Browsing by Subject "Pore wall"

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Open Access
Periodic mesoporous hydridosilica-synthesis of an "impossible" material and its thermal transformation into brightly photoluminescent periodic mesoporous nanocrystal silicon-silica composite
(2011) Xie, Z.; Henderson, E. J.; Dag, Ö.; Wang, W.; Lofgreen, J. E.; Kübel, C.; Scherer, T.; Brodersen, P. M.; Gu, Zhong-Ze; Ozin, G. A.
There has always been a fascination with "impossible" compounds, ones that do not break any rules of chemical bonding or valence but whose structures are unstable and do not exist. This instability can usually be rationalized in terms of chemical or physical restrictions associated with valence electron shells, multiple bonding, oxidation states, catenation, and the inert pair effect. In the pursuit of these "impossible" materials, appropriate conditions have sometimes been found to overcome these instabilities and synthesize missing compounds, yet for others these tricks have yet to be uncovered and the materials remain elusive. In the scientifically and technologically important field of periodic mesoporous silicas (PMS), one such "impossible" material is periodic mesoporous hydridosilica (meso-HSiO1.5). It is the archetype of a completely interrupted silica open framework material: its pore walls are comprised of a three-connected three-dimensional network that should be so thermodynamically unstable that any mesopores present would immediately collapse upon removal of the mesopore template. In this study we show that meso-HSiO1.5 can be synthesized by template-directed self-assembly of HSi(OEt)3 under aqueous acid-catalyzed conditions and after template extraction remains stable to 300 °C. Above this temperature, bond redistribution reactions initiate a metamorphic transformation which eventually yields periodic mesoporous nanocrystalline silicon-silica, meso-ncSi/SiO2, a nanocomposite material in which brightly photoluminescent silicon nanocrystallites are embedded within a silica matrix throughout the mesostructure. The integration of the properties of silicon nanocrystallinity with silica mesoporosity provides a wealth of new opportunities for emerging nanotechnologies.
Open Access
Synthesis of stable mesostructured coupled semiconductor thin films: meso-CdS-TiO2 and meso-CdSe-TiO2
(2010) Okur, H. İ.; Türker, Y.; Dag, Ö.
Cd(II) ions can be incorporated into the channels of mesostructured titania films, using the evaporation-induced self-assembly (EISA) approach, up to a record high Cd/Ti mole ratio of 25%. The film samples were obtained by spin or dip coating from a mixture of 1-butanol, [Cd(H20)4] (N03)2, HNO3, and Ti(OC4H 9)4 and then aging the samples under 50% humidity at 30 0C (denoted as meso-xCd(II)-y TiO2). The nitrate ions, from nitric acid and cadmium nitrate, play important roles in the assembly process by coordinating as bidentate and bridged ligands to Cd(II) and Ti(IV) sites, respectively, in the mesostructured titania films. The film samples can be reacted under a H 2S (or H2Se) gas atmosphere to produce CdS (or CdSe) on the channel surface and/or pore walls. However, the presence of such a large number of nitrate ions in the film samples also yields an extensive amount of nitric acid upon H2S (or H2Se) reaction, where the nanoparticles are not stable (they undergo decomposition back to metal ion and H2S or H2Se gas). However, this problem can be overcome by further aging the samples at 130 °C for a few hours before H2S (or H2Se) reaction. This step removes about 90% of the nitrate ions, eliminates the nitric acid production step, and stabilizes the CdS nanoparticles on the surface and/or walls of the pores of the coupled semiconductor films, denoted as meso-xCdS-yTiO2. However, the H2Se reaction, additionally, needs to be carried at lower H2Se pressures in an N2 atmosphere to produce stable CdSe nanoparticles on the surface and/or walls of the pores of the films, denoted as meso-xCdSe-.yTiO2. Otherwise, an excessive number of Se8 particles form in the film samples.