Direct Covalent Chemical Functionalization of Unmodified Two-Dimensional Molybdenum Disulfide

Two-dimensional semiconducting transition metal dichalcogenides (TMDCs) like molybdenum disulfide (MoS2) are generating significant excitement due to their unique electronic, chemical, and optical properties. Covalent chemical functionalization represents a critical tool for tuning the properties of TMDCs for use in many applications. However, the chemical inertness of semiconducting TMDCs has thus far hindered the robust chemical functionalization of these materials. Previous reports have required harsh chemical treatments or converting TMDCs into metallic phases prior to covalent attachment. Here, we demonstrate the direct covalent functionalization of the basal planes of unmodified semiconducting MoS2 using aryl diazonium salts without any pretreatments. Our approach preserves the semiconducting properties of MoS2, results in covalent C–S bonds, is applicable to MoS2 derived from a range of different synthesis methods, and enables a range of different functional groups to be tethered directly to the Mo...