Hydrophilic ionic liquid assisted hydrothermal synthesis of ZnO nanostructures with controllable morphology

Nanostructured ZnO with controllable morphology was prepared by a hydrothermal method in the presence of three different hydrophilic ionic liquids (ILs), 1-ethyl-3-methylimidazolium methylsulfate, ([C₂mim]CH₃SO₄), 1-butyl-3-methylimidazolium methylsulfate, ([C₄mim]CH₃SO₄) and 1-ethyl-3-methylimidazolium ethylsulfate, ([C₂mim]C₂H₅SO₄) as soft templates. The formation of ZnO nanoparticles (NPs) with and without IL was verified using FT-IR and UV-visible spectroscopy. X-ray diffraction (XRD) and selected area electron diffraction (SAED) patterns indicated the formation of pure crystalline ZnO with a hexagonal wurtzite phase. Field emission scanning electron microscopic (FESEM) and high-resolution transmission electron microscopic (HRTEM) images confirmed the formation of rod-shaped ZnO nanostructures without using IL, whereas the morphology varied widely following addition of ILs. With increasing concentrations of [C₂mim]CH₃SO₄, the rod-shaped ZnO nanostructures transformed into flower-shaped nanostructures whereas with rising concentrations of [C₄mim]CH₃SO₄ and [C₂mim]C₂H₅SO₄ the morphology changed into petal- and flake-like nanostructures, respectively. The selective adsorption effect of the ILs could protect certain facets during the formation of ZnO rods and promote the growth in directions other than [0001] to yield petal- or flake-like architectures. The morphology of ZnO nanostructures was, therefore, tunable by the controlled addition of hydrophilic ILs of different structures. The size of the nanostructures was widely distributed and the Z-average diameter, evaluated from dynamic light scattering measurements, increased as the concentration of the IL increased and passed through a maximum before decreasing again. The optical band gap energy of the ZnO nanostructures decreased when IL was added during the synthesis which is consistent with the morphology of the ZnO nanostructures. Thus, the hydrophilic ILs serve as self-directing agents and soft templates for the synthesis of ZnO nanostructures and the morphology and optical properties of ZnO nanostructures are tunable by changing the structure of the ILs as well as systematic variation of the concentration of ILs during synthesis.