Mineralization of unique barium carbonate crystal superstructures controlled by a liquid crystalline phase polymer

Barium carbonate (BaCO3) crystals with unique hierarchical superstructures have been fabricated through a facile and controlled solution self-assembly mode in the presence of a tri-block copolymer PEO70–PPO20–PEO70 (P123). The powder X-ray diffraction (XRD) results revealed that the obtained BaCO3 product was indexed to pure orthorhombic phase. Notably, BaCO3 samples with well-defined hierarchical morphologies, including spherical, rod, hexangular prism, and porous spherical aggregates can be prepared by simply adjusting the polymer P123 concentrations and the ratios of [Ba2+]/[P123]. Specifically, layered screw cap, double-taper, and shuttle-shaped superstructures were formed through choosing N,N-bimethylformamide (DMF), tetrahydrofuran (THF), and/or toluene mixed with de-ionised water (DIW) as the reaction media in the current system, respectively. It is clearly demonstrated that varying liquid crystal-phase aggregating structures of the polymer P123 and using different solvents can indeed exert a significant influence over the selective nucleation, crystal facets preferable adsorption, and consequent over-growth for the BaCO3 primary particles. Moreover, a possible formation process for the hierarchical superstructures of BaCO3 crystals is proposed.