Selective Oxidation of Short-Chain Alcohols on Spinel CoFe2O4 (001) Surfaces: Mechanistic Insights from DFT

The selective oxidation of short-chain alcohols is a key transformation in green chem- istry, providing sustainable routes to aldehydes and ketones for industrial applications. In this study, we present a mechanistic density functional theory (DFT) investigation of alcohol oxidation on spinel CoFe 2 O 4 (001) surfaces. Using an embedded cluster model, we compare the reactivity of the A- and B-layer terminations, focusing on the role of monoatomic reactive oxygen species (ROS) and lattice oxygen in the Langmuir– Hinshelwood and Mars–van Krevelen pathways. Adsorption energies, deprotonation barriers, and product stabilization are evaluated for methanol, ethanol, and 2-propanol, highlighting the interplay of surface cation identity and local coordination environment. Our results reveal that Fe O oxyl species on the A-layer provide thermodynamically and kinetically favorable pathways, while the B-layer favors lattice oxygen participation with lower barriers in the second deprotonation step. The findings rationalize exper- imental observations of superior activity associated with Co 3+ -rich environments and offer molecular-level insights into tailoring spinel oxide catalysts for selective alcohol oxidation.