Unusual CO₂ Adsorption in ZIF-7: Insight from Raman Spectroscopy and Computational Studies

Here, we use Raman spectroscopy to investigate temperature-dependent changes in the atomic-scale structure of the zeolitic imidazolate framework ZIF-7 in a CO₂ atmosphere and uncover the mechanism of maximal CO₂ adsorption at 206 K. At 301 K, the Raman spectra of ZIF-7 at various CO₂ gas pressures reveal a narrow-pore (np) to large-pore (lp) phase transition commencing at 0.1 bar as a result of adsorption of CO₂, as evident in the appearance of Fermi resonance bands of CO₂ at 1272 and 1376 cm^-1. Moreover, the Raman inactive bending mode of CO₂ becomes active due to geometrical distortion of adsorbed CO₂. It further splits into two peaks due to hydrogen bonding interactions between CO₂ and the benzene ring of the benzimidazole linker ZIF-7, as supported by our computational studies. In addition, the interaction between CO₂ molecules plays a key role. Upon reducing the temperature at 1 bar CO₂ gas pressure, ZIF-7 exhibits softening of the imidazole puckering mode and the Fermi resonance CO₂ band due to interactions between CO₂ and the framework through hydrogen bonding. At 206 K, substantial modification in the lattice mode and disappearance of the Raman inactive CO₂ bending mode confirm the changes in the size of the pore cavity through structural rearrangements of CO₂.