Characterization of polyoxometalate/polymer photo-composites: A toolbox for the photodegradation of organic pollutants

Different inorganic/organic photocomposites based on polyoxometalate (POM) nanoparticles have been developed for photocatalytic applications. Currently, polyoxometalate nanoparticles have been successfully in-situ embedded into an acrylate polymer network by photopolymerization upon mild visible light irradiation at 405 nm. The proposed POM/polymer photocomposites have been characterized using complementary techniques for a better understanding of their photocatalytic activity. Interestingly, the obtained photocomposites exhibit high rigidity, excellent thermal stability, a non-negligible porosity and new functionalities such as light reactivity and redox properties. Moreover, developed composites showed efficient catalytic activity for the color removal of aqueous solutions of erythrosine and rose Bengal under Light Emitting Diodes LED@375 nm irradiation reaching 80 and 90% as a final color removal, respectively.     

Gas‐phase interactions of organotin compounds with glycine

Gas‐phase interactions of organotins with glycine have been studied by combining mass spectrometry experiments and quantum calculations. Positive‐ion electrospray spectra show that the interaction of di‐ and tri‐organotins with glycine results in the formation of [(R)₂Sn(Gly)‐H]⁺and [(R)₃Sn(Gly)]⁺ ions, respectively. Di‐organotin complexes appear much more reactive than those involving tri‐organotins. (MS/MS) spectra of the [(R)₃Sn(Gly)]⁺ ions are indeed simple and only show elimination of intact glycine, generating the [(R)₃Sn]⁺ carbocation. On the other hand, MS/MS spectra of [(R)₂Sn(Gly)‐H]⁺complexes are characterized by numerous fragmentation processes. Six of them, associated with elimination of H₂O, CO, H₂O + CO and formation of [(R)₂SnOH]⁺ (?57 u),[(R)₂SnNH₂]⁺( ?58 u) and [(R)₂SnH]⁺ (?73 u), are systematically observed. Use of labeled glycines notably concludes that the hydrogen atoms eliminated in water and H₂O + CO are labile hydrogens. A similar conclusion can be made for hydrogens of [(R₂)SnOH]⁺and [(R₂)SnNH₂]⁺ions. Interestingly, formation [(R)₂SnH]⁺ ions is characterized by a migration of one the α hydrogen of glycine onto the metallic center. Finally, several dissociation routes are observed and are characteristic of a given organic substituent. Calculations indicated that the interaction between organotins and glycine is mostly electrostatic. For [(R)₂Sn(Gly)‐H]⁺complexes, a preferable bidentate interaction of the type η²‐O,NH2 is observed, similar to that encountered for other metal ions. [(R)₃Sn]⁺ ions strongly stabilize the zwitterionic form of glycine, which is practically degenerate with respect to neutral glycine. In addition, the interconversion between both forms is almost barrierless. Suitable mechanisms are proposed in order to account for the most relevant fragmentation processes. Copyright © 2013 John Wiley & Sons, Ltd.     

Simplification of the 1H NMR spectra of enantiomers dissolved in chiral liquid crystals, combining variable angle sample spinning and selective refocusing experiments

This work presents a technique to simplify overcrowded proton spectra in chiral liquid crystal solvents using rotation of the sample near the magic angle, VASS, combined with homonuclear selective refocusing 2D NMR experiments, SERF. This methodology provides a powerful tool to visualise enantiomers out of unresolved proton spectra. A modified SERF sequence is presented where the resulting 2D spectrum can be phased to increase the resolution. Accurate enantiomeric excesses are determined that are not possible to measure on static samples. Two examples are presented.     

Kinetics of formation of barium tungstate in equimolar powder mixture of BaCO<Subscript>3</Subscript> and WO<Subscript>3</Subscript>

The formation of Barium monotungstate (BaWO₄) particles in equimolar powder mixtures of BaCO₃ and WO₃ was examined under isothermal and non-isothermal conditions upon heating in air at 25–1200 °C, using thermogravimetry. Concurrence of the observed mass loss (due to the release of CO₂) to the occurrence of the formation reaction was evidenced. Accordingly, the extent of reaction (x) was determined as a function of time (t) or temperature (T). The x–t and x–T data thus obtained were processed using well established mathematical apparatus and methods, in order to characterize nature of reaction rate-determining step, and derive isothermal and non-isothermal kinetic parameters. Moreover, the reaction mixture quenched at various temperatures (600–1,000 °C) in the reaction course was analyzed by various spectroscopic and microscopic techniques, for material characterization. The results obtained indicated that the reaction rate may be controlled by unidirectional diffusion of WO₃ species across the product layer (BaWO₄), which was implied to form on the barium carbonate particles. The isothermally determined activation energy (118–125 kJ/mol) was found to be more credible than that (245 kJ/mol) determined non-isothermally.     

Investigation of the isothermal (vapour + liquid) equilibria of aqueous 2-amino-2-methyl-1-propanol (AMP), N-benzylethanolamine,or 3-dimethylamino-1-propanol solutions at several temperatures

The vapour pressures of (2-amino-2-methyl-1-propanol (AMP) + water), (N-benzylethanolamine + water), or (3-dimethylamino-1-propanol + water) binary mixtures, and of pure AMP and 3-dimethylamino-1-propanol components were measured by means of two static devices at temperatures between 283 K and 363 K. The data were correlated with the Antoine equation. From these data, excess Gibbs functions (G^E) were calculated for several constant temperatures and fitted to a fourth-order Redlich–Kister equation using the Barker’s method. The {2-amino-2-methyl-1-propanol (AMP) + water} binary mixture exhibits negative deviations in G^E (at T < 353.15 K) and a sinusoidal shape for G^E for the higher temperatures over the whole composition range. For the aqueous N-benzylethanolamine solution, a S shape is observed for the G^E for all investigated temperatures over the whole composition range. The (3-dimethylamino-1-propanol + water) binary mixture exhibits negative deviations in G^E (at T < 293.15 K), positive deviations in G^E (for 293.15 K < T < 353.15 K) and a sinusoidal shape for G^E for the higher temperatures over the whole composition range.     

Experimental determination of the isothermal (vapour + liquid) equilibria of binary aqueous solutions of sec-butylamine and cyclohexylamine at several temperatures

The vapour pressures of (sec-butylamine + water), (cyclohexylamine + water) binary mixtures, and of pure sec-butylamine and cyclohexylamine components were measured by means of two static devices at temperatures between 293 (or 273) K and 363 K. The data were correlated with the Antoine equation. From these data, excess Gibbs functions (G^E) were calculated for several constant temperatures and fitted to a fourth-order Redlich–Kister equation using the Barker’s method. The (cyclohexylamine + water) system shows positive azeotropic behaviour for all investigated temperatures. The two binary mixtures exhibit positive deviations in G^E for all investigated temperatures over the whole composition range.