Investigating the Influence of Hexanuclear Clusters in Isostructural Metal-Organic Frameworks on Toxic Gas Adsorption

The efficient capture of toxic gases, such as ammonia (NH₃) and sulfur dioxide (SO₂), can protect the general population and mitigate widespread air pollution. Metal-organic frameworks (MOFs) comprise a tunable class of adsorbents with high surface areas that can meet this challenge by selectively capturing these gases at low concentrations. In this work, we explored how modifying the metal ions in the node of an isostructural MOF series from a transition metal to a lanthanide or actinide influences the electronic environment of the node-based active site. Next, we investigated the adsorption properties of each MOF toward the relatively basic NH₃ and relatively acidic SO₂ gases. Within the NU-907 family of MOFs, we found that Zr₆-NU-907 exhibits the best uptake toward NH₃ at low pressures, while Th₆-NU-907 demonstrates the best low-pressure performance for SO₂ adsorption. Tracking the infrared (IR) stretching frequency of the node-based μ₃-OH groups provides insights into the electronegativity of the metal ion and suggests that the most electronegative metal ion (Zr) affords the node with the best NH₃ uptake at low pressures. In contrast, the Th₆ node contains additional coordinated water groups relative to the other M₆ nodes, which appears to yield the MOF with the greatest affinity for SO₂ uptake that occurs predominately through reversible physisorption interactions. Finally, in situ NH₃ IR spectroscopic studies indicate that both NH₄⁺ and Lewis-bound NH₃ species form during adsorption. Combined, these results suggest that tuning the electronic properties and structure of the node-based active site in an MOF presents a viable strategy to change the affinity of an MOF toward toxic gases.