Micrometric drilling of (meta-)studtite square platelets formed by pseudomorphic conversion of UO2 under high-frequency ultrasound.

Pseudomorphic transformations are related to chemical conversions of materials while conserving their shape and structural features. Structuring ceramic shapes this way can be used to tailor the physico-chemical properties of materials that can benefit particular applications. In the context of spent nuclear fuel storage interacting with radiolysis products, the sonochemical behavior of powdered UO2 was investigated in dilute aqueous solutions saturated with Ar/(20 %)O2 (20 °C). Optimized parameter settings enabled the complete conversion of UO2 micrometric platelets into uranyl peroxide precipitates, referred to as (meta-)studtite [(UO2(O2)(H2O)2)xH2O] with x = 2 or 4. While the most acidic conditions yielded elongated crystal shapes in agreement with a dissolution/reprecipitation mechanism, softer conditions allowed the pseudomorphic transformation of the platelet shape oxide suggesting a complex formation mechanism. For specific conditions, this unprecedented morphology was accompanied with the formation of a hole in the platelet center. Investigations revealed that the formation of the drilled polymorphs is related to a perfect blend of H+, in-situ generation of H2O2 and high-frequency ultrasound, and is most probably related to the sono-capillary effect. These insights pave the way for new sonochemical approaches dedicated to the preparation of material polymorphs tailoring specific structural properties.

Sonochemically-Induced Reduction of Alkenes to Alkanes with Ammonia.

With the progressive defossilization of our industry, hydrogen (H2 ) has been identified as a central molecule to store renewable electricity. In this context, ammonia (NH3 ) is now rapidly emerging as a promising hydrogen carrier for the future. This game change indirectly impacts the field of fine chemistry where hydrogenation reactions are widely deployed. In particular, the possibility of performing hydrogenation reactions using ammonia directly instead of hydrogen has become highly desirable but it remains a very difficult scientific task, which we address in this communication. Here we show that the N-H bond of NH3 can be cleaved within cavitation bubbles, generated by ultrasonic irradiation at a high frequency, leading to the in situ formation of a diimide, which then induces the hydrogenation of alkenes. Advantageously, this work does not involve any transition metal and releases N2 as a sole co-product.

Simultaneous H/D and 13C/12C Anomalous Kinetic Isotope Effects during the Sonolysis of Water in the Presence of Carbon Monoxide.

Splitting of water molecules driven by ultrasound plays a central role in sonochemistry. While studies of sonoluminescence revealed the formation of a plasma inside the cavitation bubble, much less is known about the contribution of plasma chemical processes to the sonochemical mechanisms. Herein, we report for the first time sonochemical processes in water saturated with pure CO. The presence of CO causes a large increase in the H/D kinetic isotope effect (KIE) to αH = 14.6 ± 1.8 in a 10% H2O/D2O mixture under 20 kHz ultrasound. The anomalous H/D KIE is attributed to electron quantum tunneling in the plasma produced by cavitation. In addition, CO2 formed simultaneously with hydrogen during the sonochemical process is enriched with the 13C isotope, which indicates a V-V pumping mechanism typical for non-equilibrium plasma. Both observed KIEs unambiguously point to the contribution of quantum effects in sonochemical mechanisms.

Conversion of Ammonia to Hydrazine Induced by High-Frequency Ultrasound.

Hydrazine is a chemical of utmost importance in our society, either for organic synthesis or energy use. The direct conversion of NH3 to hydrazine is highly appealing, but it remains a very difficult task because the degradation of hydrazine is thermodynamically more feasible than the cleavage of the N-H bond of NH3 . As a result, any catalyst capable of activating NH3 will thus unavoidably decompose N2 H4 . Here we show that cavitation bubbles, created by ultrasonic irradiation of aqueous NH3 at a high frequency, act as microreactors to activate and convert NH3 to NH species, without assistance of any catalyst, yielding hydrazine at the bubble-liquid interface. The compartmentation of in-situ-produced hydrazine in the bulk solution, which is maintained close to 30 °C, advantageously prevents its thermal degradation, a recurrent problem faced by previous technologies. This work also points towards a path to scavenge . OH radicals by adjusting the NH3 concentration.

Sonocatalytic degradation of EDTA in the presence of Ti and Ti@TiO2 nanoparticles.

The sonocatalytic degradation of EDTA (C0 = 5 10-3 M) in aqueous solutions was studied under 345 kHz (Pac = 0.25 W mL-1) ultrasound at 22-51 °C, Ar/20%O2, Ar or air, and in the presence of metallic titanium (Ti0) or core-shell Ti@TiO2 nanoparticles (NPs). Ti@TiO2 NPs have been obtained using simultaneous action of hydrothermal conditions (100-214 °C, autogenic pressure P = 1.0-19.0 bar) and 20 kHz ultrasound, called sonohydrothermal (SHT) treatment, on Ti0 NPs in pure water. Ti0 is composed of quasi-spherical particles (30-150 nm) of metallic titanium coated with a metastable titanium suboxide Ti3O. SHT treatment at 150-214 °C leads to the oxidation of Ti3O and partial oxidation of Ti0 and formation of nanocrystalline shell (10-20 nm) composed of TiO2 anatase. It was found that Ti0 NPs do not exhibit catalytic activity in the absence of ultrasound. Moreover, Ti0 NPs remain inactive under ultrasound in the absence of oxygen. However, significant acceleration of EDTA degradation was achieved during sonication in the presence of Ti0 NPs and Ar/20%O2 gas mixture. Coating of Ti0 with TiO2 nanocrystalline shell reduces sonocatalytic activity. Pristine TiO2 anatase nanoparticles do not show a sonocatalytic activity in studied system. Suggested mechanism of EDTA sonocatalytic degradation involves two reaction pathways: (i) sonochemical oxidation of EDTA by OH/HO2 radicals in solution and (ii) EDTA oxidation at the surface of Ti0 NPs in the presence of oxygen activated by cavitation event. Ultrasonic activation most probably occurs due to the local heating of Ti0/O2 species at cavitation bubble/solution interface.

Physical and chemical characterization of shock-induced cavitation.

A strong impact on a water surface induces a shock wave propagation with a significant pressure variation leading to cavitation bubble formation. A new shock induced cavitation reactor described in this work was characterized by physical and chemical techniques. Water hammer model verification with Joukowsky approach allowed to determine the wave speed propagation and gas fraction in water submitted to shock. These values were used for frequency analysis and compared with direct bubble visualization in order to estimate the influence of the experimental parameters on the shock-induced cavitation. Thereby, the shock wave contains a broad spectrum as decomposed into frequencies. This multi-frequency nature induces heterogeneous bubbles with calculated radii of 0.01 to 3.5 mm and observed radii of 0.01 to 2.8 mm depending on experimental conditions (initial pressure, impact height, gas atmosphere). For the first time, the formation of hydroxyl radicals was proven under impact-induced cavitation. The concentration of radicals increases with increasing number of successive impacts, reaching ca. 1.3 µmol.L-1 after 500 impacts in the presence of 20% O2-Ar as saturating gas. Radical generation seems to be relatively independent of the impact height but strongly depend on the type of gas saturating water, being substantially lower in the presence of air. Moreover, radical generation increases when decreasing the initial pressure and depends on the frequency at which water is impacted by the piston. Nevertheless, yield of OH radicals during shock-induced cavitation remains much lower than that produced by power ultrasound.

Selective radical depolymerization of cellulose to glucose induced by high frequency ultrasound.

The depolymerization of cellulose to glucose is a challenging reaction and often constitutes a scientific obstacle in the synthesis of downstream bio-based products. Here, we show that cellulose can be selectively depolymerized to glucose by ultrasonic irradiation in water at a high frequency (525 kHz). The concept of this work is based on the generation of H˙ and ˙OH radicals, formed by homolytic dissociation of water inside the cavitation bubbles, which induce the cleavage of the glycosidic bonds. The transfer of radicals on the cellulose particle surfaces prevents the side degradation of released glucose into the bulk solution, allowing maintaining the selectivity to glucose close to 100%. This work is distinguished from previous technologies in that (i) no catalyst is needed, (ii) no external source of heating is required, and (iii) the complete depolymerization of cellulose is achieved in a selective fashion. The addition of specific radical scavengers coupled to different gaseous atmospheres and ˙OH radical dosimetry experiments suggested that H˙ radicals are more likely to be responsible for the depolymerisation of cellulose.

Hypothesis about electron quantum tunneling during sonochemical splitting of water molecule.

Quantum tunneling in chemistry is often attributed to the processes at low or near room temperatures when the rate of thermal reactions becomes far less than the rate of quantum tunneling. However, in some rapid processes, quantum tunneling can be observed even at high temperatures. Herein, we report the experimental evidence for anomalous H/D kinetic isotope effect (KIE) during sonochemical dissociation of water molecule driven by 20 kHz power ultrasound measured in H2O/D2O mixtures saturated with Ar or Xe. Hydrogen released during ultrasonic treatment is enriched by light isotope. The observed H/D KIE (α = 2.15-1.50) is much larger than what is calculated assuming a classical KIE for Tg = 5000 K (α = 1.15) obtained from the sonoluminescence spectra in H2O and D2O. Furthermore, the α values sharply decrease with increasing of H2O content in H2O/D2O mixtures reaching a steady-state value close to α = 1.50, which also cannot be explained by O-H/O-D zero-point energy difference. We suggest that these results can be understood in terms of quantum electron tunneling occurring in nonequilibrium picosecond plasma produced at the last stage of cavitation bubble collapse. Thermal homolytic splitting of water molecule is inhibited by extremely short lifetime of such plasma. On the contrary, immensely short traversal time for electron tunneling in water allows H2O dissociation by quantum tunneling mechanism.

Insights into the sonochemical synthesis and properties of salt-free intrinsic plutonium colloids.

Fundamental knowledge on intrinsic plutonium colloids is important for the prediction of plutonium behaviour in the geosphere and in engineered systems. The first synthetic route to obtain salt-free intrinsic plutonium colloids by ultrasonic treatment of PuO2 suspensions in pure water is reported. Kinetics showed that both chemical and mechanical effects of ultrasound contribute to the mechanism of Pu colloid formation. In the first stage, fragmentation of initial PuO2 particles provides larger surface contact between cavitation bubbles and solids. Furthermore, hydrogen formed during sonochemical water splitting enables reduction of Pu(IV) to more soluble Pu(III), which then re-oxidizes yielding Pu(IV) colloid. A comparative study of nanostructured PuO2 and Pu colloids produced by sonochemical and hydrolytic methods, has been conducted using HRTEM, Pu LIII-edge XAS, and O K-edge NEXAFS/STXM. Characterization of Pu colloids revealed a correlation between the number of Pu-O and Pu-Pu contacts and the atomic surface-to-volume ratio of the PuO2 nanoparticles. NEXAFS indicated that oxygen state in hydrolytic Pu colloid is influenced by hydrolysed Pu(IV) species to a greater extent than in sonochemical PuO2 nanoparticles. In general, hydrolytic and sonochemical Pu colloids can be described as core-shell nanoparticles composed of quasi-stoichiometric PuO2 cores and hydrolyzed Pu(IV) moieties at the surface shell.

Ultrasound-assisted reductive dissolution of CeO2 and PuO2 in the presence of Ti particles.

PuO2 is considered an important material for current and future nuclear fuel; however it is a very refractive compound towards dissolution. Among other techniques, its reprocessing can be performed via complexing dissolution in concentrated and boiling nitric acid containing hydrofluoric acid, or via oxidant dissolution in the presence of reagents with redox couples having high potentials such as Ce(iv)/Ce(iii), or Ag(ii)/Ag(i). Reductive dissolution can be performed under softer conditions and is considered an alternative to these methods which may suffer from several drawbacks (corrosion, effluent management, compatibility with nuclear waste disposal, etc.). In this study, a sonochemical and reductive approach is investigated for PuO2 dissolution under relatively mild conditions. At the first stage, the experiments are performed with CeO2 as an inactive surrogate for PuO2. The quantitative dissolution of both oxides can be achieved under ultrasound (20 kHz, 0.35-0.70 W mL(-1)) in 0.5 M HNO3/0.1 M [N2H5NO3]/2 M HCOOH sparged with Ar at 33-35 °C in the presence of Ti particles as a generating source of reductive species. Ultrasound enables the depassivation of the Ti surface (usually strongly passivated in nitric solutions) through acoustic cavitation which then allows further generation of the intermediate Ti(iii) reductive species. Dissolution rates and yields can be further increased with the injection of dilute fluoride aliquots (NH4F or HF) in the sonicated solution to favor Ti chemical depassivation. The rapid and complete dissolution of PuO2 under selected conditions is accompanied by Pu(iii) accumulation in solution.

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.

Effect of operational conditions on sonoluminescence and kinetics of H2O2 formation during the sonolysis of water in the presence of Ar/O2 gas mixture.

Ultrasonic frequency is a key parameter determining multibubble sonoluminescence (MBSL) spectra of water saturated with Ar/O2 gas mixtures. At 20 kHz, the MBSL is quenched by oxygen. By contrast, at high-frequency ultrasound the maximal MBSL intensity is observed in the presence of Ar/20%O2 gas mixture. Nevertheless, oxygen has no influence on the shape of MBSL spectra. The effect of oxygen on MBSL is explained by oxygen dissociation inside the collapsing bubble which is much more effective at high ultrasonic frequency compared to 20 kHz ultrasound. In contrast to MBSL, a higher yield of H2O2 is observed in Ar/20%O2 gas mixture whatever the ultrasonic frequency. At 20°C and 20% of oxygen the maximal yield of H2O2 is observed at 204-362 kHz. The maximal yield of H2O2 is shifted to 613kHz when the bulk temperature is raised up to 40°C. Coupling of high-frequency ultrasound with mechanical stirring and intensive Ar/O2 bubbling improves H2O2 production. Comparison of MBSL and sonochemistry allowed to conclude that H2O2 is formed from non-excited OH (X(2)Π) and HO2 radicals. Finally, it was shown that at the studied conditions the efficiency of ultrasonic degassing is hardly influenced by frequency.

Influence of ultrasonic frequency on Swan band sonoluminescence and sonochemical activity in aqueous tert-butyl alcohol solutions.

The multibubble sonoluminescence (MBSL) spectra of t-BuOH aqueous solutions submitted to power ultrasound at 20, 204, 362, and 613 kHz show emissions for the Δυ = -1 to Δυ = +2 vibrational sequences of C2* Swan system (d(3)Πg → a(3)Πu). The Δυ=+2 emission overlaps with the CH(A-X) emission band. The maximal Swan band emission is observed when the MBSL of water itself is almost completely quenched. In general, MBSL is more intense at high-frequency compared to 20 kHz ultrasound. However, in the presence of Xe, the MBSL of C2* at 20 kHz is so bright that it can be seen by the unaided eye as a blue glow in the close vicinity of the ultrasonic tip. The intensity of the C2* band emission exhibits a maximum vs t-BuOH concentration: 0.1-0.2 M at 20 kHz and (1-8) × 10(-3) M at high-frequency ultrasound. Such a huge difference is attributed to a much smaller bubble size at high ultrasonic frequency or, in other words, to a much higher bubble surface/volume ratio providing more efficient saturation of the bubble interior with t-BuOH vapors and to the fact that high frequency bubbles remain active for many more cycles than 20 kHz ones, thus accumulating more hydrocarbon decomposition products. Simulation of the emission spectra using Specair software demonstrated the absence of thermal equilibrium for C2* radicals (Tv > Tr), where Tv and Tr are the vibrational and the rotational temperature, respectively. In Ar, Tv decreases with increasing t-BuOH concentration reaching a steady value in the concentration domain that corresponds to C2* emission maximum intensity. In the presence of Xe an extremely high Tv is obtained, which is explained by the relatively low ionization potential of Xe providing a higher electron temperature of nonequilibrium plasma generated during bubble collapse. Analysis of the gaseous products of t-BuOH sonolysis reveals a significant sonochemical activity even at high t-BuOH concentration when MBSL is totally quenched, indicating that drastic conditions could be produced also within nonsonoluminescing cavitation bubbles.

Activating molecules, ions, and solid particles with acoustic cavitation.

The chemical and physical effects of ultrasound arise not from a direct interaction of molecules with sound waves, but rather from the acoustic cavitation: the nucleation, growth, and implosive collapse of microbubbles in liquids submitted to power ultrasound. The violent implosion of bubbles leads to the formation of chemically reactive species and to the emission of light, named sonoluminescence. In this manuscript, we describe the techniques allowing study of extreme intrabubble conditions and chemical reactivity of acoustic cavitation in solutions. The analysis of sonoluminescence spectra of water sparged with noble gases provides evidence for nonequilibrium plasma formation. The photons and the "hot" particles generated by cavitation bubbles enable to excite the non-volatile species in solutions increasing their chemical reactivity. For example the mechanism of ultrabright sonoluminescence of uranyl ions in acidic solutions varies with uranium concentration: sonophotoluminescence dominates in diluted solutions, and collisional excitation contributes at higher uranium concentration. Secondary sonochemical products may arise from chemically active species that are formed inside the bubble, but then diffuse into the liquid phase and react with solution precursors to form a variety of products. For instance, the sonochemical reduction of Pt(IV) in pure water provides an innovative synthetic route for monodispersed nanoparticles of metallic platinum without any templates or capping agents. Many studies reveal the advantages of ultrasound to activate the divided solids. In general, the mechanical effects of ultrasound strongly contribute in heterogeneous systems in addition to chemical effects. In particular, the sonolysis of PuO2 powder in pure water yields stable colloids of plutonium due to both effects.

Thermal and sonochemical synthesis of porous (Ce,Zr)O2 mixed oxides from metal ß-diketonate precursors and their catalytic activity in wet air oxidation process of formic acid.

Porous (Ce0.5Zr0.5)O2 solid solutions were prepared by thermolysis (T=285 °C) or sonolysis (20 kHz, I=32 W cm(-2), Pac=0.46 W mL(-1), T=200 °C) of Ce(III) and Zr(IV) acetylacetonates in oleylamine or hexadecylamine under argon followed by heat treatment of the precipitates obtained in air at 450 °C. Transmission Electron Microscopy images of the samples show nanoparticles of ca. 4-6 nm for the two synthetic approaches. The powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray and µ-Raman spectroscopy of solids obtained after heat treatment indicate the formation of (Ce0.5Zr0.5)O2 solid solutions with a metastable tetragonal crystal structure for the two synthetic routes. The specific surface area of the samples varies between 78 and 149 m(2) g(-1) depending on synthesis conditions. The use of Barrett-Joyner-Halenda and t-plot methods reveal the formation of mixed oxides with a hybrid morphology that combines mesoporosity and microporosity regardless of the method of preparation. Platinum nanoparticles were deposited on the surface of the mixed oxides by sonochemical reduction of Pt(IV). It was found that the materials prepared by sonochemistry exhibit better resistance to dissolution during the deposition process of platinum. X-ray photoelectron spectroscopy analysis shows the presence of Pt(0) and Pt(II) on the surface of mixed oxides. Porous (Ce0.5Zr0.5)O2 mixed oxides loaded with 1.5%wt. platinum exhibit high activity in catalytic wet air oxidation of formic acid at 40 °C.

Sonochemical deposition of platinum nanoparticles on polymer beads and their transfer on the pore surface of a silica matrix.

This study reported the sonochemical deposition of platinum on the surface of polystyrene beads (PSBs) and the transfer of obtained Pt nanoparticles into a porous silica matrix using the PSB as a sacrificial template. Platinum nanoparticle deposition was ensured by the sonochemical reduction of Pt(IV) at room temperature in latex solutions containing polystyrene beads in the presence of formic acid under Ar or under Ar/CO atmosphere without any additives. After ultrasonic treatments for few hours, well dispersed Pt nanoparticles within the range of 3-5 nm deposited on PSB were obtained in both studied conditions. Samples were then mixed with TEOS, dried, and heated at 450°C to ensure the PSB removal from the silica matrix. TEM and SEM results clearly show that final silica pore size is within the same order of magnitude than initial PSB. Finally, platinum decorated silica matrix with chosen pore sizes was successfully prepared.

Mechanism of Pt(IV) sonochemical reduction in formic acid media and pure water.

Sonochemical synthesis of platinum nanoparticles (Pt NPs) in formic acid solutions and pure water was investigated using a 20 kHz ultrasonic irradiation. The obtained results gave new insights on the underneath Pt(IV)  reduction mechanism in formic acid media under argon and in pure water under Ar/CO atmosphere. It was shown that in pure water sonochemical reduction of platinum ions occurs by hydrogen issued from homolytic water molecule split. Pt(IV) ion reduction appears to be a very slow process under argon atmosphere in pure water due to formation of oxidizing species like OH radicals and H(2)O(2) leading to reoxidation of intermediate Pt(II)  ions. Sonochemical reduction is accelerated manifold in the presence of formic acid or Ar/CO gas mixture. Solution and gas-phase analyses reveal that both CO and HCOOH act as OH(.) radical scavenger and reducing agent under ultrasonic irradiation. Their ability to reduce platinum ions at room temperature is enhanced due to the local heating in the liquid shell surround the cavitation bubble. An innovative synthesis route for monodispersed Pt NPs in pure water without any templates or capping agents in the presence of Ar/CO gas mixture is then proposed. Obtained Pt NPs within the range of 2-3 nm exhibited a strong stability towards sedimentation in water. Since Ar/CO atmosphere is the only restriction of the process, this procedure can be applied in various media and is also compatible with a large array of experimental conditions.

Effect of ultrasonic frequency on the mechanism of formic acid sonolysis.

The kinetics and mechanism of formic acid sonochemical degradation were studied at ultrasonic frequencies of 20, 200, and 607 kHz under argon atmosphere. Total yield of HCOOH sonochemical degradation increases approximately 6-8-fold when the frequency increased from 20 to 200 or to 607 kHz. At low ultrasonic frequencies, HCOOH degradation has been attributed to oxidation with OH(•) radicals from water sonolysis and to the HCOOH decarboxylation occurring at the cavitation bubble-liquid interface. With high-frequency ultrasound, the sonochemical reaction is also influenced by HCOOH dehydration. Whatever the ultrasonic frequency, the sonolysis of HCOOH yielded H(2) and CO(2) in the gas phase as well as trace amounts of oxalic acid and formaldehyde in the liquid phase. However, CO and CH(4) formations were only detected under high-frequency ultrasound. The most striking difference between low-frequency and high-frequency ultrasound is that the sonolysis of HCOOH at high ultrasonic frequencies initiates Fischer-Tropsch hydrogenation of carbon monoxide.

First synthesis of uranyl aluminate nanoparticles.

This paper describes, for the first time, a simple method for the synthesis of uranyl aluminate (URAL) nanoparticles. URAL was prepared by U(VI) hydrolytic precipitation with ammonia at pH = 11 in the presence of mesoporous alumina MSU-X under 20 kHz of sonication followed by annealing of the obtained solids at 800 degrees C. TEM, XAFS, powder XRD, and (27)Al MAS NMR studies revealed that the speciation of uranium in this system strongly depends on uranium concentration. The sample with 5 wt % of uranium yields air-stable nanoparticles ( approximately 5 nm) of URAL. Presumably, UO(2)(2+) cations in this compound are coordinated with bidentate AlO(2)(-) groups. The increase of uranium concentration to 30 wt % causes mostly formation of U(3)O(8) fine particles ( approximately 50 nm) and small amounts of URAL.