Syntheses of Specialty Nanomaterials at the Multibubble Sonoluminescence Condition

In recent years, a large number of nano-size semiconductors have been investigated for their potential applications in photovoltaic cells, optical sensor devices, and photocatalysts [1, 2, 3]. Nano-size semiconductor particles have many interesting properties due mainly to their size-dependent electronic and optical properties. Appropriately, many speciality of nanomaterials such as CdS and ZnS semiconductor particles, and other metal oxides such as ZnO and lithium-titanate oxide (LTO) have been prepared. However, most of them were prepared with toxic reactants and/or complex multistep reaction processes. Particularly, it is quite difficult to produce LTO nanoparticles, since it typically requires wearisome conditions such as very high temperature over 1000 °C, long producing times, and so on. To overcome such problems, various core/shell type nanocrystals were prepared through different methods such as the hydrothermal synthetic method, microwave, and sonochemistry. Also many coating methods on inorganic oxide nanoparticles were tried for the preparations of various core-shell type nanocrystals. Sonoluminescence (SL) is a light emission phenomenon associated with the catastrophic collapse of a gas bubble oscillating under an ultrasonic field [4]. Light emission of single bubble sonoluminescence (SBSL) is characterized by picosecond flashes of the broad band spectrum extending to the ultraviolet [5, 6]. The bubble wall acceleration has been found to exceed 10¹¹ g at the moment of bubble collapse. Recently observed results of the peak temperature and pressure from the sonoluminescing gas bubble in sulfuric acid solutions [9] were accurately predicted by the hydrodynamic theory for sonoluminescence phenomena [7, 10, 11, 12], which provides a clue for understanding sonochemical reactions inside the bubble and liquid layer adjacent to the bubble wall. Sonochemistry involves an application of sonoluminescence. The intense local heating and high pressure inside the bubbles and liquid adjacent bubble wall from such collapse can give rise to unusual effects in chemical reactions. The estimated temperature and pressure in the liquid zone around the collapsing bubble with equilibrium radius 5 μm, an average radius of bubbles generated in a sonochemical reactor at a driving frequency of 20 kHz with an input power of 179 W, is about 1000 °C and 500 atm, respectively. At the proper condition, a lot of transient bubbles are generated and collapse synchronistically to emit blue light when high power ultrasound is applied to liquid, and it is called multibubble sonoluminescence (MBSL). Figure 1 shows an experimental apparatus for MBSL with a cylindrical quartz cell, into which a 5 mm diameter titanium horn (Misonix XL2020, USA) is inserted [13]. The MBSL facilitates the transient supercritical state [14].in the liquid layer where rapid chemical reactions can take place. In fact, methylene blue (MB), which is one of a number of typical textile dyestuffs, was degraded very fast at the MBSL condition while MB does not degrade under simple ultrasonic irradiation [13]. MBSL has been proven to be a useful technique to make novel materials with unusual properties. In our study, various metal oxides such as ZnO powder [15], used as a primary reinforcing filler for elastomer, homogeneous Li₄Ti₅O₁₂ nanoparticles [16], used for electrode materials, and core/shell nanoparticles such as CdS coating on TiO₂ nanoparticles [17] and ZnS coating on TiO₂ nanoparticles [18], which are very likely to be useful for the development of inorganic dye-sensitized solar cells, were synthesized through a one pot reaction under the MBSL condition. Figure 2 shows the XRD pattern of ZnO nanoparticles synthesized from zinc acetate dehydrate (Zn(CH₃CO₂)₂ · 2H₂O, 99.999%, Aldrich) in various alcohol solutions with sodium hydroxide (NaOH, 99.99%, Aldrich) at the MBSL condition. The XRD patterns of all powers indicate hexagonal zincite. The XRD pattern for the ZnO nanoparticles synthesized is similar to the ZnO powder produced by a modified sol-gel process and subsequent heat treatment at about 600 °C [19] as shown in Fig.3. The average particle diameter of ZnO powder is about 7 nm. A simple sonochemical method for producing homogeneous LTO nanoparticles, as shown schematically in Fig. 4. First, LiOH and TiO₂ nanoparticles were used to prepare LiOH-coated TiO₂ nanoparticles as shown in Fig.5. Second, the resulting nanoparticles were thermally treated at 500 °C for 1 hour to prepare LTO nanoparticles. Figure 6 shows a high resolution transmission electron microscope image of LTO nanoparticles having an average grain size of 30–40 nm. All the nanoparticle synthesized are very pure in phase and quite homogeneous in their size and shape. Recently we succeeded in synthesizing a supported nickel catalyst such as Ni/Al_2sO₃, MgO/Al₂O₃ and LaAlO₃, which turned out to be effective for methane decomposition [20]. Sonochemistry may provide a new way to more rapidly synthesize many specialty nanoparticles with less waste [21]. This clean technology enables the preparation of new materials such as colloids, amorphous particles [22], and various alloys.