First-Principles Perspective on Gas Adsorption by [Fe4S4]-Based Metal-Organic Frameworks

[Fe4S4] or [4S-4Fe] clusters are responsible for storing and transferring electrons in key cellular processes and interact with their microenvironment to modulate their oxidation and magnetic states. Therefore, these clusters are ideal for the metal node of chemically and electromagnetically tunable metal- organic frameworks (MOFs). To examine the adsorption-based applications of [Fe4S4]-based MOFs, we used density functional theory calculations and studied the adsorption of CO2, CH4, H2O, H2, N2, NO2, O2, and SO2 onto [Fe4S4]0, [Fe4S4]2+, and two 1D MOF models with the carboxylate and 1,4-benzenedithiolate organic linkers. Our reaction kinetics and thermodynamics results indicated that MOF formation promotes the oxidative and hydrolytic stability of the [Fe4S4] clusters but decreases their adsorption efficiency. Our study suggests the potential industrial applications of these [Fe4S4]-based MOFs because of their limited capacity to adsorb CO2, CH4, H2O, H2, N2, O2, and SO2 and high selectivity for NO2 adsorption.

Automated summary

[Fe4S4] or [4S-4Fe] clusters play a crucial role in storing and transferring electrons in cellular processes and have the potential to be used in metal-organic frameworks (MOFs) for various applications. By studying the adsorption of different molecules onto [Fe4S4]-based MOFs, we found that while MOF formation improves the stability of [Fe4S4] clusters, it reduces their adsorption efficiency. Our findings suggest the potential industrial applications of these [Fe4S4]-based MOFs, particularly for selective NO2 adsorption.