Ultrasonics Sonochemistry 11 (2004) 47–55

www.elsevier.com/locate/ultsonch

Ultrasonic Sonochemistry Invited Contributions––part of an occasional series

reviewing ‘‘hot topics’’ in sonochemistry

Using sonochemistry for the fabrication of nanomaterials

Aharon Gedanken *

Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel

Received 30 December 2003; accepted 19 January 2004

Abstract

One of the reasons for the huge interest in nanomaterials originated because of the prohibitive price that commercial companies
have to pay for introducing new materials into the market. Nanotechnology enables these companies to obtain new properties using
old and recognized materials by just reducing their particle size. For these known materials no government approval has to be
obtained. Thus, the interest in nanomaterials has led to the development of many synthetic methods for their fabrication. Sono-
chemistry is one of the earliest techniques used to prepare nanosized compounds. Suslick [1], in his original work, sonicated Fe(CO)5
either as a neat liquid or in a decalin solution and obtained 10–20 nm size amorphous iron nanoparticles.
A literature search that was conducted by crossing Sono* and Nanop* has found that this area is expanding almost exponen-
tially. It started with two papers published in 1994, two in 1995, and increased to 59 papers in 2002. A few authors have already
reviewed the fields of Sono and Nano. It should be mentioned that in 1996 [2], Suslick et al. published an early review on the
nanostructured materials generated by ultrasound radiation. Suslick and Price [3] have also reviewed the application of ultrasound
to materials science. This review [3] dealt with nanomaterials, but was not directed specifically to this topic. The review concentrated
only on the sonochemistry of transition metal carbonyls and catalytic reactions that involve the nanoparticles resulting from their
sonochemical decomposition. Grieser and Ashokkumar [4] have also written a review on a similar topic. A former coworker, Zhu,
has recently submitted for publication a review article [5] entitled ‘‘Novel Methods for Chemical Preparation of Metal Chalcogenide
Nanoparticles’’ in which he reviews three synthetic methods (sonochemistry, sonoelectrochemistry, and microwave heating) and
their application in the synthesis of nanosized metal chalcogenides. Although still unpublished, I myself have recently written a
review discussing novel methods (sonochemistry, microwave heating, and sonoelectrochemistry) for making nanosized materials [6].
The current review will: (1) Present the four main advantages that sonochemistry has over other methods related to materials science
and nanochemistry; (2) concentrate on the more recent (2003) literature that was not reviewed in the previously-mentioned reviews,
and (3) focus on a specific question, such as what is the typical shape of products obtained in sonochemistry?
This review will not survey the literature related to sonoelectrochemistry.

2004 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48

2. Sonochemical synthesis of nanoparticles: recent literature (2003) . . . . . . . . . . . . . . . . . . . . . . . 48

3. Shapes of nanomaterials created sonochemically . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

3.1. One-dimensional structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

*
Tel.: +97-235318315; fax: +97-235351250.
E-mail address: gedanken@mail.biu.ac.il (A. Gedanken).

1350-4177/$ - see front matter
2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultsonch.2004.01.037
48 A. Gedanken / Ultrasonics Sonochemistry 11 (2004) 47–55
1. Introduction
Sonochemistry is the research area in which mole-
cules undergo a chemical reaction due to the application
of powerful ultrasound radiation (20 kHz–10 MHz) [7].
The physical phenomenon responsible for the sono-
chemical process is acoustic cavitation. Let us first ad-
dress the question of how 20 kHz radiation can rupture
chemical bonds (the question is also related to 1 MHz
radiation), and try to explain the role of a few para-
meters in determining the yield of a sonochemical
reaction, and then describe the unique products
obtained when ultrasound radiation is used in materials
science.
A number of theories have been developed in order to
explain how 20 kHz sonic radiation can break chemical
bonds. They all agree that the main event in sono-
chemistry is the creation, growth, and collapse of a
bubble that is formed in the liquid. The stage leading to
the growth of the bubble occurs through the diffusion of
solute vapor into the volume of the bubble. The last
stage is the collapse of the bubble, which occurs when
the bubble size reaches its maximum value.
From here we will adopt the hot spot mechanism, one
of the theories that explains why, upon the collapse of a
bubble, chemical bonds are broken. This theory claims
that very high temperatures (5000–25,000 K) [7] are
obtained upon the collapse of the bubble. Since this
collapse occurs in less than a nanosecond [8,9], very high
cooling rates, in excess of 1011 K/s, are also obtained.
This high cooling rate hinders the organization and
crystallization of the products. For this reason, in all
cases dealing with volatile precursors where gas phase
reactions are predominant, amorphous nanoparticles
are obtained. While the explanation for the creation of
amorphous products is well understood, the reason for
the nanostructured products is not clear. One explana-
tion is that the fast kinetics does not permit the growth
of the nuclei, and in each collapsing bubble a few
nucleation centers are formed whose growth is limited
by the short collapse. If, on the other hand, the pre-
cursor is a non-volatile compound, the reaction occurs
in a 200 nm ring surrounding the collapsing bubble [10].
In this case, the sonochemical reaction occurs in the li-
quid phase. The products are sometimes nanoamor-
phous particles, and in other cases, nanocrystalline. This
depends on the temperature in the ring region where the
reaction takes place. The temperature in this ring is
lower than inside the collapsing bubble, but higher than
the temperature of the bulk. Suslick has estimated the
temperature in the ring region as 1900 C [10]. In short,
in almost all the sonochemical reactions leading to
inorganic products, nanomaterials were obtained. They
varied in size, shape, structure, and in their solid phase
(amorphous or crystalline), but they were always of
nanometer size.
As mentioned above, many methods have been
developed to make nanoparticles. There are, however,
four topics related to materials science and nanotech-
nology in which the sonochemical method is superior to
all other techniques. These areas are:
(1) Preparation of amorphous products. Although
amorphous metals can be obtained by the cold
quenching of bulk metals, when this is extended to metal
oxides the cooling rate required for many oxides is well
beyond that which can be obtained using the cold
quenching method. This is why glass-former materials
are added to the mixture to form the amorphous prod-
ucts [11,12]. When sonochemistry is applied for the
synthesis of amorphous metal oxides (or sulfides or
other chacogenides) there is no need to add these glass
formers, and as a bonus the amorphous products are
obtained in nanometer size.
(2) Insertion of nanomaterials into mesoporous mate-
rials. Ultrasonic waves are used for the insertion of
amorphous nanosized catalysts into the mesopores
[13,14]. A detailed study demonstrates that the nano-
particles are deposited as a smooth layer on the inner
mesopores walls, without blocking them. When com-
pared to the other methods such as impregnation or
thermal spreading, sonochemistry shows better proper-
ties.
(3) Deposition of nanoparticles on ceramic and poly-
meric surfaces. Sonochemistry is used to deposit various
nanomaterials (metals, metal oxides, semiconductors)
on the surfaces of ceramic [15,16] and polymeric mate-
rials. A smooth homogeneous coating layer is formed on
the surface. The nanoparticles are anchored to the sur-
face by forming chemical bonds or chemical interac-
tions with the substrate and cannot be removed by
washing.
(4) The formation of proteinaceous micro- and nano-
spheres. We have demonstrated recently that any protein
(e.g., polyglutamic acid) can be converted into a sphere
upon sonication [17a]. We have also illustrated that we
can encapsulate a drug, such as tetracycline, in the
sphere [17b]. Our studies have shown that the spherical
protein is biologically active, although its biological
activity is reduced. The sonochemical spherization pro-
cess is only 3 min shorter than any other process.
2. Sonochemical synthesis of nanoparticles: recent lite-
rature (2003)
The goal of this chapter is to scan recent literature for
nanomaterials that have been synthesized using ultra-
sound radiation. Chalcogenides (S
2 , Se
2 , and Te
2 )
are the most popular materials among the materials that
were prepared in the last year. The reason for their
popularity are their semiconductive properties, which
are of importance to fields such as non-linear optic
 A. Gedanken / Ultrasonics Sonochemistry 11 (2004) 47–55
detectors, photorefractive devices, photovoltaic solar
cells, and optical storage media. The nanochalcogenides,
whose synthesis was reported, are ZnS [18,19], Sb2 S3
[20,21], HgSe [22], SnS2 [23], CdS [24], CdSe [24],
PbE(E ¼ S, Se, Te) [25], CuS [26].
The synthesis of the sulfides was carried out in sol-
vents such as ethanol [18], water [23], or ethylenediamine
[25]. The metal ion sources were the acetates [18,25] or
the chlorides [23]. The precursors for the sulfur were
sulfur, thioacetamide, or thiourea. Pristine Se and Te
served as the precursors for the synthesis of the selenides
and tellurides, respectively. For the Sb2 S3 , different
shapes of products were obtained [20], including amor-
phous nanospheres, irregular short nanorods, needle-
shaped nanowhiskers, and regular nanorods. Their band
gaps were investigated by diffuse reflection spectroscopic
measurements and were found to be 2.45, 1.99, 1.85, and
1.94 eV, respectively. A similar synthesis of the stibnite
has yielded, in addition to the above-mentioned struc-
tures, a star-like morphology [21]. A blue shift of about
500 nm in the absorption peak is observed, as compared
to the bulk band gap of Sb2 S3 [21]. The preparation of
the nanoselenides afforded the involvement of a salt of
the desired cation (mercury acetate in Ref. [22]), sele-
nium, a solvent, and a reducing agent. If PEG (poly-
ethylene glycol 400) is used as a solvent, it also serves as
a reducing agent, thus serving two purposes [22]. In
addition, two other reducing agents, dextrose and
hydroxylamine, were used [22]. According to the pro-
posed mechanism for the synthesis of the lead chalcog-
enides [25], which might be true for all other syntheses,
the dissolution of the chalcogenide in the solvent is the
rate-determining step. Indeed, the sonication at room
temperature of the lead acetate and the chalcogenide (S,
Se or Te) lead to the formation of the corresponding
sulfide and selenide, but not the telluride, because of
difficulty in its dissolution. However, when the reaction
was conducted at elevated temperatures, lead telluride
was obtained [25]. The authors conclude that the ultra-
sonic irradiation was found to have two main effects.
One favored the dissolution of chalcogens and the for-
mation of E
2 , thus accelerating the reaction, and the
second prevented the aggregation of the resulting
nanoparticles. Nanocrystalline chalcogenides were ob-
tained in all the reactions due the low vapor pressure of
the reactant, which did not react inside the bubble, but
rather in the ring surrounding the bubble.
Metallic and alloyed nanoparticles have continued to
be of interest to synthetic sonochemists. Reports on the
synthesis of nanosized Gold [26], cobalt [27], iron [27],
Pd [28], Ni [29] and of two nanometric alloys, Au/Pd [30]
and Fe/Co [31], were published in 2003.
A variety of reducing agents were employed to obtain
the nanometals, including ascorbic acid [26,28], zinc
powder [27], hydrazine [29], and ethylene glycol [30].
Diphenylmethane was used as the solvent in the for-
49
mation of the Fe/Co alloy nanoparticles [31], because
upon its decomposition when heated in Argon it creates
a protective layer, which makes the product air-stable.
SmCo5ð1
xÞ Fex (x ¼ 0:2, 0.4, 0.6, and 0.7) nanocom-
posites were synthesized by ball milling a mixture of
SmCo5 and nanosize iron powders. Composites were
made using a-Fe crystallized from amorphous iron
generated by the sonochemical decomposition of
Fe(CO)5 [32]. One of the composites showed a stronger
magnetic coupling than pure SmCo5; which is one of the
strongest known hard magnets.
The sonochemical preparation of nanophased oxides
started long ago and is still continuing. Titania [33,34],
strontium titanate [33], silica [35], ZnO [36], ZrO2 [37],
and MnOx [38], were prepared by employing ultrasound
radiation. Precursors such as titanium isopropoxides
[33] (with and without Sr(OH)2 ), titanium ethoxide [34],
tetraethoxy silane [35], Zn(acetate)2 [36], Zr(NO3 )4 [37],
MnSO4 , MnCl2 , Mn(NO3 )2 , Mn(OAc)2 , Mn(II) acetyl-
acetonate, and MnCO3 [38], were used for the sono-
chemical fabrication of the nanooxides.
Awati et al. [34] demonstrated the advantages of
sonication versus the conventional method of preparing
titania. They found that the more uniform distribution/
dispersion of the nanoparticles, a marginally higher
surface area, better thermal stability, and phase purity,
are some of the advantages of the preparation of
nanocrystalline titania by the ultrasonication method
[34].
As stated above, sonochemistry is an excellent
method for coating the surfaces of various particles and
for forming a smooth layer of the coated materials.
LiMn2 O4 spinel was coated sonochemically with MgO
[39]. The composite was studied as an active mass in
composite cathodes in standard Li electrolyte solutions
for Li-ion batteries at 60 C. Electrodes comprising
LiMn2 O4 , modified by MgO, showed a higher capacity
retention compared to the electrodes comprising an
uncoated active mass, especially at elevated tempera-
tures [39]. Gold nanoparticles with an average size of
about 5 nm were deposited on the surface of preformed
silica submicrospheres with the aid of power ultrasound
[40]. A unique crystallization process of the silica par-
ticles at low temperatures is observed. Air-stable iron
nanoparticles with an average size of about 10 nm were
deposited on the surface of preformed carbon spherules
with the aid of power ultrasound [41].
In many cases, it can be shown that by refluxing the
same precursors used in the sonochemical reaction,
identical nanoproducts to those obtained sonochemi-
cally can be obtained either solvothermally or even in an
open heated reaction. In all these cases, the advantages
of using ultrasound radiation are that it yields smaller
particles [42], and because of the different shape of the
products obtained sonochemically. A special paragraph
will be devoted to the latter topic. Finally, the Prozorov
50 A. Gedanken / Ultrasonics Sonochemistry 11 (2004) 47–55
family [43] has shown that the sonication of magnesium
diboride slurries in decalin produces material with a
significant intergrain fusion. Sonication of the MgB2 in
the presence of Fe(CO)5 produces magnetic Fe2 O3
nanoparticles embedded in the MgB2 bulk. The resulting
superconductor–ferromagnet composite exhibits a con-
siderable enhancement of its magnetic hysteresis, which
implies an increase of vortex pinning strength due to
embedded magnetic nanoparticles.
More popular than the use of ultrasonics for coating
surfaces was their use in the field of mesoporous mate-
rials. It involved both the preparation of mesoporous
products as well as the insertion of nanoparticles into
the pores by sonochemical methods.
3. Shapes of nanomaterials created sonochemically
Sonochemical reactions yield, in all cases, nanosized
products. As stated above, they might be amorphous in
cases of volatile solutes, or crystalline when the solutes
undergoing sonochemistry are non-volatile (not in all
cases). The products differ also in their morphology. The
first nanoproducts were either spherical or close to a
spherical structure. Over the years, research groups all
around the world obtained nanoproducts having unique
shapes, such as nanotubes, nanorods, nested fullerenes,
hollowed spheres, and many others. This section is de-
voted to these shapes and to the understanding of how
and why such products result from ultrasound radia-
tion.
3.1. One-dimensional structures
The dimensionality of nanostructures and their
importance is perhaps best demonstrated in the field of
semiconductors, where a variety of different nanostruc-
tures were produced for manipulating the optical
properties of materials. This includes 0D (quantum
dots), 1D (nanowires), 2D (films), and 3D (bulk) con-
figurations.
More reports have appeared on the fabrication of
nanorods than on nanotubes. We know about at least
four compounds, carbon [44], hydrocarbon [45], TiO2
[46], and MeTe2 [47], for which a sonochemical synthesis
yielding nanotubes is reported. The most exciting work
is that of Katoh [44], which has produced carbon na-
notubes sonochemically. The carbon nanotubes are
produced by applying ultrasound to liquid chloroben-
zene with ZnCl2 particles, and to o-dichlorobenzene
with ZnCl2 and Zn particles. The authors have sug-
gested that the polymer and the disordered carbon,
which are formed by cavitational collapse in homoge-
neous liquid, are annealed by the interparticle collision
induced by the turbulent flow and by shockwaves [44].
They conclude that in the present study, using relatively
small particles (<200 mm in diameter), a size at which
inter-particle collision frequently occurs and for which
micro-jet formation is not efficient. Under these condi-
tions, a high temperature can be achieved at the site of
particle collision. After the collision, polymers, which
are produced by the homogeneous process, can be
converted into carbon nanotube.
A new type of hydrocarbon nanotube and onion,
with interlayer spacing ranging from 3.4 to 5.8 A,  was
discovered by sonicating Si nanowires with common
organic solvents under ambient conditions (room tem-
perature and atmospheric pressure) [45]. Lee and asso-
ciates believe that sonication not only promotes the
reaction between SiHx and the organic molecules, but
also facilitates the formation of the different types/
shapes of carbon nanostructures, as well as causing the
extrusion (or demolding) of the products.
In a typical synthesis, titania powder consisting of
particles with a diameter of 20 nm was sonicated in a 10
M NaOH aqueous solution in a Teflon vessel [46]. The
mixture was sonicated for 60 min. The sonicated solu-
tion in the Teflon vessel was then placed in an oil-bath
and maintained at 110 C for 4 h. Under similar (but
different) conditions, nanowhiskers were obtained
(shown in Fig. 2(b)). XRD analysis (Fig. 1(b)) shows
that when the raw material of titania particles is soni-
cated with the NaOH aqueous solution under conditions
of low power, thin small titanate sheets are formed.
When the products are heated at 110 C for 4 h, the
small titanate sheets increase in size. The titanate sheets
are exfoliated into nanosheets and the nanosheets roll
Fig. 1. TEM images of (a) titania nanotubes, (b) powders obtained by
heat-eating sonicated products for 4 h at 110 C followed by washing
with water for 5 min.
 A. Gedanken / Ultrasonics Sonochemistry 11 (2004) 47–55
into nanotubes when they are washed with water. The
layered structure of the titanate sheets and the nanotu-
bes formed at the edge of the sheet are shown in Fig.
1(b). It is assumed that residual electrostatic repulsion
due to Ti–O–Na bonds may lead to a connection be-
tween the ends of the sheets, and thus, to the formation
of a tube structure. The process has a shorter reaction
time and produces longer nanotubes compared to the
hydrothermal method for which 20 h are required to
prepare titania nanotubes.
In the synthesis of MoTe2 nanotubes [47], a solution
of Mo(CO)6 in decalin is reacted with small particles of
tellurium, which are added to the solution at a molar
ratio of Mo:Te ¼ 1:2. The mixture is sonicated for 4 h
while cooled in a dry ice-acetone bath at )30 C. The as-
prepared sample is calcined at 650 C under an N2
atmosphere for 4–10 h. The results show that the molar
ratios of Mo:Te are 1:2.48 in the as-sonicated sample
and 1:1.93 in the calcined product, respectively. In the
as-sonicated sample, a 23% of excess Te is measured
when compared with the initial reactant ratio. The as-
prepared material is amorphous, and the only diffraction
peaks observed are due to the Te excess. The XRD
pattern of the calcined sample shows only peaks of the
pure crystals of b-type monoclinic MoTe2 already at 650
C. The peaks of the unreacted elemental tellurium have
disappeared completely after heating [47]. The appear-
ance of the beta phase is a size effect (the as-prepared
particles are 2–4 nm). Indeed, when heating the amor-
phous MoTe2 prepared by refluxing Mo(CO)6 and Te in
xylene under the same conditions, we obtained an a-type
MoTe2 . This is because regular refluxing yields larger
particles. This is another demonstration of our claim
that a sonochemical reaction yields smaller particles
compared with a regular thermochemical reaction of the
same reactants producing the same products. According
to our hypothesis, the amorphous MoTe2 nanoparticles
in the as-sonicated sample have a strong tendency in the
first stage to form nanolayers, which are then converted
into nanotubes. The formation of the tubular structures
of MoTe2 might be assisted by the well-known rolling-
up mechanism [48], according to which the driving force
for the curling of the lamellar sheets could be ascribed
to: (1) the reduction of interlayer interaction at the edge
of the sheet during the heating process, and (2) the
thermal stress existing at high temperature, which initi-
ates the scrolling of the layered sheets with reduced in-
terlayer forces at the edges. Narrower layers may
therefore roll up into nanotubes more easily than the
relatively wider ones. This may directly result in the
formation of nanotubes with widely distributed dimen-
sions.
The mechanism by which nanorods are formed so-
nochemically is much simpler. In almost all cases the
first step in the formation of the nanorods are nano-
particles that, under the microjets and shockwaves
51
formed at the collapse of the bubble, are pushed towards
each other and are held by chemical forces.
Zhu and his students [49] performed a very detailed
study on the sonochemical reaction leading to the for-
mation of nanorods of Bi2 S3 . They have explored the
role of various sulfur sources, complexing agents (such
as ethylenediaminetetraacetic acid, triethanolamine, and
sodium tartrate), and solvents. They describe the for-
mation of the nanorods as follows: it was observed that
after sonication for about 20 min, the solution turned
light brown and turbid, indicating the formation of
Bi2 S3 nuclei. These freshly formed nuclei in the solution
are unstable and have the tendency to grow into larger
particles. Once the nuclei are formed, there are a large
number of dangling bonds, defects, or traps on the nu-
clei surfaces. During the sonication time, the surface
state might change. The dangling bonds, defects, or
traps will decrease gradually, and the particles will grow
until the surface state becomes stable and the size of the
particles ceases to increase. During the crystal growth
process, Bi2 S3 presents a preferential directional growth
due to its inherent chain-type structure. As a result, the
product presents a rod-type morphology. They observed
that after the formation of Bi2 S3 nuclei, the color of the
reactant mixture gradually turns darker, and finally re-
sults in a black turbidity after 90 min of sonication,
indicating the formation of the final product. The
gradual change in color may be indicative of the growth
process of Bi2 S3 nanorods. More recently, nanorods of
Sb2 S3 have also been prepared by the same group [20].
The source of Sb was SbCl3 , thioacetamide was the
origin of the sulfur, and ethanol served as the solvent for
this reaction. The product was composed of nanorods
with diameters of 20–40 nm and lengths of 220–350 nm.
The nanorods were found to crystallize in a single-
crystalline orthorhombic structure. In addition, the au-
thors observed that the Sb2 S3 nanorods have a very thin
fuzzy shell. This is probably due to the amorphous
species absorbed on the surface of the crystalline
nanorods. HRTEM images show clearly that Sb2 S3
nanorods preferentially grow along the (0 0 1) direction.
The sonochemical mechanism by which the nanorods
are formed was investigated. Short sonication times (30
min) led to the formation of amorphous Sb2 S3 mon-
odispersed nanospheres with diameters in the range of
25–40 nm. Prolonging the sonication time (60 min) has
resulted in irregular, short nanorod structures of
orthorhombic Sb2 S3 . The above-mentioned nanorods
were reached after 120 min of irradiation. The nanorods
are formed as a result of the interparticle collisions
capable of inducing striking changes in the morphology,
composition, and reactivity of the solids. During the
interparticle collisions, the particles can be driven to-
gether at sufficiently high speeds to induce effective
melting at the point of collision. The energy generated
during collision can induce the crystallization of the
52 A. Gedanken / Ultrasonics Sonochemistry 11 (2004) 47–55
amorphous Sb2 S3 particles. During the crystallization
process, Sb2 S3 presents a preferential 1D growth along
the (0 0 1) crystal face.
This idea of nanoparticles created at the early stages
of the sonochemical reaction and further colliding to
form nanorods was also mentioned by others as the
explanation for the formation of nanorods [50]. For
example, europium oxide nanorods have been prepared
[50] by the sonication of an aqueous solution of euro-
pium nitrate in the presence of ammonia. The difference
between the formation of the europia nanorods and the
Bi2 S3 [49] and Sb2 S3 [20] is that in the former case the
collisions also cause the loss of water molecules, and
the Eu(OH)3 particles are converted to Eu2 O3 nanorods
[50]. Nikitenko has prepared amorphous WS2 by the
ultrasound irradiation of a W(CO)6 solution in diph-
enylmethane (DPhM) in the presence of a slight excess
of sulfur at 90 C under argon. Heating the amorphous
powder at 800 C under argon yields WS2 nanorods [51].
The mechanism of the nanorods’ formation involves the
sonopolymer, which is the product of the polymeriza-
tion [52]. The WS2 is obtained as very small dense par-
ticles that are dispersed in a polymer matrix. Annealing
of the nanocomposite causes WS2 particles to agglom-
erate, and then crystallize. It can be assumed that the
products of the sonopolymer destruction-coated WS2
agglomerates at the initial stage of crystallization, and
thus prevents the rolling of WS2 layered particles to
nanotubes. The rod-like shape observed in our WS2
crystals is probably due to specific interactions of the
sonopolymer with different WS2 crystal faces. A sono-
chemical reaction with the same reactants as in Ref. [51]
that was carried out under an Ar (80%)–O2 (20%) gas-
eous mixture at 90 C has led to a WOx amorphous
product [53]. Heating this amorphous powder at 550 C
under Ar yields snowflake-like dendritic particles con-
sisting of a mixture of WO2 monoclinic and ortho-
rhombic crystals. Heating of the as-prepared product at
1000 C for 3 h under Ar forms nanorods (20–50 nm
wide and 50–500 nm long), consisting of monoclinic
WO2 . Partial WO2 oxidation by traces of O2 causes
the formation of triclinic WO3 nanoparticles. Annealing
the material at 1000 C in the presence of air leads to the
complete oxidation into WO3 . The average WO3 parti-
cle size is about 50–70 nm.
Zhang and his associates proposed a different mecha-
nism for the sonochemical formation of nanorods.
They have prepared nanorods of CdS [54] and PbS
[55] by sonicating an aqueous solution containing
Cd(EDTA) {or Pb(EDTA)} and Na2 S2 O3 . The nano-
rods appear to be structurally uniform with a diameter
of about 80 nm and length of up to 1.3 lm. The pro-
posed mechanism stresses the involvement of EDTA
in determining the structure. EDTA and Cd can form
a very stable pentadentate ligand complex. Therefore,
there is only one direction for S
2 ions to coordinate
facilely to the above complex according to CdY
2 +
S
2 fi CdSðnanorodÞ + Y
4 . Because of this, the growth of
CdS crystals is faster along this direction, which may be
in a preferential orientation of [0 0 1]. The anisotropic
growth character determines the resulting crystal shape.
Clearly, a nearly spherical shape that minimizes the
surface area is favored if the overall growth rate is very
slow; however, the products are rod-like if the rate of the
crystals is increased significantly.
Magnetite (Fe3 O4 ) nanorods have been obtained by
the sonochemical oxidation of the aqueous solution of
iron(II) acetate in the presence of b-cyclodextrin as a
templating agent [56].
The number of sonochemical reactions resulting in
the preparation of nanowires is limited. They include the
work of Xia et al. [57,58] in which they have prepared Se
nanowires and trigonal Se (t-Se) nanowires [57,58]. A
solid–solution–solid transformation from amorphous
selenium (a-Se) to t-Se nanowires is based on the
anisotropic characteristic of the target material. The
extended spiral chains of Se atoms in the trigonal phase
provide a natural template to define and guide the
growth along one particular axis. This process is also a
self-seeded process in which nanocrystalites of t-Se are
formed upon cooling of a-Se colloids. The hot spots in
the sonochemical process cause local fluctuation in the
solubility of selenium, and thus induce the formation of
nanosized seeds to t-Se in an alcohol solution that
contained a-Se colloids. The various stages of the
nanowires’ growth are presented in Fig. 2.
In extending our survey to two-dimensional struc-
tures, we will not discuss the topic of the sonochemical
deposition of nanomaterials on prefabricated spherical
particles in this review. Many papers have been pub-
lished on this topic and have been reviewed in [6]. We
have, on the other hand, searched for papers describing
the use of ultrasound for the deposition of nanoproducts
on flat surfaces. I could not find a direct process in
which a flat surface was introduced into a sonication
bath and was removed with a thin coating of a film. On
the other hand, papers were found where, at the end of
the sonication, a flat surface was dipped in the solution.
Feng et al. [59,60] described such a process. Using a
sonochemical [59] method, they have prepared a com-
posite film containing finely dispersed polyoxometalates
nanoparticles with narrow size distribution in poly-
acrylamide. The composite product exhibits a spherical
structure with a narrow size distribution in which more
than 90% of the population are within the 45–55 nm
range. After dipping the various substrates into the
transparent solution, the films were dried in a chamber
by controlling air humidity that should not exceed 60%
in order to obtain optically perfect films. The thickness
of the hybrid films was approximately 2.1 mm.
The first observation of 3-D features such as the
Olympic Rings was reported by Shafi et al. [61]. They
 A. Gedanken / Ultrasonics Sonochemistry 11 (2004) 47–55 53

Fig. 2. SEM images detailing various stages of t-Se wire growth: (a) Spherical colloids of a-Se synthesized by reducing selenious acid with hydrazine.
(b) Colloidal particles recovered from an ethanol dispersion right after sonication (for 30 s). Note that these particles have undergone a morpho-
logical change due to sonication-inducted fusion. (c) A sample obtained at the initial stage of wire growth, suggesting that these nanowires originated
from seeds deposited on the surfaces of a-Se colloids. (d) The final product, in which all a-Se colloids have already been transformed into t-Se
nanowires with a uniform diameter.

were observed for amorphous BaFe12 O19 nanoparticles,
which were prepared by a sonochemical decomposition
technique. The barium hexaferrite was formed as a
colloidal solution without the use of a surfactant. Rings
of smaller dimensions trapped inside the larger ones (see
Fig. 4) were another unique observation. The intersec-
tion of two rings is amazing (Fig. 3), as this is in direct
contradiction to the proposed mechanism for the ring
formation, based on the dry hole formation on an
evaporating thin film completely wetted to the substrate.
The creation of this unique feature is attributed to the
interplay of magnetic forces with the regular particle-
substrate interactions. The diameter of the rings varied
in the range of 0.5–1.5 lm, and the annular width is
about 25 nm.
A unique 3-D structure, inorganic fullerenes, were
obtained in the sonohydrolysis of TlCl3 [62]. The soni-
cation of an aqueous solution of TlCl3 under a flow of

Fig. 3. TEM micrograph showing rings of various sizes. The rings seem Fig. 4. TEM micrograph showing rings at various stages of growth.
to intersect each other forming the so-called Olympic Rings. The scale Rings of smaller dimensions are seen trapped inside the larger one. The
bar is 0.7 lm. annular width of the ring is about 10 nm. The scale bar is 1 lm.
54 A. Gedanken / Ultrasonics Sonochemistry 11 (2004) 47–55
argon has led to a precipitate, which is composed of two
products. The major product is Tl2 OCl2 , while Tl2 O is
obtained in small quantities. The latter has the structure
of a multi-shell closed compound. The identification of
the inorganic fullerenes in the TEM picture (see Figs. 1
and 2 in Ref. [62]) as the thallium(I) oxide is based on
SAED measurements.
The formation of the closed curved structures is ex-
plained as follows: in the first stage, Tl2 O is formed via
the sonochemical reduction of Tlþ3 . It is known that the
sonohydrolysis of aqueous solutions of metal ions is
caused by high local temperatures in or near the cavi-
tation bubbles. If the original Tl2 O particle is planar
(two-dimensional), curvature and closure of the fuller-
ene-like structures may occur around the collapsing
bubble. The temperature gradient from the bubble sur-
face into the solution should cause a temperature gra-
dient across the particle that causes the curvature. This
is helped by the energetics, which favor sheet closure due
to the bond energy released by eliminating reactive edges
in the planar structures.
Various sonochemical methods have been designed
for the preparation of hollow spheres. Zheng [63] re-
ported on the formation of vesicle-templated CdSe
hollow spheres in an ultrasound-induced anionic sur-
factant solution. He demonstrated that hollow spheres
of CdSe with sizes of 100–200 nm can be templated from
anionic surfactant sodium dodecyl sulfate (SDS) vesicles
induced by ultrasonic irradiation. The successful vesicle
templating indicated that the outer leaflet of the bilayer
is the receptive surface in the controlled growth of CdSe
nanoparticles, which provide the unique reactor for the
nucleation and mineralization growth of CdSe nano-
particles. In the ultrasound irradiation process, it was
found that the concentration of surfactant in the system
plays an important role in the formation of the CdSe
hollow sphere. When the concentration was lower than
0.15 mol/l, the obtained CdSe were nanoparticles with
dense agglomeration. The surfactant molecules are re-
moved by extraction, using repeated water and ethanol
washings. CdSe hollow spherical assemblies composed
of 5 nm nanoparticles have been synthesized sono-
chemically [64]. The preparation method did not include
a surfactant. During the process, amorphous Cd(OH)2 ,
which acts as the in situ template, directs the growth of
primary CdSe nanoparticles on its surface and their
assembly into hollow spherical structures. Hollow ZnS
spheres were prepared by Yin [65] using sonochemical
methods. Core-shell ZnS/PolyStyrene(PS) microspheres
were obtained through the sonochemical treatment of
the PS in an ethanol solution containing zinc acetate and
thioacetamide. The composite particles were ‘‘optically
hollow’’ due to the large refractive index contrast be-
tween the core and shell materials. Hollow ZnS spheres
were formed by annealing the core-shell spheres in a
muffle oven under a stream of 3:1 nitrogen and hydro-
gen gas at 600 C. In fact, Ref. [64] followed in the
footsteps a previous work by Breen et al. [66], with just
some minor changes.
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