摘要
采用B3LYP/cc-pVTZ理论水平系统研究了Ca+离子催化N2O+CO→N2+CO2反应的微观机理.反应分两步进行:第一步Ca+夺取N2O中的O原子有两条反应通道,其中优势通道为Ca+金属离子与N2O分子中O作用,形成线性分子复合物,活化N2O分子中的N—O键,之后的反应路径为O—N键断裂机理;第二步为CaO+金属氧化物阳离子与CO反应,反应过程遵循插入消去机理.纵观整个Ca+金属离子催化过程,计算结果表明反应不需要吸收能量,大约放热358 kJ.mol-1,所得计算结论与实验结果吻合,Ca+是将N2O,CO转化为N2和CO2这一循环催化反应的理想金属阳离子催化剂.
The mechanism of the gas-phase reaction N2O and CO catalyzed by Ca^＋ has been investigated on doublet electronic state potential energy surface. The reactions are studied by using the B3LYP density functional method and the cc-pVTZ basis set. Our calculated results show that both steps of the reaction are exothennic and the overall exothermicity is 358 kJ· mol^-1, which are close to the experimental observations. The O-atom affinities of the correlative species were calculated, which testified that the cyclic, catalytic function of Ca^ ＋ was thermodynamically allowed. Our results may be helpful for future experimental investigation of the title reaction.
出处
《分子科学学报》
CAS
CSCD
北大核心
2011年第5期354-357,共4页
Journal of Molecular Science
基金
牡丹江师范学院博士科研启动基金资助项目(MSB200907
MSB200908)
牡丹江师范学院教学改革工程建设项目(11-XJ12063)
黑龙江省教育厅科学技术研究项目(11551511)
