DFT Study on the Catalytic Activity of ALD-Grown Diiron Oxide Nanoclusters for Partial Oxidation of Methane to Methanol

Using density functional theory (DFT), we studied the catalytic activity of iron oxide nanoclusters that mimic the structure of the active site in the soluble form of methane monooxygenase (sMMO) for the partial oxidation of methane to methanol. Using N₂O as the oxidant, we consider a radical-rebound mechanism and a concerted mechanism for the oxidation of methane on either a bridging oxygen (O_b) or a terminal oxygen (O_t) active site. We find that the radical-rebound pathway is preferred over the concerted pathway by 40-50 kJ/mol, but the desorption of methanol and the regeneration of the oxygen site are found to be the highest barriers for the direct conversion of methane to methanol with these catalysts. As demonstrated by a population analysis, the O (x = b or t) site behaves as an oxygen radical during the H abstraction, and the [Fe⁺-O^-] site behaves as a Lewis acid-base pair during the concerted C-H cleavage. Molecular orbital decomposition analysis further demonstrates electron transfer during the oxidation and reduction steps of the reaction. High-level multireference calculations were also carried out to further assess the DFT results. Understanding how these systems behave during the proposed reaction pathways provides new insights into how they can be tuned for methane partial oxidation.