Theoretical study of the dissociation of N2O in a transition metal ion-catalyzed reaction
Theoretical study of the dissociation of N2O in a transition metal ion-catalyzed reaction
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DOI：
10.1021/jp0313167
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发表时间：
2004-07-01
影响因子：
3.3
通讯作者：
Delahay, G
中科院分区：
文献类型：
--
作者：
Martínez, A;Goursot, A;Delahay, G
铁沸石模型已被用于研究N2O的解离，有和没有氨的存在下。从密度泛函理论计算，N2O分解路径的机制和能量的介绍和讨论。分析了氨的影响。得到的结果为一个单一的金属离子和模型，包括沸石簇进行了比较。用该团簇模型计算的近似活化能垒与实验符合得很好。两个氨配体的存在降低了计算的活化势垒，从而得出氨在N2O分解的两个步骤中起作用的结论，即，ON 2键的断裂和铁氧化合物的还原。
Models of Fe-zeolites have been used to study the dissociation of N2O, with and without the presence of ammonia. From Density Functional Theory calculations, the mechanism and energetics of N2O decomposition paths are presented and discussed. The influence of ammonia is analyzed. The results obtained for a single metal ion and for models including a zeolite cluster are compared. The approximate activation barrier calculated with this cluster model is in good agreement with experiment. The presence of two ammonia ligands reduces the calculated activation barrier, leading to the conclusion that ammonia plays a role in both steps of the N2O decomposition, i.e., the breaking of the ON2 bond and the reduction of the iron-oxo compounds.