Activation of Methane and Carbon Dioxide Mediated by Transition-Metal Doped Magnesium Oxide Clusters [MMgO](+/0/-) (M = Sc-Zn)

作者：Li Jilai; Gonzalez Navarrete Patricio; Schlangen Maria; Schwarz Helmut^*

来源：Chemistry - A European Journal, 2015, 21(21): 7780-7789.

DOI：10.1002/chem.201500715

• carbon dioxide
• computational chemistry
• kinetics
• methane
• thermodynamics

The reaction enthalpies for the activation of CH4 and CO2 mediated by heteronuclear magnesium oxide clusters [MMgO](+/0/-) (M = Sc-Zn) in different charge states have been systematically evaluated by means of density functional theory (DFT). Thermodynamic trends have been elucidated. Regarding the activation of methane, those mixed cluster oxides that contain a late 3d transition metal are in general more promising; in contrast, clusters doped with an early 3d transition metal are predicted to be more suitable for CO2 activation. The effects of the charge of the cluster and the oxidation states of the metals M towards both the activation of CH4 and of CO2 have also been addressed. Promising reagents, such as [MMgO2](+) (M = Cu, Zn) for methane activation, are recommended based on a systematic and comprehensive analysis of thermodynamic and kinetic properties. Finally, based on the evaluation of the individual reactions, the task of identifying "simple" reagents with a single reactive site that could mediate efficiently the industrially important coupling of CH4 and CO2 to CH2CO seems extremely challenging.

• 出版日期2015-5-18
• 单位吉林大学