Titanium dioxide (TiO(2)) is a preferred catalyst for photocatalytic oxidation of many air pollutants. In an effort to enhance its photocatalytic activity, TiO(2) was modified by pulsed plasma treatment. In this work, TiO(2) nanoparticles, coated on a glass plate, were treated with a plasma discharge of hexafluoropropylene oxide (HFPO) gas. By appropriate adjustment of discharge conditions, it was discovered that the TiO(2) particles can be either directly fluorinated (Ti-F) or coated with thin perfluorocarbon films (C-F). Specifically, under relatively high power input, the plasma deposition process favored direct surface fluorination. The extent of Ti-F formation increased with increasing power input. In contrast, at lower average power inputs, perfluorocarbon films are deposited on the surface of the TiO(2) particles. The plasma surface modified TiO(2) nanoparticles were subsequently employed as catalysts in the photocatalytic oxidation of m-xylene in air, as carried out inside a batch reactor with closed loop constant gas circulation. Both types of modified TiO(2) were significantly more catalytically active than that of the unmodified particles. For example, the rate constant of m-xylene degradation was increased from 0.012 min(-1) with untreated TiO(2) to 0.074 min(-1) with fluorinated TiO(2). Although it is not possible to provide unequivocal reasons for this increased photocatalytic activity, it is noted that the plasma surface treatment converted the TiO(2) from hydrophilic to highly hydrophobic, which would provide more facile catalyst adsorption of the xylene from the flowing air. Also, based on literature reports, the use of fluorinated TiO(2) reduces electron-hole recombination rates, thus increasing the photocatalytic activity.

Solid-state nanopores have emerged as sensors for single molecules and these have been employed to examine the biophysical properties of an increasingly large variety of biomolecules. Herein we describe a novel and facile approach to precisely adjust the pore size, while simultaneously controlling the surface chemical composition of the solid-state nanopores. Specifically, nanopores fabricated using standard ion beam technology are shrunk to the requisite molecular dimensions via the deposition of highly conformal pulsed plasma generated thin polymeric films. The plasma treatment process provides accurate control of the pore size as the conformal film deposition depends linearly on the deposition time. Simultaneously, the pore and channel chemical compositions are controlled by appropriate selection of the gaseous monomer and plasma conditions employed in the deposition of the polymer films. The controlled pore shrinkage is characterized with high resolution AFM, and the film chemistry of the plasma generated polymers is analyzed with FTIR and XPS. The stability and practical utility of this new approach is demonstrated by successful single molecule sensing of double-stranded DNA. The process offers a viable new advance in the fabrication of tailored nanopores, in terms of both the pore size and surface composition, for usage in a wide range of emerging applications.

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