TiO2-Based Nanomaterials for Gas Sensing-Influence of Anatase and Rutile Contributions.

The paper deals with application of three nanomaterial systems: undoped TiO2, chromium-doped TiO2:Cr and TiO2-SnO2 synthesized by flame spray synthesis (FSS) technique for hydrogen sensing. The emphasis is put on the role of anatase and rutile polymorphic forms of TiO2 in enhancing sensitivity towards reducing gases. Anatase-to-rutile transformation is achieved by annealing of undoped TiO2 in air at 700 °C, specific Cr doping and modification with SnO2. Undoped TiO2 and TiO2-SnO2 exhibit n-type behaviour and while TiO2: 5 at.% Cr is a p-type semiconductor. X-ray diffraction (XRD) has been applied to determine anatase-to-rutile weight ratio as well as anatase and rutile crystal size. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) have been used to characterize the structure and morphological parameters. Optical reflectometry enabled to find and compare the band gaps E g of anatase and rutile predominated compositions. Electrical properties, i.e. the electrical conductivity and values of constant phase element (CPE), have been established on the basis of impedance spectroscopy. Dynamic responses of the electrical resistance as a function of hydrogen concentration revealed that predominance of rutile in anatase/rutile mixture is beneficial for gas sensing. Partial transformation to rutile in all three material systems under study resulted in an increased sensitivity towards hydrogen. It is proposed that this effect can be explained in a similar way as in photocatalysis, i.e. by specific band alignment and electron transfer from rutile to anatase to facilitate oxygen preadsorption on the surface of anatase grains.

Visual processing of emotional dynamic faces in 22q11.2 deletion syndrome.

INTRODUCTION: The 22q11.2 deletion syndrome (22q11DS) is a neurogenetic syndrome. Individuals affected by this syndrome present poor social functioning and a high risk for the development of psychiatric disorders. Accurate emotion recognition and visual exploration of faces represent important skills for appropriate development of social cognition in individuals with 22q11DS. For these reasons, there is elevated interest in establishing relevant ways to test the mechanisms associated with emotion recognition in patients with 22q11DS. METHODS: This study investigated emotional recognition and visual exploration of emotional faces in persons with 22q11DS, with a dynamic emotion task using an eye-tracking device. To our knowledge, no previous studies have used emotional dynamic stimuli with 22q11DS, despite improved ecological validity of dynamic stimuli compared with static images. Furthermore, these stimuli provide the opportunity to collect reaction times, as indicators of the emotional intensity necessary for identifying each emotion. RESULTS: In our task, we observed comparable accuracy in emotion recognition in the 22q11DS and healthy control groups. However, individuals with 22q11DS were slower to recognise the emotions. They also spent less time looking at the nose during happy and fearful faces. CONCLUSIONS: These results suggest that individuals with 22q11DS may need either more time or more pronounced emotional cues to correctly label facial expressions.

Thin films of TiO2:N for photo-electrochemical applications.

Dc-pulsed magnetron sputtering from Ti target in reactive Ar+O2+N2 atmosphere was used to grow stoichiometric TiO2:N and non-stoichiometric TiO2-x:N thin films. X-ray diffraction at glancing incidence, atomic force microscopy AFM, scanning electron microscopy SEM, X-ray photoelectron spectroscopy XPS, and optical spectrophotometry were applied for sample characterization. Measurements of photocurrent versus voltage and wavelength over the ultraviolet uv and visible vis ranges of the light spectrum were performed in order to assess the performance of nitrogen-doped titanium dioxide thin films as photoanodes for hydrogen generation in photoelectrochemical cells, PEC. Undoped TiO2 and TiO2-x films were found to be composed of anatase and rutile mixture with larger anatase crystallites (25-35 nm) while the growth of smaller rutile crystallites (6-10 nm) predominated at higher nitrogen flow rates etaN2 as measured in standard cubic centimeters, sccm. Nitrogen-to-titanium ratio increased from N/Ti = 0.05 at etaN2 = 0.8 sccm for stoichiometric TiO2:N to N/Ti = 0.11 at etaN2 = 0.8 sccm for nonstoichiometric TiO2-x:N thin films. A red-shift in the optical absorbance was observed with an increase in etaN2. Doping with nitrogen improved photoelectrochemical properties over the visible range of the light spectrum in the case of nonstoichiometric samples.

TiO2-based nanopowders and thin films for photocatalytical applications.

TiO2-based nanopowders are elaborated by flame spray synthesis, FSS from organic precursors of titanium and chromium with the Cr content changing from 0 to 15 at.%. Well-crystallized nanopowders with high specific surface area SSA reaching 107 m2/g for undoped TiO2 and 177 m2/g for TiO2 + 15 at.% Cr are obtained. Thin films are deposited by rf reactive sputtering from metallic Ti and Ti-Cr targets in Ar + O2 flow controlled atmosphere. The adjustable area of Cr/Ti allows to obtain up to 16 at.% Cr in TiO2 thin films. X-ray diffraction, transmission electron spectroscopy, TEM, atomic force microscopy, AFM and optical spectrophotometry over the ultraviolet UV and visible VIS range of the light spectrum have been performed in order to characterize the nanomaterials. The particle size of nanopowders is within the range of 5-42 nm. Anatase is the predominating polymorphic form while the amount of rutile increases with Cr content to reach of about 25 wt.% at 15 at.% Cr. The post-deposition annealing of thin films in air at temperatures from 770 K to 1280 K modifies the phase composition, leads to irreversible transformation from anatase to rutile and affects the surface roughness. Structural and optical properties of TiO2-based nanopowders and thin films are compared. The effect of grain size and the level of chromium doping on the band gap E(g) is discussed. Photocatalytic activity of the nanopowders is tested for degradation of methylene blue, MB.