SOLID-STATE MATERIALS SYNTHESIS METHODS 固体材料的合成方法.pptVIP

TOPOTACTIC SOLID-STATE SYNTHESIS METHODS: HOST-GUEST INCLUSION CHEMISTRY Ion-exchange, injection, intercalation type synthesis Ways of modifying existing solid state structures while maintaining the integrity of the overall structure Precursor structure Open structure or porous framework Ready diffusion of guest atoms, ions, organic molecules, polymers, organometallics, coordination compounds, nanoclusters, bio(macro)molecules into and out of the structure/crystals TOPOTAXY: HOST-GUEST INCLUSION TOPOTACTIC SOLID-STATE SYNTHESIS METHODS: HOST-GUEST INCLUSION CHEMISTRY Penetration into interlamellar spaces: 2-D intercalation Into 1-D channel voids: 1-D injection Into cavity spaces: 3-D injection Classic materials for this kind of topotactic chemistry Zeolites, TiO2, WO3: channels, cavities Graphite, TiS2, NbSe2, MoO3: interlayer spaces Beta alumina: interlayer spaces, conduction planes Polyacetylene, NbSe3: inter chain channel spaces TOPOTACTIC SOLID-STATE SYNTHESIS METHODS: HOST-GUEST INCLUSION CHEMISTRY Ion exchange, ion-electron injection, atom, molecule intercalation and occlusion, achievable by non-aqueous, aqueous, gas phase, melt techniques Chemical, electrochemical synthesis methods This type of topotactic solid state chemistry creates new materials with novel properties, useful functions and wide ranging applications and myriad technologies GRAPHITE GRAPHITE INTERCALATION COMPOUNDS GRAPHITE INTERCALATION ELECTRON DONORS AND ACCEPTORS INTERCALATION REACTIONS OF GRAPHITEOxidative, Reductive or Charge Neutral? G (HF/F2/25oC) ? C3.3F to C40F (white) intercalation via HF2- not F- - relative size, charge, ion, dipole, polarizability effects - less strongly interacting - more facile diffusion G (HF/F2/450oC) ? CF0.68 to CF (white) G (H2SO4 conc.) ? C24(HSO4).2H2SO4 + H2 G (FeCl3 vapor) ? CnFeCl3 G (Br2 vapor) ? C8Br PROPERTIES OF INTERCALATED GRAPHITE Structural planarity of layers often unaffected by intercalation - bending of l