Scavenging of OH radicals produced in the sonolysis of water.

The yield of hydrogen peroxide in the sonication of argon-saturated water was studied in the presence of various solutes. The efficiency of OH radical scavenging is expressed by the reciprocal value of C 1/2, the solute concentration at which the H2O2 yield is decreased by 50 per cent. C 1/2 ranges over several orders of magnitude. It is not related to the specific reactivity towards OH in homogeneous solution. However, it is correlated to the hydrophobicity of the solutes. The competition of I- and a second solute for OH was also studied. The competition between I- and HCO2- follows similar kinetics as in homogeneous solution. However, many other solutes compete in the manner which would be expected if radical scavenging occurred in different phases. The effects are explained in terms of OH radical formation in gaseous argon bubbles, combination of OH radicals to form H2O2 in an interfacial area, and enrichment of hydrophobic solutes in the bubbles.

Chemical reactions by pulsed ultrasound: memory effects in the formation of NO3- and NO2- in aerated water.

The formation of nitrate and nitrite in the sonolysis of aerated water was studied using pulses of 300 kHz ultrasound. At very low on/off ratios, the yield decreases with decreasing pulse duration. At a pulse length of 3 X 10(-3) s, the yield is zero. This time is identified as the 'activation' time tau 1 of small gas bubbles formed by cavitation. At larger on/off ratios, a pulse is more effective the shorter the time interval between the pulses. This memory effect is described by a 'deactivation' time tau 2 of the system, which amounts to about 6 X 10(-2) s. At large on/off ratios (1:3 and 1:1) the yield never becomes zero. It first decreases with decreasing pulse length (increasing modulation frequency) and increases again for very short pulses. The results are also discussed with respect to the use of pulsed ultrasound in diagnostic applications.

Hot spot kinetics of the sonolysis of aqueous acetate solutions.

Water and acetate solutions were irradiated under argon by 300 kHz ultrasonic waves. Oxygen was found to be generated besides the products H2 and H2O2, already known. In the presence of acetate the O2 yield decreased rapidly while that of H2O2 decreased more slowly. Succinic acid was found as a product of the attack of OH radicals on acetate. Appreciable amounts of glyoxylic and glycolic acid and smaller amounts of formaldehyde and carbon dioxide were also detected. They resulted from the reaction of sonolytically generated oxygen with CH2CO2- radicals, produced upon attack of OH on acetate. Methane was a minor product of sonolysis. At acetate concentrations above 0.4 mol dm-3 CO2 and CO became the predominant products of sonolysis. This is explained by a second kind of action of ultrasound on dissolved acetate, i.e. by a thermal decomposition. This decomposition is possibly facilitated by radical attack on acetate. The results are discussed in terms of a 'structured hot spot' model, in which three regions for the occurrence of chemical reactions are postulated: a hot gaseous nucleus, an interfacial region with radial gradient in temperature and local radical density; and the bulk solution at ambient temperature.

XAFS studies of gold and silver-gold nanoparticles in aqueous solutions.

The x-ray absorption fine structure (XAFS) of colloidal Au and Au/Ag nanoparticles (3.5nm and 20nm mean diameter) in an aqueous solution has been investigated. Size dependent alloying was observed upon deposition of Ag on Au core. Ag forms distinct layers around the 20 nm Au nanoparticles. In contrast, random mixing is found for Ag deposited on 3.5nm Au particles.

Shape-Controlled Synthesis of Colloidal Platinum Nanoparticles

The shapes and sizes of platinum nanoparticles were controlled by changes in the ratio of the concentration of the capping polymer material to the concentration of the platinum cations used in the reductive synthesis of colloidal particles in solution at room temperature. Tetrahedral, cubic, irregular-prismatic, icosahedral, and cubo-octahedral particle shapes were observed, whose distribution was dependent on the concentration ratio of the capping polymer material to the platinum cation. Controlling the shape of platinum nanoparticles is potentially important in the field of catalysis.