Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands

A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.

Enhancing photoactivity of TiO2(B)/anatase core-shell nanofibers by selectively doping cerium ions into the TiO2(B) Core

Cerium ions (Ce3+) can beselectively doped into the TiO2(B) core of TiO2(B)/anatase core–shell nanofibers by means of a simple one-pot hydrothermal treatment of a starting material of hydrogen trititanate (H2Ti3O7) nanofibers. These Ce3+ ions (≈0.202 nm) are located on the (110) lattice planes of the TiO2(B) core in tunnels (width≈0.297 nm). The introduction of Ce3+ ions reduces the defects of the TiO2(B) core by inhibiting the faster growth of (110) lattice planes. More importantly, the redox potential of the Ce3+/Ce4+ couple (E0(Ce3+/Ce4+)=1.715 V versus the normal hydrogen electrode) is more negative than the valence band of TiO2(B). Therefore, once the Ce3+-doped nanofibers are irradiated by UV light, the doped Ce3+ ions in close vicinity to the interface between the TiO2(B) core and anatase nanoshell can efficiently trap the photogenerated holes. This facilitates the migration of holes from the anatase shell and leaves more photogenerated electrons in the anatase nanoshell, which results in a highly efficient separation of photogenerated charges in the anatase nanoshell. Hence, this enhanced charge-separation mechanism accelerates dye degradation and alcohol oxidation processes. The one-pot treatment doping strategy is also used to selectively dope other metal ions with variable oxidation states such as Co2+/3+ and Cu+/2+ ions. The doping substantially improves the photocatalytic activity of the mixed-phase nanofibers. In contrast, the doping of ions with an invariable oxidation state, such as Zn2+, Ca2+, or Mg2+, does not enhance the photoactivity of the mixed-phase nanofibers as the ions could not trap the photogenerated holes.

LIII absorption edge studies of mixed valent cerium intermetallics and related systems

LIII absorption edge measurements clearly delineate 3+ and 4+ states of Ce. Absorption edges of 3+ compounds show a single peak, while those of 4+ compounds show two peaks, both appearing at higher energies than the characteristic peaks of 3+ compounds. In systems where there is interconfigurational fluctuation, features due to both 3+ and 4+ states are distinctly seen.

Precursor Dependent Microstructure Evolution and Nonstoichiometry in Nanostructured Cerium Oxide Coatings Using the Solution Precursor Plasma Spray Technique

A solution precursor plasma spray (SPPS) technique has been used for direct deposition of cerium oxide nanoparticles (CNPs) from various cerium salt solutions as precursors. Solution precursors were injected into the hot zone of a plasma plume to deposit CNP coatings. A numerical study of the droplet injection model has been employed for microstructure development during SPPS. The decomposition of each precursor to cerium oxide was analyzed by thermogravimetric-differential thermal analysis and validated by thermodynamic calculations. The presence of the cerium oxide phase in the coatings was confirmed by X-ray diffraction studies. Transmission electron microscopy studies confirmed nanocrystalline (grain size <14 nm) characteristic of the coatings. X-ray photoelectron spectroscopy studies indicated the presence of a high concentration of Ce3+ (up to 0.32) in the coating prepared by SPPS. The processing and microstructure evolution of cerium oxide coatings with high nonstoichiometry are reported.

Rearrangements in the cerium(IV) and manganese(III) oxidations of substituted naphthalenes and the nih shift mechanism

Ceric ammonium sulphate oxidation of 1- and 1,4- disubstituted naphthalenes gives 2- and/or 2,3- disubstituted 1,4- naphthoquinones through migration of substituents (D, Br, Ph). Similar rearrangements are also observed in the manganese(III) oxidation and also in the anodic oxidation of these substrates. The results are consistent with the proposal that these oxidations go through the formation of radical cation followed by reaction with H2O and further oxidation of the radical to the carbocationic intermediate on the way to the corresponding 1,4-naphthoquinone. Oxidation of 1,4-diphenylnaphthalene gives 2,3-diphenyl-1,4-naphthoquinone or 4-hydroxy- 2,4- diphenyl - 1(4)R - naphthalenone. The results are in accordance with the conclusion that such rearrangements do not require prior formation of arene oxide intermediates, originally proposed for the NM shift mechanism.

XPS and x-ray absorption-edge studies of the surface and bulk valence states of cerium in ceco2

XPS and LIII X-ray absorption edge studies regarding the valence state of cerium have been carried out on the intermetallic compounds CeCo2, which becomes superconducting at low temperatures. It is observed from XPS that the surface shows both Ce3+ and Ce4+ valence states, while the X-ray absorption edge studies reveal only Ce4+ in the bulk. Thus valence fluctuation and superconductivity do not coexist in the bulk of this compound.

Heat and mass transfer and chemical transformation in a cerium nitrate droplet

This paper deals with the thermo-physical changes that a droplet undergoes when it is radiatively heated in a levitated environment. The heat and mass transport model has been developed along with chemical kinetics within a cerium nitrate droplet. The chemical transformation of cerium nitrate to ceria during the process is predicted using Kramers' reaction mechanism which justifies the formation of ceria at a very low temperature as observed in experiments. The rate equation modeled by Kramers is modified suitably to be applicable within the framework of a droplet, and predicts experimental results well in both bulk form of cerium nitrate and in aqueous cerium nitrate droplet. The dependence of dissociation reaction rate on droplet size is determined and the transient mass concentration of unreacted cerium nitrate is reported. The model is validated with experiments both for liquid phase vaporization and chemical reaction. Vaporization and chemical conversion are simulated for different ambient conditions. The competitive effects of sensible heating rate and the rate of vaporization with diffusion of cerium nitrate is seen to play a key role in determining the mass fraction of ceria formed within the droplet. Spatially resolved modeling of the droplet enables the understanding of the conversion of chemical species in more detail.

Metal-metal charge transfer and interfacial charge transfer mechanism for the visible light photocatalytic activity of cerium and nitrogen co-doped TiO2

Nanosized cerium and nitrogen co-doped TiO2 (Ce-TiO2-xNx) was synthesized by sol gel method and characterized by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), FESEM, Fourier transform infrared, N-2 adsorption and desorption methods, photoluminescence and ultraviolet-visible (UV-vis) DRS techniques. PXRD analysis shows the dopant decreases the crystallite sizes and slows the crystallization of the titania matrix. XPS confirm the existence of cerium ion in +3 or +4 state, and nitrogen in -3 state in Ce-TiO2-xNx. The modified surface of TiO2 provides highly active sites for the dyes at the periphery of the Ce-O-Ti interface and also inhibits Ce particles from sintering. UV-visible DRS studies show that the metal-metal charge transfer (MMCT) of Ti/Ce assembly (Ti4+/Ce3+ -> Ti3+/Ce4+) is responsible for the visible light photocatalytic activity. Photoluminescence was used to determine the effect of cerium ion on the electron-hole pair separation between the two interfaces Ce-TiO2-xNx and Ce2O3. This separation increases with the increase of cerium and nitrogen ion concentrations of doped samples. The degradation kinetics of methylene blue and methyl violet dyes in the presence of sol gel TiO2, Ce-TiO2-xNx and commercial Degussa P25 was determined. The higher visible light activity of Ce-TiO2-xNx was due to the participation of MMCT and interfacial charge transfer mechanism.

Comparison of Convective and Radiative Heating Modes on the Thermophysical Changes of a Cerium Nitrate Droplet

In this paper, we try to establish the equivalence or similarity in the thermal and physiochemical changes in precursor droplets (cerium nitrate) in convective and radiative fields. The radiative field is created through careful heating of the droplet using a monochromatic light source (CO2 laser). The equivalence is also established for different modes of convection like droplet injected into a high-speed flow and droplet experiencing a convective flow due to acoustic streaming (levitated) only. The thermophysical changes are studied in an aqueous cerium nitrate droplet, and the dissociation of cerium nitrate to ceria is modeled using modified Kramers' reaction rate formulation. It is observed that vaporization, species accumulation, and chemical characteristics obtained in a convectively heated droplet are retained in a radiatively heated droplet by careful adjustment of the laser intensity. The timescales and ceria yield match reasonably well for both the cases. It is also noted that similar conclusions are drawn in both levitated droplet and a nonlevitated droplet.

Effect of cerium oxide on the precipitation of silver nanoparticles in femtosecond laser irradiated silicate glass

We investigated the effect of cerium oxide on the precipitation of Ag nanoparticles in silicate glass via a femtosecond laser irradiation and successive annealing. Absorption spectra show that Ce3+ ions may absorb part of the laser energy via multiphoton absorption and release free electrons, resulting in an increase of the concentration of Ag atoms and a decrease of the concentration of hole-trapped color centers, which influence precipitation of the Ag nanoparticles. In addition, we found that the formed Ag-0 may reduce Ce4+ ions to Ce3+ ions during the annealing process, which inhibits the growth of the Ag nanoparticles.

Comparison of cerium-doped Lu2Si2O7 and Lu2SiO5 scintillators

In this paper, high optical quality cerium-doped lutetium pyrosilicate(LPS:Ce) crystal has been grown by Czochralski method with the seed oriented along cleavage plane (1 1 0). The structure, segregation coefficient of Ce3+ and optical characterization of LPS:Ce crystal have been compared with those of LSO:Ce crystal. The results show that LPS:Ce has the advantage over LSO:Ce by having a larger segregation coefficient of Ce3+, lower cost of starting material, lower melting point and only one luminescence mechanism. Thus, LPS:Ce crystal offers an attractive alternative to LSO:Ce for scintillator applications. (c) 2005 Elsevier B.V. All rights reserved.

Czochralski growth and crystal structure of cerium-doped Lu2Si2O7 scintillator

Cerium-doped lutetium pyrosilicate crystal, Ce:Lu2Si2O7 (Ce:LPS), was grown by the Czochralski method. The segregation coefficient of Ce3+ ion was studied by the ICP-AES method. X-ray diffraction analysis showed that the structure of Ce:LPS crystal was monoclinic symmetry with space group of C2/m. Perfect cleavage planes (110) and imperfect cleavage planes (001) were observed by optical microscope. The reasons why it is difficult to grow crack-free crystals were studied. After optimized growth parameters, a Ce:LPS crystal with dimension of Phi 25 x 30 mm was grown, which is colorless, high optical quality, cracking-free and no inclusions. The transmittance of Ce:LPS crystal from 380 to 800 nm is over 82% and there is no observable absorption. (c) 2005 Elsevier B.V. All rights reserved.

Synthesis and luminescence characterization of cerium doped Lu2O3-Y2O3-La2O3 solid solution transparent ceramics

Ce3+:( Lu0.7Y0.25La0.05)(2)O-3 transparent ceramics were fabricated with nanopowders and sintered in H-2 atmosphere. The spectral properties of Ce3+:( Lu0.7Y0.25La0.05)(2)O-3 transparent ceramics were investigated and the luminescence of Ce3+ in the solid solution of Lu2O3, Y2O3 and La2O3 has been found. The ceramics has high density of 8.10g/cm(3) and short fluorescence lifetimes of 7.15 ns and 26.92 ns. It is expected to be a good fast response high temperature inorganic scintillating materials. (C) 2008 Optical Society of America.

The PL "violet shift" of cerium dioxide on silicon

CeO2 thin film was fabricated by dual ion beam epitaxial technique. The phenomenon of PL violet shift at room temperature was observed, and the distance of shift was about 65 nm. After the analysis of crystal structure and valence in the compound were carried out by XRD and XPS technique, it was concluded that the PL shift was related with valence of cerium ion in the oxides. When the valence of cerium ion varied front tetravalence to trivalence, the PL peak position would move from blue region to violet region and the phenomenon of "violet shift" was observed.