Concentration-driven polymorphic mesocrystal and morphosynthetic transformation toward omni-adsorbent with the widest range of pores

Abstract

• Synthetic strategy for Zn–NDC polymorphic mesocrystals (ZPM) is developed. • Initial concentration of precursor governs assembly behavior of primary building units. • Morphosynthetic transformation of ZPM produces exceptionally pore-diversified mesocarbon. • Hierarchical pore architecture of mesocarbons provides “omni-scale” adsorptive capability. Mesocrystal constituted by individual nanocrystals is of particular interest owing to its combinative and exceptional features. In this study, we present a synthesis strategy for polymorphic metal–organic mesocrystal governed by different building principles through bio-inspired particle-mediated growth. The control of initial nucleation density enables the primary structure to be differentiated into various morphologies composed of identical crystalline building units. The varying primary structures produce distinctive mesocrystals with unique hierarchical architecture through particle-mediated growth. Furthermore, the hierarchical architectures of the mesocrystals, which originated from their polymorphism, are inherited into respective mesocarbon through a simple thermal conversion process. The atomic-distributed Zn species throughout the mesostructure further contribute to the development of micro- and mesopores by self-vanishing reduction. As a result, the mesocarbon has diversified pore architecture with an unexpectedly wide range of pores. The exceptional pore architecture of the mesocrystal exhibits universal adsorption capability for “omni-scale” adsorbate molecules from angstrom and nano to micro scale.