Direct Methylation of Benzene with Methane Catalyzed by Co/MFI Zeolite.

Cobalt-loaded MFI zeolite showed distinct activity for direct methylation of benzene with methane into toluene. High activity was found at around 0.6 of Co/Al molar ratio. Incorporation of carbon from methane into the methyl group of toluene was confirmed with isotope tracer experiments and mass spectroscopy. Ammonia infrared-mass spectroscopy temperature-programmed desorption, transmission electron microscopy, X-ray absorption near edge spectroscopy and extended X-ray absorption fine structure indicated that Lewis acidic divalent (+II of oxidation state) Co species mono-atomically dispersed on the ion exchange site of MFI zeolite was the active species.

Study of molecular arrangement of organized molecular films of charge-transfer complexes containing 1,3-dithiole-2-thione-4,5-dithiolate by in-plane and out-of-plane X-ray diffractions.

We investigated the molecular arrangement and surface morphology of organized molecular films of alkylammonium-M bis(1,3-dithiole-2-thione-4,5-dithiolate) ((dmit)(2), M = Ni, Au, and Pd) charge-transfer complexes using the surface pressure-area (pi-A) isotherm, polarized visible spectroscopy, in-plane and out-of-plane X-ray diffractions (XRD), and atomic force microscopy (AFM). Since Langmuir-Blodgett films of alkylammonium-M(dmit)(2) generally exhibit superconductivity, it may be possible to develop novel electronic molecular devices on the subnanometer scale. In the bulk state, several alkylammonium-M(dmit)(2) molecules could not form a highly ordered layered structure along the c-axis and a subcell structure of the alkyl chain in the ab-plane; however, almost all molecules formed a layered structure in the film multilayers. Monolayers of alkylammonium-M(dmit)(2) molecules on the water surface were extremely condensed. Out-of-plane and in-plane XRD measurements revealed that over a long period, systematic changes occurred in the two-dimensional lattice structure of alkylammonium-M(dmit)(2) molecules and not in their bulk state. These structural changes appear to be caused by enhancement of the van der Waals interaction among long hydrocarbons and the pi-pi interaction among (dmit)(2) units arranged two dimensionally. In addition, both the molecular arrangement and the structural morphology of the films showed dependence on the hydrocarbon chain length, number of long alkyl chains, and kind of central metal. In particular, the molecular arrangement of materials having didecyl chains changed drastically and (dmit)(2) units were highly oriented in the ab-plane. Such structural formations are suggested to significantly influence the stacking of functional dmit units presiding over the conductive properties.