Nat Mater. 2010 Oct;9(10):810-5. doi: 10.1038/nmat2848. Epub 2010 Sep 19.
Cage structures exhibit inherent high symmetry and beauty, and both naturally occurring and synthetic molecular-scale cages have been discovered. Their characteristic high surface area and voids have led to their use as catalysts and catalyst supports, filtration media and gas storage materials. Nanometre-scale cage structures have also been synthesized, notably noble-metal cube-shaped cages prepared by galvanic displacement with promising applications in drug delivery and catalysis. Further functionality for nanostructures in general is provided by the concept of hybrid nanoparticles combining two disparate materials on the same system to achieve synergistic properties stemming from unusual material combinations. We report the integration of the two powerful concepts of cages and hybrid nanoparticles. A previously unknown edge growth mechanism has led to a new type of cage-structured hybrid metal-semiconductor nanoparticle; a ruthenium cage was grown selectively on the edges of a faceted copper(I) sulphide nanocrystal, contrary to the more commonly observed facet and island growth modes of other hybrids. The cage motif was extended by exploiting the open frame to achieve empty cages and cages containing other semiconductors. Such previously unknown nano-inorganic cage structures with variable cores and metal frames manifest new chemical, optical and electronic properties and demonstrate possibilities for uses in electrocatalysis.
笼状结构表现出固有的高度对称性和美感,已经发现了天然存在和合成的分子尺度的笼状结构。它们的高表面积和空隙特征导致了它们在催化剂和催化剂载体、过滤介质和气体储存材料方面的应用。纳米尺度的笼状结构也已被合成,特别是通过电置换制备的贵金属立方笼状结构,在药物输送和催化方面具有广阔的应用前景。一般来说,纳米结构的进一步功能是通过杂化纳米粒子的概念提供的,该概念将两种截然不同的材料结合在同一个系统上,以实现源自不寻常材料组合的协同特性。我们报告了笼状结构和杂化纳米粒子这两个强大概念的整合。一个以前未知的边缘生长机制导致了一种新型的笼状杂化金属-半导体纳米粒子;与其他杂化材料中更常见的面和岛生长模式相反,在面心立方的硫化亚铜纳米晶体的边缘上选择性地生长了钌笼。通过利用开放框架来实现空笼和包含其他半导体的笼,扩展了笼状结构。这种具有可变核和金属框架的以前未知的纳米无机笼状结构表现出新的化学、光学和电子性质,并展示了在电催化方面的应用可能性。