摘要：

选用合理简化的含氮焦炭模型，使用密度泛函理论对含氮焦炭异相还原NO释放出N₂的反应机理在分子水平上进行了研究。使用B3LYP/6-31G(d)方法优化得到了含氮焦炭模型、产物、中间体和过渡态的几何构型。在相同水平上计算得到了优化所得结构的单点能并进行了零点能校正，从而得到整个反应的势能面及各中间反应的活化能和反应热。NO吸附在含氮焦炭表面后N、O原子倾向于分离，吸附反应释放出98.1 kJ·mol^-1的热量。吸附产物可分别经历最高能垒为87.7 kJ·mol^-1和253 kJ

关键词: 一氧化氮, 含氮焦炭, 异相还原, 密度泛函理论

Abstract:

Heterogeneous reduction mechanism of NO on the surface of nitrogen-containing char was investigated at molecular level using density functional theory.The char model, products, stable intermediates and transition states were optimized at B3LYP/6-31G(d）level.The whole potential energy surface was obtained by calculating single point energies with zero point energy corrections for geometries.The results are as follows.The first step of the heterogeneous reduction is NO adsorption on the surface of nitrogen-containing char, releasing heat energy of 98.1 kJ·mol^-1 .N and O atoms tend to separate after chemisorption.N₂ is desorbed with the production of P1 by a series of rearrangement reactions, in which the highest energy barrier is 87.7 kJ·mol^-1.The highest energy barrier for CO desorption is 253 kJ·mol^-1 and P2 is left on the char surface.Desorption of N₂ and CO from reactions between NO and nitrogen-containing char are 187 kJ·mol^-1 exothermic and 302 kJ·mol^-1 endothermic, respectively.CO is further released from P1 with 138 kJ·mol^-1 endothermic, and N₂ is desorbed from P2 with 352 kJ·mol^-1 released.About 49 kJ·mol^-1 is released throughout the overall heterogeneous reduction of NO on the surface of nitrogen-containing char.

Key words: 一氧化氮, 含氮焦炭, 异相还原, 密度泛函理论