Size-Controlled Synthesis of Luminescent Few-Atom Silver Clusters via Electron Transfer in Isostructural Redox-Active Porous Ionic Crystals
Size-Controlled Synthesis of Luminescent Few-Atom Silver Clusters via Electron Transfer in Isostructural Redox-Active Porous Ionic Crystals
复制标题
通过同结构氧化还原活性多孔离子晶体中的电子转移控制尺寸合成发光少原子银簇
DOI：
10.1002/smll.202300743
复制
发表时间：
2023-02-24
期刊：
影响因子：
13.3
通讯作者：
Uchida，Sayaka
中科院分区：
文献类型：
--
作者：
Haraguchi，Naoya;Ogiwara，Naoki;Uchida，Sayaka
原子数量可控的银团簇已经引起了人们的极大兴趣，因为它们具有尺寸依赖性的催化、光学、电子或磁性。然而，制备尺寸可控、无配体和空气稳定的高产银簇的方法尚未得到很好的证实。本研究表明，具有氧化还原活性的多金属氧酸盐（POMs）的等结构多孔离子晶体（PICs）可以通过电子从POMs转移到Ag+来合成银簇。在没有任何保护配体的环境条件下，在PICs中形成并稳定了平均数目为3、4或6原子的Ag团簇，分别发出蓝色、绿色或红色。簇大小仅与电子转移的程度有关，而电子转移的程度是由还原时间和离子或元素的类型控制的。因此，利用POMs作为电子源和PICs作为支架的优势，证明了一种获得少原子银簇的简便方法。
Ag clusters with a controlled number of atoms have received significant interest because they show size‐dependent catalytic, optical, electronic, or magnetic properties. However, the synthesis of size‐controlled, ligand‐free, and air‐stable Ag clusters with high yields has not been well‐established. Herein, it is shown that isostructural porous ionic crystals (PICs) with redox‐active polyoxometalates (POMs) can be used to synthesize Ag clusters via electron transfer from POMs to Ag+. Ag clusters with average numbers of three, four, or six atoms emitting blue, green, or red colors, respectively, are formed and stabilized in the PICs under ambient conditions without any protecting ligands. The cluster size solely correlates with the degree of electron transfer, which is controlled by the reduction time and types of ions or elements of the PICs. Thus, advantages have been taken of POMs as electron sources and PICs as scaffolds to demonstrate a convenient method to obtain few‐atom Ag clusters.