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要旨:
Stable gold clusters around 1 nm in size have been prepared by evaporation of the metal into an organosilicon polymer solution. A controlled particle growth of the entrapped gold particles was achieved by annealing in helium at ∼410 °C. Above 460 °C the growth rate is dramatically increased, concurrent with the onset of pyrolysis of polysilazane to form a porous solid. X-ray diffraction and simulation calculations using Debye functions of model clusters of different sizes and both crystallographic and noncrystallographic symmetry were used to characterize these particles. The exclusive presence of noncrystallographic (decahedral and icosahedral) multiply twinned particles (MTPs) in the as-prepared material is confirmed by EXAFS. The high precision of the XRD experiments and theoretical data fits gives detailed insight into the thermally induced growth process, during which the MTPs progressively disappear and are replaced by singly twinned fcc particles of larger size. This transition occurs in the range ∼2−3 nm. This analysis requires the introduction of a size-dependent contraction for the Au−Au distance in the order of 1−3% compared to bulk gold. This is discussed in the context of theoretical predictions.
