Synthesis of ZIF-8 Nanocrystals Mediated by CO₂ Gas Bubbling: Dissolution and Recrystallization

Crystal size and morphology of zeolitic imidazolate frameworks (ZIFs) can be generally controlled based on the classical theory of nucleation and growth. Herein, we have developed an alternative method to adjust the nucleation and growth kinetics of microporous ZIF-8 nanocrystals mediated by continuous CO₂ gas bubbling. In particular, CO₂ bubbling led to the dissolution of ZIF-8 slurry, while the evacuation of CO₂ bubbling resulted in the formation of new ZIF-8 nanoparticles with a considerably smaller size. A plausible mechanism of the CO₂-mediated synthesis of ZIF-8 nanoparticles was proposed based on comprehensive characterizations and analyses, which indicated that the dissolved CO₂ in methanol was able to perturb the pre-equilibrium states of crystallization intermediates and led to a comparatively fast nucleation rate due to a low number of overcoordinated species between the metal ion and the ligand. Both methanol and the base were critically important to the dissolution-recrystallization of ZIF-8, wherein the methyl carbonate linker might be reversibly produced by CO₂ insertion into the methoxide group (Zn-OCH₃). Also, the CO₂-mediated synthesis led to the small particle size, high crystallinity, good thermal stability, and high purity of ZIF-8, as compared to the conventional ZIF-8 prepared without CO₂ gas bubbling. As proof of workability, the prepared monodispersed ZIF-8 nanoparticles showed a much higher photocatalytic activity toward various organic dyes' decomposition than the conventional ZIF-8. Also, the CO₂ bubbling-mediated method could be further extended to prepare other ZIFs (e.g., ZIF-67).