Thermal Structural Transitions and Carbon Dioxide Adsorption Properties of Zeolitic Imidazolate Framework‑7 (ZIF-7)

As a subset of the metal–organic frameworks, zeolitic imidazolate frameworks (ZIFs) have potential use in practical separations as a result of flexible yet reliable control over their pore sizes along with their chemical and thermal stabilities. Among many ZIF materials, we explored the effect of thermal treatments on the ZIF-7 structure, known for its promising characteristics toward H₂ separations; the pore sizes of ZIF-7 (0.29 nm) are desirable for molecular sieving, favoring H₂ (0.289 nm) over CO₂ (0.33 nm). Although thermogravimetric analysis indicated that ZIF-7 is thermally stabile up to ∼400 °C, the structural transition of ZIF-7 to an intermediate phase (as indicated by X-ray analysis) was observed under air as guest molecules were removed. The transition was further continued at higher temperatures, eventually leading toward the zinc oxide phase. Three types of ZIF-7 with differing shapes and sizes (∼100 nm spherical, ∼400 nm rhombic-dodecahedral, and ∼1300 nm rod-shaped) were employed to elucidate (1) thermal structural transitions while considering kinetically relevant processes and (2) discrepancies in the N₂ physisorption and CO₂ adsorption isotherms. The largest rod-shaped ZIF-7 particles showed a delayed thermal structural transition toward the stable zinc oxide phase. The CO₂ adsorption behaviors of the three ZIF-7s, despite their identical crystal structures, suggested minute differences in the pore structures; in particular, the smaller spherical ZIF-7 particles provided reversible CO₂ adsorption isotherms at ∼30–75 °C, a typical temperature range of flue gases from coal-fired power plants, in contrast to the larger rhombic-dodecahedral and rod-shaped ZIF-7 particles, which exhibited hysteretic CO₂ adsorption/desorption behavior

Thermosensitive Structural Changes and Adsorption Properties of Zeolitic Imidazolate Framework‑8 (ZIF-8)

We compared four types of ZIF-8 with varying sizes and shapes to determine their thermal-structural stability and derive appropriate thermal activation conditions and correlation between structural characteristics and adsorption properties. Under air, the ZIF-8 phase for all the samples was converted completely into the zinc oxide phase above ∼300 °C, though thermalgravimetric analysis (TGA) indicated that the original structure was stable to ∼300–350 °C. Longer exposures (∼30 d) suggested that thermal activation at ∼200 °C was appropriate for the removal of guest and/or solvent molecules under air without structural damage. Despite no noticeable change in X-ray diffraction (XRD) patterns after activation at 250 °C under air, the resulting BET surface areas and CO₂ adsorption amounts (at 1 bar and 30 °C) of ZIF-8s were reduced to ∼44–54 and ∼72–87%, respectively, as compared to those of appropriately activated ZIF-8s. It appears that after the activation at 250 °C under air, some Zn and N atoms were dissociated and converted to ZnOH and NOH, respectively, causing the partial structural damage of ZIF-8s