Water mediated growth of oriented single crystalline SrCO₃ nanorod arrays on strontium compounds

Morphology-controlled strontianite nanostructures have attracted interest in various fields, such as electrocatalyst and photocatalysts. Basic additives in aqueous strontium solutions is commonly used in controlling strontianite nanostructures. Here, we show that trace water also serves an important role in forming and structuring vertically oriented strontianite nanorod arrays on strontium compounds. Using in situ Raman spectroscopy, we monitored the structural evolution from hydrated strontium to strontianite nanorods, demonstrating the epitaxial growth by vapor-liquid-solid mechanism. Water molecules cause not only the exsolution of Sr liquid droplets on the surface but also the uptake of airborne CO₂ followed by its ionization to CO₃^2-. The existence of intermediate SrHO⁺-OCO₂^2- phase indicates the interaction of CO₃^2- with SrOH⁺ in Sr(OH)_x(H₂O)_y cluster to orient strontianite crystals. X-ray diffraction simulation and transmission electron microscopy identify the preferred-orientation plane of the 1D nanostructures as the (002) plane, i.e., the growth along the c-axis. The anisotropic growth habit is found to be affected by the kinetics of carbonation. This study paves the way for designing and developing 1D architecture of alkaline earth metal carbonates by a simple method without external additives at room temperature.