CAJ | 학술논문

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>PtRu2.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.
채용밀도범함이론연구료PtnRum (n+m=3, n≠0)단족활화갑순C―H화O―H건적반응활성화궤리.분별급출이O―H화C―H건활화위초시보취적세능곡선.계산결과표명반응시이C―H건적활화위초시보취；삼충단족여갑순반응적활성순서위Pt2Ru>Pt3>PtRu2.전선궤도분석표명PtnRum단족활화초시적C―H화O―H건적활화과정시질자전이(PT).차외환토론료용제화대반응적영향.본연구가위C―H건화O―H건적활화제공경심입적리해,위갑순활화반응최화제선택이급기사용조건적우화제공신사로.
Density functional theory calculations were performed to study the mechanism and reactivity of methanol oxidation mediated by PtnRum (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 preferential y along the C―H bond activation pathway. The calculated reactivity order was Pt2Ru>Pt3>PtRu2. 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 wil enable a deeper understanding of C/O―H bond activation and provide new ideas for catalyst selection and optimizing conditions for methanol activation.