Growth of Single-Crystal Mesoporous Carbons with Im(3)over-barm Symmetry

Highly ordered mesoporous carbon FDU-16 rhombic dodecahedral single crystals with body-centered cubic structure (space group Im (3) over barm) have been successfully synthesized by employing an organic-organic assembly of triblock copolymer Pluronic F127 (EO106PO70EO106) and phenol/formaldehyde resol in basic aqueous solution. Synthetic factors (including reaction time, temperature, and stirring rate) are explored for controlling the formation of rhombic dodecahedral single crystals. The optimal stirring rate and the reaction temperature are 300 +/- 10 rpm and similar to 66 degrees C, respectively. High-resolution scanning electron microscopy (HRSEM), scanning transmission electron microscopy (STEM), and ultramicrotomy are applied to study the fine structures of the carbon single crystals. The mesopores are arranged in body-centered cubic symmetry throughout the entire particle. Surface steps are clearly observed in the {110} surface, which suggests a layer-by-layer growth of the mesoporous carbon FDU-16 single crystals. Cryo-SEM results from the reactant solution confirm the formation of resol/F127 unit micelles, further supporting the layer-by-layer growth process. The mesoporous carbon FDU-16 single crystals grow up to the final size of 2-4 mu m within 2 days. These findings may have consequences for the growth mechanism of other carbon materials in aqueous solution; moreover, the high-quality single crystals also have potential applications in nanodevice technologies.