期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 18, 期 15, 页码 9969-9978出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6cp00336b
关键词
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资金
- National Natural Science Foundation of China [NSFC 21303027, 21473166]
- Natural Science Foundation of Guizhou Province [QKJ[2013]2254, QKJ[2013]2245, QKJ[2015]2122]
- Program for Innovative Research Team of Guizhou Province [QKTD[2012]4009]
- Natural Science Foundation of Department of Education of Guizhou Province [QJTD[2015]55]
- Excellent Innovation Scientific and Technological Talents of Guizhou Province [QJKY[2014]248]
Using density functional theory (DFT) calculations, we performed a thorough theoretical investigation on the catalytic mechanism of oxidative self-coupling of methanol with molecular oxygen on Au-Ag catalysts. It is found that molecular oxygen can be activated via a hydroperoxyl (OOH) intermediate by taking a hydrogen atom from co-adsorbed methanol with an energy barrier of 0.51 eV, which is actually the rate determining step for the overall reaction. The O, OH and OOH oxidant formation proceeds via two channels of I and II with low barriers. We demonstrated that the oxidative coupling of methanol by OOH, atomic oxygen, and hydroxyl is much more favorable than the total oxidation of methanol, and is responsible for the high selectivity of Au-Ag catalysts in methanol oxidation. The revealed activation mechanism provides an efficient pathway for optimizing the selective coupling of methanol with dioxygen.
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