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A new air and moisture stable antimony thiolate compound has been prepared that spontaneously forms stable hollow vesicles. Structural data reveals that pnictogen bonding drives the self-assembly of these molecules into a reversed bilayer. The ability to make these hollow, spherical, and chemically and temporally stable vesicles that can be broken and reformed by sonication allows these systems to be used for encapsulation and compartmentalisation in organic media. This was demonstrated through the encapsulation and characterization of several small organic reporter molecules., (This journal is © The Royal Society of Chemistry 2020.)

Relatively little is known concerning the application of concurrent and coaxial multi-frequency ultrasound on the facilitation of chemical reactivity. When two or more acoustic frequencies are input into a solution, frequencies corresponding to the sum of the frequencies with an amplitude related to the difference between the two frequencies (both known in acoustics as heterodyne frequencies) are produced. Given the fact that cavitation dynamics are dependent upon frequency and power among other variables, the generation of additional waves should produce a situation where the cavitation bubbles produced by the two coincident frequencies are out of resonance with the heterodyne frequency, resulting in an increase in cavitation collapse efficiency. The resulting cavitation efficiency is expected to be higher than that which is observed from the simple sum of the acoustic energy transferred from each single frequency. As such, the energy and cavitation efficiency of this technique for bond breakage and formation is expected to be significantly higher than using either a single ultrasonic frequency or two frequencies acting separately. In this study we have embarked on a comparison of the efficacy of heterodyne sonochemistry with more traditional single-frequency or dual frequency ultrasound where the heterodyne frequency is zero. As a prototypical reaction, we have explored the effects of multi-frequency ultrasound on the degradation of acid orange, a common industrial colorant. An increase in the degradation rate by a factor of 500% was observed using incident frequencies of 305 and 310 kHz heterodyne ultrasound (5 kHz heterodyne) compared with what would be expected theoretically were the two frequencies to act independently. Reasons for the increase in efficiency are discussed., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The synthesis, characterization, photophysical properties, theoretical calculations, and catalytic applications of 2,9-di(aryl)-1,10-phenanthroline copper(i) complexes are described. Specifically, this study made use of di(aryl)-1,10-phenanthroline ligands including 2,9-di(4-methoxyphenyl)-1,10-phenanthroline (1), 2,9-di(4-hydroxyphenyl)-1,10-phenanthroline (2), 2,9-di(4-methoxy-3-methylphenyl)-1,10-phenanthroline (3), and 2,9-di(4-hydroxy-3-methylphenyl)-1,10-phenanthroline (4). The 2 : 1 ligand-to-metal complexes, as PF 6 - salts, i.e., ([Cu·(1) 2 ]PF 6 , [Cu·(2) 2 ]PF 6 , [Cu·(3) 2 ]PF 6 , and [Cu·(4) 2 ]PF 6 ) have been isolated and characterized. The structures of ligands 1 and 2 and complexes [Cu·(1) 2 ]PF 6 and [Cu·(3) 2 ]PF 6 have been determined by single-crystal X-ray analysis. The photoredox catalytic activity of these copper(i) complexes was investigated in an atom-transfer radical-addition (ATRA) reaction and the results showed fairly efficient activity, with a strong wavelength dependence. In order to better understand the observed catalytic activity, photophysical emission and absorption studies, and DFT calculations were also performed. It was determined that when the excitation wavelength was appropriate for exciting into the LUMO+1 or LUMO+2, catalysis would occur. On the contrary, excitations into the LUMO resulted in no observable catalysis. In light of these results, a mechanism for the ATRA photoredox catalytic cycle has been proposed.

Sonochemically prepared PtRu (3 : 1) and Johnson Matthey PtRu (1 : 1) were analyzed by X-ray absorption spectroscopy in operating liquid feed direct methanol fuel cells. The total metal loadings were 4 mg cm(-2) unsupported catalysts at the anode and cathode of the membrane electrode assembly. Ex situ XRD lattice parameter analysis indicates partial segregation of the Ru from the PtRu fcc alloy in both catalysts. A comparison of the in situ DMFC EXAFS to that of the as-received catalyst shows that catalyst restructuring during DMFC operation increases the total metal coordination numbers. A combined analysis of XRD determined grain sizes and lattice parameters, ex situ and in situ EXAFS analysis, and XRF of the as-received catalysts enables determination of the catalyst shell composition. The multi-spectrum analysis shows that the core size increases during DMFC operation by reduction of Pt oxides and incorporation of Pt into the core. This increases the mole fraction of Ru in the catalyst shell structure.

A novel sonochemical method for the preparation of MP (M=Ga, In) nanocrystalline materials has been developed. The procedure consists of the in situ synthesis of sodium phosphide and its subsequent reaction with the appropriate metal chloride using ultrasound. The products were characterized by X-ray powder diffraction, electron microscopy, and energy dispersive X-ray microanalysis (EDX). The choice of solvent and the use of high-power ultrasound are both important in the formation of the products.

Properties of PtRu nanoparticles prepared using high-intensity sonochemistry are reported. Syntheses were carried out in tetrahydrofuran (THF) containing Ru3+ and Pt4+ in a fixed mole ratio of either 1:10 or 1:1. X-ray diffraction measurements confirmed sonocation produces an alloy phase and showed that the composition of the nanometer scale metal particles is close to the mole fraction of Ru3+ and Pt4+ in solution with deviations that tend toward Ru enrichment in the alloy phase. The materials gave responses that are similar in terms of peak potential and current density, referenced to the catalyst active surface area, to those of bulk alloys in voltammetry experiments involving CO stripping and CH3OH electrochemical oxidation in 0.1 M H2SO4. The results show that sonochemical methods have the potential to produce nanometer scale bimetallic electrocatalysts that possess alloy properties. The materials have application in mechanistic studies of fuel cell reactions and as platforms for the development of CO tolerant fuel cell catalyst.

Infrared spectroscopy was applied to probe water inside pores and channels of Nafion membrane exchanged with either proton (H+) or sodium ions (Na+). Transmission measurements were performed on freestanding Nafion 112 (approximately 50 microm thickness) in a cell that enabled adjustment of the relative humidity. Experiments that employed Na+-exchanged Nafion focused on relative humidity environments at or below about 32% generated through the use of humectants. Under these conditions, narrow features in the O-H stretching spectral region near 3650-3720 cm(-1), previously attributed to interfacial water, were detected and matched to bands in vibrational sum frequency (VSF) spectra of water/air, water/organic, and salt-solution/air interfaces. The features correspond to the stretching mode of the "free" OH group of water oriented with one hydrogen atom toward other water molecules and interacting through hydrogen bonding and the other straddling the interface extending into fluorocarbon-rich regions (approximately 3668 cm(-1)) or air-filled segments (approximately 3700 cm(-1)) in the membrane. For membrane exchanged with H+, -SO3- groups were easily shifted to -SO3H as water was removed upon exposure to a few Torr of vacuum at 95 degrees C. In contrast, residual water was retained by membrane exchanged with Na+ after exposure to these conditions for up to 72 h. The permeation of methanol and acetone into Na+-exchanged Nafion 112 was also examined. The C-H and O-H stretching modes of methanol were perturbed in a manner that suggests the polymer disrupts hydrogen bonding interactions within the solvent, similar to the effect it exerts on pure water. For acetone, the C-H stretching modes were not shifted appreciably compared to those of the bulk liquid. However, the carbonyl band was affected, indicating the likely importance of dipolar interactions between solvent molecules and polar groups on the polymer. Control experiments performed with poly(hexafluoropropylene-co-tetrafluoroethylene) (FEP) membrane did not show evidence for water or methanol permeation, which demonstrates the critical role played by the ion-filled channels and pores in facilitating solvent transport within Nafion membrane.

Relatively little is known about the effects of pulsed ultrasound on the facilitation of chemical reactivity and remediation. Previous studies have indicated that sonochemistry using pulses may be either more or less effective than continuous wave (CW) ultrasonic irradiation. However, because of the time-modulated nature of the pulses used in these studies, less acoustic energy in general was transmitted to the solutions compared to CW sonication. The effectiveness of ultrasound when the pulse is adjusted so that the same amount of acoustic energy is input compared to continuous irradiation over a given time has not been previously explored. In this study we have embarked on a comparison of the efficacy of power-modulated pulsed (PMP) sonochemistry with more traditional time-modulated pulsing. As a prototypical reaction, we have explored the effects of pulse type on the degradation of acid orange, a common industrial colorant. An increase in the degradation rate by a factor of three was observed using PMP ultrasound compared with continuous irradiation under conditions of equivalent acoustic input power, while the use of time-modulated pulsed ultrasound from a commercially available direct-immersion (DI) horn-type sonicator exhibited a rate decrease compared to CW sonication. Possible mechanisms for the enhancement are discussed.

Relatively little is known about the effects of pulsed ultrasound on the facilitation of chemical reactivity. Previous studies have indicated that sonochemistry using pulses is generally less effective than continuous ultrasonic irradiation. However, the pulse trains employed were such that the peak power of the pulses was the same as the maximum power used in continuous irradiation. As a result, less acoustic energy was transmitted to the solutions over the same period of time. The effectiveness of ultrasound when the pulse is adjusted so that the same amount of acoustic energy is input compared to continuous irradiation over a given time has not been previously explored. In this study we have embarked on an examination of the efficacy of power-modulated pulsed (PMP) sonochemistry. Specifically, we have explored the effects of pulse type and pulse frequency on the oxidation of potassium iodide and the degradation of acid orange, a common industrial colorant. A rate increase by a factor of three was observed compared with continuous irradiation under conditions of equivalent acoustic input power.

[reaction: see text] Graphite intercalation compounds (GICs) are useful as powerful reducing agents in organic chemistry and are typically prepared by anaerobic solid-state reactions at high temperatures for 1-8 h. We have been able to prepare KC(8) in situ in toluene using ultrasound in less than 5 min. This allows for a convenient approach to reductive chemical syntheses involving GICs.

The effect of ultrasonic frequency on the sonodegradation of alachlor is described. The rate observed for the destruction of alachlor is approximately 25 times faster at 300 kHz under argon saturation than at 20 kHz under comparable acoustic input energy. The effect of variation of a number of extrinsic parameters such as dissolved gases, radical scavengers and hydroxyl radical promoters is also explored. Argon-saturated solutions display an enhancement in rate by a factor of two compared to either oxygen- or air-saturated solutions upon sonication at 300 kHz. The principal ultrasonic degradation products have been determined in air, argon, and oxygen. The products results primarily from cleavage of the N-methoxymethyl unit when sonication occurs in argon and air. Oxygen addition has been observed when the saturating gas is oxygen. The nature of the active site for reactivity of alachlor is discussed.

The design of a novel single-transducer variable-frequency sonication system capable of operating at constant acoustic power over the range 20-500 kHz is described. The system employs a mass-loaded sandwich transducer arrangement and a series of transformers to provide an accurate impedance matching circuit. Approximately 0-5 W of acoustic power are produced by the system at typical operating frequencies of 20, 40, 150, 200, 300, and 450 kHz. As a first test of the single-transducer variable-sonication system we have re-examined the frequency dependence of the sonochemical oxidation of potassium iodide. Previous investigators have monitored the frequency dependence using a multi-transducer system to obtain the different frequencies required. In accordance with the earlier findings, we have observed an eightfold increase in the rate of potassium iodide oxidation at 300 kHz compared to 20 kHz, as well as an inversion in the rate of oxidation for argon and air-saturated solutions at 300 kHz. Possible reasons for the rate variations are discussed.

The sonochemical reaction of Fe(CO)5 and triethylphosphine has been found to produce solid amorphous iron phosphide of composition FeP. The resulting compound was characterized by elemental microanalysis, scanning electron microscopy, energy-dispersive X-ray analysis, and Debye-Scherrer powder X-ray diffraction. X-ray powder patterns were obtained after the amorphous material had been heated above 950 degrees C and then slowly cooled to induce crystallization. This reaction provides the first use of ultrasound to sonochemically synthesize amorphous phosphide semiconductor materials from organometallic precursors.

Ultrasonic irradiation dramatically affects the reactivity of a variety of inorganic solids. We have found, for example, large increases in the rates of intercalation of a wide range of compounds into various layered inorganic solids (such as ZrS2, V2O5, TaS2 and MoO3. High intensity ultrasound also enhances the heterogeneous catalysis of alkene hydrogenation by Ni powders. Scanning electron microscopy reveals that ultrasound has multiple effects on the morphology and surface characteristics of inorganic solids, creating substantial surface damage, increasing surface areas significantly and causing increased particle aggregation.