Methanol Activation: Strategies for Utilization of Methanol as C1 Building Block in Sustainable Organic Synthesis.

The development of efficient and sustainable chemical processes which use greener reagents and solvents, currently play an important role in current research. Methanol, a cheap and readily available resource from chemical industry, could be activated by transition metal catalysts. This review focuses in covering the recent five-years literature and provides a systematic summary of strategies for methanol activation and the use in organic chemistry.

Localized Oxidative Catalytic Reactions Triggered by Cavitation Bubbles Confinement on Copper Oxide Microstructured Particles.

Efficient energy transfer management in catalytic processes is crucial for overcoming activation energy barriers while minimizing costs and CO emissions. We exploit here a concept of CuO particle design with multiple gas-stabilizing sites, engineered to function as cavitation nuclei and catalysts. This concept facilitates the selective and efficient acoustic energy transfer directly to the catalyst surface, avoiding the undesired dissipation of acoustic energy into the bulk solution while demonstrating superior cavitation properties at lower acoustic pressure amplitudes.

Harnessing Ultrasound-Derived Hydroxyl Radicals for the Selective Oxidation of Aldehyde Functions.

Ultrasonic irradiation holds potential for the selective oxidation of non-volatile organic substrates in the aqueous phase by harnessing hydroxyl radicals as chemical initiators. Here, a mechanistic description of hydroxyl radical-initiated glyoxal oxidation is constructed by gleaning insights from photolysis and radiation chemistry to explain the yields and kinetic trends for oxidation products. The mechanistic description and kinetic measurements reported herein reveal that increasing the formation rate of hydroxyl radicals by changing the ultrasound frequency increases both the rates of glyoxal consumption and the selectivity towards C acid products over those from C-C cleavage.

Sonochemically-Induced Reduction of Alkenes to Alkanes with Ammonia.

With the progressive defossilization of our industry, hydrogen (H ) has been identified as a central molecule to store renewable electricity. In this context, ammonia (NH ) 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.

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 NH 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 NH . As a result, any catalyst capable of activating NH will thus unavoidably decompose N H .

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.

Synergistic Effect of High-Frequency Ultrasound with Cupric Oxide Catalyst Resulting in a Selectivity Switch in Glucose Oxidation under Argon.

We report here, and rationalize, a synergistic effect between a non-noble metal oxide catalyst (CuO) and high-frequency ultrasound (HFUS) on glucose oxidation. While CuO and HFUS are able to independently oxidize glucose to gluconic acid, the combination of CuO with HFUS led to a dramatic change of the reaction selectivity, with glucuronic acid being formed as the major product. By means of density functional theory (DFT) calculations, we show that, under ultrasonic irradiation of water at 550 kHz, the surface lattice oxygen of a CuO catalyst traps H· radicals stemming from the sonolysis of water, making the ring-opening of glucose energetically unfavorable and leaving a high coverage of ·OH radical on the CuO surface, which selectively oxidizes glucose to glucuronic acid.

The effect of titanium dioxide synthesis technique and its photocatalytic degradation of organic dye pollutants.

Nanostructured mesoporous titanium dioxide (TiO) particles with high specific surface area and average crystallite domain sizes within 2 nm and 30 nm have been prepared the sol-gel and hydrothermal procedures. The characteristics of produced nanoparticles have been tested using X-Ray Diffraction (XRD), Brunauer-Emmett-Teller () surface area analysis, Scanning Electron Microscopy (SEM), Fourier Transform Infra-Red (FTIR), and Raman Spectroscopy as a function of temperature for their microstructural, porosity, morphological, structural and absorption properties. The as-synthesized TiO nanostructures were attempted as catalysts in Rhodamine B and Sudan III dyes' photocatalytic decomposition in a batch reactor with the assistance of Ultra Violet (UV) light.

Catalyst-Free Synthesis of Alkylpolyglycosides Induced by High-Frequency Ultrasound.

The irradiation of concentrated feeds of carbohydrates in alcoholic solution by high-frequency ultrasound (550 kHz) induces the formation of alkylpolyglycosides (APGs). This work is distinct from previous reports in that it does not involve any (bio)catalyst or activating agent, it takes place at only 40 °C, thus avoiding degradation of carbohydrates, and it selectively yields APGs with a degree of polymerization in a window of 2-7, an important limitation of the popular Fischer glycosylation. This ultrasound-based technology proved successful with a range of different valuable carbohydrates and alkyl alcohols.

Mechanocatalytic Depolymerization of Cellulose With Perfluorinated Sulfonic Acid Ionomers.

Here, we investigated that the mechanocatalytic depolymerization of cellulose in the presence of Aquivion, a sulfonated perfluorinated ionomer. Under optimized conditions, yields of water soluble sugars of 90-97% were obtained using Aquivion PW98 and PW66, respectively, as a solid acid catalyst. The detailed characterization of the water soluble fraction revealed (i) the selective formation of oligosaccharides with a DP up to 11 and (ii) that depolymerization and reversion reactions concomitantly occurred during the mechanocatalytic process, although the first largely predominated.

Selective and Catalyst-free Oxidation of D-Glucose to D-Glucuronic acid induced by High-Frequency Ultrasound.

This systematic experimental investigation reveals that high-frequency ultrasound irradiation (550 kHz) induced oxidation of D-glucose to glucuronic acid in excellent yield without assistance of any (bio)catalyst. Oxidation is induced thanks to the in situ production of radical species in water. Experiments show that the dissolved gases play an important role in governing the nature of generated radical species and thus the selectivity for glucuronic acid.

Determination of optimal conditions for electrodeposition of Tin(II) in the presence of Alizarin Red S.

A detailed physicochemical properties of aqueous solutions of alizarin red S - tin (II) chloride, has been thoroughly investigated by extensively exploring the effect of pH, concentration and temperature on the optimal conditions for the formation of tin (II)-alizarin red S (ARS-Sn II) complex. UV-Vis spectra, electrical conductivity and pH method were also used to characterize the final product. The stoichiometry of the reaction complex formation was determined different referential methods.

Biomass Oxidation: Formyl C-H Bond Activation by the Surface Lattice Oxygen of Regenerative CuO Nanoleaves.

An integrated experimental and computational investigation reveals that surface lattice oxygen of copper oxide (CuO) nanoleaves activates the formyl C-H bond in glucose and incorporates itself into the glucose molecule to oxidize it to gluconic acid. The reduced CuO catalyst regains its structure, morphology, and activity upon reoxidation. The activity of lattice oxygen is shown to be superior to that of the chemisorbed oxygen on the metal surface and the hydrogen abstraction ability of the catalyst is correlated with the adsorption energy.

One-pot transformation of cellobiose to formic acid and levulinic acid over ionic-liquid-based polyoxometalate hybrids.

Currently, levulinic acid (LA) and formic acid (FA) are considered as important carbohydrates for the production of value-added chemicals. Their direct production from biomass will open up a new opportunity for the transformation of biomass resource to valuable chemicals. In this study, one-pot transformation of cellobiose into LA and FA was demonstrated, using a series of multiple-functional ionic liquid-based polyoxometalate (IL-POM) hybrids as catalytic materials.