Wet-chemically synthesized 2D transition metal sulfides (TMS) are promising materials for catalysis, batteries and optoelectronics, however a firm understanding on the chemical conditions which result in selective lateral growth has been lacking. In this work we demonstrate that Ni9S8, which is a less common nonstoichiometric form of nickel sulfide, can exhibit two-dimensional growth when halide ions are present in the reaction. We show that the introduction of halide ions reduced the rate of formation of the nickel thiolate precursor, thereby inhibiting nucleation events and slowing growth kinetics such that plate-like formation was favored. Structural characterization of the Ni9S8 nanoplates produced revealed that they were single-crystal with lateral dimensions in the range of ∼100–1000 nm and thicknesses as low as ∼4 nm (about 3 unit cells). Varying the concentration of halide ions present in the reaction allowed for the shape of the nanostructures to be continuously tuned from particle- to plate-like, thus offering a facile route to controlling their morphology. The synthetic methodology introduced was successfully extended to Cu2S despite its different growth mechanism into ultrathin plates. These findings collectively suggest the importance of halide mediated slow growth kinetics in the formation of nanoplates and may be relevant to a wide variety of TMS.
Promoting 2D Growth in Colloidal Transition Metal Sulfide SemiconductorNanostructures via Halide Ions. -Halide ions play a decisive role in determining the morphology of Ni 9S8 nanostructures, and the use of sufficiently large molar equivalents of halides results in the formation of nanoplates that exhibit an unusual cross--like structure filled with steplike edges. These Ni9S8 nanoplates are potential electrocatalysts for dye-sensitized solar cells or hydrogen evolution from water. The use of halides in promoting sheetlike growth is also extended to Cu 2S, where ultrathin triangular nanoplates are produced. Additionally, monodisperse spheres, disks, and plates of Cu2S are obtained by simply increasing the amount of Clpresent in the reaction mixture. -(WU, W.-Y.; CHAKRABORTTY, S.; CHANG, C. K. L.; GUCHHAIT, A.; LIN*, M.; CHAN, Y.; Chem. Mater. 26 (2014) 21, 6120-6126, http://dx.doi.org/10.1021/cm502281e ; Inst. Mater. Res. Eng., Singapore 117602, Singapore; Eng.) -W. Pewestorf 03-220
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