Sonochemical conversion of CO2 into hydrocarbons: The Sabatier reaction at ambient conditions

In this study, we investigated an alternative method for the chemical CO₂ reduction reaction in which power ultrasound (488 kHz ultrasonic plate transducer) was applied to CO₂-saturated (up to 3%) pure water, NaCl and synthetic seawater solutions. Under ultrasonic conditions, the converted CO₂ products were found to be mainly CH₄, C₂H₄ and C₂H₆ including large amount of CO which was subsequently converted into CH₄. We have found that introducing molecular H₂ plays a crucial role in the CO₂ conversion process and that increasing hydrogen concentration increased the yields of hydrocarbons. However, it was observed that at higher hydrogen concentrations, the overall conversion decreased since hydrogen, a diatomic gas, is known to decrease cavitational activity in liquids. It was also found that 1.0 M NaCl solutions saturated with 2% CO₂ + 98% H₂ led to maximum hydrocarbon yields (close to 5%) and increasing the salt concentrations further decreased the yield of hydrocarbons due to the combined physical and chemical effects of ultrasound. It was shown that CO₂ present in a synthetic industrial flue gas (86.74% N₂, 13% CO₂, 0.2% O₂ and 600 ppm of CO) could be converted into hydrocarbons through this method by diluting the flue gas with hydrogen. Moreover, it was observed that in addition to pure water, synthetic seawater can also be used as an ultrasonicating media for the sonochemical process where the presence of NaCl improves the yields of hydrocarbons by ca. 40%. We have also shown that by using low frequency high-power ultrasound in the absence of catalysts, it is possible to carry out the conversion process at ambient conditions i.e., at room temperature and pressure. We are postulating that each cavitation bubble formed during ultrasonication act as a “micro-reactor” where the so-called Sabatier reaction -$C{O}_2+4H_2\stackrel{\mathit{Ultrasonication}}{\to }C{H}_4+2H_{2}O$ - takes place upon collapse of the bubble. We are naming this novel approach as the “Islam-Pollet-Hihn process”.     

Sonochemistry and its dosimetry

The effects of ultrasound originate primarily in acoustic cavitation. The cavitation bubbles collapse violently enough to lead to interesting chemical effects, known as sonochemistry. There is a great need to relate the efficiency of sonochemical reaction to the energy of ultrasonic irradiation used to produce them. In this paper, three OH radical dosimeters, Fricke dosimeter, terephthalate dosimeter, and iodide dosimeter, are compared from the analytical point of view. The dosimeters based on photometry, i.e., Fricke and iodide, produced reliable and reproducible results, but the sensitivity is not enough for special applications, such as chemical monitoring of single bubble cavitation. The dosimeter based on fluorometry, terephthalate dosimeter, offered high sensitivity, 1.2×10¹¹ molecules ml⁻¹. The effects of some experimental parameters in sonochemistry, i.e., solution temperature and the dissolved gas species, were evaluated with the dosimeters.     

Sonochemical synthesis of mass single-crystal PbS nanobelts

Based on sonochemical technique, large-scale PbS nanobelts are successfully synthesized in the mixed solution of PbCl₂ and Na₂S₂O₃. These nanobelts are characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy (TEM), selected area electronic diffraction, energy dispersive X-ray spectroscopy, and high-resolution TEM. The as-synthesized PbS nanobelts have width of about 80 nm, length up to several millimeters, and width-to-thickness ratio of about 5. In addition, the growth mechanism of PbS nanobelts is suggested.     

Depositing nanoparticles inside millimeter-size hollow tubing

The inner and the outer walls of hollow tubing with an inner diameter of 0.4-0.9 cm and an outer diameter of 0.6-1.3 cm were coated with silver nanoparticles (NPs) by a one-step process using ultrasound irradiation. The structure and morphology of the nanoparticles (NPs) inside the hollow tubing and on the outer surface were characterized using methods such as XRD, TEM, HR-TEM, and HRSEM. The inner surface of the tubing was found to be coated with more silver than the outer surface. The coating was done on tubing made of rubber, PVC, Teflon and polyethylene. Sonochemistry is demonstrated as a method for depositing nanoparticles on the inner wall of a tube.     

Ultrasound-enhanced chemiluminescence tomography in biological tissue

This paper reports ultrasound-assisted optical imaging of chemiluminescent probes in biological tissue. A focused low power ultrasound sonochemically enhances a peroxyoxalate chemiluminescence (CL) that involves indocyanine green (ICG) as luminescent pigments. By scanning the focus, it produces tomographic images of CL in scattering media. The authors demonstrate imaging using a slab of porcine muscle measuring 50 × 50 × 75 mm, in which a capsuled CL reagent is embedded at 25 mm depth. Spatial resolution of imaging and concentration characteristics of CL reagents to enhanced CL intensity are also studied to evaluate the potential for use in bio-imaging applications with exploring the CL enhancement mechanisms. CL enhancement ratio, defined as the ratio of ultrasonically enhanced CL intensity to the base intensity without ultrasound irradiation, was found to be constant even in varying ICG and oxidizer concentrations, implying to be applicable for quantitative determination of these molecules.     

Sonochemical coating of magnetite nanoparticles with silica

Magnetite nanoparticles were coated with silica through the hydrolysis and condensation of tetraethyl orthosilicate (TEOS) under ultrasonic irradiation. The ultrasonic irradiation was used to prevent the agglomeration of the magnetite particles and accelerate the hydrolysis and condensation of TEOS. TEM, DLS, XRF, VSM, TG and sedimentation test were used to characterize the silica-coated magnetite particles. The dispersibility of silica-coated magnetite particles in aqueous solution was improved significantly and the agglomerate particle size was decreased to 110 nm. It was found that the agglomerate particle size of silica-coated magnetite particles was mainly decided by the coating temperature and the pH value in the silica-coating process. The weight ratio of silica in silica-coated magnetite particles was mainly decided by the pH value in the silica-coating process. The dispersibility of silica-coated magnetite particles was mainly decided by the agglomerate particle size of the suspension. The oxidation of magnetite particles in air was limited through the coated silica. The magnetism of silica-coated magnetite particles decreased slightly after silica-coating.     

High-frequency acoustic emissions generated by a 20 kHz sonochemical horn processor detected using a novel broadband acoustic sensor: a preliminary study

This paper describes the application of a novel broadband acoustic sensor to evaluating the acoustic emissions from cavitation produced by a typical commercial 20 kHz sonochemical horn processor. Investigations of the reproducibility of the processor, and of the variation in cavitation emissions as a function of output setting and sensor location are described, and resulting trends discussed in terms of the broadband integrated power in the megahertz frequency range. Companion studies with a conventional membrane hydrophone have illustrated for the first time that cavitation emissions produced by a sonochemical horn processor can extend to frequencies beyond 20 MHz, and the sensor shows that significant nonlinearity can be seen in measured cavitation activity with increasing nominal output power.     

Characterization of transient cavitation activity during sonochemical modification of magnesium particles

Investigation of the cavitation activity during ultrasonic treatment of magnesium particles during nanostructuring has been performed. Cavitation activity is recorded in the continuous mode after switching the ultrasound on with the use of ICA-5DM cavitometer. It has been demonstrated that this characteristic of the cavitation zone may be varied in a wide range of constant output parameters of the generator. The speed and nature of the cavitation activity alteration depended on the concentration of Mg particles in the suspension and the properties of the medium in which the sonochemical treatment has been performed. Three stages of the cavitation area evolution can be distinguished: 1 – the initial increase in cavitation activity, 2 – reaching a maximum with a subsequent decrease, and 3 – reaching the plateau (or the repeated cycles with feedback loops of enlargement/reduction of the cavitation activity).The ultrasonically treated magnesium particles have been characterized by scanning electron microscopy, X-ray diffraction analysis and thermal analysis. Depending on the nature of the dispersed medium the particles can be characterized by the presence of magnesium hydroxide (brucite) and magnesium hydride. It is possible to reach the incorporation of magnesium hydride in the magnesium hydroxide/magnesium matrix by varying the conditions of ultrasonic treatment (duration of treatment, amplitude, dispersed medium etc.). The influence of the magnesium reactivity is also confirmed by the measurements of cavitation activity in organic dispersed media (ethanol, ethylene glycol) and their aqueous mixtures.     

Self-cleaning of SiO2-TiO2 coating: Effect of sonochemical synthetic parameters on the morphological,mechanical, and photocatalytic properties of the films

Among the different properties of the hydrophobic semiconductor surfaces, self-cleaning promoted by solar illumination is probably one of the most attractive from the technological point of view. The use of sonochemistry for nanomaterials' synthesis has been recently employed for the associated shorter reaction times and efficient route for control over crystal growth and the management of the resulting material's photocatalytic properties. Moreover, the sol–gel method coupled to sonochemistry modifies the chemical environment, with reactive species such as •OH and H₂O₂, which yield a homogeneous synthesis. Therefore, in the following investigation, the sol–gel method was coupled to sonochemistry to synthesize a SiO₂@TiO₂ composite, for which the sonochemical amplitude of irradiation was varied to determine its effect on the morphology and mechanical and self-cleaning properties. SEM and AFM characterized the samples of SiO₂@TiO₂ composite, and while the micrographs indicate that a high ultrasonic energy results in an amorphous SiO₂@TiO₂ composite with a low rugosity, which was affected in the determination of the contact angle on the surface. On the other hand, FTIR analysis suggests a significant change in both SiO₂-SiO and SiO₂-TiO₂ chemical bonds with changes in vibrations and frequency, corroborating an important influence of the sonochemical energy contribution to the hydrolysis process. Raman spectroscopy confirms the presence of an amorphous phase of silicon dioxide; however, the vibrations of TiO₂ were not visible. The evaluation of hydrophobic and self-cleaning properties shows a maximum of ultrasonic energy needed to improve the contact angle and rhodamine B (RhB) removal.     

Sonochemically prepared hierarchical MFI-type zeolites as active catalysts for catalytic ethanol dehydration

In this paper, the ultrasonic-assisted desilication technique was reported as an attractive and efficient way for the preparation of hierarchical zeolites with MFI structure type. The prepared materials were used as active catalysts for the dehydration of ethanol into diethyl ether and ethylene. For all catalysts, the selectivity to diethyl ether was ca 95% or higher up to 210 °C, with catalytic activity in the range of 40–68%. In case of desilicated zeolites, at 270–290 °C, the conversion of ethanol was full with selectivity to ethylene ca 80%. MFI-type commercial zeolite was treated with a sodium and/or tetrabutylammonium hydroxide aqueous solutions (NaOH or NaOH/TBAOH) for 30 min. In the case of the application of ultrasounds, a QSonica Q700 sonicator (60 W and 20 kHz) equipped with a “1” diameter horn was used. In all cases, desilication was performed in an ice bath in order to keep the procedure conditions at low temperature.It was indicated that the use of ultrasounds during desilication procedure caused higher extraction of silicon and aluminum, which was connected with an elevated mesoporosity in relation to the samples modified in the absence of ultrasounds. Ultrasonic-assisted treatment of MFI-type zeolite caused also an apparent formation of numerous holes inside zeolite grains, resembling the look of “swiss cheese”. Furthermore, it was indicated that the samples prepared using ultrasonic irradiation exhibited enhanced catalytic properties in the dehydration of ethanol. For instance, MFI-type zeolite treated with NaOH/TBAOH alkaline mixture containing 10 mol% of TBAOH in the presence of ultrasounds (M−10 s) demonstrated higher both conversion of ethanol (59% vs. 47%) and selectivity to diethyl ether (95% vs. 93%) in comparison with zeolite modified conventionally (M−10c).The best catalyst was zeolite ultrasonically desilicated with NaOH/TBAOH solution of 70 mol% of TBAOH (M-70s). Generally, this catalyst indicated the highest conversion of ethanol, very high selectivity to diethyl ether (94-100%) at 150-210  °C and the highest selectivity to ethylene among investigated catalysts (21%, 66% and 84%) at 230  °C, 250 ^oC and 270  °C.