Nonaqueous reactions between titanium(IV) chloride and alcohols (benzyl alcohol or n-butanol) were used for the synthesis of anatase TiO2 particles, while rutile TiO2 particles were synthesized in aqueous media by acidic hydrolysis of titanium(IV) chloride. The X-ray diffraction measurements proved the exclusive presence of either the anatase or the rutile phase in prepared samples. The photoluminescence of both kinds of particles (anatase and rutile) with several well-resolved peaks extending in the visible spectral region was observed, and the quantum yield at room temperature was found to be 0.25%. Photon energy up-conversion from colloidal anatase and rutile TiO2 particles was observed at low excitation intensities. The energy of up-converted photoluminescence spans the range of emission of normal photoluminescence. The explanation of photon energy up-conversion involves mid-gap energy levels originating from oxygen vacancies.
Titanium dioxide nanopowders doped with different amounts of Fe ions were prepared by coprecipitation method. Obtained materials were characterized by structural (XRD), morphological (TEM and SEM), optical (UV/vis reflection and photoluminescence, and Raman), and analytical techniques (XPS and ICP-OES). XRD analysis revealed rutile crystalline phase for doped and undoped titanium dioxide obtained in the same manner. Diameter of the particles was 5–7 nm. The presence of iron ions was confirmed by XPS and ICP-OES. Doping process moved absorption threshold of TiO2into visible spectrum range. Photocatalytic activity was also checked. Doped nanopowders showed normal and up-converted photoluminescence.
Nitrogen-doped TiO (N-TiO) is considered as one of the most promising materials for various photocatalytic applications, while noble metals Pd and Pt are known as good catalysts for hydrogen evolution. This work focuses on the determination of structural and electronic modifications of N-TiO, achieved by noble metal deposition at the surface, as a starting indicator for potential applications. We focus on the properties of easily synthesized nanocrystalline nitrogen-doped anatase TiO, modified by depositing small amounts of Pd (0.05 wt%) and Pt (0.10 wt%), aiming to demonstrate efficient enhancement of optical properties. The chemical states of dopants are studied in detail, using X-ray photoemission spectroscopy, to address the potential of N-TiO to act as a support for metallic nanoparticles. DFT calculations are used to resolve substitutional from interstitial nitrogen doping of anatase TiO, as well as to study the combined effect of nitrogen doping and oxygen vacancy formation. Based on the binding energies calculated using Slater's transition state theory, dominant contribution to the N 1s binding energy at 399.8 eV is ascribed to interstitially doped nitrogen in anatase TiO. Given that both structure and photocatalytic properties depend greatly on the synthesis procedure, this work contributes further to establishing correlation between the structure and optical properties of the noble metal modified N-TiO system.
We report a simple colloidal synthesis of two types of Sb 2 S 3 nanowires with small band gap and high aspect ratio. Field-emission scanning electron and transmission electron microscopies confirmed formation of high aspect ratio Sb 2 S 3 nanowires, separated in the form of bundles and coalesced with each other in long bars. Diffuse reflectance and absorption spectroscopies revealed that the optical band-gap energies of the synthesized nanowires separated in the form of bundles are 1.56 and 1.59 eV, and coalesced with each other in long bars are 1.36 and 1.28 eV, respectively. The structure refinement showed that Sb 2 S 3 powders belong to the orthorhombic structure with space group Pnma (no. 62). It was found that Sb 2 S 3 nanowires separated in the form of bundles predominantly grow along the [0 1 0] direction being in the needle-like shape. The nanowires coalesced with each other in long bars rise in the form of long bars, are ribbon-like in shape and have expressed {1 0 1} facets which grow along the [0 1 0] direction. No peaks in photoluminescence spectra were observed in the spectral range from 250 to 600 nm. In order to shed more light on the experimental results concerning the band-gap energies and, in the literature generally poorly investigated electronic properties of the synthesized material, we performed theoretical calculations of the electronic structure and optical properties of the Sb 2 S 3 samples synthesized here. This was done on the basis of density functional theory with the generalized gradient approximation, and also with an improved version of the exchange potential suggested recently by Tran and Blaha. The main characteristic is the significant improvement of the band gap value.
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