A facile route for the synthesis of nanostructured oxides and hydroxides of cobalt using laser ablation synthesis in solution (LASIS)

Abstract

We used a pulsed laser ablation synthesis in solution (LASIS) to produce cobalt oxide/hydroxide nanoparticles (NPs) with tailored size, morphology and structure at different laser fluences, wavelengths (532 and 1064 nm) and solvent conditions. Specifically, LASIS on bulk Co in the presence and absence of O₂ in an aqueous solution initially produces cobalt monoxide (CoO) and single crystal β-cobalt hydroxide (β-Co(OH)₂) nanoparticles (NPs) respectively that finally transform into cobaltosic oxide (Co₃O₄) through oxidation and/or thermal decomposition. Transmission electron microscopy (TEM) and scanning mobility particle sizer (SMPS) measurements on the final products reveal a bimodal size distribution of agglomerated NPs (for the 1064 and 532 nm laser) at low laser fluences, where the ablation mechanism is dominated by vaporization and normal boiling. In contrast, more efficient and predominant explosive boiling at higher laser fluences produces a mono-modal size distribution of spherically shaped primary NPs in agglomerates. Furthermore, higher absorbance of the 532 nm laser by solution-phase colloidal NPs re-ablates them into spherical shapes of larger size (∼13–22 nm) as compared to the ones from using 1064 nm LASIS (∼10–14 nm), while rendering 532 nm LASIS less productive than 1064 nm LASIS over an extended period of time. Finally, Co₃O₄ nanorods with enhanced localized surface plasmon resonance (LSPR) are synthesized at high pH (pH ≥ 13) and low laser fluence (<5 mJ cm⁻²) conditions. Such nanostructured materials are promising candidates as photocatalysts or additives in nanocomposite materials with enhanced light absorption properties.