物理化学学报 >> 2018, Vol. 34 >> Issue (7): 740-754.doi: 10.3866/PKU.WHXB201712111

所属专题: 原子水平上精确控制纳米簇和纳米粒子

综述 上一篇    下一篇

多策略可控合成原子精度合金纳米团簇

郑有坤,姜晖,王雪梅*()   

  • 收稿日期:2017-11-09 发布日期:2018-03-26
  • 通讯作者: 王雪梅 E-mail:xuewang@seu.edu.cn
  • 作者简介:WANG Xuemei is currently a full professor of Biomedical Engineering, Southeast University. She obtained her PhD in Chemistry from Nanjing University, China in 1994 and became a lecturer in Nanjing University in 1995. She was an Alexander von Humboldt Fellow in the Chemistry Department, University of Saarland, Germany, before she joined the State Key Laboratory of Bioelectronics, Southeast University in 1998. Her research focuses on bioelectronics and biosensors, biomaterials for multimode bioimaging and nanomedicine
  • 基金资助:
    国家高技术与发展研究计划(2015AA020502);国家重点研发计划(2017YFA0205300);国家自然科学基金(81325011);国家自然科学基金(21175020)

Multiple Strategies for Controlled Synthesis of Atomically Precise Alloy Nanoclusters

Youkun ZHENG,Hui JIANG,Xuemei WANG*()   

  • Received:2017-11-09 Published:2018-03-26
  • Contact: Xuemei WANG E-mail:xuewang@seu.edu.cn
  • Supported by:
    The project was supported by the National High Technology Research and Development Program of China(2015AA020502);the National Key Research and Development Program of China(2017YFA0205300);the National Natural Science Foundation of China(81325011);the National Natural Science Foundation of China(21175020)

摘要:

合金纳米团簇作为一类新兴的多功能纳米材料已被广泛用于催化、光学传感以及生物医学成像等研究领域,而纳米团簇的可控合成和结构特征是调节纳米团簇性质并对其进一步利用的基础。尽管当前有关金属纳米团簇可控合成和结构特征的研究主要集中在单金属纳米团簇中,但有关合金纳米团簇原子精度的可控合成也取得了显著的进展。本文综述了配体保护的合金金属纳米团簇原子精度可控合成策略,包括一步合成法、金属交换、配体交换、化学刻蚀、簇间反应、原位两相配体交换以及最新的表面模体交换反应,并对相关合成策略的优缺点进行了详细的讨论和阐述。

关键词: 合金纳米团簇, 原子精度, 合成策略, 晶体结构

Abstract:

Alloy metal nanoclusters (NCs), including bimetallic and multimetallic clusters, have recently emerged as a novel class of multifunctional nanomaterials. They are widely used in catalysis, optical sensing, and biological imaging due to their excellent physicochemical properties such as unique electronic structure, ultrasmall size, strong photoluminescence, and rich surface chemistry. Although much progress has been made in the development of NCs, a major challenge in the synthesis of the relevant multifunctional nanomaterial is to achieve the synthetic methodological breakthrough, especially for controlling the synthesis and structure of NCs with atomic precision. It is evident that by realizing controlled synthesis and structural regulation at the atomic scale, we can better understand and tune the fundamental properties of NCs for efficient use in various application areas; this could also shed light on the development of new functionalized nanomaterials. Most of the recent research on the controlled synthesis and structural characterization of metal clusters with atomic precision has focused on monometallic NCs, and significant progress has been realized with respect to alloy metal NCs. A number of synthetic strategies have been developed for synthesizing high-quality alloy NCs with well-defined compositions, sizes, and architectures. In this review, we have highlighted some recent advances in strategies for the precise synthesis of ligands-protected alloy metal NCs, especially thiolate-stabilized gold-based alloy NCs. We classified the synthetic strategies for alloy NCs into several strategies, which include one-pot synthesis, metal exchange, ligand exchange, chemical etching, intercluster reactions, surface motif exchange reaction, and in situ two-phase ligand exchange strategy. One-pot synthesis is facile and widely used as a synthetic strategy for monodisperse alloy NCs with well-defined compositions, sizes, architectures, and surface chemistries. However, the alloy NCs obtained through the one-pot strategy often exhibits a relatively somber fluorescence. Therefore, other synthesis strategies have been exploited that can fabricate alloy NCs exhibiting strong photoluminescence. Among them, the surface motif exchange reaction is expected to be extended to the fabrication of new binary alloy NCs with precise alloy sites to broaden the physicochemical properties of the NCs; intercluster reactions has been explored as an emerging and efficient strategy to fabricate atomically precise alloy NCs. It is noted that the two or multiple metal species incorporated in a single alloy NC usually show unexpected synergistic properties like adjustable electronic structures and strong photoluminescence. Such unique properties have rapidly motivated the research community to use alloy NCs in many applications such as catalysis, biosensors, and biomedicine.

Key words: Alloy nanoclusters, Atomically precise, Synthetic strategy, Crystal structure

MSC2000: 

  • O641