Single-Crystalline Organic–Inorganic Layered Cobalt Hydroxide Nanofibers: Facile Synthesis, Characterization, and Reversible Water-Induced Structural Conversion

New pink organic-inorganic layered cobalt hydroxide nanofibers intercalated with benzoate ions [Co(OH)(C6H5COO)·H2O] have been synthesized by using cobalt nitrate and sodium benzoate as reactants in water with no addition of organic solvent or surfactant. The high-purity nanofibers are single-crystalline in nature and very uniform in size with a diameter of about 100 nm and variable lengths over a wide range from 200 μm down to 2 μm by simply adjusting reactant concentrations. The as-synthesized products are well-characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), fast Fourier transforms (FFT), X-ray diffraction (XRD), energy dispersive X-ray spectra (EDX), X-ray photoelectron spectra (XPS), elemental analysis (EA), Fourier transform infrared (FT-IR), thermogravimetric analysis (TGA), and UV-vis diffuse reflectance spectra (UV-vis). Our results demonstrate that the structure consists of octahedral cobalt layers and the benzoate anions, which are arranged in a bilayer due to the π-π stacking of small aromatics. The carboxylate groups of benzoate anions are coordinated to Co(II) ions in a strong bridging mode, which is the driving force for the anisotropic growth of nanofibers. When NaOH is added during the synthesis, green irregular shaped platelets are obtained, in which the carboxylate groups of benzoate anions are coordinated to the Co(II) ions in a unidentate fashion. Interestingly, the nanofibers exhibit a reversible transformation of the coordination geometry of the Co(II) ions between octahedral and pseudotetrahedral with a concomitant color change between pink and blue, which involves the loss and reuptake of unusual weakly coordinated water molecules without destroying the structure. This work offers a facile, cost-effective, and green strategy to rationally design and synthesize functional nanomaterials for future applications in catalysis, magnetism, gas storage or separation, and sensing technology.