DFT Study on the Effect of Na on NO Reduction with Nitrogen-Containing Char from Zhundong Coal

The effect mechanism of Na on reduction of NO with nitrogen-containing char, char(N) still lacks an in-depth study. Based on density functional theory, this study systematically discussed the heterogeneous reaction of NO with four char(N) models, that is, zigzag(N), zigzag(N)@Na, armchair(N), and armchair(N)@Na. Results show that the presence of Na promoted the chemisorption of NO on both zigzag(N) and armchair(N), especially zigzag(N). Mayer bond order analysis revealed that during NO reduction, Na catalyzed the breaking of N-O and C-N bonds in both models as well as dissociation of the N-N structure from the zigzag(N). Dynamics in the 300-1000 K range revealed that the rate constant for the decisive step increased in the order of zigzag(N) < zigzag(N)@Na < armchair(N) < armchair(N)@Na, while the activation energy presented a reverse order. The addition of Na promoted the electron transfer between NO and char(N) and exhibited an obvious catalytic effect on the NO-char(N) reaction by reducing activation energy and increasing the reaction rate constant for the decisive step.