Oxygen Healing and CO₂ /H₂ /Anisole Dissociation on Reduced Molybdenum Oxide Surfaces Studied by Density Functional...

Reduced molybdenum oxides are versatile catalysts for deoxygenation and hydrodeoxygenation reactions. In this work, we have performed spin-polarized DFT calculations to investigate oxygen healing energies on reduced molybdenum oxides (reduced α-MoO₃ , γ-Mo₄ O₁₁ and MoO₂ ). We find that Mo⁺⁴ on MoO₂ (100) is the most active for abstracting an oxygen from the oxygenated compounds. We further explored CO₂ adsorption and dissociation on reduced α-MoO₃ (010) and MoO₂ (100). In comparison to reduced α-MoO₃ (010), CO₂ adsorbs more strongly on MoO₂ (100). We find that CO₂ dissociates on MoO₂ (100) via a two-step process, the overall barrier for which is 0.6 eV. This barrier is 1.7 eV lower than that on reduced α-MoO₃ (010), suggesting a much higher activity for deoxygenation of CO₂ to CO. As H₂ dissociation is shown to be the rate-limiting step for hydrodeoxygenation reactions, we also studied activation barriers for H₂ chemisorption on MoO₂ (100). We find that the chemisorption barriers are 0.7 eV lower than that reported on reduced α-MoO₃ (010). Finally, we have studied the dissociation (C-O cleavage) of anisole (a lignin-based biofuel model compound) on MoO₂ (100). We find that anisole binds very strongly on MoO₂ (100) with an adsorption energy of -1.47 eV. According to Sabatier's principle, strongly adsorbing reactants poison the catalyst surface, which may explain the low activity of MoO₂ observed during experiments for hydrodeoxygenation of anisole.