One-Dimensional Assemblies of Co3O4 Nanoparticles Formed from Cobalt Hydroxide Carbonate Prepared by Bio-Inspired Precipitation within Confined Space

Abstract

Nanostructured spinel-type cobalt(II,III) oxide (Co3O4) finds applications in a wide range of technological fields including clean energy conversion systems and electrochemical devices. Low-dimensional morphologies have been identified as particularly promising for the optimization of transport characteristics and the design of anisometric building blocks for the controlled assembly into higher order superstructures. We here introduce a facile bio-inspired room-temperature approach to direct precipitation of one-dimensional basic cobalt carbonate as a precursor to Co3O4 by combining confined submicrometer reaction environments with a carboxylated structure-directing polyelectrolyte. Variation of the polymer concentration and molecular weight then affords control over the mode of infiltration into cylindrical track-etch membrane pores. While a high concentration of the polyelectrolyte additive induces the formation of high aspect ratio smooth fibers with a length resembling the entire pore volume, shorter porous rods with a needle-like substructure are deposited at low polymer concentrations or higher molecular weights. The generality of the infiltration mechanism is demonstrated by gradual substitution of Co2+ ions by Mn2+. Calcination pseudomorphically transforms the resulting intramembrane basic cobalt and manganese carbonate rods and fibers into hierarchical one-dimensional oxides with a porous nanoparticle-based mesostructure.