Photoinduced radical processes on the spinel (MgAl2O4) surface involving methane, ammonia, and methane/ammonia

The present study explored photoinduced radical processes caused by interaction of CH(4) and NH(3) with a photoexcited surface of a complex metal oxide: magnesium-aluminum spinel (MgAl(2)O(4); MAS). UV irradiation of MAS in vacuo yielded V-type color centers as evidenced by the 360 nm band in difference diffuse reflectance spectra. Interaction of these H-bearing molecules with photogenerated surface-active hole states (O(S)(-)?) yielded radical species which on recombination produced more complex molecules (including heteroatomic species) relative to the initial molecules. For the MAS/CH(4) system, photoinduced dissociative adsorption of CH(4) on surface-active hole centers produced ?CH(3) radicals that recombined to yield CH(3)CH(3). For MAS/NH(3), a similar dissociative adsorption process led to formation of ?NH(2) radicals with formation of NH(2)NH(2) as an intermediate product; continued UV irradiation ultimately yielded N(2). For the mixed MAS/CH(4)/NH(3) system, however, interaction of adsorbed NH(3) and CH(4) on the UV-activated surface of MAS yielded ?NH(2) and ?CH(3) radicals, respectively, which produced CH(3)-NH(2) followed by loss of the remaining hydrogens to form a surface-adsorbed cyanide, CN(S), species. Recombination of photochemically produced radicals released sufficient energy to re-excite the solid spinel, generating new surface-active sites and a flash luminescence (emission decay time at 520 nm, τ ~ 6 s for the MAS/NH(3) case) referred to as the PhICL effect.     

Properties of Bromine Fused Salts Based on Quaternary Ammonium Molecules and Their Relevance for Use in a Hydrogen Bromine Redox Flow Battery

Bromine complexing agents (BCA) in aqueous electrolytes for hydrogen bromine flow batteries are used to reduce bromine‘s vapour pressure, while an insoluble and liquid fused salt is formed. The properties (concentrations, composition, conductivity and viscosity) of this fused salt are investigated in this study systematically ex situ by using 7 BCAs at different state of charge in HBr/Br₂/H₂O electrolytes with a theoretical capacity of 179.6 Ah L⁻¹. Bromine is stored in the fused salt at concentrations up to 13.6 M, reaching theoretical volumetrical capacities up to 730 Ah L⁻¹ in fused salts. The fused salt consists of a pure, bromine- and water-free ionic liquid of organic [BCA]⁺ cations and polybromides, and its conductivity bases on a hopping mechanism among the polybromides. Alkyl side chain length of the BCAs and distribution of polybromides influence strongly the conductivity and viscosity of the fused salts. 1-ethylpyridin-1-iumbromide results to be favoured BCA for application.     

Microwaves in advanced oxidation processes for environmental applications. A brief review

This review article focuses, albeit non-exhaustively, on the influence of microwave radiation on photoassisted processes often referred to as Advanced Oxidation Processes. In particular, we describe and illustrate the possible advantages of microwaves in TiO₂-assisted photodegradations and photomineralizations of various organic pollutants such as herbicides and endocrine disruptors, among others. Described are also various reactor configurations involving UV/visible radiation and microwaves, with the former being supplied either by traditional Hg lamps or alternatively by electrodeless lamps activated by microwaves. To place the use of microwaves on processes occurring in aqueous TiO₂ dispersions in perspective regarding environmental applications, we first introduce the various sources of pollutants and subsequently describe in brief the various advanced oxidation processes such as UV/peroxidation, UV/ozonation and the photo-Fenton process(es) in addition to direct photolysis either by sunlight or by artificial light sources.     

Desymmetrization of 7-dimethylphenylsilylcycloheptatriene. Towards the synthesis of new aminocycloheptitols

Desymmetrization of 7-silylcycloheptatriene through consecutive dihydroxylation and acyl-nitroso cycloaddition of the resulting diene moiety is described. Dihydroxylation occurred anti relative to the resident silicon group in line with previous observations made in the cyclohexadiene series. In contrast, the subsequent acyl-nitroso cycloaddition occurred with poor regiocontrol but good level of diastereocontrol syn to the bulky silyl substituent. The resulting cycloadducts were then elaborated further to provide a straightforward entry toward aminocycloheptitols in ten steps from commercially available tropylium salts.     

Double-layered TiO2-SiO2 nanostructured films with self-cleaning and antireflective properties

Dual function of self-cleaning and antireflection can be created in double-layered TiO2-SiO2 nanostructured films. The film were prepared by (1) layer-by-layer deposition of multilayered SiO2 nanoparticles with polydiallyldimethylammonium (PDDA) cations, (2) layer-by-layer deposition of multilayered titanate nanosheets with polications on PDDA/SiO2 multilayer films, and (3) burning out the polymer and converting titanate nanosheets into TiO2 by hearing at 500 degrees C. The as-prepared films, consisting of a porous SiO2 bottom layer and a dense TiO2 top layer, improved the transmittance of glass or quartz substrates, as demonstrated by transmission spectra collected at normal incidence. The photocatalytic properties of the films were studied by the change of the water contact angle together with the decay of the IR absorption of the hydrocarbon chain of octadecylphosphonic-acid-modified films under 2.6 mW cm-2 UV illumination. Both the antireflective and the photocatalytic properties of the films were dependent on the number of PDDA/nanosheet bilayers deposited. however, excellent surface wettability of the films for water was obtained, independent of the preparation conditions. The experimental findings are discussed in terms of the special structure of the double-layered nanostructured film.     

Photoelectrochemical behavior of Nb-doped TiO2 electrodes

The photoelectrochemical behavior of degenerate Nb-doped TiO2 (Ti(1-x)Nb(x)O2: x = 0, 0.01, 0.03, 0.06, 0.1) electrodes prepared by pulsed laser deposition on LaAlO3 (LAO) and SrTiO3 (STO) was examined, revealing that an increase in Nb concentration causes a significant decay of titania photoactivity. One reason for such behavior may be a Burstein-Moss effect, which leads to a blue shift of the spectral limit of photoactivity. Another reason typical for metal-doped photocatalysts is the increase of the efficiency of charge carrier recombination.     

Interactions underpinning the plasticization of a polymer matrix: a dynamic and structural analysis of DMP-plasticized cellulose acetate

This work establishes that the plasticization effect of a classical petrochemical plasticizer, dimethyl phthalate (DMP), on a polymer matrix, cellulose acetate (CA), is due to the development of intermolecular interactions of dipolar type. Plasticized cellulose acetate films are studied with regard to the interactions between the polymer and plasticizer at the macroscopic scale by thermogravimetric analysis and differential scanning calorimetry. At the molecular level, Fourier transform infrared spectroscopy and dielectric relaxation spectroscopy are used to elucidate the nature of interactions that are responsible for the plasticizing effects. These static and dynamic complementary analyses evidenced that DMP does not establish H-bonding interactions with the polymer chains of cellulose acetate but rather weaker interactions of dipolar type. These dipole–dipole interactions that develop between acetyl side groups of CA and the ester phthalate moieties of DMP increase the overall mobility of CA chains and also locally influence the molecular mobility and the water uptake tendency.     

Preparation of thin-sections of painting fragments: Classical and innovative strategies

For more than a century, the analyses of painting fragments have been carried out mainly through the preparation of thick resin-embedded cross-sections. Taking into account the development of innovative micro-analytical imaging techniques, alternatives to this standard preparation method are considered. Consequently, dedicated efforts are required to develop preparation protocols limiting the risks of chemical interferences (solubilisation, reduction/oxidation or other reactions) which modify the sample during its preparation, as well as the risks of analytical interferences (overlap of detected signals coming from the sample and from materials used in the preparation). This study focuses particularly on the preparation of thin-sections (1–20 μm) for single or combined fourier transform infrared (FTIR) spectroscopy and X-ray 2D micro-analysis. A few strategies specially developed for the μFTIR analysis of painting cross-sections have already been reported and their potential extrapolation to the preparation of thin-sections is discussed. In addition, we propose two new specific methods: (i) the first is based on a free-embedding approach, ensuring a complete chemical and analytical neutrality. It is illustrated through application on polymeric design objects corpus; (ii) the second is based on a barrier coating approach which strengthens the sample and avoids the penetration of the resin into the sample. The barrier coating investigated is a silver chloride salt, an infrared transparent material, which remains malleable and soft after pellet compression, enabling microtoming. This last method was successfully applied to the preparation of a fragment from a gilded Chinese sculpture (15th C.) and was used to unravel a unique complex stratigraphy when combining μFTIR and μXRF.     

Flash Latex Production in a Continuous Helical Photoreactor: Releasing the Brake Pedal on Acrylate Chain Radical Polymerization

The continuous photopolymerization of acrylate and methacrylate monomer miniemulsions (25% solids content) is investigated at room temperature in a compact helix minireactor. Using n‐butyl acrylate, the process yields 95% conversion after only 27 s residence time, and gel‐free high‐molecular‐weight products. Under optimized conditions, a 25‐fold increase in efficiency is obtained when compared to a batch photopolymerization. The reaction set‐up offers a frugal process because of moderate irradiance (2.6 mW cm^?2), photoinitiator concentration (0.75 wt%), and low‐power UV‐A fluorescent lamp.