Theoretical Investigations of the Catalytic Role of Water in Propene Epoxidation on Gold Nanoclusters: A HydroperoxylMediated Pathway
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We report a comprehensive theoretical investigation of the catalytic reaction mechanisms of propene epoxidation on gold nanoclusters using density functional theory (DFT). We have shown that water acts as a catalytic promoter for propene epoxidation on gold catalysts. Even without reducible supports, hydroperoxyl (OOH) and hydroxyl (OH) radicals are readily formed on small-size gold clusters from co-adsorbed H2O and O2, with energy barriers as low as 4-6 kcal/mol (1 cal = 4.186 J). Propene epoxidation occurs easily through reactions between C3H6 and the weakened O-O bond of the OOH radicals on the surfaces of gold clusters.
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Theoretical Investigations of the Catalytic Role of Water in Propene Epoxidation on Gold Nanoclusters: A HydroperoxylMediated Pathway
)
Abstract
We report a comprehensive theoretical investigation of the catalytic reaction mechanisms of propene epoxidation on gold nanoclusters using density functional theory (DFT). We have shown that water acts as a catalytic promoter for propene epoxidation on gold catalysts. Even without reducible supports, hydroperoxyl (OOH) and hydroxyl (OH) radicals are readily formed on small-size gold clusters from co-adsorbed H2O and O2, with energy barriers as low as 4-6 kcal/mol (1 cal = 4.186 J). Propene epoxidation occurs easily through reactions between C3H6 and the weakened O-O bond of the OOH radicals on the surfaces of gold clusters.
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Acknowledgements
The authors thank the referees for pointing out the two-step mechanism involving the OMME intermediate. This work was supported by the National Key Basic Research Special Foundation (NKBRSF) (Nos. 2007CB815200 and 2011CB932400) and the National Nature Science Foundation of China (NSFC) (No. 20933003). The calculations were performed by using supercomputers at the Computer Network Information Center, Chinese Academy of Sciences, Tsinghua National Laboratory for Information Science and Technology, and the Shanghai Supercomputing Center.
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