title: Periodic mesoporous hydridosilica--synthesis of an "impossible" material and its thermal transformation into brightly photoluminescent periodic mesoporous nanocrystal silicon-silica composite.
abstract: 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-HSiO(1.5)). 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-HSiO(1.5) 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/SiO(2), 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.
authors.affiliation: Materials Chemistry and Nanochemistry Research Group, Center for Inorganic and Polymeric Nanomaterials, Chemistry Department, 80 St. George Street, University of Toronto, Toronto, Ontario, Canada M5S 3H6.
authors.forename: Zhuoying
authors.initials: Z
authors.lastname: Xie
authors.forename: Eric J
authors.initials: EJ
authors.lastname: Henderson
authors.forename: Ömer
authors.initials: Ö
authors.lastname: Dag
authors.forename: Wendong
authors.initials: W
authors.lastname: Wang
authors.forename: Jennifer E
authors.initials: JE
authors.lastname: Lofgreen
authors.forename: Christian
authors.initials: C
authors.lastname: Kübel
authors.forename: Torsten
authors.initials: T
authors.lastname: Scherer
authors.forename: Peter M
authors.initials: PM
authors.lastname: Brodersen
authors.forename: Zhong-Ze
authors.initials: ZZ
authors.lastname: Gu
authors.forename: Geoffrey A
authors.initials: GA
authors.lastname: Ozin
mesh_terms: D049449:Luminescence; D008422:Materials Testing; D053758:Nanoparticles / Q000737:chemistry*; D017646:Organosilicon Compounds / Q000138:chemical synthesis / Q000737:chemistry; D010316:Particle Size; D016062:Porosity; D012825:Silicon / Q000737:chemistry*; D012822:Silicon Dioxide / Q000138:chemical synthesis / Q000737:chemistry*; D013499:Surface Properties; D013696:Temperature
chemical_list: D017646:Organosilicon Compounds; D012822:Silicon Dioxide; D012825:Silicon