The internal luminescence quantum efficiency and color properties of AVO3 (A: Li, Na, K, Rb, and Cs), M2V2O7 (M: Mg, Ca, Sr, Ba, and Zn), and M3V2O8 (M: Mg, Ca, Sr, Ba, and Zn) have been investigated. These vanadate phosphors exhibited broadband emission from 400 nm to over 800 nm due to the one-electron charge transfer transition in the VO4 tetrahedra, and the color of the luminescent materials ranged from green to yellow-orange via white, corresponding to 0.277 < x < 0.494 and 0.389 < y < 0.488 on the CIE chromaticity diagram. We found that the luminescence quantum efficiency of the vanadate phosphors with VO4 tetrahedra was strongly enhanced by the strong interaction between V ions and the weak interaction between V and A(M) ions in the crystal structures. We hypothesize that the long exciton diffusion lifetime induced by these structural features enhanced luminescence, leading to high quantum efficiency.
Abstract:We apply high-energy proton ion-implantation to modify TiO 2 nanotubes selectively at their tops. In the proton-implanted region we observe the creation of intrinsic co-catalytic centers for photocatalytic H 2 -evolution. We find proton implantation to induce specific defects and a characteristic modification of the electronic properties not only in nanotubes but also on anatase single crystal (001) surfaces. Nevertheless, for TiO 2 nanotubes a strong synergetic effect between implanted region (catalyst) and implant-free tube segment (absorber) can be obtained. Keywords:nanotubes; photocatalysts; water-splitting; titania; self-organization; ion-implantation 2 Ever since 1972, when Honda and Fujishima introduced photolysis of water using a single crystal of TiO 2 , photocatalytic water splitting has become one of the most investigated scientific topics of our century [1]. The concept is strikingly simple: light (preferably sunlight) is absorbed in a suitable semiconductor and thereby generates electron-hole pairs. These charge carriers migrate in valence and conduction bands to the semiconductor surface where they react with water to form O 2 and H 2 , respectively. Thus hydrogen, the energy carrier of the future, could be produced using just water and sunlight.Key factors for an optimized conversion of water to H 2 are i) as complete as possible absorption of solar light (small band gap) while ii) still maintaining the thermodynamic driving force for water splitting (sufficiently large band-gap), including suitable band-edge positions relative to the water red-ox potentials, and iii) possibly most challenging -a sufficiently fast carrier transfer from semiconductor to water to obtain a reasonable reaction kinetics as opposed to carrier recombination or photo-corrosion [2][3][4][5][6][7].In spite of virtually countless investigations on a wide range of semiconductor materials that in many respects are superior to titania (mostly in view of solar light absorption and carrier transport), TiO 2 still remains one of the most investigated photocatalysts. This is only partially due to suitable energetics but more so because of its outstanding (photo-corrosion) stability [2][3][4][5][6][7].In general, the main drawbacks of TiO 2 are on the one hand its too large band-gap of 3-3.2 eV that allow only for about 7% of solar light absorption, and on the other hand that although a charge transfer to aqueous electrolytes is thermodynamically possible, the kinetics of these processes at the TiO 2 /water interface are extremely slow if no suitable co-catalysts such as Pt, Au, Pd or similar are used [8][9][10]. Mao demonstrated a significantly increased photocatalytic activity for water splitting when black TiO 2 was loaded with a Pt co-catalyst and used under bias-free conditions (i.e. used directly as a nanoparticle suspension in an aqueous/methanol solution under sunlight (AM 1.5) conditions). The high catalyst activity was attributed to a thin amorphous TiO 2 hydrogenated layer that was formed under high pressure tre...
New metal-ordered manganites RBaMn2O6 have been synthesized and investigated in the structures and electromagnetic properties. RBaMn2O6 can be classified into three groups from the structural and electromagnetic properties. The first group (R = La, Pr and Nd) has a metallic ferromagnetic transition, followed by an A-type antiferromagnetic transition in PrBaMn2O6. The second group (R = Sm, Eu and Gd) exhibits a charge-order transition, followed by an antiferromagnetic long range ordering. The third group (R = Tb, Dy and Ho) shows successive three phase transitions, the structural, charge/orbital-order and magnetic transitions, as observed in YBaMn2O6. Comparing to the metal-disordered manganites (R 3+ 0.5 A 2+ 0.5 )MnO3, two remarkable features can be recognized in RBaMn2O6; (1) relatively high charge-order transition temperature and (2) the presence of structural transition above the charge-order temperature in the third group. We propose a possible orbital ordering at the structural transition, that is a possible freezing of the orbital, charge and spin degrees of freedom at the independent temperatures in the third group. These features are closely related to the peculiar structure that the MnO2 square-lattice is sandwiched by the rock-salt layers of two kinds, RO and BaO with extremely different lattice-sizes.PACS numbers:
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