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Efficient energy transfer management in catalytic processes is crucial for overcoming activation energy barriers while minimizing costs and CO2 emissions. We exploit here a concept of CuO particle design with multiple gas-stabilizing sites, engineered to function as cavitation nuclei and catalysts. This concept facilitates the selective and efficient acoustic energy transfer directly to the catalyst surface, avoiding the undesired dissipation of acoustic energy into the bulk solution while demonstrating superior cavitation properties at lower acoustic pressure amplitudes. Utilizing a chemical thermometric approach, we demonstrate that the local temperature on the surface of our CuO particles during cavitation bubble implosions can create an effective equivalent temperature of about 360°C. This temperature effect facilitates the efficient catalysis of oxidative reactions using an organic probe molecule. Density functional theory (DFT) calculations were used to assess the decomposition of H2O2 and of pollutant probe molecule on CuO (111). Our work represents a significant advance in sonocatalytic systems, promising efficient energy use in catalytic reactions., (© 2024 Wiley‐VCH GmbH.)

The sonohydrothermal (SHT) treatment is an innovative technique allowing the simultaneous coupling of low frequency ultrasound and hydrothermal conditions for the synthesis of materials. The aim of the present work was to investigate, for the first time, the synthesis of zeolite A and its formation mechanism under SHT conditions. The zeolite synthesis was carried out under sonohydrothermal conditions using a specially designed reactor that allows the application of ultrasonic irradiation at 20 kHz in an autoclave-type reactor heated up to 200 °C under autogenous pressure. The conversion kinetics of the amorphous hydrogel to zeolite A and its further conversion to sodalite were studied. Syntheses were performed in the SHT reactor at 80 and 100 °C, varying the synthesis time from 15 minutes to several hours. The required time to obtain fully crystalline zeolite A under sonohydrothermal conditions was only 25 minutes, highlighting a significantly improved crystallization rate compared to silent conditions (a 9.6-fold kinetic gain). In addition, the resulting zeolite A has smaller particles and a more homogeneous particle size distribution than the zeolite synthesized by hydrothermal treatment. These results can be explained by the sonofragmentation of the amorphous gel and the concomitant enhanced mass transfer of the building units at the interface between the crystallite surface and the solution resulting from the acoustic cavitation activity under SHT conditions. Compared to classical hydrothermal heating, a drastic kinetic increase of the transformation of zeolite A into the more stable sodalite phase was also observed under sonohydrothermal conditions.

Ultrasonic irradiation holds potential for the selective oxidation of non-volatile organic substrates in the aqueous phase by harnessing hydroxyl radicals as chemical initiators. Here, a mechanistic description of hydroxyl radical-initiated glyoxal oxidation is constructed by gleaning insights from photolysis and radiation chemistry to explain the yields and kinetic trends for oxidation products. The mechanistic description and kinetic measurements reported herein reveal that increasing the formation rate of hydroxyl radicals by changing the ultrasound frequency increases both the rates of glyoxal consumption and the selectivity towards C2 acid products over those from C-C cleavage. Glyoxal consumption also occurs more rapidly and with greater selectivity towards C2 acids under acidic conditions, which favor the protonation of carboxylate intermediates into their less reactive acidic forms. Leveraging such pH and frequency effects is crucial to mitigating product degradation by secondary reactions with hydroxyl radicals and oxidation products (specifically hydrogen peroxide and superoxide). These findings demonstrate the potential of ultrasound as a driver for the selective oxidation of aldehyde functions to carboxylic acids, offering a sustainable route for valorizing biomass-derived platform molecules., (© 2024 Wiley‐VCH GmbH.)