Basal-Plane Functionalization of Chemically Exfoliated Molybdenum Disulfide by Diazonium Salts

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• 作者：Kathrin C. Knirsch ; Nina C. Berner ; Hannah C. Nerl ; Clotilde S. Cucinotta ; Zahra Gholamvand ; Niall McEvoy ; Zhenxing Wang ; Irena Abramovic ; Philipp Vecera ; Marcus Halik ; Stefano Sanvito ; Georg S. Duesberg ; Valeria Nicolosi ; Frank Hauke ; Andreas Hirsch ; Jonathan N. Coleman ; Claudia Backes
• 刊名：ACS Nano
• 出版年：2015
• 出版时间：June 23, 2015
• 年：2015
• 卷：9
• 期：6
• 页码：6018-6030
• 全文大小：745K
• ISSN：1936-086X

文摘

Although transition metal dichalcogenides such as MoS₂ have been recognized as highly potent two-dimensional nanomaterials, general methods to chemically functionalize them are scarce. Herein, we demonstrate a functionalization route that results in organic groups bonded to the MoS₂ surface via covalent C鈥揝 bonds. This is based on lithium intercalation, chemical exfoliation and subsequent quenching of the negative charges residing on the MoS₂ by electrophiles such as diazonium salts. Typical degrees of functionalization are 10鈥?0 atom % and are potentially tunable by the choice of intercalation conditions. Significantly, no further defects are introduced, and annealing at 350 掳C restores the pristine 2H-MoS₂. We show that, unlike both chemically exfoliated and pristine MoS₂, the functionalized MoS₂ is very well dispersible in anisole, confirming a significant modification of the surface properties by functionalization. DFT calculations show that the grafting of the functional group to the sulfur atoms of (charged) MoS₂ is energetically favorable and that S鈥揅 bonds are formed.