1,2-Ethanediol and 1,3-Propanediol Conversions over (MO3)3 (M = Mo, W) Nanoclusters: A Computational Study

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• 作者：Zongtang Fang ; Patrick Zetterholm ; David A. Dixon
• 刊名：Journal of Physical Chemistry A
• 出版年：2016
• 出版时间：March 24, 2016
• 年：2016
• 卷：120
• 期：11
• 页码：1897-1907
• 全文大小：589K
• ISSN：1520-5215

文摘

The dehydration and dehydrogenation reactions of one and two 1,2-ethanediol and 1,3-propanediol molecules on (MO₃)₃ (M = Mo, W) nanoclusters have been studied computationally using density functional and coupled cluster (CCSD(T)) theory. The reactions are initiated by the formation of a Lewis acid–base complex with an additional hydrogen bond. Dehydration is the dominant reaction proceeding via a metal bisdiolate. Acetaldehyde, the major product for 1,2-ethanediol, is produced by α-hydrogen transfer from one CH₂ group to the other. For 1,3-propanediol, the C–C bond breaking pathways to produce C₂H₄ and HCH═O simultaneously and proton transfer to generate propylene oxide have comparable barrier energies. The barrier to produce propanal from the propylene oxide complex is less than that for epoxide release from the cluster. On the Mo₃O₉ cluster, a redox reaction channel for 1,2-ethanediol to break the C–C bond to form two formaldehyde molecules and then to produce C₂H₄ is slightly more favorable than the formation of acetaldehyde. For W^VI, the energy barrier for the reduction pathway is larger due to the lower reducibility of W₃O₉. Similar reduction on Mo^VI for 1,3-propanediol to form propene is not a favorable pathway compared with the other pathways as additional C–H bond breaking is required in addition to breaking a C–C bond. The dehydrogenation and dehydration activation energies for the selected glycols are larger than the reactions of ethanol and 1-propanol on the same clusters. The CCSD(T) method is required because density functional theory with the M06 and B3LYP functionals does not predict quantitative energies on the potential energy surface. The M06 functional performs better than does the B3LYP functional.