School of Chemical and Biomedical Engineering, Nanyang Technological University , 62 Nanyang Drive, Singapore 637459, Singapore.
J Am Chem Soc. 2015 Aug 26;137(33):10735-44. doi: 10.1021/jacs.5b06323. Epub 2015 Aug 17.
In recent years, enormous attention has been paid to the construction of metal cluster-semiconductor nanocomposites because of the fascinating and unique properties of metal clusters; however, investigations on photoelectrochemical (PEC) and photocatalytic properties of metal cluster-semiconductor systems are still rare. Moreover, to date, intrinsic correlation between metal clusters and bulk metal nanocrystals has yet to be elucidated. In this work, a facile layer-by-layer (LbL) self-assembly strategy has been developed to judiciously and intimately integrate gold nanocrystals (Au) within the interface between gold clusters (Au(x)) and hierarchically ordered TiO2 nanotube arrays framework, by which imperative roles of Au nanocrystals as electron relay mediator and plasmonic sensitizer for Aux clusters were revealed. In addition, it was found that synergistic interaction between Au nanocrystals and Aux clusters contributed to promising visible-light-driven photocatalytical and PEC performances. It is anticipated that our work could provide a general way for rationally constructing metal and metal clusters codecorated semiconductor heterostructures and, more significantly, bridge the gap between metal clusters and metal nanocrystals for a diverse range of applications.
近年来，由于金属团簇的迷人而独特的性质，人们对金属团簇-半导体纳米复合材料的构建给予了极大的关注；然而，对金属团簇-半导体系统的光电化学（PEC）和光催化性能的研究仍然很少。此外，迄今为止，金属团簇与体相金属纳米晶体之间的内在相关性尚未阐明。在这项工作中，开发了一种简便的层层（LbL）自组装策略，通过该策略可以在金团簇（Au(x)）和分级有序 TiO2 纳米管阵列框架之间的界面上巧妙且紧密地集成金纳米晶体（Au），揭示了 Au 纳米晶体作为电子中继介体和Aux 团簇的等离子体敏化剂的重要作用。此外，还发现 Au 纳米晶体和 Aux 团簇之间的协同相互作用有助于实现有前途的可见光驱动光催化和 PEC 性能。预计我们的工作可以为合理构建金属和金属团簇修饰的半导体异质结构提供一种通用方法，更重要的是，为金属团簇和金属纳米晶体之间的各种应用架起桥梁。
