Atomically precise metal nanoclusters: stable sizes and optical properties
Atomically precise metal nanoclusters: stable sizes and optical properties
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DOI：
10.1039/c4nr05794e
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发表时间：
2015-01-01
期刊：
影响因子：
6.7
通讯作者：
Jin, Rongchao
中科院分区：
文献类型：
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作者：
Jin, Rongchao
以原子精度控制纳米粒子长期以来一直是纳米化学家的主要梦想。金纳米粒子已经取得了突破，至少对于直径小于 3 nm 的纳米粒子来说是这样。由于量子尺寸效应以及极高的表面积与体积比，这种超小的金纳米颗粒确实表现出与等离激元对应物根本不同的特性。这些独特的纳米颗粒通常被称为纳米团簇，以区别于传统的等离子体纳米颗粒。过去几年进行的大量工作已经产生了原子精确金纳米团簇的稳定尺寸（或稳定化学计量）库，这为基础研究和技术应用开辟了新的令人兴奋的机会。在这篇综述中，我们总结了硫醇盐（SR）保护的金纳米团簇研究的最新进展，重点是报道的稳定尺寸及其光学吸收光谱。纳米团簇的结晶仍然具有挑战性；尽管如此，自从早期在Au-102(SR)(44)、Au-25(SR)(18)和Au-38(SR)(24)纳米团簇中取得成功以来，已经实现了更多的结构，新报道的结构包括Au-20(SR)(16)、Au-24(SR)(20)、Au-28(SR)(20)、Au30S(SR)(18)和Au-36(SR)(24)。本综述还简要讨论了磷化氢保护的金和硫醇盐保护的银纳米团簇。报道的金纳米簇尺寸可作为研究其尺寸依赖性特性以及催化、传感、生物标记、光学等应用开发的基础。未来的工作将继续解决存在哪些稳定的尺寸，更重要的是，哪些因素决定其稳定性。结构测定和理论模拟将有助于深入了解结构-性能关系。
Controlling nanoparticles with atomic precision has long been a major dream of nanochemists. Breakthroughs have been made in the case of gold nanoparticles, at least for nanoparticles smaller than similar to 3 nm in diameter. Such ultrasmall gold nanoparticles indeed exhibit fundamentally different properties from those of the plasmonic counterparts owing to the quantum size effects as well as the extremely high surface-to-volume ratio. These unique nanoparticles are often called nanoclusters to distinguish them from conventional plasmonic nanoparticles. Intense work carried out in the last few years has generated a library of stable sizes (or stable stoichiometries) of atomically precise gold nanoclusters, which are opening up new exciting opportunities for both fundamental research and technological applications. In this review, we have summarized the recent progress in the research of thiolate (SR)-protected gold nanoclusters with a focus on the reported stable sizes and their optical absorption spectra. The crystallization of nanoclusters still remains challenging; nevertheless, a few more structures have been achieved since the earlier successes in Au-102(SR)(44), Au-25(SR)(18) and Au-38(SR)(24) nanoclusters, and the newly reported structures include Au-20(SR)(16), Au-24(SR)(20), Au-28(SR)(20), Au30S(SR)(18), and Au-36(SR)(24). Phosphine-protected gold and thiolate-protected silver nanoclusters are also briefly discussed in this review. The reported gold nanocluster sizes serve as the basis for investigating their size dependent properties as well as the development of applications in catalysis, sensing, biological labelling, optics, etc. Future efforts will continue to address what stable sizes are existent, and more importantly, what factors determine their stability. Structural determination and theoretical simulations will help to gain deep insight into the structure-property relationships.