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.