On the Selectivity of Simultaneous CO2 and N2 Reduction Using TiO2/Carbon Sphere Photocatalysts Prepared by Microwave Treatment and Mounted on Silica Cloth.

This paper presents new photocatalysts obtained by treating carbon spheres (CS) and TiO2 in a microwave reactor at a pressure of 20 atm and a temperature of up to 300 °C for 15 min and then depositing TiO2/CS composites on glass fibre cloths. Such highly CO2-adsorbing photocatalysts showed photoactivity in the simultaneous water-splitting process, generating H2, reducing CO2 to CO and CH4, and reducing N2 to NH3. In addition, calculations of the hydrogen balance involved in all reactions were performed. Adding 1 g of carbon spheres per 1 g of TiO2 maintained the high selectivity of nitrogen fixation at 95.87-99.5%, which was continuously removed from the gas phase into the water as NH4+ ions.

Chiral Pyrrolidinium Ionic Liquids with (-)-Borneol Fragment in the Cation - Synthesis, Physicochemical Properties and Application in Diels-Alder Reaction.

A series of chiral pyrrolidinium salts containing (1 S)-endo-(-)-born-2-yloxymethyl substituent in the structure of the cation and six different anions: chloride, tetrafluoroborate [BF4 ]- , hexafluorophosphate [PF6 ]- , trifluoromethanesulfonate [OTf]- , bis(trifluoromethylsulfonyl)imide [NTf2 ]- , bis(pentafluoroethylsulfonyl)imide [NPf2 ]- and perfluorobutanesulfonate [C4 FS]- were efficiently prepared and extensively characterized. The enantiomeric purity of them was confirmed by NMR analysis with a chemical shift reagent. All salts were characterized with the specific rotation, the solubility in commonly used solvents, thermal properties, including phase transition temperatures and thermal stability. Salts with [PF6 ]- , [C4 FS]- , [NTf2 ]- and [NPf2 ]- anions were classified as chiral ionic liquids (CILs). Moreover, salts with [NTf2 ]- and [NPf2 ]- anions were in the liquid state at room temperature and below. Therefore, density and dynamic viscosity, the surface tension and the contact angle on three different surfaces were also measured for them. Additionally, these chiral ionic liquids were tested as solvents in Diels-Alder reaction.

New Insight on Carbon Dioxide-Mediated Hydrogen Production.

A new approach to hydrogen production from water is described. This simple method is based on carbon dioxide-mediated water decomposition under UV radiation. The water contained dissolved sodium hydroxide, and the solution was saturated with gaseous carbon dioxide. During saturation, the pH decreased from about 11.5 to 7-8. The formed bicarbonate and carbonate ions acted as scavengers for hydroxyl radicals, preventing the recombination of hydroxyl and hydrogen radicals and prioritizing hydrogen gas formation. In the presented method, not yet reported in the literature, hydrogen production is combined with carbon dioxide. For the best system with alkaline water (0.2 m NaOH) saturated with CO2 under UV-C, the hydrogen production amounted to 0.6 µmol h-1 during 24 h of radiation.

Chiral protic imidazolium salts with a (-)-menthol fragment in the cation: synthesis, properties and use in the Diels-Alder reaction.

New chiral protic imidazolium salts containing a (1R,2S,5R)-(-)-menthol substituent in the cation and four different anions (chloride, hexafluorophosphate, trifluoromethanesulfonate and bis(trifluoromethylsulfonyl)imide) were efficiently prepared and extensively characterized. Detailed NMR analysis was performed, and a comparison of the chemical shifts of the protons and carbons of the imidazolium cation as a function of the combined anion was discussed. The specific rotation, solubility in commonly used solvents, thermal properties including phase transition temperatures, and thermal stability were also determined. Three of the synthesized tertiary salts (Cl, PF6 or OTf anion) were crystalline solids; 1-H-3-[(1R,2S,5R)-(-)-menthoxymethyl]-imidazolium bis(trifluoromethylsulfonyl)imide, (-)[H-Ment-Im][NTf2] was a liquid at room temperature. The chiral protic salts were used in a Diels-Alder reaction as a test reaction, and the results were compared with those from aprotic chiral ionic liquids having the same chiral substituent in the cation (1R,2S,5R)-(-)-menthol with a bis(trifluoromethylsulfonyl)imide anion. Both protic and aprotic chiral salts, used in a Diels-Alder reaction, were pure (-)-enantiomers, which was determined by NMR with Δ-TRISPHAT tetrabutylammonium salt as a chiral shift reagent. Protic salts offered distinctly higher endo/exo ratios than aprotic ones, but an enantiomeric excess was not obtained. The stereoselectivity reached the same high level even after the fourth recycle of (-)[H-Ment-Im][NTf2] in the reaction of ethyl-vinyl ketone with cyclopentadiene at temperature of -35 °C.