Anatase, rutile, and especially brookite nanocrystals have been selectively synthesized in this work via a redox route under mild hydrothermal conditions (180 °C, 3 h), employing trichloride as the titanium source and ammonium peroxodisulfate (APS), hydrogen peroxide, nitric acid, or perchloric acid as the oxidant. Characterizations of the three pure phases were achieved by XRD, Raman spectroscopy, FTIR, TG, HRTEM, UV−vis, and BET. The use of APS consistently yields anatase, but the particle morphology can be tuned from wormhole-structured agglomerates to more dispersed nanocrystallites. The use of other oxidants yields almost identical results, and phase selection can be attained in this case by controlling the reactant concentration and solution pH. The three phases show their distinctive crystal shapes:  rounded nanocrystals for anatase, nanoplates for brookite, and nanorods for rutile. Both the optical band gap (3.11 eV) and the indirect band gap (2.85 eV) of brookite were found to lie in between those of anatase and rutile. Under the same surface area of loaded TiO2, the brookite nanoplates exhibit the highest efficiency in the beaching of methyl orange solution under UV irradiation. The mechanism of phase selection was discussed based upon a systematic investigation into the effects of synthetic parameters on phase constituents of the hydrothermal products.

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Iron(III)-doped TiO(2) nanopowders, with controlled iron to titanium atomic ratios (R(Fe/Ti)) ranging from nominal 0 to 20%, were synthesized using oxidative pyrolysis of liquid-feed metallorganic precursors in a radiation-frequency (RF) thermal plasma. The valence of iron doped in the TiO(2), phase formation, defect structures, band gaps, and magnetic properties of the resultant nanopowders were systematically investigated using Mössbauer spectroscopy, XRD, Raman spectroscopy, TEM/HRTEM, UV-vis spectroscopy, and measurements of magnetic properties. The iron doped in TiO(2) was trivalent (3+) in a high-spin state as determined by the isomer shift and quadrupole splitting from the Mössbauer spectra. No other phases except anatase and rutile TiO(2) were identified in the resultant nanopowders. Interestingly, thermodynamically metastable anatase predominated in the undoped TiO(2) nanopowders, which can be explained from a kinetic point of view based on classical homogeneous nucleation theory. With iron doping, the formation of rutile was strongly promoted because rutile is more tolerant than anatase to the defects such as oxygen vacancies resulting from the substitution of Fe(3+) for Ti(4+) in TiO(2). The concentration of oxygen vacancies reached a maximum at R(Fe/Ti) = 2% above which excessive oxygen vacancies tended to concentrate. As a result of this concentration, an extended defect like crystallographic shear (CS) structure was established. With iron doping, red shift of the absorption edges occurred in addition to the d-d electron transition of iron in the visible light region. The as-prepared iron-doped TiO(2) nanopowders were paramagnetic in nature at room temperature.

Well-crystallized iron(III)-doped TiO2 nanopowders with controlled Fe3+ doping concentration and uniform dopant distribution, have been synthesized with plasma oxidative pyrolysis. The photocatalytic reactivity of the synthesized TiO2 nanopowders with a mean particle size of 50-70 nm was quantified in terms of the degradation rates of methyl orange (MO) in aqueous TiO2 suspension under UV (mainly 365 and 316 nm) and visible light irradiation (mainly 405 and 436 nm). The photodecomposition of MO over TiO2 nanopowders followed a distinct two-stage pseudo first order kinetics. Interestingly, the photocatalytic reactivity depends not only on the iron doping concentration but also on the wavelength of the irradiating light. Under UV irradiation, nominally undoped TiO2 had much higher reactivity than Fe3+ -doped TiO2, suggesting that Fe3+ doping (> 0.05 at. %) in TiO2 with a mean particle size of approximately 60 nm was detrimental to the photocatalytic decomposition of methyl orange. Whereas, under visible light irradiation, the Fe3+ -doped TiO2 with an intermediate iron doping concentration of approximately 1 at. % had the highest photocatalytic reactivity due to the narrowing of band gap so that it could effectively absorb the light with longer wavelength. A strategy for improving the photocatalytic reactivity of Fe3+ -doped TiO2 used in the visible light region is also proposed.

Uniform red-phosphor spheres (∼60-300 nm in diameter) of Y 2 O 3 :Eu 3+ binary and (Y,Gd) 2 O 3 :Eu 3+ ternary systems exhibiting excellent emission at 610 nm have been converted from their colloidal precursor spheres synthesized via homogeneous precipitation. The precursor spheres (approximate composition: [(Y 1-x Gd x ) 1-y -Eu y ](OH)CO 3 • 1.3H 2 O, x ) 0-0.5 and y ) 0-0.11) are directly solid solutions, but arising from sequential nucleation each of the spheres has more Gd and especially Eu while having less Y going from the particle surface to the core. Eu 3+ is more effective than Gd 3+ in raising nucleation density, leading to rapidly decreased average size of the precursor particles at a higher Eu 3+ addition. Diminishing the concentration gradients through adequate annealing is identified to be crucial to high luminous intensity of the oxide particles. At the optimal annealing temperature of 1000 °C, cation homogenization is achieved and the oxide particles largely retain their precursor morphologies, yielding dispersed uniform spheres of excellent luminescence. The (Y 1-x -Eu x )O 1.5 phosphor particles exhibit typical red emissions at 610 nm upon UV excitation into the charge transfer band at ∼255 nm, and the quenching concentration of Eu 3+ is found to be ∼5 at. %. Partially replacing Y 3+ with Gd 3+ (up to 50 at. %) while keeping Eu 3+ at the optimal content of 5 at. % linearly improves the 610 nm emission, and the phosphor particles of [(Y 0.5 Gd 0.5 ) 0.95 Eu 0.05 ]O 1.5 exhibit an luminous intensity ∼103% of that of a commercially available Y 2 O 3 :Eu red phosphor. The uniform phosphor spheres obtained in this work are expected to have wide applications in high-resolution display technologies of contemporary interest.

Eu3+-doped TiO2 luminescent nanocrystals have been synthesized in this work via Ar/O2 thermal plasma oxidizing mists of liquid precursors containing titanium tetra-n-butoxide and europium(III) nitrate, with varied O2 input in the plasma sheath (10-90 L/min) and Eu3+ addition in the precursor solution (Eu/(Ti + Eu) = 0-5 atom%). The resultant nanopowders are mixtures of the anatase (30-36 nm) and rutile (64-83 nm) polymorphs in the studied range, but the rutile fraction increases steadily at a higher Eu3+ addition, as revealed by X-ray diffraction (XRD) and Raman spectroscopy, because of the creation of oxygen vacancies in the TiO2 gas clusters by substitutional Eu3+ doping. The amount of Eu3+ that can be doped into a TiO2 lattice was limited up to 0.5 atom%, above which Eu2Ti2O7 pyrochlore was formed in the final products. High resolution transmission electron microscopy (HRTEM) observation indicates that the particles are dense and have sizes ranging from several nanometers up to 180 nm. Efficient nonradiative energy transfer from the TiO2 host to Eu3+ ions, which was seldom reported in the wet-chemically derived nanoparticles or thin films of the current system, was confirmed by combined studies of excitation, UV-vis (ultraviolet-visible), and PL (photoluminescence) spectroscopy. As a consequence of this, bright red emissions were observed from the plasma-generated nanopowders either by exciting the TiO2 host with UV light shorter than 405 nm or by directly exciting Eu3+ at a wavelength beyond the absorption edge (405 nm) of TiO2.

Uniform spheres of (Y 1-x Gd x ) 2 O 3 (x ) 0-1) are valuable for applications in phosphors, in optical ceramics fabrication, and in combinatorial synthesis. We made in this work such particles by thermal decomposition of precursors synthesized via homogeneous precipitation. Growth kinetics and composition evolution of the precursor spheres were investigated in detail, and it was identified for the first time that (1) differential nucleation occurs with regard to Y and Gd, and as a result concentration gradients exist within each precursor particle of the mixed Y/Gd system (more Gd and less Y from particle surface to the core), (2) average particle size of the colloidal sphere is inversely proportional to nucleation density and is significantly affected by the Gd content, (3) growth of the colloidal spheres is diffusion controlled and follows the cubic-root law, and (4) the dried precursor spheres directly convert to cubic-structured (Y 1-x Gd x ) 2 O 3 (x ) 0-1) oxides at 1000 °C while largely retaining their morphologies. The resultant oxides exhibit linearly increased lattice parameters and linearly decreased bandgaps (from 5.57 eV for Y 2 O 3 to 5.20 eV for Gd 2 O 3 ) with increased Gd addition. The findings of this work may have wide implications to other mixed materials systems.

A pulse-modulated plasma irradiation technique was applied to hydrogenation of ZnO. Three kinds of ZnO samples were employed to investigate the electronic state of hydrogen in ZnO. Secondary-ion-mass-spectroscopy analysis using isotope tracer revealed that the surface layer to 100 nm was doped with hydrogen after the irradiation and its concentration was in the order of 1016 cm−3. The efficiency of band edge emission was increased by the hydrogenation. However, the the degree of the improvements depended on impurity and defect concentration in the original samples. It was concluded that hydrogen in ZnO passivates deep donor and acceptor states by electron transfer from hydrogen to the defects.