Physical insights into the sonochemical degradation of recalcitrant organic pollutants with cavitation bubble dynamics

This paper tries to discern the mechanistic features of sonochemical degradation of recalcitrant organic pollutants using five model compounds, viz. phenol (Ph), chlorobenzene (CB), nitrobenzene (NB), p-nitrophenol (PNP) and 2,4-dichlorophenol (2,4-DCP). The sonochemical degradation of the pollutant can occur in three distinct pathways: hydroxylation by OH radicals produced from cavitation bubbles (either in the bubble–bulk interfacial region or in the bulk liquid medium), thermal decomposition in cavitation bubble and thermal decomposition at the bubble–liquid interfacial region. With the methodology of coupling experiments under different conditions (which alter the nature of the cavitation phenomena in the bulk liquid medium) with the simulations of radial motion of cavitation bubbles, we have tried to discern the relative contribution of each of the above pathway to overall degradation of the pollutant. Moreover, we have also tried to correlate the predominant degradation mechanism to the physico-chemical properties of the pollutant. The contribution of secondary factors such as probability of radical–pollutant interaction and extent of radical scavenging (or conservation) in the medium has also been identified. Simultaneous analysis of the trends in degradation with different experimental techniques and simulation results reveals interesting mechanistic features of sonochemical degradation of the model pollutants. The physical properties that determine the predominant degradation pathway are vapor pressure, solubility and hydrophobicity. Degradation of Ph occurs mainly by hydroxylation in bulk medium; degradation of CB occurs via thermal decomposition inside the bubble, degradation of PNP occurs via pyrolytic decomposition at bubble interface, while hydroxylation at bubble interface contributes to degradation of NB and 2,4-DCP.     

Sonochemical growth of antimony sulfoiodide in multiwalled carbon nanotube

This paper presents for the first time the nanocrystalline, semiconducting ferroelectrics antimony sulfoiodide (SbSI) grown in multiwalled carbon nanotubes (CNTs). It was prepared sonochemically using elemental Sb, S and I in the presence of methanol under ultrasonic irradiation (35 kHz, 2.6 W/cm²) at 323 K for 3 h. The CNTs filled with SbSI were characterized by using techniques such as powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, high-resolution transmission electron microscopy, selected area electron diffraction, and optical diffuse reflection spectroscopy. These investigations exhibit that the SbSI filling the CNTs is single crystalline in nature and in the form of nanowires. It has indirect forbidden energy band gap E_gIf = 1.871(1) eV.     

Ultrasonic cavitation induced water in vegetable oil emulsion droplets--a simple and easy technique to synthesize manganese zinc ferrite nanocrystals with improved magnetization

In the present investigation, synthesis of manganese zinc ferrite (Mn_0.5Zn_0.5Fe₂O₄) nanoparticles with narrow size distribution have been prepared using ultrasound assisted emulsion (consisting of rapeseed oil as an oil phase and aqueous solution of Mn²⁺, Zn²⁺ and Fe²⁺ acetates) and evaporation processes. The as-prepared ferrite was nanocrystalline. In order to remove the small amount of oil present on the surface of the ferrite, it was subjected to heat treatment at 300 °C for 3 h. Both the as-prepared and heat treated ferrites have been characterized by X-ray diffraction (XRD), infrared spectroscopy (IR), TGA/DTA, transmission electron microscopy (TEM) and energy dispersion X-ray spectroscopy (EDS) techniques. As-prepared ferrite is of 20 nm, whereas the heat treated ferrite shows the size of 33 nm. In addition, magnetic properties of the as-prepared as well as the heat treated ferrites have also been carried out and the results of which show that the spontaneous magnetization (σ_s) of the heat treated sample (24.1 emu/g) is significantly higher than that of the as-synthesized sample (1.81 emu/g). The key features of this method are avoiding (a) the cumbersome conditions that exist in the conventional methods; (b) usage of necessary additive components (stabilizers or surfactants, precipitants) and (c) calcination requirements. In addition, rapeseed oil as an oil phase has been used for the first time, replacing the toxic and troublesome organic nonpolar solvents. As a whole, this simple straightforward sonochemical approach results in more phase pure system with improved magnetization.     

Ultrasound promoted Wurtz coupling of alkyl bromides and dibromides

Sonochemically enhanced Wurtz coupling using lithium metal has been investigated for a number of isomeric alkyl bromides under a variety conditions. The products result from direct coupling of short lived radicals formed at the metal surface rather than the secondary radicals which can be formed during coupling of aromatic halides and thus give rise to a single major product. Coupling has been extended to dibrominated aryl and alkyl compounds as well as showing that aryl-alkyl coupling is possible. Dibrominated alkyls were found to give low molecular weight oligomers although no reaction occurred for 1,2-isomers. The growth of oligomers in THF may be solubility limited. A simple model is proposed to explain these findings.     

Sonochemical growth of antimony selenoiodide in multiwalled carbon nanotube

This paper presents, for the first time, the nanocrystalline, semiconducting antimony selenoiodide (SbSeI) grown in multi-walled carbon nanotubes (CNTs). It was prepared sonochemically using elemental Sb, Se, and I in the presence of ethanol under ultrasonic irradiation (35 kHz, 2.6 W/cm²) at 323 K for 3 h. The CNTs filled with SbSeI were characterized by using techniques such as powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, high-resolution transmission electron microscopy, selected area electron diffraction, and optical diffuse reflection spectroscopy. These investigations exhibit that the SbSeI filling the CNTs is single crystalline in nature and in the form of nanowires. It has indirect allowed energy band gap E_gIf = 1.61(6) eV.     

Ultrasound-assisted synthesis of magnesium hydroxide nanoparticles from magnesium

Acoustic cavitation in water provides special kinetic and thermodynamic conditions for chemical synthesis and nanostructuring of solids. Using cavitation phenomenon, we obtained magnesium hydroxide from pure magnesium. This approach allows magnesium hydroxide to be synthesized without the requirement of any additives and non-aqueous solvents. Variation of sonochemical parameters enabled a total transformation of the metal to nanosized brucite with distinct morphology. Special attention is given to the obtaining of platelet-shaped, nanometric and de-agglomerated powders. The products of the synthesis were characterized by transmission electron microscopy (TEM), electron diffraction (ED), scanning electron microscopy (SEM) and X-ray diffraction (XRD).     

Magnetic properties,anticancer and antibacterial effectiveness of sonochemically produced Ce3+/Dy3+ co-activated Mn-Zn nanospinel ferrites

Some new types of Ce³⁺ and Dy³⁺ co-doped manganese-zinc nanospinel ferrites (CDMZNSFs) of the form (Mn_0.5Zn_0.5)[Fe_2-2xCe_xDy_x]O₄ (with 0.0 ≤ x ≤ 0.1) were sonochemically produced and characterized. The structure, morphology, optical and magnetic properties of these NSFs were determined as a function of co-dopant (Ce³⁺ and Dy³⁺) contents. The direct optical band gap energies of the studied NSFs were ranged from 1.54 to 1.85 eV. The measurements of magnetization versus magnetic field of the prepared NSFs disclosed a superparamagnetic (SPM) behavior at room temperature (RT). The measurements of temperature-dependent magnetizations revealed a transition from superparamagnetic (SPM) state above blocking temperature T_B to a ferromagnetic (FM) state below T_B. The saturation magnetization and T_B decreased with the increase in co-dopant contents. In addition, the bactericidal (on the gram-positive and gram-negative bacterial strains) and anti-cancerous effectiveness of these NSFs were assessed. The cancer cells' growth inhibitory action of these NSFs was tested against both normal (HEK-293) and cancerous (HCT-116) human cells. After 48 h of treatment of the cancerous cells with the NSFs, their population was significantly dropped as shown by the MTT assay, indicating the selective inhibition of the cancer cells growth by the proposed NSFs. Conversely, the non-cancerous cells (HEK-293) population remained unaffected. The IC₅₀ values of the NSFs-treated cancerous cells (HCT-116) were in the range of 0.74–2.35 µg/mL. The results of the MIC and MBC assays revealed the reasonable antibacterial efficacy (growth inhibitory activity) of these NSFs when tested against the E. coli and S. aureus bacterial strains. It is established that the proposed Ce³⁺/Dy³⁺ co-activated CDMZNSFs may be beneficial for the anti-cancerous and bactericidal applications.     

The pH-dependent reactions in the sonochemical synthesis of luminescent fluorides: The quest for the formation of KY3F10 crystal phases

In this study Eu³⁺-doped yttrium fluorides were designed by ultrasound-assisted processes at different pH values (4.0–9.0). This novel strategy has enabled to obtain materials with intriguing morphologies and modulated crystal structures: α-KY₃F₁₀, δ–KY₃F₁₀·xH₂O, and Y(OH)_3–xF_x. To date, the literature has primarily focused only on the α-phase of KY₃F₁₀. Yet, explaining the formation of the mostly uncharted δ-phase of KY₃F₁₀ remains a challenge. Thus, this paper offers the key to synthesizing both the α and the δ-phases of KY₃F₁₀ and also reports the first ultrasound-assisted process for the preparation of yttrium hydroxyfluorides. It is also unraveled the connection between the different pH-dependent reactions and the formation mechanisms of the compounds. In addition to this, the unique features of the Eu³⁺ ion have allowed to conduct a thorough study of the different materials and have endowed the compounds with photoluminescent properties. The results underscore a highly tunable optical response, with a wide gamut of color emissions (from orangish to red hues), lifetimes (from 7.9 ms to 1.1 ms) and quantum efficiencies (98–28%). The study unveils the importance of sonochemistry in obtaining luminescent fluorides with controlled crystal structures that can open up new avenues in the synthesis and design of inorganic materials.     

Sonochemical fabrication of gradient antibacterial materials based on Cu-Zn alloy

At present research, we highlight ultrasonic treatment as a new way to create materials with a gradient change of chemical or physical properties. We demonstrate the possibility to fabricate novel materials with biocide activity based on simple and cheap Cu-Zn alloy. In this research, we propose a green preparative technique for the sonication of an alloy in an alkali solution. The method leads to a significant visual change and differentiation of particles into three different fractions. Due to the chemical micro gradients in media near the solid surface under intensive sonication, fast formation of specific functional groups occurs on the particles’ surface. The particles were studied X-ray diffraction analysis (XRD) analysis, the field-emission scanning electron microscope (SEM) as well as electron backscatter diffraction (EBSD) mode, X-ray Photoelectron Spectroscopy (XPS), the differential pulse anodic stripping voltammetry (DPASV) technique. A strong correlation of both methods proves a redistribution of copper ions from Fraction I to Fraction III that influence for the antibacterial properties of the prepared material. The different biocidal activity was demonstrated for each separated Fraction that could be related to their different phase content and ability to release the different types of ions.     

Energetic balance in an ultrasonic reactor using focused or flat high frequency transducers

In order to undertake irradiation of polymer blocks or films by ultrasound, this paper deals with the measurements of ultrasonic power and its distribution within the cell by several methods. The electric power measured at the transducer input is compared to the ultrasonic power input to the cell evaluated by calorimetry and radiation force measurement for different generator settings. Results obtained in the specific case of new transducer types (composites and focused composites i.e., HIFU: high intensity focused ultrasound) provide an opportunity to conduct a discussion about measurement methods. It has thus been confirmed that these measurement techniques can be applied to HIFU transducers. For all cases, results underlined the fact that measurement of radiation pressure for power evaluation is more adapted to low powers (<15 W) and that measurement by calorimetry is a valid technique for global energy measurements. Composites and monocomponent transducers were compared and it appears that the presence of an adaptation glass plate reduces the efficiency of the monocomponent transducers. The distribution of ultrasonic intensity is qualitatively depicted by sono-chemiluminescence of luminol. Finally, the quantity of energy absorbed by samples placed in the sound field is determined and the temperature distribution monitored as a function of wall distance. This energetic balance allows us to understand the global behaviour of all experimental set-ups made up of a generator–transducer–liquid and sample.