Density functional theory evaluation of cation-doped bismuth molybdenum oxide photocatalysts for nitrogen fixation

This study investigates the photocatalytic nitrogen fixation on a cation-doped surface (BixMy)2MoO6 where (M = Fe, La, Yb) in both the orthorhombic and monoclinic configurations using a density functional theory (DFT) approach with experimentally validated model inputs. The proceeding discussion focuses on the Heyrovsky-type reactions for both the associative and dissociative reaction pathway related to nitrogen reduction. Key fundamental insight in the reduction mechanism is discussed that relates the material properties of the substitutional ions to the nitrogen and hydrogen affinities. Physical insight is gathered through interpretation of bound electronic states at the surface. Compositional phases of higher Fe and Yb concentrations resulted in decreased MoO binding and increased affinity between Mo and the N and H species on the surface. The modulation of the MoO binding is induced by strain as Yb and Fe are implemented, this, in turn, shifts energy levels and modulates the band gap energy by approximately 0.2 eV. This modification of MoO bond as substitution occurs is a result of the orbital hybridization of MO (M = Fe, Yb) that causes a strong orbital interaction that shifts states up toward the Fermi. The optimal composition was predicted to be an orthorhombic configuration of (Bi0.75Fe0.25)2MoO6 with a predicted maximum thermodynamic energy barrier of 1.4 eV. This composition demonstrates effective nitrogen and hydrogen affinity that follows the associative or biological nitrogen fixation pathway.