Identification of the structural phases of Ce(x)Zr(1-x)O2 by Eu(III) luminescence studies.
ABSTRACT Despite the wide application of ceria-zirconia based materials in Three Way Catalysts (TWCs), Solid Oxides Fuel Cells (SOFCs), and H(2) production and purification reactions, an active debate is still open on the correlation between their structure and redox/catalytic performances. Existing reports support the need of either (i) a homogeneous solid solution or (ii) materials with nanoscale heterogeneity to obtain high activity and stability. Here we report on a simple and inexpensive approach to solve this problem taking advantage of the luminescence properties of Eu(III), used as a structural probe introduced either in the bulk or on the surface of the samples. In this way, the real structure of ceria-zirconia materials can be revealed even for amorphous high surface area samples. Formation of small domains is observed in catalytically important metastable samples which appear homogeneous by conventional XRD.
- SourceAvailable from: Shyam Sarkar[show abstract] [hide abstract]
ABSTRACT: Heavy metal fluorides like BiF3 as a host for lanthanide ions are of interest as bismuth is the only heavy metal that is nontoxic. In this work, we report the synthesis of highly water-dispersible ultrasmall BiF3 nanoparticles about 6 nm in size within a poly(vinyl pyrrolidone) matrix by a hydrothermal method. Microscopy analysis reveals that the nanoparticles are well separated and confined within the polymer network. These nanoparticles were found to be excellent hosts for lanthanide (Ln(3+) ) ions. Through suitable Ln(3+) doping, BiF3 exhibits strong emissions in the visible region upon both UV and near infrared (NIR) excitations. The non-toxicity of both bismuth and PVP can be advantageous for the potential use of BiF3 nanoparticles in drug delivery and bioimaging.Chemistry - An Asian Journal 11/2013; · 4.57 Impact Factor
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ABSTRACT: Selection of the excitation wavelength at nonresonant and resonant Raman conditions provided detection selectivity in the tetragonal and cubic phases in CeO(2)-ZrO(2) nanocrystals, respectively. It was suggested that cubic-phase domains containing Ce(3+) deficiencies were involved in the tetragonal-phase matrix.Nanoscale 08/2010; 2(8):1426-8. · 6.23 Impact Factor
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ABSTRACT: Pure and europium (Eu(3+)) doped ZrO(2) 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 ZrO(2) 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 Eu(3+) f-f transitions or indirect excitation into UV charge-transfer bands. After annealing at 500 °C, the overall Eu(3+) emission is dominated by Eu(3+) located in tetragonal symmetry lattice sites with a crystal-field splitting of the (5)D(0)-(7)F(1) emission of 20 cm(-1). Annealing of ZrO(2) at 1000 °C leads to a superposition of Eu(3+) emissions from tetragonal and monoclinic lattice sites with monoclinic crystal-field splitting of 200 cm(-1) for the (5)D(0)-(7)F(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 Eu(3+) doped ZrO(2) 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.Physical Chemistry Chemical Physics 08/2012; 14(37):12970-81. · 3.83 Impact Factor