Site-Selective Surface Modification of 2D Superatomic Re 6 Se 8
Site-Selective Surface Modification of 2D Superatomic Re 6 Se 8
复制标题
二维超原子 Re 6 Se 8 的位点选择性表面修饰
DOI：
10.1021/jacs.1c10833
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发表时间：
2022
影响因子：
15
通讯作者：
Steigerwald, Michael L.
中科院分区：
文献类型：
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作者：
He, Shoushou;Evans, Austin M.;Meirzadeh, Elena;Han, Sae Young;Russell, Jake C.;Wiscons, Ren A.;Bartholomew, Amymarie K.;Reed, Douglas A.;Zangiabadi, Amirali;Steigerwald, Michael L.
用具有可调性质的分子涂覆二维（2D）材料赋予其表面用于传感、纳米电子学、纳米纤维和电化学的功能。在这里，我们报告了一种方法的二维超原子Re 6Se 8 Cl 2单分子膜的位点选择性表面功能化。首先，我们通过嵌入锂来激活块状层状Re_6Se_8Cl_2，然后在N-甲基甲酰胺（NMF）中剥离嵌入化合物Li_2Re_6Se_8Cl_2。加热所得溶液消除LiCl以产生作为高质量纳米片的单层Re 6Se 8（NMF）2-x（x ≤ 0.4）。Re 6Se 8（NMF）2-x中每个簇上的未配对电子通过基于自由基的化学实现共价表面官能化。我们证明了这一点，以产生四个以前未知的表面功能化的二维超原子材料：Re 6Se 8I 2，Re 6Se 8（SPh）2，Re 6Se 8（SPhNH 2）2和Re 6Se 8（SC 16 H33）2。透射电子显微镜，化学分析和振动光谱表明，在平面结构的2D Re 6Se 8材料通过表面功能化被保存。我们发现，传入的基团控制的空位缺陷的密度和2D材料的溶解度。这种方法将在2D超原子材料的表面上安装广泛的化学功能，作为系统地调整其物理性质，化学反应性和溶液加工性的手段。
Coating two-dimensional (2D) materials with molecules bearing tunable properties imparts their surfaces with functionalities for applications in sensing, nanoelectronics, nanofabrication, and electrochemistry. Here, we report a method for the site-selective surface functionalization of 2D superatomic Re6Se8Cl2monolayers. First, we activate bulk layered Re6Se8Cl2by intercalating lithium and then exfoliate the intercalation compound Li2Re6Se8Cl2inN-methylformamide (NMF). Heating the resulting solution eliminates LiCl to produce monolayer Re6Se8(NMF)2–x(x≈ 0.4) as high-quality nanosheets. The unpaired electrons on each cluster in Re6Se8(NMF)2–xenable covalent surface functionalization through radical-based chemistry. We demonstrate this to produce four previously unknown surface-functionalized 2D superatomic materials: Re6Se8I2, Re6Se8(SPh)2, Re6Se8(SPhNH2)2, and Re6Se8(SC16H33)2. Transmission electron microscopy, chemical analysis, and vibrational spectroscopy reveal that the in-plane structure of the 2D Re6Se8material is preserved through surface functionalization. We find that the incoming groups control the density of vacancy defects and the solubility of the 2D material. This approach will find utility in installing a broad array of chemical functionalities on the surface of 2D superatomic materials as a means to systematically tune their physical properties, chemical reactivity, and solution processability.