Hierarchically Ordered Nanoporous Pd/SBA-15 Catalyst for the Aerobic Selective Oxidation of Sterically Challenging Allylic Alcohols

The utility of a hierarchically ordered nanoporous SBA-15 architecture, comprising 270 nm macropores and 5 nm mesopores (MM-SBA-15), for the catalytic aerobic selective oxidation of sterically challenging allylic alcohols is shown. Detailed bulk and surface characterization reveals that incorporation of complementary macropores into mesoporous SBA-15 enhances the dispersion of sub 2 nm Pd nanoparticles and thus their degree of surface oxidation. Kinetic profiling reveals a relationship between nanoparticle dispersion and oxidation rate, identifying surface PdO as the catalytically active phase. Hierarchical nanoporous Pd/MM-SBA-15 outperforms mesoporous analogues in allylic alcohol selective oxidation by (i) stabilizing PdO nanoparticles and (ii) dramatically improving in-pore diffusion and access to active sites by sesquiterpenoid substrates such as farnesol and phytol

Reactive-Atom Scattering from Liquid Crystals at the Liquid–Vacuum Interface: [C₁₂mim][BF₄] and 4‑Cyano-4′-Octylbiphenyl (8CB)

Two complementary approaches were used to study the liquid–vacuum interface of the liquid-crystalline ionic liquid 1-dodecyl-3-methyl­imidazolium tetrafluoroborate ([C₁₂mim]­[BF₄]) in the smectic A (SmA) and isotropic phases. O atoms with two distinct incident translational energies were scattered from the surface of [C₁₂mim]­[BF₄]. Angle-dependent time-of-flight distributions and OH yields, respectively, were recorded from high- and low-energy O atoms. There were no significant changes in the measurements using either approach, nor the properties derived from them, accompanying the transition from the SmA to the isotropic phase. This indicates that the surface structure of [C₁₂mim]­[BF₄] remains essentially unchanged across the phase boundary, implying that the bulk order and surface structure are not strongly correlated for this material. This effect is ascribed to the strong propensity for the outer surfaces of ionic liquids to be dominated by alkyl chains, over an underlying layer rich in anions and cation head groups, whether or not the bulk material is a liquid crystal. In a comparative study, the OH yield from the surface of the liquid crystal, 8CB, was found to be affected by the bulk order, showing a surprising step increase at the SmA–nematic transition temperature, whose origin is the subject of speculation