非均相体系中的形状依赖催化作用.pptVIP

Seminar Ⅱ outline Shape control of nanostructures Catalytic properties on facets of nanomaterials Summary and perspective Shape control of nanostructures nucleus Polyhedron 2-D 1-D Shape control of nanostructures Nucleation and growth in liquid: La Mar's model Fievet, F. et al, Solid State Ionics 1989, 32/33, 198 Growth mechanism: Gas (solution)-liquid-solid; Ostwald ripening; surfactant-induced selective growth; Oriented attachment, etc. Shape control of nanostructures Gas (solution)-liquid-solid growth Super-saturated liquid alloy Element semiconductor: Si, Ge; Ⅲ-Ⅳ semiconductor: GaN, GaAs, GaP, InP, InAs; Ⅱ-Ⅵ semiconductor: ZnS, ZnSe, CdS, CdSe; Metal oxide: ZnO, Ga2O3, SiO2; Ge time Lieber, C. M. et al Acc. Chem. Res. 1999, 32, 435. Kodambaka, S. et al Science 2007, 316, 729. Au Condition: Ge2H6, 340 ℃ Shape control of nanostructures: Ostwald ripening 10min 20min 40min 50min 60min nucleus AgNO3, PtCl2 (seed), PVP, glycol, 160 ℃ Ag nanowire Xia, Y. N. et al Chem. Mater. 2002, 14, 4736. Cs Cl > Ostwald ripening: Shape control of nanostructures: selective absorption of surfactant Ag nanorod Multiply twinned nanoparticle Passivated by PVP Xia, Y. N. et al Nano Lett. 2003, 3, 955. Shape control of nanostructures: polyhedron  Shapes of the polyhedral nanocrystals γ{111｝ < γ{100｝ < γ{110｝; R=r{100 ｝/r{111 ｝ Wang, Z. L. J. Phys. Chem. B 2000, 104, 1153. Shape control of nanostructures: polyhedron Song, H. et al J. Am. Chem. Soc. 2006, 128, 14863. Ag/Au=1/600 Ag/Au=1/500 Ag/Au=1/400 Ag/Au=1/200 Ag/Au=1/60 Condition: AgNO3, HAuCl4.3H2O, 1,5-pentanediol, PVP, 240 ℃ Song, H. et al J. Am. Chem. Soc. 2006, 128, 14863. 2-Theta (deg.) XRD patterns of gold with different shapes (100) (111) corner edge Nanoparticle surface: enclosed by different planes Catalytic site on which planes? Shape-dependent catalysis: in the case of Ag γ{111｝<γ{100｝ Li, Y. D. et al Chem. Asian J. 2006, 1, 888. Specific reaction rate Shape-dependent catalysis: in the case of Pt Tetrahexahedr