CrystEngComm

HIGHLIGHT
Cite this: CrystEngComm, 2014, 16,
2550
Received 24th June 2013,
Accepted 1st November 2013
DOI: 10.1039/c3ce41203b
www.rsc.org/crystengcomm
The art of using ionic liquids in the synthesis of
inorganic nanomaterials
Xiaochuan Duan,
a
Jianmin Ma,*
b
Jiabiao Lian
c
and Wenjun Zheng*
a
Wet chemistry using ionic liquids as the medium has proven to be highly efficient for the preparation of
several types of metallic, metal oxides, and other kinds of semiconductor nanostructures, and so on. This
article reviews state-of-the-art research activities in the field, focusing on the use of ionic liquids as a
versatile regent for the synthesis of various nanoparticle systems. We begin with a survey of choices to
explore the ability of ionic liquids to act as a reactant, solvent, and surfactant, as a function of other
synthesis parameters, also denoted as ionic liquid precursors (or task-special ionic liquids), which offer
many advantages over traditional solution-phase methods. We then examine the design and fabrication
of functional inorganic materials by means of optimizing the effect models of ionic liquids. Many of the
most recent advances in ionothermal or ionic liquid-assisted synthesis have been realized by appropriate
choice of cations or anions of ionic liquids according to the need. This review also highlights crucial
issues that should be addressed in future research activities.
Introduction
Over the past few decades, nanoscience has experienced
exponential growth in its research activities, since nanoscale
materials can exhibit physical and chemical properties that
are different from those of their bulk counterparts.
1,2
There-
fore, the design and optimization of synthetic methods for
the preparation of nanomaterials have been intensively inves-
tigated. As a result, important progress has been achieved on
the synthesis of nanomaterials with tailored composition,
size and shape using various synthetic methods, especially
solution-phase methods. Generally, in conventional synthesis,
nanomaterials are fabricated in molecular solvents (organic
solvents or water); nevertheless, a limited number of molecular
solvents can be used and some of them may cause environ-
mental problems. In this regard, it is still a big challenge to
explore novel and green media that allow particular reactions
to occur.
3
As a new type of green alternative to conventional organic
solvents, ionic liquids (ILs) have found widespread applica-
tion in organic chemistry and organometallic catalysis exactly
from the discovery of water-stable ionic liquids by Wilkes and
Zaworotko in 1992,
4
whilst their use in inorganic synthesis is
just about to begin.
521
Different from the conventional
molecular solvents, ionic liquids are usually composed of
larger organic cations and smaller organic or inorganic
anions. Due to the asymmetry of volume, ionic liquids have
some distinctive features, such as low melting point, negligible
vapor pressure, non-volatility, high thermal stability, and high
ionic conductivity. More importantly, these properties are
strongly dependent on the species of cations and anions;
therefore, ionic liquids can be referred to as designed
liquids with tunable properties by adjusting their cations
and anions. Mainly on account of these unique properties,
ionic liquids show an increasing potential to innovate in the
synthesis techniques. Although there are many excellent char-
acteristics as stated above, we here should point out that any
ionic liquid can hardly take on all these characteristics
together, and we should carefully check them for any given
ionic liquid before use.
The first attempt at using ionic liquids as the reaction
medium instead of conventional molecular solvents for the
synthesis of inorganic materials was pioneered by Dai and
co-workers in 2000.
22
They introduced ionic liquids for the
preparation of porous silica gels termed as ionogels, which
are being extensively investigated. Subsequently, ionic liquids
have been actively employed for the synthesis of a broad
range of inorganic materials, and many interesting inorganic
materials with various properties have been fabricated. Notably,
Dupont's group prepared uniform Ir nanoparticles in ionic
liquid media.
23
Kimizuka and Nakashinma reported the
2550 | CrystEngComm, 2014, 16, 25502559 This journal is The Royal Society of Chemistry 2014
a
Department of Materials Chemistry, Key Laboratory of Advanced Energy
Materials Chemistry and TKL of Metal and Molecule-Based Material Chemistry,
College of Chemistry, Nankai University, Tianjin, PR China.
E-mail: zhwj@nankai.edu.cn
b
Key Laboratory for Micro-Nano Optoelectronic Devices of Ministry of Education,
State Key Laboratory for Chemo/Biosensing and Chemometrics, Hunan University,
Changsha, PR China. E-mail: nanoelechem@hnu.edu.cn
c
Department of Physics, The Chinese University of Hong Kong, Hong Kong,
PR China
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synthesis of hollow titania microspheres in a toluene/ionic
liquid medium.
24
Antonietti and Zhou obtained spherical
TiO
2
aggregates composed of nanoparticles using an ionic
liquid.
25
Correspondingly, the concepts ionothermal and
all-in-one for the synthesis of materials using an ionic liquid
as the solvent were proposed in 2004 by the respective groups
of Morris and Taubert.
26,27
It is worth mentioning that
ionothermal synthesis is quite different from hydro- or solvo-
thermal conditions, which may lead to new materials with
interesting morphologies and that are not accessible by using
conventional organic solvents or water due to the unique
physicochemical properties of the ionic liquids. Gradually, the
advantages of ionic liquids in inorganic synthetic procedures
have been realized, for instance: (i) ionic liquids have low
interface tensions in spite of their polar features, resulting in
a high nucleation rate; (ii) ionic liquids can form extended
hydrogen bond systems in the liquid state and are therefore
highly structured, and thus can further affect the structures of
resulting products; and (iii) as a tunable medium, ionic liquids
are immiscible with a number of organic solvents and can
provide a non-aqueous and polar alternative for two-phase
systems. Thus, it is rational to expect that the application of
ILs may offer a wide variety of possibilities for the fabrication
of nanomaterials and develop into a mainstream area in the
field of synthetic chemistry.
However, although great efforts have been made on con-
trolling the crystal phase and morphology of inorganic mate-
rials using ionic liquids, a consistent and fundamental
understanding of the effect between ionic liquids and prod-
ucts has still not been achieved.
2852
As a consequence of this
situation, most of the syntheses are not predicted and simply
use an IL or a mixture of an IL with a conventional solvent
just like a common surfactant, which does not sufficiently
exhibit the main advantages of ILs. There may be mainly two
reasons that have led to this status: (i) A molecular-based
understanding of the physicochemical properties of ILs is a
great challenge since different ionic liquids have different
physicochemical properties, and since reliable parameters are
sometimes not available, it is urgent to build up a systematic
database on the physicochemical properties of ILs. (ii) The
research on well-established rules and correlations between
molecular structures of the adopted ILs and the morphologies
of the resulting inorganic materials is limited.
53
We believe that
the realization of the general trends may be utilized in the
rational design of desired inorganic materials with the desired
polymorph and the desired morphology using ILs. For this
regard, this review will focus on the rational design of ionic
liquids and an understanding of the ionic liquid's effect at the
molecular level based on solution-phase methods. Although
the use of ILs for the synthesis of inorganic nanomaterials has
been reviewed in some inspiring short accounts or perspec-
tives,
3,5,6,12,54,55
a relatively comprehensive and fundamental
review of this subject is still lacking, especially considering the
rational design of ionic liquids at the molecular level. In addi-
tion, as a burgeoning field, there are hundreds of relevant
papers, and only typical examples and key concepts proposed
especially in the past five years are highlighted here. In order to
facilitate discussion, the range of properties and functions of
ionic liquids for the synthesis of inorganic nanomaterials has
been divided into two major aspects: the ionic liquid precursor
and the effect model of ionic liquids.
Ionic liquid precursor
Since ionic liquids can serve as tailored solvents, they thus
give us an opportunity for designing the ionic liquid precur-
sors according to the crystal structures, compositions, and
crystal habits of the target products. The ionic liquid precur-
sors can act as the reactant and solvent for the reaction,
as well as the template over the final inorganic material mor-
phology at the same time. Accordingly, ionic liquids can be
promising all-in-one solvents for the synthesis of inorganic
materials, which can make the reaction system simpler, and
thus with easier control over the phases and morphologies of
the final products. The ultimate goal of ionic liquid precursor
research is to understand and design the task-special ionic
liquids at the molecular level and to synthesize inorganic
materials with the desired phase and shape. The hypothesis
of ionic liquids as all-in-one solvents was first tested
on cuprous chloride by Taubert and co-workers.
27
In that
study, they introduced a protocol for the synthesis of CuCl
nanoplatelets from a Cu-containing IL 1 and 6-O-palmitoyl
ascorbic acid 2. It was found that the mixtures of 1 and 2
could form thermotropic liquid crystals with lamellar self-
assembled structures and the plate morphology was therefore
caused (Fig. 1). Subsequently, a large range of inorganic
Fig. 1 (a) Components of the ionic liquid precursors used for CuCl
platelet synthesis: Cu-containing IL 1 and 6-O-palmitoyl ascorbic acid
2. (b) Optical micrograph (crossed polarizers) of a demixed ionic liquid
precursor.
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nanomaterials with interesting phases and morphologies
were fabricated from various all-in-one ILs. Here, we present
some selected examples to highlight how the ionic liquid
precursors work in the synthesis of inorganic nanomaterials.
[Bmim][BF
4
]
Apparently, 1-n-butyl-3-methylimidazolium tetrafluoroborate
([Bmim][BF
4
]) is one of the most widely used ionic liquids in
the synthesis of inorganic nanomaterials, especially for inor-
ganic fluorides. However, the [BF
4
]

counterions are unstable

in aqueous solution at higher temperature, and will decom-
pose thermally and hydrolyze slowly under the appropriate
conditions to release F

ions, which may be a drawback for

organic synthesis and catalysis but is extremely helpful for
the synthesis of fluoride nanomaterials. Compared with
the common fluoride sources HF, NaF, or NH
4
F, which
are often toxic and need additional templates or structure-
directing agents to obtain better control of the final products,
[Bmim][BF
4
] acting as a fluoride source is environmentally-
friendly and operationally safe. In a typical synthesis, when
heating the reaction medium up to a sufficiently high tem-
perature, the [BF
4
]

ions chemically transform into active ions

and are rapidly hydrolyzed with water molecules, which can
be formulated as: BF
4

(IL) + H
2
O BF
3
H
2
O(IL) + F

. In addi-
tion, [Bmim][BF
4
] can also serve as a soft-template in the
formation of the resulting products, which has a significant
influence on the structures and shapes of the samples involving
various mechanisms, including hydrogen bonding and
stacking interactions, self-assembly mechanisms, electrostatic
attraction, and so on. Based on the above analysis, [Bmim][BF
4
]
as an ionic liquid precursor serves not only as a reagent to
provide the necessary fluoride source, but also as a solvent and
soft template for nanostructure control.
Yan and co-workers have introduced the [Bmim][BF
4
]-
based route into the synthesis of novel spherical NaYF
4
nanoclusters with diameters ranging from 200 to 430 nm
self-assembled by small nanoparticles.
56
Their experimental
results indicate that [Bmim][BF
4
] plays a key role in the
formation NaYF
4
nanocrystals and the diameters of the
nanoclusters could be easily tuned just by changing the
amount of the ionic liquid precursor. Using the same ionic
liquid precursor, Lin's group has reported a fast, facile and
environmentally-friendly microwave-assisted ionic liquid
method to fabricate REF
3
(RE = LaLu, Y) nano/microcrystals
with multiform crystal structures (hexagonal and orthorhombic)
and morphologies (nanodisks, secondary aggregates constructed
from nanoparticles, and elongated nanoparticles), where
[Bmim][BF
4
] plays a multiple role as the reactant, solvent and
template in the reaction system.
57
Similarly, Mudring and
co-workers reported the microwave reaction of Ln(OAc)
3
xH
2
O,
and in the ionic liquid [Bmim][BF
4
] allows the fast and efficient
synthesis of small, uniform, oxygen-free lanthanide nanofluorides
with excellent photophysical behaviour.
58
Li and co-workers have reported a novel low-temperature
non-aqueous based route using the [Bmim][BF
4
] medium
to fabricate well-defined iron-based fluoride nanomaterials
(Fe
1.9
F
4.75
0.95H
2
O and FeF
3
0.33H
2
O).
59
The ionic liquid pre-
cursor [Bmim][BF
4
] played an important role in the formation
of the fluoride nanomaterials, as illustrated in Fig. 2. After
the addition of Fe(NO
3
)
3
0.33H
2
O powder to the [Bmim][BF
4
]
medium, Fe
3+
ions and NO
3

ions could be coordinatedly

dissolved by the BF
4

anion and large imidazolium cation,

respectively. Furthermore, the Fe
3+
BF
4

interaction layer is
expectedly surrounded by imidazolium cations. In contrast,
in the presence of water for hydration, the weakly coordinat-
ing BF
4

anion is prone to hydrolyze and form BF

3
H
2
O and
F

. Consequently, the solvated Fe

3+
ion combines with the F

ion to form precipitated iron-based fluorides, whose nano-

grains are well separated due to the interfacial tension. Inter-
estingly, Cui's group has successfully synthesized high-quality
lanthanide-doped NaGdF
4
upconversion nanocrystals in a
newly-developed facile OA[Bmim][BF
4
] two-phase system
(Fig. 3). Oil-dispersible cubic-phase NaGdF
4
nanocrystals with
ultra-small size (~5 nm) and monodispersity were obtained in
the oleic acid (OA) phase. Meanwhile, water-soluble hexagonal-
phase NaFdF
4
nanocrystals were obtained in the same system
simply by adopting an extremely facile method to complete the
dual phase-transition (crystal-phase transition and OA-phase to
IL-phase transition) simultaneously.
60
Most recently, Zhu and
co-workers have reported a microwave-assisted ionic liquid
solvothermal method to prepare CaF
2
double-shelled hollow
microspheres using [Bmim][BF
4
] as the ionic liquid precursor,
which can also be extended to prepare hollow microspheres of
MgF
2
and SrF
2
.
61
Their experimental results also demonstrated
that the concentration of the ionic liquid precursor played
an important role in the formation of double-shelled hollow
microspheres self-assembled by polyhedral particles.
[Bmim][SeO
2
(OCH
3
)]
Recently, more and more research has focused on the con-
trolled synthesis of metal selenides due to their remarkable
properties and potential applications. Up to now, only a few
Se sources have been developed for fabricating metal sele-
nides. For example, Na
2
SeO
3
was widely used due to its high
activity and good water solubility. However, Na
2
SeO
3
could
react with metal ions (M
n+
) to form precipitates in some
systems. In order to make up uniform reaction conditions,
M
n+
ions are usually transformed into stable complexes,
Fig. 2 Scheme of hydrated iron-based fluoride formation mechanism
from ionic liquid precursor [Bmim][BF
4
].
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which would make the reaction systems more complicated,
and uncertain factors influence the morphology of the final
products. In view of this, we have recently designed 1-n-butyl-
3-methylimidazolium methylselenite ([Bmim][SeO
2
(OCH
3
)])
as a new Se precursor. For this ionic liquid, the reactivity of
the anion ([SeO
2
(OCH
3
)]

ions) is similar to SeO

3
2
ions, and
the formation of metal selenides can be formulated as (taking
a divalent metal as an example): 2M
2+
+ 2[SeO
2
(OCH
3
)]

+
3N
2
H
4
+ 2OH

2MSe + 3N
2
+ 2CH
3
OH + 6H
2
O. More
importantly, one oxygen among SeO
3
2
ions is replaced by
methoxy, leading to the weaker polarizing capability of
[SeO
2
(OCH
3
)]

, and thus M
n+
ions can exist as free ions in the
solution. In addition, the cation ([Bmim]
+
ions) can serve as a
stabilizer: along with the anions, [Bmim]
+
will also adsorb on
the resulting particle surfaces possibly driven by the electro-
static attractions, which is similar to the classic, DLVO
(DerjauginLandauVerweyOverbeek) type Coulombic repul-
sion model. Under this guidance, our group has successfully
prepared various metal selenides with controlled phases and
shapes, including ZnSe hollow nanospheres (Fig. 4),
62
CdSe
nanospheres and nanodendrites,
63
Cu
2x
Se nanocrystals and
CuSe nanoflakes.
64
It could be highly expected that this ionic
liquid precursor would be used to prepare other metal sele-
nide nanomaterials with novel morphologies.
[C
n
mim]X (X = Cl, Br, I)
Recently, more and more attention has paid to halides due to
their excellent optical and photocatalytic properties. Although
the synthesis of halides in ionic liquids or mixed solutions
containing ionic liquids has just begun, this new type of
halide source, ionic liquid precursor 1-butyl-3-methylimidazolium
halide [C
n
mim]X (X = Cl, Br, I), has exhibited distinctive fea-
tures compared with other halide sources. Our group has suc-
cessfully synthesized ultrathin BiOCl nanoflakes, nanoplate
arrays and curved nanoplates via an ionothermal synthetic
route by using the ionic liquid 1-hexadecyl-3-methylimidazolium
chloride ([C
16
mim]Cl) as the ionic liquid precursor.
65
Along
with the Cl

ion, [C
16
mim]
+
ion will also be aligned and arrayed
along the BiOCl layer driven by the Coulomb coupling force. It
is reasonable to deduce that [C
16
mim]Cl, which is considered
as a supramolecular solvent involved ordered structure, is
selectively adsorbed on the (001) plane of BiOCl to effectively
inhibit crystalline growth in the [001] direction. Therefore,
the growth of BiOCl crystals are inhibited along the c-axis
to form ultrathin BiOCl nanoflakes. Hereafter, Huang and
co-workers reported a facile, one-pot approach to the uniform
BiOBr hollow microspheres in the ionic liquid precursor
1-hexadecyl-3-methylimidazolium bromide ([C
16
mim]Br).
66
The
possible formation mechanism is proposed in Fig. 5. Due to
the limited miscibility of the ionic liquid precursor ([C
16
mim]Br)
and co-solvent 2-methoxyethanol, micronized ionic liquid
emulsions are formed under vigorous stirring, which are
surrounded by 2-methoxyethanol containing Bi
3+
ions. These
miniemulsions can perform as microreaction chambers, and
thus Bi
3+
ions react accordingly with [C
16
mim]Br at the
miniemulsion interface to form BiOBr nuclei at elevated
temperature. In the subsequent growth process, the BiOBr
nanoparticles at the miniemulsion interface grow and assem-
ble to construct the shell of the microspheres, retaining the
hollow interiors. In the following study, they used different
ionic liquid precursors, 1-butyl-3-methylimidazolium bromide
([C
4
mim]Br), 1-octyl-3-methylimidazolium bromide ([C
8
mim]Br),
1-dodecyl-3-methylimidazolium bromide ([C
12
mim]Br), and
1-hexadecyl-3-methylimidazolium bromide ([C
16
mim]Br), as a
bromide source to prepare AgBr microcrystals with different
morphologies.
67
Structurally, the {001} facet growth of silver
Fig. 3 Schematic diagram showing the mechanism for the formation
NaGdF
4
nanocrystals from OA[Bmim][BF
4
] two-phase system.
Fig. 4 Schematic illustration of the formation process of ZnSe hollow
nanospheres from ionic liquid precursor [Bmim][SeO
2
(OCH
3
)].
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halide crystals has been studied and {100} facets are easily
exposed due to the lower surface energy than that of {111}
and {110} facets, leading to the cubic shape. However, when
introducing the ionic liquid precursor into the reaction system,
as the length of ionic liquid alkyl chain is increased, the steric
hindrance of the ionic liquid will restrict the diffusion of Ag
+
ions, and convex facets of the near-spherical AgBr are formed.
Zhang and co-workers have investigated the photocatalysis
mechanism of BiOI and therefore demonstrated that the
photocatalytic activity of BiOI could be enhanced greatly
by the in situ modification of the ionic liquid precursor
1-butyl-3-methylimidazolium iodide ([Bmim]I).
68
They found
that ionic liquid modification could trap the photo-excited
electron at the conduction band of BiOI, thus inhibiting the
recombination of photoinduced electronhole pairs, and
leading to the enhancement of its photocatalytic activity
on the degradation of organic pollutants. Recently, Li and
co-workers have successfully synthesized BiOI uniform
flower-like hollow microspheres with a single hole in their
surface structures through an EG-assisted solvothermal
process in the presence of the same ionic liquid precursor,
[Bmim]I.
69
Similar to the above formation mechanism,
[Bmim]I can easily form ionic liquid micelles, resulting in the
BiOI hollow microspheres through a self-assembly process.
During the process, ionic liquid precursor [Bmim]I plays
an important role as reactant, solvent and template. Subse-
quently, they also successfully synthesized BiOBr uniform
flower-like hollow microsphere and porous nanosphere struc-
tures using a similar route in the presence of ionic liquid
1-hexadecyl-3-methylimidazolium bromide ([C
16
mim]Br).
70
[Choline][H
2
PO
4
] and [Bmim][H
2
PO
4
]
Nanophosphates are of tremendous interest as optical mate-
rials since they are known to combine a high energy-
absorption edge (band gap) with excellent chemical and
mechanical stability. Compared with other inorganic nano-
materials, which have already been prepared based on an
ionic liquid all-in-one solvent, there are few studies on the
synthesis of nanophosphates using an ionic liquid precursor.
Mudring and co-workers have presented a universal, fast, and
facile microwave synthesis process using an ionic liquid pre-
cursor [choline][H
2
PO
4
] acting as both the reagent and
surface-modifying agent.
71
In the typical synthesis, lantha-
nide acetate hydrates can be converted to lanthanide single
phosphate (LnPO
4
) with the use of an ionic liquid precursor:
Ln(OAc)
3
+ [choline][H
2
PO
4
] LnPO
4
+ 2HOAc +
[choline][OAc]. Here, the ionic liquid precursor is truly
multifunctional: (1) it serves as reaction medium due
to its ionic, highly polarizable character it guarantees an
excellent microwave susceptibility; (2) it helps to control the
resulting particle size and morphology; and (3) it acts as a
reaction partner. Most recently, our group has successfully
synthesized well-dispersed ferric giniite microcrystals with
controlled sizes and shapes from ionic liquid precursors
using 1-n-butyl-3-methylimidazolium dihydrogenphosphate
([Bmim][H
2
PO
4
]) as the phosphate source.
72
The success
of this synthesis relies on the concentration and composition
of the ionic liquid precursors. By adjusting the molar ratios
of Fe(NO
3
)
3
9H
2
O to [Bmim][H
2
PO
4
] as well as the composi-
tion of the ionic liquid precursors, we obtained uniform
microstructures such as bipyramids exposing {111} facets,
plates exposing {001} facets, hollow spheres, tetragonal
hexadecahedra exposing {441} and {111} facets, and truncated
bipyramids with carved {001} facets. Our experimental results
have demonstrated that [Bmim][H
2
PO
4
] plays an important
role in stabilizing the {111} facets of ferric giniite crystals,
leading to the different morphologies in the presence of ionic
liquid precursors with different compositions, as illustrated
in Fig. 6.
Tetrabutylammonium hydroxide (TBAH)
Li and Taubert have developed a new type of powerful ionic
liquid precursor tetrabutylammonium hydroxide (TBAH) to
synthesize a series of inorganic nanomaterials with desired
morphologies. First, they successfully highly hydrated TBAH
as the ionic liquid precursor for the controlled fabrication of
zinc oxide mesocrystals with various shapes and sizes by sim-
ply adjusting the zinc acetate concentrations (Fig. 7).
73
In the
following study, they modified the synthesis method to
obtain zinc oxide mesocrystals using the same ionic liquid
precursor at room temperature.
74
Their results revealed that,
unlike ZnO grown from aqueous solution, the particle number
in the TBAHwater mixtures decreases with prolonged reaction
time. Initially, numerous small particles precipitate, then these
primary particles transform into fewer, but larger, mesocrystals
composed of rod-like particles. Then, they proved that this
facile synthesis route using TBAH as the ionic liquid precursor
can also be extended to the preparation of other inorganic
materials.
75
Simply by replacing the zinc acetate precursor with
other metal acetates (M(OAc)
2
, M = Mn, Fe, Co, Ni, Cu, etc.), it
Fig. 5 Formation mechanism of BiOBr hollow microspheres
synthesized by using ionic liquid precursor [C
16
mim]Br.
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is possible to synthesize a wide variety of metal (hydr)oxides
with uniform size, morphology, and chemical composition.
Compared with the previous synthesis of metal (hydr)oxides,
this facile approach avoids the synthesis of complex organic
precursors. Rather, simple salts like metal acetates can be used
as precursors for the synthesis of inorganic materials with well-
defined shapes. Later on, Li's group reported a facile route
using TBAH as an efficient ionic liquid precursor to prepare
hollow ZnO mesocrystals with various morphologies, including
flower-like particles of which the rod is composed of ZnO nano-
particle subunits, ZnO plates composed of ZnO rods whose tip
has a lotus leaf-like structure, and porous ZnO plates.
76
In
addition, they also investigated the effect of the chain length of
the cation of the ionic liquid precursor on the formation of
ZnO. They successfully prepared different ZnO nanostructures
with uniform size and morphology from tetrabutylammonium
hydroxide (TBAH), tetraethylammonium hydroxide (TEAH),
tetramethylammonium hydroxide (TMAH) and benzyltri-
methylammonium hydroxide (BTMAH) ionic liquid precursors
with different chain lengths on the surface of zinc foil.
77
Effect model of ionic liquids
Ionic liquids cannot be regarded as merely a green alterna-
tive to conventional organic solvents. The most important
advantage of using ionic liquids for the preparation of inor-
ganic materials is that ionic liquids form extended hydrogen
bond systems in the liquid state and are therefore highly
structured, which can be defined as supramolecular fluids.
This property of structural organization makes ionic liquids
suitable for use as entropic drivers for the generation of
well-defined nanostructures with extended order. Consider-
ing that ionic liquids have both cations and anions, to obtain
a molecular level perspective of this structural organization,
Fig. 6 Schematic illustration of the formation of ferric giniite crystals with various morphologies from an ionic liquid precursor: all the crystals
were formed originally from the truncated bipyramid seeds. The formation of different morphologies was mainly attributed to the differences in
the growth rate of the ferric giniite seeds under the assistance of the strong adsorption of [Bmim]
+
ions on the {111} facets.
Fig. 7 SEM images of ZnO mesocrystals precipitated at different zinc
acetate concentrations: (a) 10, (b) 16, and (c) 35 mg in the ionic liquid
precursor TBAH.
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we first need an answer to a simple question: which ions
(cations or anions) are closest to the liquidsolid interface
between ionic liquids and resulting materials? This is not
easy to answer, although great efforts have been carried out
on related experiments or computer simulations.
Cationic dominant
Several studies suggest that the cationic species of ionic
liquids can interact with nanoparticles and stabilize them.
Finke and co-workers reported that imidazolium-based ionic
liquids can react with Ir nanoparticles to form surface-attached
N-heterocyclic carbenes, contributing to the stabilization of the
Ir nanoparticles.
78
These carbene-ligand-stabilized nanoclusters
could also provide some stabilization to other transition-metal
nanoclusters. Similarly, Bockstaller and co-workers prepared
Au nanorods in 1-ethyl-3-methylimidazolium ethylsulfate
([Emim][ES]) without the addition of stabilizing agents.
79
It
was proposed that the imidazolium cations seem to have
different binding affinities for different crystal facets of the
Au nanoparticles, resulting in the formation of Au nanorods.
Furthermore, Bouvy and co-workers systematically investigate
the cation effect of a series of pyrrolidinium-, imidazolium-,
and quaternary amine-based ionic liquids on the resulting
morphologies of Au nanostructures.
80
Their experimental
results demonstrate that the ionic liquids favor the anisotropic
growth of gold by acting as template agents.
Previously, our group has demonstrated that the interaction
between imidazolium cations and TiO
6
octahedra could be a
decisive factor for the formation of the rutile phase in a
water[Emim]Br composite system.
81
It was found that
[Emim]Br served as a capping agent based on its strong
hydrogen-bonding and stacking interaction with the (110)
facet of rutile and accordingly played a critical role in the
control of the phase and morphology of TiO
2
nanoparticles. In
the synthesis, we considered that there were mainly two
reasons for the formation of interactions between [Emim]Br
and TiO
2
: (1) in the imidazole-based ionic liquid, the H atom
at position-2 of the imidazole ring (C(2)H) has a positive
charge due to the delocalization of positive charge locating
on the imidazole ring, which enhances the ability of the
H atom (C(2)H) to form hydrogen bonds between the O(rutile
surface)HC([Emim]
+
); (2) if [Emim]
+
can vertically adsorb on
the (110) plane via a rutile(110)c(2 2)-[Emim]
+
original cell
(Fig. 8), the distance between [Emim]
+
along the [001] direction
is 0.592 nm, which is in accord with the mutual -stacking
distance between the aromatic rings. Thus, stacking inter-
actions exist between the cations and [Emim]
+
can form a rela-
tively tight coverage layer on the rutile surface. As a result,
[Emim]
+
could form relatively strong interactions with TiO
6
octahedra, which could be a decisive factor for the formation
of the rutile phase due to the spatial effect.
Anionic dominant
On the other hand, anionic species of ILs can also interact
with nanoparticles and play an important role in the growth
stage. Zhou and co-workers successfully synthesized mesoporous
SiO
2
using 1-butyl-3-methylimidazolium tetrafluoroborate
([Bmim][BF
4
]) as the template and proposed hydrogen bonds
formed between [BF
4
]

ions and the SiO

2
surface together
with the stacking interaction of the neighboring
imidazolium rings, leading to the mutual packing and forma-
tion of mesoporous SiO
2
.
82
It was believed that [BF
4
]

ions
interacted with the silanol groups and formed hydrogen
bonds, which might induce the oriented arrangement of
[BF
4
]

ions along the pore walls. Along with [BF

4
]

ions, as
presented in Fig. 9, driven by the Coulomb coupling force
with the anion, [Bmim]
+
ions were also arrayed along the
silica. Moreover, the fluid state of [Bmim][BF
4
] facilitated
the proposed relocation of molecules, which could be
then stabilized by the additional stacking interaction
between the imidazolium rings of [Bmim][BF
4
]. Taubert
and co-workers also found the strong anion effect on Au
nanoparticle formation including sizes and shapes in
imidazolium-based ionic liquids.
83
They successfully synthe-
sized Au nanoparticles in a set of ionic liquids based on
the same cation (1-ethyl-3-methyl-imidazolium) and three types
of anion, namely triflate ([Emim][TfO]), methanesulfonate
([Emim][MS]), and ethyl sulfate ([Emim][ES]). With the MS
anion, Au nanoparticles with diameters between 5 and 7 nm
Fig. 8 (a) Surface structure of rutile cleaved along the [110] direction
and schematic illustration of rutile (110)c(2 2)-[Emim]
+
original cell;
moreover, [Emim]
+
ions locate in the ae sites, whereas [Emim]
+
units
are omitted for clarity. The large and small rectangles represent the
original cell and rutile cell, respectively. (b) Schematic illustration of a
projected view of [Emim]
+
ions anchored onto the rutile (110) plane to
form a tight coverage layer via the original cell.
Fig. 9 Schematic illustration of the hydrogen bond-co- stack
mechanism for the formation of mesoporous SiO
2
.
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form, which increasingly aggregate at higher reaction tempera-
tures. With TfO, also small 57-nm particles form, but only at
low temperatures. With ES, polydisperse samples form at all
temperatures except for 160 C. These results demonstrated
that the anion of the ionic liquid has a strong influence on the
particle size, shape, and aggregation. Hong and co-workers
indicated that hydrogen bonding can occur at the interface
between the anions of [C
16
mim]Cl and the building blocks
of aluminum hydroxides in the synthesis of large-mesoporous
-Al
2
O
3
.
84
In addition, Dupont and co-workers proposed
the coordination model composed of semi-organized
[(DAI)
m
(X)
mn
]
n+
[(DAI)
m
(X)
mn
]
n
supramolecular aggregates on
the formation of nanoparticles.
12
Similar conclusions have
been drawn by Sieffert and co-workers using MD simulation of
1-butyl-3-methylimidazolium octylsulfate ([Bmim][OcSO
4
]) near
a quartz surface.
85
They concluded that the imidazolium ring
and the octyl chain of the anion prefer to align near and parallel
to the surface. These findings are very useful in understanding
the type of effect of ionic liquids on the formation of
nanostructures with different morphologies despite synthesis
mechanisms in different cases being not quite clear. It is highly
expected that this understanding will improve with the accumu-
lation of knowledge and the systematic design of experiments.
Most recently, our group has successfully prepared well-
dispersed NH
4
-Dw and -AlOOH nanostructures with controlled
morphologies using the 1-butyl-2,3-dimethylimidazolium chloride
([Bdmim]Cl)-assisted hydrothermal process.
53
Based on the
experimental results, the ionic liquid effect models on the
synthesis of NH
4
-Dw and -AlOOH nanostructures can be
divided into cationic- or anionic-dominant effect models deter-
mined by the different surface structure of the targets, as illus-
trated in Fig. 10. Specifically, under the cationic dominant
regime, ionic liquids mainly show a dispersion effect for NH
4
-
Dw nanostructures; meanwhile, the anionic dominant model
can induce -AlOOH particle self-assembly to form hierarchical
structures. Under the guidance of the models proposed, the
effect of ionic liquids would be optimized by the appropriate
choice of cations or anions when considering the different
effect model with substrate surface. It is highly expected that
such effect models between ionic liquids and target products
are helpful for the understanding and rational design of ionic
liquids consisting of specific functional groups, and will thus
open up new opportunities for the synthesis of inorganic nano-
materials with novel morphology and improved properties.
Summary and outlook
In summary, we have briefly highlighted the applications of
ionic liquids in the preparation of inorganic nanomaterials.
Compared with conventional molecular solvents, ionic liquids
cannot be only regarded as a green alternative, but also
provide a powerful medium for the synthesis of inorganic
nanomaterials with unique morphologies and controlled
phases. As one of the most rapidly growing fields, one can
envision that there will certainly be intensified interest in this
promising direction, especially in the following aspects: on
the one hand, one of the most distinctive features of ionic
liquids is that they can be treated as tailored solvents due to
their unlimited flexibility of combinations of anions and
cations. So one can design the appropriate ionic liquid precur-
sor according to the initial crystal structures, compositions,
and crystal habits of target products. These precursors are
molecularly defined entities, which can serve as both the reac-
tant and solvent for the reaction, and as the template over the
final inorganic material morphology at the same time. This
all-in-one synthesis route which can make the reaction
system simpler, and thus giving more control over the phases
and morphologies of the final products. The ultimate goal of
ionic liquid precursor research is to understand and design the
task-special ionic liquids at the molecular level and provide a
more efficient strategy to synthesize inorganic materials with
novel structures and interesting properties. On the other hand,
we believe that the synthesis of new inorganic materials should
go hand-in-hand with the development of understanding of
the effect type of ionic liquids. Since the research on well-
established rules and correlations between molecular struc-
tures of the adopted ionic liquids and the morphologies of the
resulting inorganic materials is limited, it is highly expected
that this understanding will improve with the accumulation of
knowledge and the systematic design of experiments.
In short, we hope that this review will not only display the
recent developments in inorganic synthesis using ionic liquids,
but also hope to give the readers some inspirations to explore
novel and effective synthesis routes for the synthesis of inor-
ganic nanomaterials with desired phases and morphologies.
Acknowledgements
This work was financially supported by National Natural
Science Foundation of China (grant no. 21371101 and
51302079) and the Young Teachers' Growth Plan of Hunan
University (grant no. 2012-118).
Fig. 10 Scheme for the different effect models of [Bdmim]Cl in the
synthesis of NH
4
-Dw and -AlOOH.
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