Oxygen vacancy defects (VO) in Ti-based oxides play important roles in catalytic processes despite limited knowledge regarding their formation and characterization. Here, we demonstrate the use of X-ray absorption spectroscopy (XAS) measurements to compare the relative proportion of VO defects in as-grown alkali hexatitanate A2Ti6O13 (A = Li, Na, K). Both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions were studied. The similarity of measured XANES spectra of Ti K-edge in all samples indicates the presence of (Ti4+)O6 units in good agreement with reported X-ray diffraction results. The small influence of cations A at the tunnel was observed and can be well reproduced in the simulated spectra. In addition, we present a semi-quantitative approach to intuitively determine the content of VO defects in oxygen-deficient K2Ti6O13-x by in situ time-resolved XAS measurements under reducing conditions (10%H2/Ar, 50-650 °C). The in situ XANES measurements indicate that the oxidation state of bulk Ti remains the same as the as-grown sample, i.e., 4+, at elevated temperatures. By in situ EXAFS measurements, the relative number of VO defects is highest at a reduction temperature of ∼550 °C and slightly decreases after that. To confirm the formation of VO defects, first-principles calculations were independently carried out using a 126-atom K2Ti6O13 supercell with VO at various positions. Based on calculated EXAFS, the removal of the oxygen atom nearest to the tunnel, which is the lowest energy structure, provides a good match to the experimental spectra.
We present an investigation of spiral waves pinned to circular and rectangular obstacles with different circumferences in both thin layers of the Belousov-Zhabotinsky reaction and numerical simulations with the Oregonator model. For circular objects, the area always increases with the circumference. In contrast, we varied the circumference of rectangles with equal areas by adjusting their width w and height h. For both obstacle forms, the propagating parameters (i.e., wavelength, wave period, and velocity of pinned spiral waves) increase with the circumference, regardless of the obstacle area. Despite these common features of the parameters, the forms of pinned spiral waves depend on the obstacle shapes. The structures of spiral waves pinned to circles as well as rectangles with the ratio w/h∼1 are similar to Archimedean spirals. When w/h increases, deformations of the spiral shapes are observed. For extremely thin rectangles with w/h≫1, these shapes can be constructed by employing semicircles with different radii which relate to the obstacle width and the core diameter of free spirals.
Spiral waves have been observed in a thin layer of excitable media. Especially, electrical spiral waves in cardiac tissues connect to cardiac tachycardia and life-threatening fibrillations. The Belousov-Zhabotinsky (BZ) reaction is the most widely used system to study the dynamics of spiral waves in experiments. When the light sensitive Ru(bpy)3
2+ is used as the catalyst, the BZ reaction becomes photosensitive and the excitability of the reaction can be controlled by varying the illumination intensity. However, the typical photosensitive BZ reaction produces many CO2 bubbles so the spiral waves are always studied in thin layer media with opened top surfaces to release the bubbles. In this work, we develop new chemical recipes of the photosensitive BZ reaction which produces less bubbles. To observe the production of bubbles, we investigate the dynamics of spiral waves in a closed thin layer system. The results show that both the speed of spiral waves and the number of bubbles increase with the concentration of sulfuric acid (H2SO4) and sodium bromate (NaBrO3). For high initial concentrations of both reactants, the size of bubbles increases with time until the wave structures are destroyed. We expect that the chemical recipes reported here can be used to study complicated dynamics of three-dimensional spiral waves in thick BZ media where the bubbles cannot escape.
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