Oxidation of Methanol to Formaldehyde on Silica-Supported Molybdena: Density Functional Theory Study on Models of Mononuclear Sites

Laurence J. Gregoriades; Jens Dobler; Joachim Sauer

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Oxidation of Methanol to Formaldehyde on Silica-Supported Molybdena: Density Functional Theory Study on Models of Mononuclear Sites

机译：二氧化硅负载的钼上甲醇氧化为甲醛：单核位点模型的密度泛函理论研究

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Isolated molybdenum centers bearing either one (oxomolybdenum system) or two (dioxomolybdenum system) terminal oxo ligands are considered, which are modeled by appropriate mononuclear oxomolybdenum methoxides and oxomolybdasilsesquioxanes. Although the oxidation process in both systems is characterized by the same fundamental steps, that is, dissociative addition of methanol followed by rate-determining hydrogen abstraction from the methoxy group, the mechanism of the oxidation reaction differs in each case. In the oxomolybdenum system, the first step leads to cleavage of a bond in a Mo-O-Si sequence and the formation of a surface molybdenum methoxide species. Hydrogen is then abstracted from the methoxide ligand by a terminal oxo ligand in a process entailing a closed-shell transition structure. In contrast, the preferred mechanism in the dioxomolybdenum system involves a hydroxomolybdenum methoxide intermediate formed without cleavage of a bond in a Mo-O-Si sequence. Furthermore, the hydrogen abstraction in the second step is effected by the hydroxide ligand formed in the first step and proceeds via an open-shell singlet transition structure.

机译：考虑了带有一个（氧钼钼系统）或两个（二氧钼钼系统）末端氧代配体的孤立的钼中心，它们通过适当的单核甲醇氧钼和氧钼硅硅倍半氧烷进行建模。尽管两个系统中的氧化过程均以相同的基本步骤为特征，即以离解的方式添加甲醇，然后确定从甲氧基夺取氢的速率，但在每种情况下，氧化反应的机理均不同。在含氧钼系统中，第一步导致Mo-O-Si序列中的键断裂并形成表面甲醇钼物种。然后在需要闭壳过渡结构的过程中，通过末端氧代配体从甲醇配体中提取氢。相反，二氧钼钼系统中的优选机理涉及形成的羟基氧钼钼中间体而没有在Mo-O-Si序列中键断裂。此外，第二步骤中的氢提取是通过第一步中形成的氢氧化物配体实现的，并通过开壳单线态过渡结构进行。

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《The journal of physical chemistry, C. Nanomaterials and interfaces》 |2010年第7期|共13页
作者
Laurence J. Gregoriades; Jens Dobler; Joachim Sauer;
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1. Oxidation of Methanol to Formaldehyde on Silica-Supported Molybdena: Density Functional Theory Study on Models of Mononuclear Sites [J] . Laurence J. Gregoriades, Jens Dobler, Joachim Sauer The journal of physical chemistry, C. Nanomaterials and interfaces . 2010,第7期

机译：二氧化硅负载的钼上甲醇氧化为甲醛：单核位点模型的密度泛函理论研究
2. Direct oxidation of methanol to formaldehyde by N_2O on [Fe] ~(1+) and [FeO]~(1+) sites in Fe-ZSM-5 zeolite: A density functional theory study [J] . Fellah M.F. Journal of Catalysis . 2011,第1期

机译：N_2O在Fe-ZSM-5沸石的[Fe]〜（1+）和[FeO]〜（1+）位上将甲醇直接氧化成甲醛：密度泛函理论研究
3. Density functional theory study of the oxidation of methanol to formaldehyde on a hydrated vanadia cluster [J] . P. Gonzá Lez-Navarrete, Gracia L., Calatayud M., Journal of Computational Chemistry: Organic, Inorganic, Physical, Biological . 2010,第13期

机译：水合钒团簇上甲醇氧化为甲醛的密度泛函理论研究
4. Density Functional Theory Modeling of A-site Cation Diffusion in Bulk LaMnO_(3±δ) for Solid Oxide Fuel Cell Cathodes [C] . Y. L. Lee, Y. Duan, D. Morgan, International Symposium on Solid Oxide Fuel Cells . 2017

机译：固体氧化物燃料电池阴极散装λ（3±δ）在散装λ（3±δ）中的现场阳离子扩散的密度函数理论建模
5. Kinetics and mechanism of methane selective oxidation over silica-supported molybdena. [D] . Ohler, Nicholas Lawrence. 2005

机译：二氧化硅负载的钼上甲烷选择性氧化的动力学和机理。
6. Which functional groups of the molybdopterin ligand should be considered when modeling the active sites of the molybdenum and tungsten cofactors? A density functional theory study [O] . Ulf Ryde, Carola Schulzke, Kerstin Starke -1

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7. Understanding the Dual Active Sites of the FeO/Pt(111) Interface and Reaction Kinetics: Density Functional Theory Study on Methanol Oxidation to Formaldehyde [O] . Zongjia Chen, Yu Mao, Jianfu Chen, 2017

机译：了解Feo / Pt（111）界面和反应动力学的双活性部位：密度函数理论研究甲醇氧化对甲醛

Oxidation of Methanol to Formaldehyde on Silica-Supported Molybdena: Density Functional Theory Study on Models of Mononuclear Sites

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