Solventless Preparation of Thoria and Its Inclusion into SiO2 and TiO2: A Luminescence and Photocatalysis Study.

Thoria was prepared using a solid-state method from the macromolecular precursor Chitosan·Th(NO3)4 (chitosan) and PS-co-4-PVP·Th(NO3)4 (PVP). The morphology and the average size of ThO2 depend of the chitosan and PS-co-4-PVP polymer forming the precursor. Their photoluminescent properties were investigated, finding a dependence of their intensity emission maxima, with the nature of the precursor polymer. The photocatalytic activity of ThO2 toward the degradation of methylene blue was measured for the first time, finding a degradation of about 66% in 300 min. The inclusion of ThO2 into SiO2 and TiO2 was achieved by the solid-state pyrolysis of the macromolecular composites Chitosan·Th(NO3)4//MO2 and PS-co-4-PVP·Th(NO3)4//MO2, MO2 = SiO2 or TiO2. The ThO2 exhibits a homogeneous dispersion inside the silica, showing sizes of about 40 and 50 nm for the chitosan and PVP polymer precursors, respectively. The luminescent properties of the ThO2/SiO2 and ThO2/TiO2 composites were also studied, finding a decrease in intensity when introducing the SiO2 or TiO2 matrices. The photocatalytic behavior to methylene blue degradation of ThO2 and their composites ThO2/SiO2 and ThO2/TiO2 was investigated for the first time, with them in the following order: ThO2 > ThO2/TiO2 > ThO2/SiO2.

Novel solid-state route to nanostructured tin, zinc and cerium oxides as potential materials for sensors.

Solid-state sensor nanostructured materials (SnO2, ZnO and CeO2) have been prepared by pyrolysis of macromolecular complexes: PSP-co-4-PVP x (SnCl2)n, PSP-co-4-PVP x (ZnCl2)n and PSP-co-4-PVP x (Ce(NO3)3)n in several molar ratios under air at 800 degrees C. The as-prepared nanostructured SnO2 exhibits morphologies and particle sizes which are dependent upon the molar ratio of the SnCl2:PSP-co-4-PVP. When a larger weight fraction of the inorganic salt in the precursor mixture is used (1:10 > 1:5 > 1.1) larger crystalline crystals are found for each oxide. For ZnO and CeO2 agglomerates of morphologies from the respective hexagonal and cubic structures were observed with typical sizes of 30-50 nm in both cases for a precursor mixture ratio of 1:1.

Solid-state synthesis of embedded single-crystal metal oxide and phosphate nanoparticles and in situ crystallization.

A new solid state organometallic route to embedded nanoparticle-containing inorganic materials is shown, through pyrolysis of metal-containing derivatives of cyclotriphosphazenes. Pyrolysis in air and at 800 °C of new molecular precursors gives individual single-crystal nanoparticles of SiP(2)O(7), TiO(2), P(4)O(7,) WP(2)O(7) and SiO(2), depending on the precursor used. High resolution transmission electron microscopy investigations reveal, in most cases, perfect single crystals of metal oxides and the first nanostructures of negative thermal expansion metal phosphates with diameters in the range 2-6 nm for all products. While all nanoparticles are new by this method, WP(2)O(7) and SiP(2)O(7) nanoparticles are reported for the first time. In situ recrystallization formation of nanocrystals of SiP(2)O(7) was also observed due to electron beam induced reactions during measurements of the nanoparticulate pyrolytic products SiO(2) and P(4)O(7). The possible mechanism for the formation of the nanoparticles at much lower temperatures than their bulk counterparts in both cases is discussed. Degrees of stabilization from the formation of P(4)O(7) affects the nanocrystalline products: nanoparticles are observed for WP(2)O(7), with coalescing crystallization occurring for the amorphous host in which SiP(2)O(7) crystals form as a solid within a solid. The approach allows the simple formation of multimetallic, monometallic, metal-oxide and metal phosphate nanocrystals embedded in an amorphous dielectric. The method and can be extended to nearly any metal capable of successful coordination as an organometallic to allow embedded nanoparticle layers and features to be deposited or written on surfaces for application as high mobility pyrophosphate lithium-ion cathode materials, catalysis and nanocrystal embedded dielectric layers.