Density Functional Theory Analysis of Anthraquinone Derivative Hydrogenation over Palladium Catalyst.
Density Functional Theory Analysis of Anthraquinone Derivative Hydrogenation over Palladium Catalyst.
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DOI：
10.1002/cphc.201600874
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发表时间：
2016-12
期刊：
影响因子：
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通讯作者：
Enxian Yuan;Li Wang;Xiangwen Zhang;R. Feng;Chan Wu;Guozhu Li
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文献类型：
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作者：
Enxian Yuan;Li Wang;Xiangwen Zhang;R. Feng;Chan Wu;Guozhu Li
采用密度泛函理论（DFT）方法研究了2-烷基蒽醌（AQ），包括2-乙基-9，10-蒽醌（eAQ）和2-乙基-5，6，7，8-四氢-9，10-蒽醌（H4 eAQ）在Pd 6 H2簇上的加氢反应.结果表明，H4 eAQ比eAQ具有更高的吸附能、更低的反应活化能和更低的脱附能，因此H4 eAQ的加氢反应比eAQ更有利.对于最可能的反应路线，AQ的第二氢化步骤的能垒比第一步骤的能垒高约8 kcal mol-1。系统地研究了这些过程的电子转移。Pd 6 H2团簇与AQ/AQH中间体之间的电子转移有利于C=O的氢化。电子在AQ/AQH中间体边界芳环上的离域和C=O的吸电子效应是电子转移的原因。此外，还提出了AQ在Pd 6 H2簇合物表面吸附和加氢的电子转移途径.电子从被夺取的H原子（反应性H）转移到相邻的Pd原子（PdH），并最终通过AQ芳环的C4原子（C4）到达羰基。
A density functional theory (DFT) analysis was conducted on the hydrogenation of 2-alkyl-anthraquinone (AQ), including 2-ethyl-9,10-anthraquinone (eAQ) and 2-ethyl-5,6,7,8-tetrahydro-9,10-anthraquinone (H4 eAQ), to the corresponding anthrahydroquinone (AQH2 ) over a Pd6 H2 cluster. Hydrogenation of H4 eAQ is suggested to be more favorable than that of eAQ owing to a higher adsorption energy of the reactant (H4 eAQ), lower barrier of activation energy, and smaller desorption energy of the target product (2-ethyl-5,6,7,8-tetrahydro-9,10-anthrahydroquinone, H4 eAQH2 ). For the most probable reaction routes, the energy barrier of the second hydrogenation step of AQ is circa 8 kcal mol-1 higher than that of the first step. Electron transfer of these processes were systematically investigated. Facile electron transfer from Pd6 H2 cluster to AQ/AQH intermediate favors the hydrogenation of C=O. The electron delocalization over the boundary aromatic ring of AQ/AQH intermediate and the electron-withdrawing effect of C=O are responsible for the electron transfer. In addition, a pathway of the electron transfer is proposed for the adsorption and subsequent hydrogenation of AQ on the surface of Pd6 H2 cluster. The electron transfers from the abstracted H atom (reactive H) to a neighbor Pd atom (PdH ), and finally goes to the carbonyl group through the C4 atom of AQ aromatic ring (C4 ).