Pt+-catalyzed oxidation of methane: Theory and experiment
Pt+-catalyzed oxidation of methane: Theory and experiment
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DOI：
10.1021/jp962966w
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发表时间：
1997-02-20
影响因子：
2.9
通讯作者：
Schwarz, H
中科院分区：
文献类型：
--
作者：
Pavlov, M;Blomberg, MRA;Schwarz, H
使用原子铂阳离子作为催化剂，用分子氧氧化甲烷，产生甲醇、甲醛和高级氧化产物，已经通过计算和实验进行了研究。详细遵循了最相关的反应途径。为此，大量的驻点，包括极小值和过渡态，都有甜菜？使用混合密度泛函理论方法（B3LYP）进行优化。在这些优化的几何结构中，使用经验缩放方案 (PCI-80) 和采用具有多个极化函数的扩展基组的 B3LYP 方法计算了能量。与现有实验数据取得了良好的一致性。对于催化循环中尚未获得详细实验结果的部分，新的计算结果补充了实验图片，以达到对反应机理的几乎完整的理解。使用经验方法将自旋轨道效应纳入其中，从而提高了与实验的一致性。本研究报告的新 FTICR 实验有助于阐明一些最复杂的反应序列。
The oxidation of methane with molecular oxygen using the atomic platinum cation as a catalyst, yielding methanol, formaldehyde, and higher oxidation products, has been studied both computationally and experimentally. The most relevant reaction pathways have been followed in detail. To this end a large number of stationary points, both minima and transition states, have beet? optimized using a hybrid density functional theory method (B3LYP). At these optimized geometries, energies have been calculated using both an empirical scaling scheme (PCI-80) and the B3LYP method employing extended basis sets with several polarization functions. Good agreement with available experimental data has been obtained. For the parts of the catalytic cycle where detailed experimental results have not been available, the new calculated results have complemented the experimental picture to reach an almost complete understanding of the reaction mechanisms. Spin-orbit effects have been incorporated using an empirical approach, which has lead to improved agreement with experiments. The new FTICR experiments reported in the present study have helped to clarify some of the most complicated reaction sequences.