To use solar irradiation or interior lighting efficiently, we sought a photocatalyst with high reactivity under visible light. Films and powders of TiO(2-x)N(x) have revealed an improvement over titanium dioxide (TiO2) under visible light (wavelength < 500 nanometers) in optical absorption and photocatalytic activity such as photodegradations of methylene blue and gaseous acetaldehyde and hydrophilicity of the film surface. Nitrogen doped into substitutional sites of TiO2 has proven to be indispensable for band-gap narrowing and photocatalytic activity, as assessed by first-principles calculations and x-ray photoemission spectroscopy.
Introduction 9824 2. Materials Design for Visible-Light-Sensitive Photocatalyst 9825 2.1. Electronic Structure of TiO 2 9825 2.2. Photoelectrochemistry of TiO 2 and Conditions for Visible-Light Sensitization 9826 2.3. Metal Doping of TiO 2 9827 2.4. Design of Nonmetal Doping for Visible-Sensitization 9828 3. Synthesis and Properties of N-Doped TiO 2 9830 3.1. Synthesis 9830 3.1.1. Powder 9830 3.
TiO2-based powder, including 0.1 at% of N doped in the rutile lattice, has been synthesized by oxidation of TiN. As a result, a significant shift of the absorption edge to a lower energy in the visible-light region has been observed. The substitutional doping of N into the TiO2 lattice is found to be effective; its 2p states contribute to the band-gap narrowing by mixing with O 2p as shown in ab initio electronic structure calculations.
N-doped TiO2 films were deposited on n+-GaN∕Al2O3 substrates by reactive magnetron sputtering and subsequently crystallized by annealing at 550 °C in flowing N2 gas. The N-doping concentration was ∼8.8%, as determined from x-ray photoelectron spectroscopy measurements. Deep-level optical spectroscopy measurements revealed two characteristic deep levels located at ∼1.18 and ∼2.48eV below the conduction band. The 1.18 eV level is probably attributable to the O vacancy state and can be active as an efficient generation-recombination center. Additionally, the 2.48 eV band is newly introduced by the N doping and contributes to band-gap narrowing by mixing with the O2p valence band.
We measured the Schottky barrier heights and specific contact resistivities of four different metals on p-type GaN. The Schottky barrier heights of Pt, Ni, Au, and Ti were obtained from the current-voltage characteristics to be 0.50, 0.50, 0.57, and 0.65 eV, respectively. The specific contact resistivities were 0.013, 0.015, 0.026, and 0.035 Ω⋅cm2, respectively. Our experimental results proved that the Schottky barrier heights and specific contact resistivities decrease with increase in metal work function as expected theoretically.
We report the photooxidation of toluene over nitrogen doped TiO(2) (TiO(2-x)N(x)) under visible light irradiation. The photocatalytic oxidation of toluene in air over TiO(2-x)N(x) powders was studied using diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), gas chromatography (GC), ion chromatography (IC), and gas chromatography mass spectrometry (GC-MS), focusing on the photocatalytic decomposition processes of toluene. Results obtained indicate that toluene, weakly adsorbed on the catalyst surface, is initially photooxidized to benzaldehyde which adsorbs onto the TiO(2-x)N(x) surface more strongly, leading to the formation of ring-opening products such as carboxylic acids and aldehydes. No gaseous intermediates were detected during the photooxidation. Major intermediates adsorbed at the catalyst surface were oxalic acid, (COOH)(2), acetic acid, CH(3)COOH, formic acid, HCOOH, and pyruvic acid, CH(3)COCOOH, whereas more complicated carboxylic species, including propionic acid, CH(3)CH(2)COOH, isovaleric acid, (CH(3))(2)CHCH(2)COOH, and succinic acid, (CH(2)COOH)(2), were also found in the early stage of the photooxidation. These intermediate products were gradually photodegraded to CO(2) and H(2)O under visible light irradiation.
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