Zhao Yue, Hu Ji-Chuang, Cui Jia-Tong, Xu Lin-Lin, Ma Jia-Bi
The Institute for Chemical Physics, Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, 102488, Beijing, P. R. China.
Chemistry. 2018 Apr 17;24(22):5920-5926. doi: 10.1002/chem.201705997. Epub 2018 Mar 24.
The mass-selected Fe O cation mediated propane oxidation by O was investigated by mass spectrometry and density functional theory calculations. In the reaction of Fe O with C H , H was liberated by C-H bond activation to give Fe OC H . Interestingly, when a mixture of C H /O was introduced into the reactor, an intense signal that corresponded to the Fe O cation was present; the experiments indicated that O was activated in its reaction with Fe O(C H ) to give Fe O and C H O (acetone or propanal). A Langmuir-Hinshelwood-like mechanism was adopted in the propane oxidation reaction by O on gas-phase Fe O cations. In comparison with the absence of Fe O in the reaction of Fe O with O , the ligand effect of C H on Fe OC H is important in the oxygen activation reaction. The theoretical results are consistent with the experimental observations. The propane oxidation by O in the presence of Fe O might be applied as a model for alkane and O activations over iron oxide catalysts, and the mechanisms and kinetic data are useful for understanding corresponding heterogeneous reactions.
通过质谱和密度泛函理论计算研究了质量选择的FeO阳离子介导的O对丙烷的氧化作用。在FeO与C₃H₈的反应中，通过C-H键活化释放出H，生成FeOC₃H₇。有趣的是，当将C₃H₈/O的混合物引入反应器时，存在与FeO阳离子相对应的强信号；实验表明，O在与FeO(C₃H₇)的反应中被活化，生成FeO和C₃H₆O（丙酮或丙醛）。在气相FeO阳离子上，O对丙烷的氧化反应采用了类似Langmuir-Hinshelwood的机理。与FeO与O的反应中不存在FeO相比，C₃H₈对FeOC₃H₇的配体效应在氧活化反应中很重要。理论结果与实验观察结果一致。在FeO存在下O对丙烷的氧化反应可作为氧化铁催化剂上烷烃和O活化的模型，其机理和动力学数据有助于理解相应的多相反应。
