Unveiling Unexpected Modulator-CO₂ Dynamics within a Zirconium Metal–Organic Framework

Carbon capture, storage, and utilization (CCSU) represents an opportunity to mitigate carbon emissions that drive global anthropogenic climate change. Promising materials for CCSU through gas adsorption have been developed by leveraging the porosity, stability, and tunability of extended crystalline coordination polymers called metal–organic frameworks (MOFs). While the development of these frameworks has yielded highly effective CO₂ sorbents, an in-depth understanding of the properties of MOF pores that lead to the most efficient uptake during sorption would benefit the rational design of more efficient CCSU materials. Though previous investigations of gas–pore interactions often assumed that the internal pore environment was static, discovery of more dynamic behavior represents an opportunity for precise sorbent engineering. Herein, we report a multifaceted <i>in situ</i> analysis following the adsorption of CO₂ in MOF-808 variants with different capping agents (formate, acetate, and trifluoroacetate: FA, AA, and TFA, respectively). <i>In situ</i> diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis paired with multivariate analysis tools and <i>in situ</i> powder X-ray diffraction revealed unexpected CO₂ interactions at the node associated with dynamic behavior of node-capping modulators in the pores of MOF-808, which had previously been assumed to be static. MOF-808-TFA displays two binding modes, resulting in higher binding affinity for CO₂. Computational analyses further support these dynamic observations. The beneficial role of these structural dynamics could play an essential role in building a deeper understanding of CO₂ binding in MOFs.