Sonochemical water splitting in the presence of powdered metal oxides

Kinetics of hydrogen formation was explored as a new chemical dosimeter allowing probing the sonochemical activity of argon-saturated water in the presence of micro- and nano-sized metal oxide particles exhibiting catalytic properties (ThO₂, ZrO₂, and TiO₂). It was shown that the conventional sonochemical dosimeter based on H₂O₂ formation is hardly applicable in such systems due to catalytic degradation of H₂O₂ at oxide surface. The study of H₂ generation revealed that at low-frequency ultrasound (20 kHz) the sonochemical water splitting is greatly improved for all studied metal oxides. The highest efficiency is observed for relatively large micrometric particles of ThO₂ which is assigned to ultrasonically-driven particle fragmentation accompanied by mechanochemical water molecule splitting. The nanosized metal oxides do not exhibit particle size reduction under ultrasonic treatment but nevertheless yield higher quantities of H₂. The enhancement of sonochemical water splitting in this case is most probably resulting from better bubble nucleation in heterogeneous systems. At high-frequency ultrasound (362 kHz), the effect of metal oxide particles results in a combination of nucleation and ultrasound attenuation. In contrast to 20 kHz, micrometric particles slowdown the sonolysis of water at 362 kHz due to stronger attenuation of ultrasonic waves while smaller particles show a relatively weak and various directional effects.     

Catalytic oxidative cleavage of olefins by RuO4 organic solvent-free under ultrasonic irradiation

All the works reported about oxidative cleavage of olefins by the RuCl₃/NaIO₄ catalytic system have been performed in biphasic water/organic solvent(s). The first organic solvent-free oxidation of CC double bond by 2% RuCl₃/4.1 equiv NaIO₄/H₂O is described here using both the emulsifier Aliquat® 336 and 20 kHz ultrasonic irradiation.     

Mechanism of W(CO)6 sonolysis in diphenylmethane

The present work analyses the mechanism of W₂C/C nanocomposite formation during sonolysis of W(CO)₆ in diphenylmethane (DPhM) solutions. Carbon supported WC_x nanoparticles attract much interest as an alternative fuel cell electrocatalysts. Sonolysis of neat DPhM under the effect of 20 kHz power ultrasound in argon at 80 °C yields a sonopolymer as a solid product and acetylene, hydrogen, methane, diacetylene and benzene as gaseous products. Diacetylene is formed due to the secondary sonochemical dimerisation of acetylene obtained at the primary stage of DPhM sonolysis. FTIR and μ-Raman studies show that the sonopolymer consists of a mixture of some polymeric partially oxidized aromatic species, and disordered carbon. Sonolysis of W(CO)₆ in diphenylmethane solutions follows the first order kinetics. This process yields monodispersed 2-3 nm X-ray amorphous WC_x nanoparticles embedded in amorphous sonopolymer. The annealing of air sensitive as-prepared solids in an inert atmosphere at 600 °C causes formation of stable W₂C/C nanocomposite with W₂C average particle size in the range of 4-7 nm and hexagonal carbon fine particles with the average size of 30-40 nm. Kinetic study revealed that tungsten carbide is formed inside the cavitation bubble due to the reaction of tungsten nanoparticles originated from primary sonolysis of W(CO)₆ with acetylene produced as a result of diphenylmethane sonochemical degradation.     

Sono-electrolysis performance based on indirect continuous sonication and membraneless alkaline electrolysis: Experiment,modelling and analysis

In the present study, experiments of membraneless alkaline sono-electrolysis are combined to a mathematical model describing the performance of a sono-electrolyzer based on the electrochemical resistances and overpotentials (activation, Ohmic and concentration) and the oscillation of the acoustic cavitation bubble, and its related sono-physical and sonochemical effects, as a single unit and within population. The study aims to elucidate the mechanism of action of acoustic cavitation when coupled to alkaline electrolysis, using a membraneless H-cell configuration and indirect continuous sonication (40 kHz, 60 W_e). The calorimetric characterization constituted the bridge between experimental results and the numerical and simulation approach, while the quantification of the rate of produced hydrogen both experimentally and numerically highlighted the absence of the contribution of sonochemistry, and explained the role of ultrasounds by the action of shockwaves and microjets. Finally, the energetic sono-physical approach allowed an estimation of the predominance of the shockwaves and microjets effects according to the bubble size distribution within the population corresponding to the acoustic conditions of the study. The resulting macroscopic effect in sono-electrolysis process has been assessed considering the induced degassing. A reduction in the fraction of electrodes’ coverage by bubbles from 76% to 42% has been recorded, corresponding to a decrease of 7.2% in Ohmic resistance and 62.35% in bubble resistance.     

From crystal phase mixture to pure metal-organic frameworks – Tuning pore and structure properties

In this study, a sonochemical route for the preparation of a new Hf-MIL-140A metal–organic framework from a mixture of UiO-66/MIL-140A is presented. The sonochemical synthesis route not only allows the phase-pure MIL-140A structure to be obtained but also induces structural defects in the MIL-140A structure. The synergic effect between the sonochemical irradiation and the presence of a highly acidic environment results in the generation of slit-like defects in the crystal structure, which increases specific surface area and pore volume. The BET-specific surface area in the case of sonochemically derived Zr-MIL-140A reaches 653.3 m²/g, which is 1.5 times higher than that obtained during conventional synthesis. The developed Hf-MIL-140A structure is isostructural to Zr-MIL-140A, which was confirmed by synchrotron X-ray powder diffraction (SR-XRD) and by continuous rotation electron diffraction (cRED) analysis. The obtained MOF materials have high thermal and chemical stability, which makes them promising candidates for applications such as gas adsorption, radioactive waste removal, catalysis, and drug delivery.