Adsorption, Migration and Reactions of Hydrocarbons on Zeolites Observed by Ftir Spectroscopy

The adsorption, migration and reactions of hydrocarbons on zeolites studied by FTIR spectroscopy are briefly reviewed. At low temperatures, alkyl-BAS (Brønsted acid sites) and -BAS complexes were first formed before protonation of olefins. For 1-butene, it underwent double bond migration (DBM) to form cis- and trans-2-butenes. With increasing temperature, oligomerization occurred and resulted in highly branched dimer, e.g., 3,4-dimethyl-3-hexene. Compared with 1-butene, isobutene can oligomerize at much lower temperature and formed dimerized alkoxy species, even on isolated silanols of zeolites. Upon adsorption of cyclic olefins such as 1-methylcyclopentene, alkenyl carbenium ions were formed at temperatures as low as 150 K. The adsorption of butenes on ferrierite indicates the existence of energy barriers for their intercalation into the pores. The H/D isotope exchange reaction of alkanes with acidic hydroxyl groups of zeolites will also be discussed.     

Self-assembled coordination cage derived from small-sized pyridinophane

The dithia[3.3]pyridinophane consisting of two pyridine rings has been found out to assume the syn-structure by the X-ray crystallography, meaning the two nitrogen atoms point in the same direction. From this cyclophane and cis-protected palladium(II), the self-assembled coordination molecular cage has been constructed.     

Water reduction and oxidation on Pt-Ru/Y2Ta2O5N2 catalyst under visible light irradiation

Y(2)Ta(2)O(5)N(2) is presented as a novel photocatalyst with high activity for water splitting under visible-light irradiation in the presence of appropriate sacrificial reagents; the activity for reduction to H(2) is increased by the incorporation of Pt or Ru as a co-catalyst, with a significant increase in production efficiency when both Pt and Ru are present.     

Catalytic Reduction of Dinitrogen into Ammonia and Hydrazine by Using Chromium Complexes Bearing PCP-Type Pincer Ligands**

A series of chromium-halide, -nitride, and -dinitrogen complexes bearing carbene- and phosphine-based PCP-type pincer ligands has been newly prepared, and some of them are found to work as effective catalysts to reduce dinitrogen under atmospheric pressure, whereby up to 11.60 equiv. of ammonia and 2.52 equiv. of hydrazine (16.6 equiv. of fixed N atom) are produced based on the chromium atom. To the best of our knowledge, this is the first successful example of chromium-catalyzed conversion of dinitrogen to ammonia and hydrazine under mild reaction conditions.     

Copper‐Catalyzed [3+2] Cycloaddition Reactions of Isocyanoacetates with Phosphaalkynes to Prepare 1,3‐Azaphospholes

A novel copper‐catalyzed synthetic method is described for phosphorous‐ and nitrogen‐containing heterocycles such as 1,3‐azaphospholes. Cycloaddition reactions of various isocyanoacetates with phosphaalkynes in the presence of copper bromide, bis(diphenylphosphino)methane (dppm), and potassium carbonate afford the corresponding 1,3‐azaphospholes in high yields with complete selectivity. Some dppm‐bridged dicopper complexes were identified as active species for the formation of 1,3‐azaphospholes.     

Temperature‐dependent location of a weakly segregated block copolymer in binary blends of block copolymers

The phase behaviors of binary blends of poly(styrene‐b‐butadiene) block copolymers were investigated by a small‐angle X‐ray scattering technique. The blends were composed of weakly segregated one in a random micellar phase and the other in a cylindrical phase with similar molecular weights and complementary volume fractions. Morphologies, domain spacings, and order–disorder transition temperatures of the blends indicated that the junctions of the constituent block copolymers share the interface at low temperatures. The domain spacing decreased as temperature increased in a blend with a small amount of the weakly segregated block copolymer. In the cases of the blends with a large amount of the weakly segregated constituent, domain spacing increased with increasing temperature. These results implied that some of the weakly segregated block copolymer moved from the interface to one microdomain at higher temperatures. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 470–476