Unsaturated Penta-Coordinated Mo5c5+ Sites Enabled Low-Temperature Oxidation of C–H Bonds in Ethers

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Abstract
Selective oxidation of C-H bonds under mild conditions is one of the most important and challenging issues in utilization of energy-related molecules. Molybdenum oxide nanostructures containing Mo5+ species are effective for these reactions, but the accurate identification of the structure of active Mo5+ species and the catalytic mechanism remain unclear. Herein, unsaturated penta-coordinated Mo-5c(5+) with a high fraction in MoO(x )fabricated by the hydrothermal method were identified as the active sites for low-temperature oxidation of dimethyl ether (DME) by the deep correlation of characterizations, density functional theory calculations, and activity results, giving a methyl formate selectivity of 96.3% and DME conversion of 12.5% at unreported 110 C-degrees. Low-temperature electron spin resonance (ESR) and quasi in situ X-ray photoelectron spectra (XPS) with the designed experiments confirm that the Mo-5c (5+) species can be formed in situ. Molybdenum located at the pentachronic site is preferable to significantly promote the oxidation of the C-H bond in CH3O* at lower temperatures.
Funding Information
  • Dalian National Laboratory for Clean Energy (DNL 201903)
  • State Key Laboratory of Physical Chemistry of Solid Surfaces, Xiamen University (201624)
  • Youth Innovation Promotion Association of the Chinese Academy of Sciences (2014155)
  • National Natural Science Foundation of China (22172187, 21773283)
  • Chinese Academy of Sciences (BK2018001)
  • Central Guidance on Local Science and Technology Development Fund of Shanxi Province (YDZJSX2022A073)

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