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.     

Sonication enhances the stability of MnO2 nanoparticles on silk film template for enzyme mimic application

We have developed an in-situ method using sonication (3 mm probe sonicator, 30 W, 20 kHz) and auto-reduction (control) to study the mechanism of the formation of manganese dioxide (MnO₂) on a solid template (silk film), and its resulting enzymatic activity on tetramethylbenzidine (TMB) substrate. The fabrication of the silk film was first optimized for stability (no degradation) and optical transparency. A factorial approach was used to assess the effect of sonication time and the initial concentration of potassium permanganate (KMnO₄). The result indicated a significant correlation with a fraction of KMnO₄ consumed and MnO₂ formation. Further, we found that the optimal process conditions to obtain a stable silk film with highly catalytic MnO₂ nanoparticles (NPs) was 30 min of sonication in the presence of 0.5 mM of KMnO₄ at a temperature of 20–24 °C. Under the optimal condition, we monitored in-situ the formation of MnO₂ on the silk film, and after thorough rinsing, the in-situ catalysis of 0.8 mM of TMB substrate. For control, we used the auto-reduction of KMnO₄ onto the silk film after about 16 h. The result from single-wavelength analysis confirmed the different kinetics rates for the formation of MnO₂ via sonication and auto-reduction. The result from the multivariate component analysis indicated a three components route for sonication and auto-reduction to form MnO₂-Silk. Overall, we found that the smaller size, more mono-dispersed, and deeper buried MnO₂ NPs in silk film prepared by sonication, conferred a higher catalytic activity and stability to the hybrid material.     

Sonication-Assisted Synthesis of Bimetallic Hg/Pd Alloy Nanoparticles for Catalytic Reduction of Nitrophenol and its Derivatives

In this article, we report a facile approach for the synthesis of an inexpensive catalyst of bimetallic Hg/Pd alloys comprising nanoparticles with various structures using a unique ultrasonic reaction that is conducted without the use of any reducing agent. The nanoparticles of Hg/Pd alloys (HgPd and Hg₂Pd₅) were achieved for the first time by sonicating an aqueous solution of Palladium (II) nitrate with metallic liquid mercury, as evidenced by XRD. EDS further confirmed the presence of Pd and Hg elements in the alloy. The surface morphology and structure of the nanoparticles have been systematically investigated by HRSEM, HRTEM and SAED pattern. In order to explore the catalytic activity of the as-synthesized nanoalloys, the catalytic reduction of 4-nitrophenol and a few other nitrophenol derivatives were investigated. Excellent catalytic activity was obtained for Hg/Pd (1:1) alloy, and the rate constant for the reduction of 4-NP with Hg/Pd at room temperature was found to be 58.4 × 10⁻³ s⁻¹, which is possibly the highest ever reported. The catalyst exhibited superior stability and reusability when compared with those reported in the literature for other catalysts based on noble metals.     

Relationship between the radial dynamics and the chemical production of a harmonically driven spherical bubble

The sonochemical activity and the radial dynamics of a harmonically excited spherical bubble are investigated numerically. A detailed model is employed capable to calculate the chemical production inside the bubble placed in water that is saturated with oxygen. Parameter studies are performed with the control parameters of the pressure amplitude, the forcing frequency and the bubble size. Three different definitions of collapse strengths (extracted from the radius vs. time curves) are examined and compared with the chemical output of various species. A mathematical formula is established to estimate the chemical output as a function of the collapse strength; thus, the chemical activity can be predicted without taking into account the chemical kinetics into the bubble model. The calculations are carried out by an in-house code exploiting the high processing power of professional graphics cards (GPUs).The results shown that chemical activity can be approximated qualitatively from the values of relative expansion. This could be helpful in order to optimise chemical output of sonochemical reactors either from measurement data or simulations as well.     

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.