanoparticles with controlled shapes and self-assembled mes-
molecules to the reaction mixture is generally achieved. The ocrystal microspheres via hydrothermal treatment of an
hydro-solvothermal capping molecule-assisted synthesis aqueous mixture of Mn(NO3)2, Na2WO4, and amino acid
involves heating the precursors in aqueous or organic media in capping molecules. ZnFe2O4 nanooctahedra were synthesized
the presence of the capping molecules at high temperature and by Yu et al.115 through the hydrothermal reaction of a FeCl2–Zn–
pressure. Aer the reaction, the oxide nanoparticle products are NH3 aqueous mixture. The phase purity of the ZnFe2O4 nano-
adsorbed by capping molecules and precipitated at the bottom particles was controlled by reaction time and temperature and
of a bomb reactor. Among different types of nanomaterials their crystallinity was signicantly enhanced by increasing the
synthesized by this method, the oxide nanoparticles have been ammonia concentration.
studied commonly.109,110 These features facilitate the synthesis Hydrothermal synthesis is usually carried out below 200 C,
of highly crystalline oxide nanoparticles due to the acceleration since the critical temperature and pressure of water are 374 C
of the surrounding aqueous solutions. The reaction parameters, and 22.1 MPa, respectively.116 The water properties for metallic
such as time, temperature, pressure, reactant concentration, salt compounds, such as dielectric constant and solubility,
pH, and capping molecules, can be tuned to attain satisfactory change dramatically under supercritical conditions. The ability
nucleation and growth rates and particle size distribution.111 of the supercritical water to provide a good environment for the
The crystal facets with higher surface energies typically have oxidation in the presence of dissolved oxygen would be
Fig. 8 ErOOH and Er2O3 micro- and nanostructures with different sizes, shapes, and phases hydrothermally synthesized as a function of reaction temperature and the
decanoic acid/erbium molar ratio. Reproduced with permission from ref. 112, copyright 2010 American Chemical Society.
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overcome. As a result, the hydrothermal synthesis in super- triethylamine, and cyclohexane. The decomposition of
critical water has advantages for the synthesis of the metal oxide NH4HCO3 to provide H2O for the hydrolysis was an important
nanoparticles with high crystallinity. To reduce the reaction rate factor for the TiO2 shape evolution. The fast hydrolysis of the
of the oxide monomers in the supercritical water, the organic titanium butoxide precursors with water derived from
ligand molecules are oen added to the supercritical water to NH4HCO3 resulted in the formation of the TiO2 nanoparticles.
limit the crystal growth and inhibit the agglomeration in favor The slow nonhydrolytic condensation of the precursors in the
of small, well-dispersed oxide particles. This organic ligand- absence of NH4HCO3 produced TiO2 nanorods. Xie and
assisted supercritical water as the reaction medium was rst Shang121 synthesized TiO2 nanowires by the solvothermal reac-
developed by Rangappa et al.117 for synthesizing mixed oxide tion of a titanium tetraoisopropoxide–ethylenediamine–
CoAl2O4 nanopigments with the particle size of 10 nm (Fig. 9). ethylene glycol mixture. This method was proposed to control
Under the supercritical water hydrothermal conditions, the the shape of the TiO2 nanoparticles including bers, belts, and
organic ligand molecules (oleic acid or decanoic acid) were sheets by changing either the concentrations of precursors,
miscible with high-temperature water, which controlled the growth temperature, or additives. Xu et al.122 synthesized SnO2
nanocrystal growth from the selective binding of the organic quantum dots and quantum wires for gas-sensing application
ligand molecules with the specic CoAl2O4 crystal surfaces. The by solvothermal treatment of tungsten chloride in benzyl
oleic acid-capped cobalt blue nanocrystals obtained can be alcohol followed by annealing in air.
dispersed well in hexane and they remained non-agglomerated Dinh et al.123 used both oleic acid and oleylamine as binary
even over several months. The authors also used this approach capping molecules and water vapor as a hydrolysis agent which
to synthesize CeO2 nanocrystals118 and Ba–hexaferrite nano- allowed for the controlled hydrolysis of titanium butoxide to
crystals119 with controllable shapes. The growth rate of {200} produce TiO2 nanoparticles. The presence of water vapor along
facets became slow when using the long alkyl chain of dicar- with the desired oleic acid : oleylamine molar ratio plays crucial
boxylic acid capping agents, producing dicarboxylic acid-stabi- roles in controlling the size and shape of the TiO2 nano-
lized CeO2 nanocrystals with cuboctahedral or cubic shape. particles. The shape of the TiO2 nanoparticles changed from
While the concentration of the oleic acid capping agents played rhombic to truncated rhombic, to sphere with an increase in the
a key role in controlling cubic and octahedral shapes of the Ba– respective oleic acid : oleylamine ratio from 4 : 6 to 5 : 5 and to
hexaferrite nanocrystals. 6 : 4. Increasing the titanium butoxide amount resulted in the
When non-aqueous solvents instead of water were used as formation of the elongated particles. When the titanium
reaction media for the autoclaving synthesis of the oxide butoxide : oleic acid : oleylamine molar ratio changed from
nanomaterials it is referred to as a solvothermal process. 1 : 6 : 4 to 2 : 6 : 4, the uniform shape of the TiO2 nanoparticles
Materials researchers have applied this method for producing evolved from sphere to dog-bone. Ghoshal et al.124 sol-
diverse oxide nanoparticles. Li et al.120 synthesized TiO2 nano- vothermally synthesized cadmium-based nanostructures using
particles with sphere and rod shapes through solvothermal the cadmium nitrate precursor and the ethanol medium.
reaction of a mixture of titanium butoxide, linoleic acid, Single-crystalline CdO micro-octahedra, polycrystalline CdO
nanowires, and Cd(OH)2 nanorods were obtained by adjusting
pH and reaction temperature. Yan et al.125 synthesized indium-
based nanoparticles through the solvothermal reaction of an
indium nitrate–H2O–N,N-dimethylformamide mixture. The
thermal composition of the nal products could be manipu-
lated from cubic In(OH)3 to orthorhombic InOOH and cubic
In2O3 structures by varying the water volume. Niederberger and
Garnweitner126 reported the nonaqueous sol–gel method for the
synthesis of various oxide nanoparticles involving sol-
vothermolysis of the metallic alkoxide precursors in benzyl
alcohol.
The solvothermal method has been extended to synthesize
the mixed oxide nanoparticles. Liang et al.127 synthesized hollow
CeO2–ZrO2 nanocages with controlled size and shape by adding
zirconium(IV) to CeO2 sphere-dispersed glycol to form cage
shaped CeO2–ZrO2 nanostructures through the Kirkendall
effect. Aer the addition of Zr4+ ions to the reaction mixture,
they were doped into CeO2 to form a Ce1xZrxO2 solid, mean-
while the diffusion rate of the secondary nanostructures of the
resulting Ce1xZrxO2 clusters was much faster than that of the
Fig. 9 (a) The organic ligand-assisted supercritical water procedure for the
single-element nanostructures, giving a hollow Ce1xZrxO2
synthesis of oleic acid-capped CoAl2O4 nanopigments. (b) Dispersion of oleic acid-
capped CoAl2O4 nanocrystal pigment in hexane (1 wt%). (c) Cobalt blue nano-
structure. Zhou et al.128 presented an ethylene glycol (EG)-
pigment powder. Reproduced with permission from ref. 117, copyright 2007 assisted solvothermal process to synthesize hierarchical FeWO4
American Chemical Society. microcrystals using FeCl3 and Na2WO4 precursors. EG plays
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critical roles as both the reducing agent and the structure- CdSe/CdS) nanoparticles have been successfully synthesized using
directing agent in driving the architecture assembly by the Brust's version.130–132 Alkylamines and trioctylphosphine oxide
oriented attachment of the primary nanoparticles. were substituted for alkanethiols to conrm the exibility of this
The hydro-solvothermal synthesis of the oxide nanoparticles method for various kinds of capping agents.
in the polar solvent oen leads to the fast growth of the The original two-phase method has been modied for the
precursor-derived nucleus. It seems to be difficult to control the synthesis of the colloidal metal oxide and mixed oxide nano-
particle shape, so that the oxide nanoparticles obtained oen particles. Fig. 10 shows two routes for the design of a two-phase
have large sizes, relatively irregular shapes, and aggregates. The aqueous–organic system: (i) inorganic salt precursors soluble in
good point of this route is the high solubility of the metallic ion the water phase and (ii) metal–ligand complex precursors
precursors in the solvent-contained bomb reactor that could soluble in the organic phase. In Fig. 10a, the metal hydroxides
facilitate the large-scale synthesis of highly crystalline oxide are formed in basic solution because the hydrolysis of tert-
nanoparticles. Because of its simplicity, low cost, and ambient butylamine as an activation agent in water generates a basic
pressure, the crystal growth from the bulk mixture is of consid- medium. Upon hydrothermal treatment, these metal hydrox-
erable interest for diverse oxide nanomaterials. This method has ides are dehydrated to oxide nuclei at the interfaces. In Fig. 10b,
advantages of being safe, utilizing low temperature, and envi- the metal–ligand complexes are decomposed at the liquid–
ronmentally friendly.108 Our recent proof-of-concept study shows liquid interfaces to form the oxide nucleus with tert-butylamine
extremely crystalline CeO2 nanocubes with an average size up to as a catalyst. In both cases, aer the synthesis reaction is
120 nm prepared from the hydrothermal reaction of a cerium terminated, the capped nanoparticle products are pulled into
nitrate–hexamethylenediamine–water mixture.56 the organic phase resulting in a good dispersion in the organic
phase (Fig. 10c and d). For the hydro-solvothermal and ther-
molysis routes, to gain the monodisperse oxide nanoparticles,
5.2 Two-phase route the burst nucleation and the subsequent separation of the
A two-phase method is performed in a two-phase water–organic nucleation and growth must occur during synthesis. However,
mixture by mixing the precursors with the capping molecules. for the two-phase system, the nucleation and growth are typi-
The two-phase reaction of the nucleation and growth of the cally much weaker compared with the one-phase system,
oxide nanoparticles typically occurs at the liquid–liquid inter- whereby the burst nucleation and the separated nucleation and
face of the water and organic phases under hydro-solvothermal growth processes are not essential and the resulting oxide
treatment. The nuclei are generated and then grow at the nanoparticles oen have narrow size distributions. In the two-
liquid–liquid interface to form capping molecule-assisted oxide
nanoparticles. The capped nanoparticle products are highly
dispersed in the nonpolar phase and no product is observed in
the water phase. The nanoparticle products dispersed in the
organic phase are precipitated by adding excess ethanol and
recovered by centrifugation. Compared to the solvothermal
route, the two-phase route could yield the products with good
crystallinity under mild conditions because the presence of the
water phase in the bulk solution accelerates the particle growth.
The particle size and shape could be controlled because the
nucleation and growth occur at slow rate at the interfaces.
As early as 1994, the two-phase route was rst developed by
Brust et al.129 for the synthesis of Au nanoparticles through phase
transfer of Au cations into a toluene phase with the assistance of a
phase transfer agent of tetraoctylammonium bromide. The
organic solution of the phase transfer reagent was added to the
aqueous solution of AuCl4 to form a two-phase system that was
then mixed with a dodecanethiol capping agent. The cationic part
of the phase transfer reagent reacted with the anionic complex of
AuCl4 and thus formed organic-soluble compounds. The forma-
tion of the Au nanoparticles is composed of a two-step process. The
rst step can be nished as soon as the aqueous phase becomes
clear, meaning that AuCl4 was quantitatively isolated from this
phase. The second step was the reduction of the metal cations Fig. 10 General two routes for the hydro/solvothermal two-phase synthesis of
within reverse micelles by adding sodium borohydride. The source oxide nanoparticles in a toluene–water system using different types of precursors:
of electrons, BH4, is also captured by free surfactant molecules, (a) metal salt precursors dissolved in the aqueous phase and (b) metal–organic
precursors dissolved in the organic phase. TEM images of (c) Sm2O3 nanorods
which were oating at the interface. This synthetic approach has synthesized using samarium nitrate precursors and (d) Er2O3 nanorods synthe-
been rened repeatedly for different inorganic precursors and sized using Er–oleate complex precursors. Reproduced with permission from ref.
stabilizing ligands. Metal (Ag, Pt, Pd) and semiconductor (CdS and 92, 104 and 133, copyright 2008, 2009, 2011 American Chemical Society.
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phase route, to gain the narrow size distribution of uniform

oxide nanoparticles, the low nucleation and growth rate is
desired and the low reactive precursors oen give a low reaction
rate.
Much recent progress of this two-phase approach has been
extended to the synthesis of a variety of the metal oxide and
mixed oxide nanomaterials under solvo/hydrothermal treat-
ment. Pan et al.134 reported the synthesis of monodisperse TiO2
nanoparticles from the hydro-solvothermal reaction of a two-
phase mixture composed of titanium precursor–tert-butyl-
amine–oleic acid. Zhao et al.135 synthesized ZrO2 nanoparticles
with sphere-, teardrop-, rod-, and rice-shapes. The nanoparticle
shape could be controlled by changing the zirconium(IV) n-
propoxide concentration, capping molecules, and reaction
temperature. Du et al.136 used the two-phase technique to
synthesize BaTiO3 nanoparticles from the hydro-solvothermal
reaction of mixed titanium(IV)-n-butoxide and barium acetate
co-precursors occurring at the liquid–liquid interface. Zhang
et al.137 modied this reaction system for the synthesis of CeO2
nanocubes using cerium hydroxide precursors under super-
critical water conditions. The nanoparticle shape can be
controlled by tuning the interaction of the oleic acid capping
molecules with various crystallographic facets of the CeO2
nanoparticles. In contrast to the metal alkoxide precursors, Fig. 11 (a) A separated two-phase hydrolysis route for the ZrO2 nanoparticles.
(1) Evaporation and diffusion of two phases in a bomb reactor. (2) Hydrolysis
metal stearates are cheaper and more stable, Zhao et al.89
reaction at the interface area. (3) The formation and crystallization of the ZrO2
synthesized Mn3O4 nanoparticles using manganese(II) stearate particles employed by depositing into the organic phase. (4) The separation of the
precursors. The spherical and cubic shapes and the particle size nanoparticles and recycling of the organic phase. (b) HRTEM image of the ZrO2
can be controlled by adjusting the reaction time and activation nanoparticles, inset: blue-light emitting ZrO2 quantum dots dispersed in chloro-
agent concentration. Zhao et al.138 also reported a general two- form. Reproduced with permission from ref. 139, copyright 2008 American
Chemical Society.
phase route to produce different monodisperse oxide nano-
particles with controlled size and shape.
The two-phase interface route was modied by Tang et al.139
to synthesize luminescent ZrO2 quantum dots as shown in separation mechanism occurring at the interfaces of the liquid–
Fig. 11. The water phase and the organic phase containing solid–solution phases during the hydrothermal process.
Zr(OC4H9)4 precursors were placed separately in the same The advantage of this two-phase route is that the formed
Teon-lined hydrothermal chamber (Fig. 11a). The hydro- highly crystalline oxide nanoparticles oen have small sizes
thermal hydrolysis reaction between precursors and water even aer using the metal salt precursors because of the slow
occurred by collision of the water vapor with the organic phase. growth of the nuclei at the interfaces. The use of the metal–
This interaction led to the two phases to be diffused gradually organic complexes oen yields tiny oxide particles that could
together that allowed formation and growth of the ZrO2 crystal orientedly aggregate to form the porous hierarchical structures
nucleus at the interface. The tiny toluene droplets dispersed in with unique properties. This could be claried by Nguyen
the water vapor act as nanoreactors that can conne the growth et al.133 for the one-pot synthesis of mixed oxide (CexLa1x)2O3d
of the particles, resulting in the formation of the small-sized nanoarchitectures that were thermally converted from meso-
ZrO2 nanocrystals (#10 nm) as shown in an electronic micros- porous CexLa1xCO3OH nanoannulars derived from the
copy image. The tiny ZrO2 particles were expected to exhibit a assembled tiny primary particles prepared by decomposing
distinct quantum size effect that was demonstrated by the CexLa1x(oleate)3 complexes in a water–toluene mixture. This
observation of their blue-light emission (Fig. 11b). This simple route is also compatible with some specic reaction systems for
route also showed a high yield and highly recyclable reaction scale up as is proved from our research results of the two-phase
solutions that could make it easy to achieve the production synthesis of a large quantity as much as 50 g of the uniform
scale-up. Further work of this scope was also developed by Sm2O3 nanorods per run.104
Wang et al.,140 who added a sodium linoleate solid phase to a
linoleic acid–ethanol/water two-phase mixture to form a liquid–
solid–solution three-phase system. The hydrothermal treatment 5.3 Thermolysis
of a three-phase mixture composed of metallic salt–water The diverse inorganic nanoparticles with controlled size and
liquid, sodium linoleate solid, and linoleic acid–ethanol solu- shape can essentially be synthesized through thermal decom-
tion yielded the family of oxide nanoparticles. The growth of the position of the organometallic compounds in high-boiling
oxide nanoparticles was based on the phase transfer and the point organic solvents containing the stabilizing capping
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agents.141,142 The procedure involves the injection of a room- WO3x nanorods by injecting [W(CO)6] into an octyl ether–
temperature precursor solution into a hot organic solvent in the oleylamine solution at a boiling solvent temperature. The
presence of capping molecules. The “heating-up” thermolysis thermolysis of lanthanum benzoylacetylacetonate complexes in
route is widely popular for the production of uniform oxide a hot oleic acid–oleylamine mixture produced rare earth oxide
nanoparticles using organometallic precursors including metal nanoparticles.152 The selective adhesion of the capping mole-
acetylacetonates, metal cupferronates, metal alkoxides, metal cules plays a critical role in the formation of the two-dimen-
carbonyls, and metal halides. Fatty acid and aliphatic amine sional nanoparticles. Cao153 achieved the self-assembly of the
compounds are oen used as capping agents. The ratios of the Gd2O3 nanoplates prepared from the thermolysis of
starting reagents including organometallic compound, capping Gd(O2CCH3)3 in a hot octadecene–oleic acid–oleylamine
agent, solvent, as well as reaction temperature and time are mixture into ribbons of the stacked plates. Cozzoli et al.154
decisive parameters for the precise control of the particle size employed the thermolysis of the Ti(OiPr)4 precursor in the
and shape. The identication of suitable molecular precursors, presence of oleic acid to produce TiO2 nanorods. The authors
the regulation of solvent-coordinating capability, and the observed that the presence of surface-selective capping agents
balance of the nucleation and growth stages are three requisites may hinder the oriented attachment during growth. Seo et al.70
for gaining high-quality nanoparticle products. In contrast to reported a general approach for the synthesis of transition-
the two-phase method, thermolysis involves the separation of metal oxide nanorods of W18O49, Mn3O4, and TiO2 structures
the nucleation and growth, because it involves the addition of through thermal reaction of a metal halide and oleylamine
the preformed nuclei to the reaction monomer solution. The mixture. The reaction of the metal halides and oleic acid
precursor monomers subsequently grow on the surface of the induced an increase of the monomer concentration and
tiny particles without further nucleation as a consequence of promoted the fast growth of the nanoparticles along the high-
the fact that this route provides an excellent control of the surface-energy directions. Jana et al.155 achieved the thermolysis
crystallite size and shape of the monodisperse inorganic of transition-metal stearate precursors in a hot stearic acid–
nanoparticle colloids. hydrocarbon mixture to produce shape-controlled magnetic (Cr,
As early as 1993, Murray et al.143 rst developed a hot injec- Mn, Fe, Co, Ni) oxide nanoparticles. Diab et al.156 achieved the
tion route for the controlled synthesis of the colloidal suspen- thermolysis of copper cupferronate on a silicon substrate to
sions of monodisperse CdE (E ¼ S, Se, Te) semiconductor yield an assembled lm of Cu nanoparticles which on oxidation
quantum dots in an organic solvent. This synthetic strategy transformed into Cu2O with retention of the assembly.
became one of the most popular liquid-phase routes to the Decomposing the binary organometallic compounds could
monodisperse oxide nanoparticles, which have been developed yield mixed oxide nanoparticles. Accordingly, cubic shaped
later by other research groups. It is interesting to note that Park CoFe2O4 nanoparticles were obtained through thermal reaction
et al. have been more successful in the use of this thermolysis to of cobalt(II) acetylacetonate and iron(III) acetylacetonate in oleic
produce diverse uniform oxide nanoparticles.38 The pioneering acid–oleylamine.157 Under mild growth conditions with low
work of the authors demonstrated the rst examples of the precursor concentration and slow heating rate, cubic shaped
reaction of the metal carbonyl precursors with a chemical CoFe2O4 nanoparticles were obtained, whereas spherical-sha-
oxidant to yield monodisperse FeO nanoparticles in the size ped nanoparticles formed under harsh growth conditions.
range of 4–16 nm by decomposing Fe(CO)5 in octyl ether at 300 Various sphere, branch, and pod shapes of MnxNi1xO and

C in the presence of oleic acid. The subsequent addition of MnyCo1yO nanoalloys synthesized by Jeong et al.158 via ther-
trimethylamine N-oxide as a mild oxidant at an elevated molysis of Mn(acac)2 and Co(OAc)2 co-precursors in an oleic
temperature to the aging solution resulted in the formation of acid–1-octadecene mixture can be controlled by changing the
monodisperse 13 nm-sized Fe2O3 nanoparticles.144 It has also co-precursors and the capping agent.
been reported that the use of this method gives the exible size The Hyeon group had also advanced this heating-up method
and shape control of the monodisperse oxide nanoparticles. by using more effective metal–oleate complexes prepared from
Park et al.145 revealed that monodisperse iron nanoparticles the phase-transfer reaction of metal(III) chloride and sodium
with tunable sizes of 4, 8, and 11 nm were prepared by changing oleate. This progress has made it possible to perform the
the Fe(CO)5 : oleic acid ratio from 1 : 1 to 1 : 2 and 1 : 3, production scale-up, while maintaining the uniform size and
respectively. These iron nanoparticles acted as seeds that reac- shape of the monodisperse oxide nanoparticles. Fig. 12 shows
ted with iron oleate solutions with dened concentrations fol- an efficient thermolysis route developed by Jongnam et al.150
lowed by further oxidation with trimethylamine N-oxide to This facile procedure is composed of decomposing the prepared
produce the iron oxide nanoparticles with tunable particle metal–oleate complexes at 300 C in different solvents, such as
diameters of 6, 7, 8, 9, 10, 11, 12, 13 nm. Using the same 1-hexadecene, octyl ether, 1-octadecene, 1-eicosene, or trioctyl-
procedure, the authors had also successfully synthesized a amine, to generate uniform transition metal oxide nanocrystals
variety of uniform, monodisperse oxide nanoparticles without a (Fe3O4, CoO, MnO, ZnO). The aging process was found to be a
size-selection process including Sm2O3 nanowires/nano- necessary step for the formation of the oxide nanoparticles. The
plates,146 Fe3O4 nanocubes,147 MnFe2O4 nanospheres,148 and authors demonstrated that the decomposition reaction of the
MnO nanospheres.149 metal (M) carboxylates occurs via breakage of M–O and MO–C
Other research groups had also applied this method for bonds of metal carboxylate, giving radical species. These radical
synthesizing the oxide nanoparticles. Lee et al.151 synthesized species can recombine, decompose into smaller molecules,
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continuous collisions between droplets. The interplay between

droplets is typically determined by disperse uid, surfactant,
and collisions. Once the droplets coalesce, the droplets tend to
break up because they are not as thermodynamically stable as

the original droplets. Thus, unless the interactions between
droplets are very repulsive, the aqueous droplets in a water-in-
oil reverse micelle could go through continuous coalescence
and break up, which results in a continuous exchange of the
droplet contents. When two microemulsions each containing
Fig. 12 A schematic illustration of the large-scale synthesis of the uniform oxide the respective reactants are mixed together, the contents of the
nanocrystals. Metal–oleate precursors were prepared from the transfer reaction
aqueous droplets are mixed and redistributed rapidly. The
of metal chloride and sodium oleate. The subsequent thermolysis of the metal–
oleate complex precursors in a high-boiling organic solvent yielded the oxide
collisions involve a temporary merging of the droplets into a
nanoparticles. The TEM image of highly uniform Fe3O4 nanospheres and a larger droplet, subsequent breakup of this larger droplet, and
photograph showing a Petri dish containing 40 g of the monodisperse magnetite nally the formation of the precipitates in the micelles. The
nanoparticles and a US penny for comparison. Reproduced with permission from mass exchange between droplets could be extremely fast and
ref. 150, copyright 2004 Nature Publishing Group.
consequently, the mass exchange is limited by the collision of
the droplets; in addition, the nanoparticles synthesized in the
reverse micelle mixture are generally very ne and
such as CO, CO2, H2, water, ketones, esters, and hydrocarbons. monodisperse.161
The particle sizes can be controlled in the range of 5–22 nm by A variety of oxide nanoparticles had been synthesized using
tuning the decomposition temperature and aging period. The the reverse micelle method. Kuiry et al.164 synthesized CeO2
colloidal MnO and Fe3O4 nanoparticles prepared using this nanorods by self-assembling the nanoparticles in a water–AOT–
alternative acted as particle precursors to fabricate uniform toluene microemulsion. The hydrogen peroxide solution was
hollow oxide nanoparticles through acid etching.149 This added to the water–AOT–toluene microemulsion containing
method was able to scale-up the synthesis with a large quantity Ce3+, mutual interactions of the micelles occurred by random
(40 g for capped iron oxide nanocrystals) of the monodisperse collisions, transfer of the reactants occurred to form the nano-
nanocrystals obtained in a single reaction without a size-sorting particles in the inner cores of reverse micelles. The presence of
process. In another report, Bao et al.159 also applied this alter- coordinated surfactants around the sphere-shaped nano-
native for synthesizing mixed Fe–Mn–oleate complexes and reactors restricted the aggregation of CeO2 nanoparticles. The
subsequently decomposed them followed by oxidizing with self-assembly of CeO2 nanoparticles led to a gradual evolution
Me3NO to yield monodisperse MnFe2O4 nanoparticles. of CeO2 nanorods during aging. The presence of nitrate ions in
the present situation from the precursor solution also affected
the interfacial properties of the micelles in such a way that the
5.4 Reverse micelle process of the formation of supraaggregates was facilitated.
A reverse micelle is a transparent and thermodynamically stable Fig. 13 shows an emulsion-based self-assembly route developed
solution of low viscosity formed spontaneously from a surfac- by Bai et al.163 for the orientation of 6.9 nm oleic acid-capped
tant–water–oil mixture.160 A water-in-oil (W/O) reverse micelle is BaCrO4 nanoparticles into 100–120 nm-sized nanospheres. The
a solution of water droplets with nanometer size dispersed in a synthetic procedure constitutes the addition of cyclohexane
hydrocarbon phase with the aid of a monolayer of the surfactant solution containing BaCrO4 building blocks to an aqueous
molecules.161 The size of the reverse micelle is determined by solution of the anionic sodium dodecylsulfate surfactant to
the ratio of water relative to the surfactant. The reverse micelles create an oil–water microemulsion by ultrasonic treatment. The
could be used as nanoreactors for the synthesis of uniform reaction system was then submerged in a heating mantle and
nanoparticles through chemical reactions occurred inside the organic solvent was evaporated at desired temperatures with
aqueous cores. The resulting nanoparticles stabilized by the constant stirring to obtain the assembled spheres. The
surfactant layer could act as steric stabilizers to inhibit the composition, size, and surface charge of the BaCrO4 nano-
aggregation of the nanoparticles.162 The addition of the solvent spheres can be controlled by rationally designing the experi-
(acetone or ethanol) to the microemulsion could result in the mental conditions. Johnson et al.165 demonstrated this principle
nanoparticles being precipitated out of the reaction system by by producing three shaped BaCrO4 nanostructures – linear
ltering or centrifuging the reaction mixture. chains, rectangular superlattices, and long laments as a
The droplet size could increase to a dimension of 2–20 nm function of the reactant molar ratio, which in turn is controlled
that is much larger than the monolayer thickness of the by fusing the microemulsion droplets containing the xed
surfactant because the inside pool of water or oil is enlarged. By concentrations of barium and chromate ions. Kim et al.166
changing the water pool size, the particle size could be synthesized uniform BaCrO4 nanorods from a reverse micelle
controlled. When further increasing the surfactant concentra- system composed of barium bis(2-ethylhexyl)sulfosuccinate–
tion, the micelles could be deformed and their particle shape sodium chromate–sodium bis(2-ethylhexyl)sulfosuccinate.
could be changed. The micelles are considered to be nearly Interestingly, the capped BaCrO4 nanorods were diluted and
monodispersed and are in a dynamic state that involves redispersed in isooctane to make a stable nanorod colloidal
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Fig. 13 Bottom-up assembly of the mixed oxide BaCrO4 nanoparticles into the spheres. (a) An oil–water mixture. (b) A microemulsion system. (c) Solvent evaporation
in the oil droplets and the assembly of the BaCrO4 nanoparticles in the confined oil droplets into spherical colloids dispersed in water. (d) Separation of the assembled
spherical solids of the BaCrO4 particles. Reproduced with permission from ref. 163, copyright 2007 Wiley-VCH.
suspension that acts as a liquid-crystalline phase, which self- aqueous droplets containing rare earth ions dispersed in a
assembled into nematic, smectic, and spiral phases of two- continuous hexane–oleic acid–oleylamine oil phase (Fig. 14a).
dimensional nanorod monolayers via a Langmuir–Blodgett Na3VO4 precursors were added to the reverse emulsion and the
technique. rare earth orthovanadate nuclei formed by diffusion of the
The sol–gel processing in the reverse microemulsion to vanadate anions into the microreactors and combining with the
produce discrete barium hexaaluminate nanoparticles was rare earth cations. The sequential solvo/hydrothermal treat-
reported by Andrey and Jackie167 The nanometer-sized aqueous ment was carried out to form square-plate nanocrystals. The
micelles dispersed in a continuous oil phase were used as shape transformation of the square plate into H-like shaped
nanoreactors for the controlled hydrolysis and condensation of CdVO4 and NdVO4 nanocrystals with an increase in the basic
Ba and Al alkoxides. The morphology, structure, and specic concentration and an extended reaction time could be attrib-
surface area of the barium hexaaluminate nanoparticles can be uted to a selective etching (Fig. 14b and c). Wu et al.168 prepared
controlled by the synthetic parameters including the composi- anatase- and rutile-phase TiO2 nanoparticles by the hydro-
tion of the reverse microemulsion, water to alkoxide ratio, aging thermal treatment of Ti(OBu)4 in a Triton X-100–n-hexanol–
time, and drying techniques. These mixed oxide nanoparticles cyclohexane microemulsion at 120 C for 12 h in a bomb
can be crystallized directly to the desired barium hexaaluminate reactor. The morphologies of the products can be controlled by
phase at 1050 C and sustained surface areas in excess of 100 m2 adjusting pH inside prior to the hydrothermal treatment,
g1 aer calcination to 1300 C. The high thermal stability of accordingly the use of the high concentration of hydrochloric
these materials might be attributed to the successful separation acid (2.0 M) resulted in the formation of rutile TiO2
of the crystallization and grain-growth processes. These barium nanocrystals.
hexaaluminate materials with high surface area and thermal The typical character of the reverse micelle route is a ne
stability provide the possibility of making a highly promising control of uniform oxide nanoparticles. Taking advantages of
methane combustion. In another report, Oh et al.169 used the the hydrophobic–hydrophilic mutual interactions in the
microemulsion process for preparing uniformly sized tantalum microemulsion could create good orientation of the co-surfac-
oxide nanoparticles. The controlled sol–gel reaction in the tants that oen form monodisperse assembled microspheres
reverse micelle composed of cyclohexane, ethanol, NaOH, Ige- derived from the uniform primary particles. However, the
pal CO-520 surfactant, and tantalum(V) ethoxide for the remarkable limitation of this route is that it is able to synthesize
formation of tantalum oxide particles was carried out at room small quantities of products while consuming relatively large
temperature. The increased amount of ethanol resulted in a volumes of the reaction solvents.
decrease of the hydrolysis rate of the tantalum ethoxide, so that From the viewpoints of the structural morphology effects,
the particle size could be controlled in the range of 5–15 nm the theoretical models combined with the typical synthesis
by varying the ethanol amount. routes, the author concludes that where the future is concerned,
Combining the reverse microemulsion with heating could along with the development of new nanomaterials, an insight
give rise to the highly crystalline oxide nanoparticles. Fig. 14 into the formation mechanisms will be needed in order to
shows the solvo-hydrothermal treatment of the reverse micro- facilitate the synthesis process. With such advances in the scope
emulsion reactors for the synthesis of uniform CeVO4 and of this experimental work, it is expected that more theoretical
NdVO4 nanoparticles with luminescent properties reported by studies will lead to a better control of the production of the
Deng et al.170 The reverse emulsion constitutes the basic desired uniformly sized and shaped oxide nanomaterials. This
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Fig. 14 Solvo/hydrothermal treatment-combined reverse micelle route for the synthesis of the rare earth orthovanadate nanoparticles. (a) A proposed mechanism for
the formation of the uniform rare earth orthovanadate nanoparticles. (b) Shape evolution from the square plate to H-like shapes of the mixed oxide nanoparticles. (c)
TEM images of the square-plate and H-like shaped CeVO4 nanoparticles. Reproduced with permission from ref. 170, copyright 2008 American Chemical Society.
in turn should lead to new nanotechnological applications; in The overall process of the size distribution control of the
particular catalysis, energy conversion, sensing, and biomedi- capping molecule-assisted route consists of burst nucleation
cine areas are expected to be fast-tracked from the laboratory to and diffusion-controlled growth for size focusing, which ts
industry. The importance of process scalability from the labo- very well to the LaMer model for the formation of the mono-
ratory to a commercial scale should not be underestimated. disperse oxide nanoparticles. Conclusive accounts of the roles
played by capping molecules, monomer concentration, and
6 Concluding remarks reaction conditions were discussed, which presented the
generalized effect principles of the reaction parameters on the
Signicant efforts over the past ten years have been made for the controlled particle shape. Yet, we also discussed the shape
synthesis of a large number of uniform, monodisperse metal control through the selective capping of the organic stabilizers
oxide nanoparticles with controlled aesthetic shapes. The shape on the particle surface.
of the oxide nanoparticles could determine not only their As a proof of concept of the uniformly shape-controlled oxide
intrinsic physicochemical properties, but also offers new nanoparticles, the four different capping molecule-assisted
nanotechnological applications in catalysis, optics, electronics, methods including the hydro-solvothermal route, the two-phase
and magnetics. This review provides a brief account of the size route, thermolysis, and reverse micelles have been reviewed in
and shape effects, the kinetic regime concepts, shape control comparison. As discussed above, we could nd the advantages
ways, and capping molecule-assisted synthetic methods toward and obstacles of the abovementioned synthetic methods. In
the formation of colloidal metal oxide nanoparticles. The size- terms of simplicity of the controlled synthesis, the two-phase
and shape-dependent properties of the oxide nanoparticles process is the preferred route for scale-up. The hydro-sol-
make them surface-active materials for manipulating the reac- vothermal synthesis is a relatively little explored method for the
tion yield and selectivity. Essential concepts of the kinetics of synthesis of oxide nanoparticles, although this process allows
the plausible nucleation and growth mechanisms were for the synthesis of highly crystalline nanoparticles. The reverse
described to elaborate on the quantitative description of the micelle allows for synthesizing uniform oxide nanoparticles,
generation of the oxide nanoparticles through mathematical however, typically requires a large amount of solvent and
equations. This could help readers clearly gure out the corre- produces small quantities of products. In terms of the size and
lations of the experimental results with synthetic conditions. shape control of the oxide nanoparticles, the heating-up
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Review Nanoscale
thermolysis seems an advanced method developed to date. This 9 T.-D. Nguyen, Portraits of Colloidal Hybrid Nanostructures:
technique oen requires the use of either organometallic or Controlled Synthesis and Potential Applications, Colloids
metal alkoxide precursors and performs at high temperatures. Surf., B, 2013, 103, 326–344.
The alternative use of the prepared metal–oleate complexes as 10 R. Sui and P. Charpentier, Synthesis of Metal Oxide
effective starting materials in the thermolysis of the precursors Nanostructures by Direct Sol–Gel Chemistry in
could overcome this obstacle, which is readily applicable for the Supercritical Fluids, Chem. Rev., 2012, 112(6), 3057–3082.
large-scale synthesis of the uniformly sized oxide nanoparticles. 11 Y. Qu and X. Duan, Progress, Challenge and Perspective of
We hope that what is presented in the review should be Heterogeneous Photocatalysts, Chem. Soc. Rev., 2013, 42(7),
considered as a collection of powerful paradigms, fundamental 2568–2580.
subjects, and guiding concepts for synthesizing the mono- 12 A. Kubacka, M. Fernández-Garcı́a and G. Colón, Advanced
disperse oxide nanoparticles and controlling their uniform Nanoarchitectures for Solar Photocatalytic Applications,
shapes. These synthetic protocols built upon the controlled Chem. Rev., 2011, 112(3), 1555–1614.
nucleation and growth allow the materials scientists to inde- 13 J. Cheon and J.-H. Lee, Synergistically Integrated
pendently tune the size, shape, and surface chemistry of the Nanoparticles as Multimodal Probes for
oxide nanoparticles, along with the design and tailoring of their Nanobiotechnology, Acc. Chem. Res., 2008, 41(12), 1630–
unique nanoscale electronic and optical properties. These 1640.
features offer diverse applications in the areas of catalysis, 14 N. A. Frey, et al., Magnetic Nanoparticles: Synthesis,
electronics, information storage, sensing, and biomedicine. To Functionalization, and Applications in Bioimaging and
date, the materials scientists can easily synthesize some nano- Magnetic Energy Storage, Chem. Soc. Rev., 2009, 38(9),
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goal to produce the extremely uniform oxide nanoparticles with 15 S. Singamaneni, et al., Magnetic Nanoparticles: Recent
exibly controlled shapes. These uniform oxide nanoparticles Advances in Synthesis, Self-Assembly and Applications, J.
could be used as ideal building blocks to construct new nano- Mater. Chem., 2011, 21(42), 16819–16845.
materials with new collective properties derived from the self- 16 S. Laurent, et al., Magnetic Iron Oxide Nanoparticles:
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17 T. Thai-Hoa and N. Thanh-Dinh, Functional Inorganic
Acknowledgements Nanohybrids for Biomedical Diagnosis, Biomedical
Engineering, InTech, 2013, vol. 13, pp. 279–325.
T.D.N is grateful to the Natural Sciences and Engineering
18 D. R. Rolison, Catalytic Nanoarchitectures – the Importance
Research Council (NSERC) of Canada for nancial support.
of Nothing and the Unimportance of Periodicity, Science,
2003, 299(5613), 1698–1701.
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From Formation Mechanisms To Synthetic Methods Toward Shape-Controlled Oxide NP (2013)

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From formation mechanisms to synthetic methods

1 Introduction large diversity of oxide nanocompounds with intriguing geom-

¼ A exp (1) where NA is the Avogadro's number.

Then, for r d, we have

the other facets. When there is a suﬃcient thermal energy in the

Fig. 6 The oriented attachment mechanism of the oxide nanoparticles. (a)

phase route, to gain the narrow size distribution of uniform

continuous collisions between droplets. The interplay between

break up because they are not as thermodynamically stable as

Barium Titanate, Cryst. Growth Des., 2012, 12(3), 1247–1253. 11233.

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