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Using a sputtering-deposited titanium substrate, incorporating six equally spaced nanolayers of Ti-W alloy, the volume and composition changes accompanying the formation of porous anodic films on titanium in 0.5 wt % NH 4 F in glycerol are investigated. The findings reveal amorphous films with nanotubes of TiO 2 , containing fluoride ions and possibly glycerol derivatives. Tungsten and titanium species are lost to the electrolyte at differing rates during anodizing, leading to an enrichment of tungsten in the film relative to the composition of the substrate. The spacing of tungsten-containing bands in the film is ϳ2.3 that of the original alloy layers during growth of the major pores. The generation of the nanotubes can be explained either by field-assisted flow of film material within the barrier layer to the pore walls, with cation and anion transport numbers of anodic titania in the barrier layer region similar to those of barrier films and with field-assisted ejection of Ti 4+ ions to the electrolyte, or by fieldassisted dissolution, but with a reduction in cation transport number.

Nanostructured niobium oxide (NO) semiconductor is gaining increasing attention as electronic, optical, and electro-optic material. However, the preparation of stable NO nanofilms with reproducible morphology and behavior remains a challenge. 10Here we show a rapid, well-controlled, and efficient way to synthesize NO films with the self-organized columnlike nanostructured morphologies and advanced functional properties. The films are developed via the growth of a nanoporous anodic alumina layer, followed by the pore-directed 15 anodizing of the Nb underlayer. The columns may grow 30-150 nm wide, up to 900 nm long, with the aspect ratio up to 20, being anchored to a thin continuous oxide layer that separates the columns from the substrate. The as anodized films have a graded chemical composition changing from amorphous Nb 2 O 5 mixed with Al 2 O 3 , Si-, and P-containing species in the surface region to NbO 2 in the lower film layer. The post-anodizing treatments result in the controlled 20 formation of Nb 2 O 5 , NbO 2 , and NbO crystal phases, accompanied by transformation from nearly perfect dielectric to n-type semiconductor behavior of the films. The approach allows for the smooth film growth without early dielectric breakdown, stress-generated defects, or destructive dissolution at the respective interfaces, which is a unique situation in the oxide films on niobium. The functional properties of the NO films, revealed to date, allow for potential applications as nanocomposite capacitor dielectrics and active 25 layers for semiconductor gas microsensors with the sensitivity to ethanol and the response to hydrogen being among best ever reported.

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Here, we report remarkable oxygen evolution reaction (OER) catalytic activity of brownmillerite (BM)-type Ca FeCoO . The OER activity of this oxide is comparable to or beyond those of the state-of-the-art perovskite (PV)-catalyst Ba Sr Co Fe O (BSCF) and a precious-metal catalyst RuO , emphasizing the importance of the characteristic BM structure with multiple coordination environments of transition metal (TM) species. Also, Ca FeCoO is clearly advantageous in terms of expense/laboriousness of the material synthesis. These facts make this oxide a promising OER catalyst used in many energy conversion technologies such as metal-air secondary batteries and hydrogen production from electrochemical/photocatalytic water splitting.