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X-ray photoelectron spectroscopy and electronic structure calculations in the framework of the coherent potential approach show that impurity Fe3+ ions substituting In in iron-doped In2O3 indium oxide(III) are in a paramagnetic state in the absence of oxygen vacancies. [ABSTRACT FROM AUTHOR]

A new ecologically clean method for the solid-phase synthesis of oxide copper-ceria catalysts with the use of the mechanochemical activation of a mixture of Cu powder (8 wt %) with CeO2 was developed. It was established that metallic copper was oxidized by oxygen from CeO2 in the course of mechanochemical activation. The intensity of a signal due to metallic Cu in the X-ray diffraction analysis spectra decreased with the duration of mechanochemical activation. The Cu1+, Cu2+, and Ce3+ ions were detected on the sample surface by X-ray photoelectron spectroscopy. The application of temperature-programmed reduction (TPR) made it possible to detect two active oxygen species in the reaction of CO oxidation in the regions of 190 and 210-220°C by a TPR-H2 method and in the regions of 150 and 180-190°C by a TPR-CO method. It is likely that the former species occurred in the catalytically active nanocomposite surface structures containing Cu-O-Ce bonds, whereas the latter occurred in the finely dispersed particles of CuO on the surface of CeO2. The maximum conversion of CO (98%, 165°C) reached by the mechanochemical activation of the sample for 60 min was almost the same as conversion on a supported CuO/CeO2 catalyst. [ABSTRACT FROM AUTHOR]

We present soft x-ray spectroscopy measurements and electronic structure calculations of ZnTiO3, a ternary oxide that is related to wurtzite ZnO and rutile TiO2. The electronic structure of ZnTiO3 was calculated using a variety of exchange-correlation functionals, and we compare the predicted band gaps of this material obtained from each functional with estimates from our experimental data and optical gaps quoted from the literature. We find that the main hybridizations in the electronic structure of ZnTiO3 can be predicted from the electronic structures of the two binary oxides. We further find that ZnTiO3 has weaker O 2p-Zn 3d repulsion than in ZnO, resulting in a relatively lower valence band maximum and consequently a larger band gap. Although we find a significant core hole shift in the measured O K XAS of ZnTiO3, we provide a simple empirical scheme for estimating the band gap that may prove to be applicable for any d10-d0 ternary oxide, and could be useful in finding a ternary oxide with a band gap tailored to a specific energy. [ABSTRACT FROM AUTHOR]

SnO 2 and Mn-doped SnO 2 single-phase tetragonal crystal structure quantum dots (QDs) of uniform size with control over dopant composition and microstructure were synthesized using the high pressure microwave synthesis technique. On a broader vision, we systematically investigated the influence of dilute Mn ions in SnO 2 under the strong quantum confinement regime through various experimental techniques and density functional theoretical (DFT) calculations to disclose the physical mechanism governing the observed ferromagnetism. DFT calculations revealed that the formation of the stable (001) surface was much more energetically favorable than that of the (100) surface, and the formation energy of the oxygen vacancies in the stable (001) surface was comparatively higher in the undoped SnO 2 QDs. X-ray photoelectron spectroscopy (XPS) and first-principles modeling of doped QDs revealed that the lower doping concentration of Mn favored the formation of MnO-like (Mn 2+ ) structures in defect-rich areas and the higher doping concentration of Mn led to the formation of multiple configurations of Mn (Mn 2+ and Mn 3+ ) in the stable surfaces of SnO 2 QDs. Electronic absorption spectra indicated the characteristic spin allowed ligand field transitions of Mn 2+ and Mn 3+ and the red shift in the band gap. DFT calculations clearly indicated that only the substitutional dopant antiferromagnetic configurations were more energetically favorable. The gradual increase of magnetization at a low level of Mn-doping could be explained by the prevalence of antiferromagnetic manganese-vacancy pairs. Higher concentrations of Mn led to the appearance of ferromagnetic interactions between manganese and oxygen vacancies. The increase in the concentration of metallic dopants caused not just an increase in the total magnetic moment of the system but also changed the magnetic interactions between the magnetic moments on the metal ions and oxygen. The present study provides new insight into the fundamental understanding of the origin of ferromagnetism in transition metal-doped QDs.