ConspectusLayered transition-metal dichalcogenides (TMDs) are intriguing two-dimensional (2D) compounds where metal and chalcogen atoms are covalently bonded in each monolayer, and the monolayers are held together by weak van der Waals forces. Distinct from graphene, which is chemically inert, layered TMDs exhibit a wide range of electronic, optical, catalytic, and magnetic properties dependent upon their compositions, crystal structures, and thicknesses, which make them fundamentally and technologically important. TMD nanostructures are traditionally synthesized using gas-phase chemical deposition methods, which are typically limited to small-scale samples of substrate-bound planar materials. Colloidal synthesis has emerged as an alternative synthesis approach to enable the scalable synthesis of free-standing TMDs. The judicious selection of precursors, solvents, and capping ligands together with the optimization of synthesis parameters such as concentrations and temperatures leads to the fabrication of colloidal TMD nanostructures exhibiting tunable properties. In addition, understanding the formation and transformation of TMD nanostructures in solution contributes to the discovery of important structure-function relationships, which may be extendable to other anisotropic systems.In this Account, we summarize recent progress in the colloidal synthesis, characterization, and applications of TMD nanostructures with tunable compositions, structures, and thicknesses. On the basis of the preparation of Mo- A nd W-based disulfide, diselenide, and ditelluride nanostructures, we discuss examples of phase engineering where various metastable TMD compounds can be directly accessed at low temperatures in solution. We also analyze the chemistry involved in broadly tuning the composition across the MoSe2-WSe2, WS2-WSe2, and MoTe2-WTe2 solid solutions as well as atomic-level microscopic characterization and the resulting composition-tunable properties. We then highlight how the high densities of defects in the colloidally synthesized TMD nanostructures enable unique catalytic properties, including their ability to facilitate the selective hydrogenation of substituted nitroarenes using molecular hydrogen. Finally, using this library of colloidal TMD nanostructures as substrates, we discuss the pathways by which noble metals deposit onto them in solution. We highlight the importance of the relative strengths of the interfacial metal-chalcogen bonds in determining the sizes and morphologies of the deposited noble metal components. These synthesis capabilities for colloidal TMD nanostructures, which have been generalized to a library of composition-tunable phases, enable new systematic studies of structure-property relationships and chemical reactivity in this important class of 2D materials.
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