Insights into the interaction between NO and char(N) containing different functional forms: Mechanistic, thermodynamic and kinetic studies

Char-bound nitrogen [char(N)] is confirmed to be the real intermediate in heterogeneous reduction during coal combustion. Aiming to have a deep insight into the interaction mechanism between NO and char(N) containing different functional forms of nitrogen, a comprehensive theoretical exploration with density functional theory at M06–2X/6–31G(d,p)//def-TZVP level is performed. The detailed electronic descriptions of char(N) surface based on spin density, Mulliken atomic charge and electrostatic potential exhibit the attack sites and electron donating capability during NO chemisorption in the following order: char(N-5) < char(N-X) < char(N-6). Oxygen surface complex, an intermediate for N 2 O formation and a catalyst for NO reduction, can weaken the connected C N bond and promote N 2 separation. The migration of oxygen atoms to adjacent active sites is thermodynamically conducive to reduction reactions, leading to the preferred pathway of N 2 release on char(N-5) and char(N-X) surfaces. Contiguous active sites remaining along char edge are unfavorable for N 2 O detaching, while beneficial to NO further chemisorption for consecutive reactions, resulting in the great contributions of char(N-5) in reducing NO. The lower energy barriers for NO reduction follow the sequence coincident with the results of electronic property analysis. The kinetically favorable temperatures and activation energies of different char(N) for reducing NO are determined, which is consistent with previous experiments. The theoretical results provide evidences to explain microscopic mechanism of NO-char(N) interaction, making contributions to effectively minimize NOx emissions in the future.