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Pure and europium (Eu3+) doped cerium dioxide (CeO2) nanocrystals have been synthesized by a novel oil-in-water microemulsion reaction method under soft conditions. In-situ X-ray diffraction and RAMAN spectroscopy, high-resolution transmission electron microscopy, UV/Vis diffuse-reflectance and Fourier transform infrared spectroscopy as well as time-resolved photoluminescence spectroscopy were used to characterize the nanaocrystals. The as-synthesized powders are nanocrystalline and have a narrow size distribution centered on 3 nm and high surface area of similar to 250 m(2) g(-1). Only a small fraction of the europium ions substitutes for the bulk, cubic Ce4+ sites in the europium-doped ceria nanocrystals. Upon calcination up to 1000 degrees C, a remarkable high surface area of similar to 120 m(2) g (-1) is preserved whereas an enrichment of the surface Ce4+ relative to Ce3+ ions and relative strong europium emission with a lifetime of similar to 1.8 ms and FWHM as narrow as 10 cm(-1) are measured. Under excitation into the UV and visible spectral range, the europium doped ceria nanocrystals display a variable emission spanning the orange-red wavelengths. The tunable emission is explained by the heterogeneous distribution of the europium dopants within the ceria nanocrystals coupled with the progressive diffusion of the europium ions from the surface to the inner ceria sites and the selective participation of the ceria host to the emission sensitization. Effects of the bulk-doping and impregnation with europium on the ceria host structure and optical properties are also discussed.
Pure and europium (Eu3+) doped ZrO2 synthesized by an oil-in-water microemulsion reaction method were investigated by in situ and ex situ X-ray diffraction (XRD), ex situ Raman spectroscopy, high-resolution transmission electron microscopy (HRTEM), steady state and time-resolved photoluminescence (PL) spectroscopies. Based on the Raman spectra excited at three different wavelengths i.e. 488, 514 and 633 nm and measured in the spectral range of 150-4000 cm(-1) the correlation between the phonon spectra of ZrO2 and luminescence of europium is clearly evidenced. The PL investigations span a variety of steady-state and time resolved measurements recorded either after direct excitation of the Eu3+ f-f transitions or indirect excitation into UV charge-transfer bands. After annealing at 500 degrees C, the overall Eu3+ emission is dominated by Eu3+ located in tetragonal symmetry lattice sites with a crystal-field splitting of the D-5(0)-F-7(1) emission of 20 cm(-1). Annealing of ZrO2 at 1000 degrees C leads to a superposition of Eu3+ emissions from tetragonal and monoclinic lattice sites with monoclinic crystal-field splitting of 200 cm(-1) for the D-5(0)-F-7(1) transition. At all temperatures, a non-negligible amorphous/disordered content is also measured and determined to be of monoclinic nature. It was found that the evolutions with calcination temperature of the average PL lifetimes corresponding to europium emission in the tetragonal and monoclinic sites and the monoclinic phase content of the Eu3+ doped ZrO2 samples follow a similar trend. By use of specific excitation conditions, the distribution of europium on the amorphous/disordered surface or ordered/crystalline sites can be identified and related to the phase content of zirconia. The role of zirconia host as a sensitizer for the europium PL is also discussed in both tetragonal and monoclinic phases.
Zeolites NaY and ZSM-5 were used as hosts for styrene polymerization after ion-exchange with europium ions. The parent and hybrid, polystyrene coated Eu-NaY (Eu-NaY/PS) and Eu-ZSM-5 (Eu-ZSM-5/PS) zeolites were investigated by using thermal analysis, SEM, PXRD, FT-IR, DR-UV/Vis, steady state and time-resolved photoluminescence spectroscopy. FT-IR spectra evidenced for the interaction between the zeolitic hosts and polystyrene while the PXRD spectra supported for the presence of the polymer inside the channels/pores of Eu-NaY/PS and Eu-ZSM-5/PS materials. The optical properties of Eu-NaY/PS and Eu-ZSM-5/PS were significantly changed relative to those of the parent zeolites, giving further evidence for the presence of polymer inside zeolites. An interesting case is presented by NaY zeolite: following styrene polymerization, the polymer interacted selectively with one of the two main species co-existing inside zeolite while for ZSM-5 a similar effect was not observed.
Two different types of mesoporous silicon-phosphate supports using different surfactants (a mixture of (CH3)(3)C13H27NBr with an organophosphorus coupling molecule (HO-PO(i-C3H7)(2)) and with a co-surfactant ((C2H5)(3)(C6H5)PCl), respectively) were synthesized. Trivalent europium (Eu) ions were immobilized via ion-exchange on these supports. The resulting materials were characterized using nitrogen adsorption isotherms at -196 degrees C, thermogravimetric analysis, SEM, TEM, FT-IR, PXRD, CP/MAS. (HSi)-H-1-Si-29 and P-31 NMR, DR-UV-vis as well as steady- state and time-resolved photoluminescence spectroscopy. The results evidenced that the co-polymerization of silicon and phosphorous yielded a unique morphology in these materials. Following calcination at 450 and 900 degrees C europium- exchanged silicon-phosphates with great surface area (BET=600-705 m(2) g(-1)) and 3.4 nm sized mesopores were obtained. The differences among the optical properties of the non-calcined europium materials such as the emission lifetimes, local environment at the europium sites or the relative contribution of the upper excited levels to the total photoluminescence were assigned to the surfactants used in the synthesis. Calcination of the silicon-phosphates at higher temperatures than 450 degrees C did not induce major changes in the structural properties: in contrast, photoluminescence properties of europium were markedly improved in terms of intensity and average lifetime.
Time-resolved photoluminescence analysis of distribution and migration of terbium ions in zeolites X
(2004)
The photoluminescence (PL) dynamics of terbium-exchanged zeolites X was investigated upon laser excitation at 355 nm. The results evidenced the presence of at least two terbium main environments with PL lifetimes varying between 391-411 and 753-770 mus. The two-site nature of terbium distribution in zeolites X permitted a quantitative analysis of the migration process of terbium ions inside the pores and cavities upon dehydration in air at 200 degreesC. Besides the increase of the PL lifetimes with about 30% and 80% compared to those of the hydrated zeolite, a fraction of almost 30% of terbium ions was estimated to migrate from the supercages to the neighboring sodalites or hexagonal prisms. Our results evidenced for the first time the capability of time-resolved luminescence spectroscopy in quantitatively tracking for the intrazeolitic migration of lanthanides. (C) 2004 Elsevier B.V. All rights reserved