摘要
对煤制气再燃低NOx燃烧过程进行分析,采用量子化学密度泛函理论(DFT)研究NH2自由基与NO的反应机理。全参数优化了各反应物、中间体、过渡态和产物的几何构型,并计算了它们的能量,通过振动频率分析证实中间体和过渡态的真实性。同时用内禀反应坐标(IRC)计算以进一步确定过渡态。为了得到更精确的能量信息,在QCISD(T)水平上计算了单点能。对NH2自由基与NO反应机理进行分析比较,并通过模拟NH2自由基与NO的反应,得出通道NH2+NO→IM1→TS1→IM3→N2+H2O的活化能最低(206.1kJ/mol),为最佳反应通道。揭示其微观机理,对进一步认识再燃脱氮的本质和主要过程提供了重要的理论依据和实践指导。
The geometries of reactants, intermediates, transition states and products for NH2 with NO reaction were optimized by the quantum chemical density functional theory（DFT）. The transition states and intermediates of the reaction were verified by frequency analysis. The authenticity of intermediates and transition states were confirmed by intrinsic reaction coordinate analysis（IRC）. To obtain more accurate energy information, the stationary points of the single point energy were further refined at the QCISD（T） level. Verified the NH2 radical and NO reaction mechanism. It is obtained that channel NH2 ＋NO→IM1→TS1→IM3→Nz ＋H20 has the lowest activation energy（206, lkJ/ mol）, which is the main reaction channel. It has important theoretical and practical significance for the understanding of the nature of NOxreburning process and the main reference value to reveale the microscopic mechanism and give pro-per interpretion in theority.
出处
《材料导报》
EI
CAS
CSCD
北大核心
2011年第20期91-94,共4页
Materials Reports
基金
国家自然科学基金(50906055)
关键词
NH2自由基
NO反应机理
活化能
free radical NH2, NO, reaction mechanism, activation energy
