Correlation of the oxidation state of cerium in sol-gel glasses as a function of thermal treatment via optical spectroscopy and XANES studies

Sol-gel glass matrices containing lanthanides have numerous technological applications and their formation involves several chemical facets. In the case of cerium, its ability to exist in two different oxidation states or in mixed valence state provides additional complexities for the sol-gel process. The oxidation state of cerium present during different facets of preparation of sol-gel glasses, and also as a function of the starting oxidation state of cerium added, were studied both by optical spectroscopy and X-ray absorption near-edge structures (XANES). The findings acquired by each approach were compared. The primary focus was on the redox chemistries associated with sample preparation, gelation, and thermal treatment. When Ce3+ is introduced into the starting sols, the trivalent state normally prevails in the wet and room temperature-dried gels. Heating in air at >100 degrees C can generate a light yellow coloration with partial oxidation to the tetravalent state. Above 200 degrees C and up to approximately 1000 degrees C, cerium is oxidized to its tetravalent state. In contrast, when tetravalent cerium is introduced into the sol, both the wet and room temperature-dried gels lose the yellow-brown color of the initial ceric ammonium nitrate solution. When the sol-gel is heated to 110 degrees C it turns yellowish as the cerium tends to be re-oxidized. The yellow color is believed to represent the effect of oxidation and oligomerization of the cerium-silanol units in the matrix. The luminescence properties are also affected by these changes, the details of which are reported herein.     

Microwave-Assisted Green Synthesis of Gold Nanoparticles Using Olibanum Gum (Boswellia serrate) and its Catalytic Reduction of 4-Nitrophenol and Hexacyanoferrate (III) by Sodium Borohydride

In this work we report straightforward, an economically viable, one-step microwave-assisted green synthesis of well stabilized gold nanoparticles (AuNPs) by reducing chloroauric acid with natural water soluble olibanum gum (Boswellia serrate). The olibanum gum acts as a dual role of reducing and capping agent for synthesis of AuNPs. The formation of AuNPs was confirmed using UV–Vis spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy and electron diffraction. The results indicated that the synthesized NPs were well dispersed and spherical in shape had an average diameter of 3 ± 2 nm. The reaction parameters significantly affected the formation of NPs, as the concentration of gum and irradiation time increases the formation of NPs particles increases and size of particles are reduced. In addition, it has been shown that these olibanum gum capped AuNPs functioned as effective homogeneous catalyst for the reduction of two model reactions hexacyanoferrate(III) and 4-nitrophenol by sodium borohydride. The kinetic investigations were carried out at different amount of AuNPs and different temperatures.     

Photoluminescence and Raman studies of Sm3+ and Nd3+ ions in zirconia matrices: example of energy transfer and host-guest interactions

Photoluminescence and Raman studies on Sm(3+)- and Nd(3+)-doped zirconia are reported. The Raman studies indicate that the monoclinic (m) phase dominates up to a 10 at.% lanthanide level, while stabilization of the cubic phase is attained at approximately 20 and approximately 25 at.% of Sm(3+) and Nd(3+), respectively. Both systems are strongly luminescent under photo-excitation. The emission spectrum at 77 K of the ZrO(2):Sm(3+) system consists of a broad band at 505 nm, that corresponds to the zirconia matrix. At room temperature the band maximum blue-shifts to 490 nm. Sharper bands corresponding to f-f transitions within the Sm(3+)ion are also exhibited in the longer wavelength region of the spectrum. Exclusive excitation of the zirconia matrix provides sensitized emission from the acceptor Sm(3+) ion. The excitation profile is dominated by a broad band at 325 nm when monitored either at the zirconia or at one of the Sm(3+) emissions. A spectral overlap between the 6H(5/2)-->(4)G(7/2) absorption of the Sm(3+) ion with the zirconia emission leads to an efficient energy transfer process in the systems. Multiple facets of the spectral behavior of the Sm(3+) or Nd(3+) in the zirconia matrices, as well as the effects of compositions on the emission and Raman properties of the materials, and the role of defect centers in photoluminescence and the energy transfer processes are discussed.