Yoshiteru Mizukoshi

Sonochemical degradation of chlorophenols in water

Sonochemical degradation of dilute aqueous solutions of 2-, 3- and 4-chlorophenol and pentachlorophenol has been investigated under air or argon atmosphere. The degradation follows first-order kinetics in the initial state with rates in the range 4.5-6.6 microM min-1 under air and 6.0-7.2 microM min-1 under argon at a concentration of 100 microM of chlorophenols. The rate of OH radical formation from water is 19.8 microM min-1 under argon and 14.7 microM min-1 under air in the same sonolysis conditions. The sonolysis of chlorophenols is effectively inhibited, but not completely, by the addition of t-BuOH, which is known to be an efficient OH radical scavenger in aqueous sonolysis. This suggests that the main degradation of chlorophenols proceeds via reaction with OH radicals; a thermal reaction also occurs, although its contribution is small. The addition of appropriate amounts of Fe(II) ions accelerates the degradation. This is probably due to the regeneration of OH radicals from hydrogen peroxide, which would be formed from recombination of OH radicals and which may contribute a little to the degradation. The ability to inhibit bacterial multiplication of pentachlorophenol decreases with ultrasonic irradiation.

Formation of noble metal particles by ultrasonic irradiation

Abstract It was found that sonochemically prepared metal particles such as Ag, Pd, Au, Pt and Rh are of nanometer size with a fairly narrow distribution (e.g., about 5 nm for Pd particles obtained from a 1.0 mM Pd(II) in polyethylene glycol monostearate solution). We have suggested three different reduction pathways under sonication: (i) reduction by H atoms, (ii) reduction by secondary reducing radicals formed by hydrogen abstraction from organic additives with OH radicals and H atoms, (iii) reduction by radicals formed from pyrolysis of the additives at the interfacial region between cavitation bubbles and the bulk solution. The reduction of Ag(I) and Pt(II) mainly proceeds through reaction pathway (ii). In the cases of Pd(II) and Au(III), the reductions mainly proceed through reaction pathway (iii). The reduction of Rh(III) was not achieved under the same conditions; however, by the addition of sodium formate, reduction occurred and the preparation of Rh particles succeeded.

Sonochemical Formation of Gold Particles in Aqueous Solution

Gold(III) ions in aqueous solutions of NaAuCl4 were reduced to form gold particles by ultrasonic irradiation. The rate of formation of gold particles was accelerated in the presence of certain organic additives such as surfactants, water-soluble polymers and aliphatic alcohols and ketones. The rates of formation of gold particles from 1 mM Au(III) ions in pure water were 3 microM min-1 under argon atmosphere and approximately zero under air, and in solutions containing additive the rates were 9-133 microM min-1 under argon and 8-40 microM min-1 under air. Surfactants stabilized the particles as colloidal state for more than several months. The rates of formation of both hydrogen atoms and hydroxyl radicals were estimated to be equal to 25 microM min-1 in the sonolysis of pure water under argon. Three reaction pathways leading to the reduction of metal ions were proposed: (1) reduction by hydrogen atoms; (2) reduction by reducing radicals formed via reactions of hydroxyl radicals or hydrogen atoms with the additives; (3) reduction by radicals formed from thermal reaction of the additives at the interfacial region between cavitation bubbles and bulk solution and/or in the cavities. The order of the contribution of these three pathways to the reduction of gold ions was (3) > (2) > (1) in most cases. The number averages of the size of gold particles formed in surfactant solutions under argon atmosphere were about 10 nm with a fairly narrow size distribution.

Preparation of platinum nanoparticles by sonochemical reduction of the Pt(IV) ions: role of surfactants

Sonochemical reduction processes of Pt(IV) ions in water have been investigated in the presence of various kinds of surfactants such as sodium dodecylsulfate (SDS) and sodium dodecylbenzenesulfonate (DBS) as anionic surfactants, and polyethylene glycol monostearate (PEG-MS) as non-ionic, dodecyltrimethylammonium chloride (DTAC) and bromide (DTAB) as cationic surfactants. An improved colorimetric determination reveals that Pt(IV) ion is reduced to zero valent metal in two steps: step (1)--Pt(IV) ion to Pt(II) ion, and step (2)--Pt(II) ion to Pt(0), and after the completion of step (1), step (2) sets in. It appears that rapid scrambling reactions among platinum ions and/or atoms, that is, Pt(I) + Pt(IV)-->Pt(II) + Pt(III), etc. take place. In the sonolysis of aqueous solutions of SDS, DBS or PEG-MS, two kinds of organic reducing radicals, R(ab) and R(py), are proposed to contribute to the reduction. Radical R(ab) is formed from the reaction of the surfactants with primary radicals such as hydroxyl radicals and hydrogen atoms originated from the sonolysis of water, and radical R(py) is formed from the direct thermal decomposition of surfactants in the interfacial region between the collapsing cavities and the bulk water. R(ab) is effective for both the reduction steps, whereas R(py) is involved only in the reduction step (1). This fact coincides with the previous reported sonochemical reduction of Pt(II) ions. Hydrogen atoms themselves scarcely participate in the reduction. The average diameter (1.0 nm) of platinum particles prepared from the system of PEG-MS is smaller than those from the aqueous solution of anionic surfactant SDS (3.0 nm) and DBS (3.0 nm).

Sonolytic degradation of hazardous organic compounds in aqueous solution

Benzene, chlorobenzene, 1,2-, 1,3-, 1,4-dichlorobenzene, biphenyl, and polychlorinated biphenyls such as 2-, 4-chlorobiphenyl and 2,2-dichlorobiphenyl in aqueous solutions have been subjected to sonolysis with 200 kHz ultrasound at an intensity of 6 W cm-2 under an argon atmosphere. 80-90% of initial amount of these compounds were degraded by 30-60 min of sonication when the initial concentrations were 10-100 mumol l-1. The degradation rate of these compounds increased with increase in their vapor pressures. In all cases of sonolysis of chlorinated organic compounds, an appreciable amount of liberated chloride ion was observed.

Sonolytical preparation of various types of metal nanoparticles in aqueous solution

Composite nanoparticles of Au, Pd and Pt, and nanoparticles of transition metal oxides, MnO2, were prepared by the sonochemical reduction of corresponding ions (Au(III), Pd(II), Pt(II), Pt(IV) and Mn(VII)) in an aqueous system in the presence of surfactants. The prepared noble metal particles were stable and the sizes were of the order of nanometer with narrow distribution. Surfactants were found to be stabilizers for the noble metal nanoparticles as well as important sources of reducing species for the metal ions. In binary metallic particles, which were prepared from aqueous mixed solutions of noble metal ions, three possible constitutional forms were obtained. MnO2 particles were reduce to water soluble Mn(II) ions by further sonication.

Electron microscopy of noble metal alloy nanoparticles prepared by sonochemical methods

Abstract Argon-saturated aqueous solutions of NaAuCl4 and PdCl2 or K2PtCl4 were reduced simultaneously by ultrasound irradiation to prepare noble metal alloy nanoparticles. Droplets recovered from colloidal dispersions were placed on carbon-supported copper grids, and dried in a vacuum. They were examined by TEM, HRTEM, and nano-area energy dispersion X-ray spectroscopy(EDX). The Au-Pd nanoparticles exhibited monodispersive distribution (8 nm), and consisted of a gold core and a palladium shell. Au-Pt alloy nano-particles could not be produced from NaAuCl4 and K2PtCl4 aqueous solutions either by simultaneous or successive reduction.