铂钌团簇活化甲醇C―H和O―H键的理论研究  被引量:2

Theoretical Study of Methanol C―H and O―H Bond Activation by PtRu Clusters

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作  者:赵俊凤[1] 孙小丽[1] 李吉来[1] 黄旭日[1] 

机构地区:[1]吉林大学理论化学研究所,长春130023

出  处:《物理化学学报》2015年第6期1077-1085,共9页Acta Physico-Chimica Sinica

基  金:国家重点基础研究发展规划项目(973)(2012CB932800);国家自然科学基金(21103064;21473070)资助~~

摘  要:采用密度泛函理论研究了PtnRum(n+m=3,n≠0)团簇活化甲醇C―H和O―H键的反应活性和机理.分别给出以O―H和C―H键活化为初始步骤的势能曲线.计算结果表明反应是以C―H键的活化为初始步骤;三种团簇与甲醇反应的活性顺序为Pt2Ru>Pt3>Pt Ru2.前线轨道分析表明PtnRum团簇活化初始的C―H和O―H键的活化过程是质子转移(PT).此外还讨论了溶剂化对反应的影响.本研究可为C―H键和O―H键的活化提供更深入的理解,为甲醇活化反应催化剂选择以及其使用条件的优化提供新思路.Density functional theory calculations were performed to study the mechanism and reactivity of methanol oxidation mediated by Pt.Rum (n+m=3, n≠0) clusters. The potential energy surfaces and pathways of the initial O-- H and C-- H bond activations were predicted. The results show that the activation of methanol proceeds preferentially along the C-- H bond activation pathway. The calculated reactivity order was Pt2Ru〉Pt3〉 Pt3Ru2. Frontier molecular orbital analysis showed that the initial C/O--H bond activation is a proton transfer process. The solvent effect was also investigated. This study will enable a deeper understanding of C/O--H bond activation and provide new ideas for catalyst selection and optimizing conditions for methanol activation.

关 键 词:密度泛函理论 团簇 甲醇 活性 质子转移 

分 类 号:O641.1[理学—物理化学]

 

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