Rice-Like, Hollow, and Rhombohedral Nano-Calcite Synthesis by Carbonization

Abstract

Controlling the morphology and size of calcium carbonate (CaCO3) remains an essential challenge in the production of high-performance fillers and advanced functional materials. Here, we report a continuous carbonization strategy that enables the synthesis of monodisperse nano-calcite particles with tunable rice-like, hollow, and rhombohedral morphologies through precise control of CO2 dissolution into a flowing Ca(OH)2 solution under diffusion-limited conditions. A two-stage reactor was designed to decouple nucleation and growth by separating the gas-liquid interaction zone from a stabilization tank. pH and conductivity analyses revealed that crystallization is primarily governed by the CO2 dissolution kinetics rather than mixing intensity in the stabilization tank. SEM and XRD analyses demonstrate a distinct crystallization sequence such that initial formation of rice-like calcite, subsequent development of hollow nanoparticles through selective tip dissolution, and final transformation into rhombohedral calcite via dissolution-reprecipitation mechanism. The method provides a reproducible, template-free route for fabricating hollow CaCO3 nanoparticles, overcoming limitations of bubbletemplating and additive-mediated techniques. This scalable process provides a robust foundation for producing high-surface-area CaCO3 nanomaterials which have potential applications in thin films, ceramics, protective coatings, lightweight composites, thermal/acoustic insulation, adsorption, and catalysis, where tailored particle morphology and size can significantly enhance performance.