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
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
amorphous Sb2 S3 particles. During the crystallization
facilely to the above complex according to CdY 2 +
process, Sb2 S3 presents a preferential 1D growth along
S 2 fi CdS
ðnanorodÞ
+ Y 4 . Because of this, the growth of
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
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
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