Effects of cerium dopant concentration on structural properties and photocatalytic activity of electrospun Ce-doped TiO2 nanofibers

Electrospun \(\hbox {TiO}_2\) and Ce-doped \(\hbox {TiO}_2\) nanofibers were prepared with 0.5, 2.0 and 8.0 % weight Ce. The structural properties and phase composition were characterized using high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction and X-ray absorption near edge spectroscopy (XANES) at the Ti K-edge. The undoped nanofibers are composed of an assembly of \(\hbox {TiO}_2\) nanoparticles and their crystal structure is a mixture of anatase and rutile phases with an anatase:rutile volume ratio close to 3:1. As Ce is introduced, the nanoparticles decrease in size and the rutile phase volume decreases. Ce \(\hbox {L}_3\) -edge XANES probed the local structure of Ce dopants. At 0.5 % Ce, most Ce ions are incorporated in the \(\hbox {Ce}^{3+}\) charge state but, at 2 % Ce, the majority are \(\hbox {Ce}^{4+}\) . Visible light absorption indicated that \(\hbox {Ce}^{3+}\) act as shallow acceptors that only participate in absorption of wavelengths below 420 nm but \(\hbox {Ce}^{4+}\) impurity states are associated with absorption of wavelengths up to 550 nm. Photocatalytic performance of the nanofibers was assessed by measuring the degradation of adsorbed Rhodamine B in aqueous solution under visible and ultraviolet light. The 0.5 % Ce-doped \(\hbox {TiO}_2\) nanofiber showed the best visible-light photocatalytic activity, which is probably due to the majority presence of \(\hbox {Ce}^{3+}\) . At higher Ce concentration, the photocatalytic reaction rate was lower than undoped nanofibers, indicating that recombination at the \(\hbox {Ce}^{4+}\) sites is rate limiting.     

Structural characterizations of sol–gel synthesized TiO2 and Ce/TiO2 nanostructures

Mixed phase TiO₂ and Ce/TiO₂ samples were synthesized by a sol–gel method using different hydrolysis conditions. In pure TiO₂ samples, traditional X-ray diffraction (XRD) and Ti K-edge synchrotron X-ray absorption near edge structures (XANES) independently revealed their anatase/rutile phase ratios. XANES results further revealed a substantial amount of Ti atoms existed in other forms beside anatase and rutile TiO₂ in the sample synthesized by the low hydrolysis condition. An increase in the extent of the hydrolysis during the synthesis leads to an increased rutile ratio and a reduction in other forms. In Ce/TiO₂ samples, the crystal sizes were too small for XRD characterization. Only XANES could be used to characterize their phase ratios. It is found that adding Ce impedes rutile formation; leading to increased anatase ratio. The difference in the fundamental aspects of XRD and XANES techniques in providing the phase ratios is discussed.     

Schiff base complex sol–gel method for LaCoO3 perovskite preparation with high-adsorbed oxygen

A novel Schiff base complex sol–gel method has been used to prepare LaCoO₃ producing high ratios of adsorbed (or surface) oxygen (α) to lattice oxygen (β). The as-prepared gels, characterized by Fourier transform infrared spectroscopy (FTIR), showed that both lanthanum and cobalt ions were complexed before calcinations. IR spectra revealed that CO₃²⁻ and NO₃⁻ presented on the sample surfaces during heat treatment. High-resolution transmission electron microscopic (HRTEM) images of all samples showed resolved lattice fringes with the inter-planar spacing 0.37–0.39 nm of the (0 1 2) plane in hexagonal perovskite. BET surface areas of LaCoO₃ nano-crystals were 11.7–18.6 m²/g. Ratios of adsorbed (or surface) oxygen (α) to lattice oxygen (β) quantified by X-ray photoemission spectroscopy showed that LaCoO₃ prepared by the Schiff base complex method produced higher ratios when bases had higher nitrogen content in molecules. Carbonate and nitrate which were resulting from the oxidation of functional groups in the Schiff base complex, can produce gaseous compounds and leave vacant sites for oxygen in the gas phase to adsorb.     

Asymmetric ethylation of aromatic aldehyde by diethylzinc in the presence of chiral auxiliaries derived from (S)-[4-HOC6H4CH2CH(NH2)CPh2OH]

A comparative study has been carried out on enantioselective ethylation of aromatic aldehydes (ArCHO) by diethylzinc (Et₂Zn) in the presence of catalytic amounts of (S)-[4-HOC₆H₄CH₂CH(NH₂)CPh₂OH] (1) or chiral auxiliaries derived from (1). Various procedures have been adopted; these involved (i) different sequences of addition of the reagents ArCHO, Et₂Zn and (1), and (ii) use of titanium(IV)isopropoxide [Ti(OPrⁱ)₄] or the boranetetrahydrofuran addition compound (BH₃ · THF) as additional reagents. In all but one of the procedures adopted, (S)-ArCH(OH)Et was selectively formed; enantiomeric excess values up to 87% were obtained.