期刊
ACS CATALYSIS
卷 3, 期 8, 页码 1693-1699出版社
AMER CHEMICAL SOC
DOI: 10.1021/cs400344r
关键词
methanol oxidation; bulk gold; O-2 activation; hydroperoxyl; water; density functional theory
资金
- National Key Basic Research Special Foundations [2011CB932400]
- National Natural Science Foundation of China [20933003]
To understand the catalytic mechanism of alcohol oxidation with molecular oxygen on bulk metallic gold catalysts, we have systematically studied the oxidative dehydrogenation of methanol on Au(111) using density functional theory. It is found that molecular oxygen can be activated via a hydroperoxyl (OOH) intermediate produced by abstracting a hydrogen atom from co-adsorbed methanol or water. Interestingly, extra water molecules significantly promote the hydrogen-transfer reactions between CH3OH center dot center dot center dot O-2 and H2O center dot center dot center dot O-2 co-adsorbates, lowering the activation barrier of OOH formation from similar to 0.90 to similar to 0.45 eV. The formed OOH intermediate either directly reacts with methanol to produce formaldehyde or dissociates into adsorbed atomic oxygen and hydroxyl. Further calculations demonstrate that the oxidative dehydrogenation of methanol by OOH, atomic oxygen, and hydroxyl is extremely facile with low barriers between 0.06 and 0.30 eV. These results provide an explanation for the activation mechanism of molecular oxygen on bulk gold and reveal a possible pathway for alcohol oxidation with dioxygen.
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