The photocatalyzed oxidation of benzylic compounds by 1,2,4,5-tetracyanobenzene (TCB) in the presence of Selectfluor provides a synthetically efficient route to electron deficient, less substituted, and otherwise inaccessible benzylic fluorides. The virtue of this system is multifold: it is metal-free and mild, and the reagents are inexpensive. Mechanistically, the data suggest the intimate formation of intermediate radical cations in the key radical forming step, as opposed to a concerted hydrogen atom transfer process.

Defects in interfacial layers and their role in the growth of ZnO nanorods by metallorganic chemical vapor deposition Appl.ZnO nanostructures were grown via carbothermal reduction vapor phase transport with carbon black, activated carbon, and graphite powders. Nanostructures can be grown at significantly lower temperatures with carbon black and activated carbon, although with different morphologies compared to graphite. The surface areas of the carbon black and activated carbon are higher than those of graphite; this has been used previously to explain the origin of such growth and morphology differences. We use different ZnO/graphite ratios to equalize surface areas compared to carbon black and eliminate this effect, but differences in nanostructure growth and morphology remain. We discuss the effects of thermodynamics and carbon purity and conclude that the high surface activities of the carbon black and activated carbon are the reason for our results.

Power generation using chemical looping combustion (CLC) technology has emerged as a promising CO 2 -capture-based alternative to conventional technology. In this study, the performance of a Ca 0.9 Mn 0.5 Ti 0.5 O 3−δ perovskite-type oxygen carrier material for use in fixed-bed CLC reactors is investigated. The main focus of the study is on the material's oxygencarrying capacity and reactivity with and conversion of syngas in the fixed-bed reactor. Pressurized thermogravimetric analysis in model gases indicates neither Boudouard coking nor reactivity of the oxygen-carrier material toward CO 2 . A fuel gas conversion of 95% was achieved in the fixed-bed reactor using this oxygen-carrier material.

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In this work the origin of permselectivity in dense silica films which possess a pore structure with pore sizes commensurate with the molecular size of the diffusing gas species is investigated. Much of the recently reported work in this field has involved the development of composite membrane films, and while it is generally assumed that the transport process of the gas species within the selective layer of these films is activated in nature, there are anomalies with this simplified picture. In this paper a new model is developed which, for the first time, explains the permselective behavior of the thin selective coatings ubiquitous to membrane separation processes. The model involves the existence of two primary transport domains within the solid film, one of which rapidly conducts the permeating gas (under non-Fickian conditions), while the second domain involves a slow diffusion mode characterized by normal Fickian transport. To validate the model, molecular dynamics simulations are conducted for diffusion of a number of simple gases (He, N(2), and CO(2)) within silica glasses over a range of solid densities. The silica media employed in these studies are based on a novel approach developed in this work for the construction of three-dimensionally periodic atomistic structures of silica of arbitrary density in which network bond connectivity is ensured. The results obtained from this work are in qualitative agreement with experimental observations and confirm the existence of dual mode transport which is central to the interpretation of the permselectivity in composite membranes systems.