化工学报2011，Vol.62Issue(4)：1048-1054,7.
含氮焦炭异相还原NO反应机理的密度泛函理论研究
Density functional theoretical study of heterogeneous reduction mechanism of NO on nitrogen-containing char surface
摘要
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.关键词
一氧化氮/含氮焦炭/异相还原/密度泛函理论Key words
NO/ nitrogen-containing char/ heterogeneous reduction/ density functional theory分类
能源科技引用本文复制引用
张秀霞,周志军,周俊虎,姜树栋,刘建忠,岑可法..含氮焦炭异相还原NO反应机理的密度泛函理论研究[J].化工学报,2011,62(4):1048-1054,7.基金项目
国家高技术研究发展计划项目(2008AA05Z304). （2008AA05Z304）
