Computational spectroscopy and DFT investigations into nitrogen and oxygen bond breaking and bond making processes in model deNOx and deN2O reactions

Molecular DFT modeling combined with computational spectroscopy (EPR and IR) were applied for analysis of the NO bond breaking and NN and OO bond making in the context of deNO_x and deN₂O reactions. Interaction of NO, N₂O and NO₂ with cationic (transition metals) and anionic (surface O²⁻ ions) centers was explored at the molecular level. The elementary events such as reactant coordination, charge and spin redistributions, which are principal molecular constraints for efficient decomposition of the nitrogen oxides (N₂O and NO) were discussed. Particular attention was paid to dynamics of the NO bond cleavage in N₂O molecule through electron and oxygen atom transfer routes, evaluation of preferable coordination modes of NO, discrimination between inner- and outer-sphere mechanism of NN bond formation, and the influence of spin and electronic redistribution on the reaction course (spin catalysis). Owing to their simplicity and well known surface chemistry, model systems selected for studies of such processes include MoO_x/SiO₂, MgO and ZSM-5 zeolite exchanged with various transition metal ions (TMI) of different electron configuration and spin multiplicity: Mo⁵⁺ (d¹, ²D) Fe³⁺, Mn²⁺, Cr⁺ (d⁵, ⁶S), Fe²⁺ (d⁶, ⁵D), Co²⁺ (d⁷, ⁴F), Ni²⁺ (d⁸, ³F), Cu²⁺ (d⁹, ²D) and Cu⁺, Zn²⁺ (d¹⁰, ¹S).