Density Functional Theory Analysis of Anthraquinone Derivative Hydrogenation over Palladium Catalyst |
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| Authors: | Enxian Yuan Li Wang Xiangwen Zhang Ren Feng Chan Wu Prof. Guozhu Li |
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| Affiliation: | 1. Key Laboratory for Green Chemica,l Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, China;2. Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, China |
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| Abstract: | ![]()
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 (H4eAQ), to the corresponding anthrahydroquinone (AQH2) over a Pd6H2 cluster. Hydrogenation of H4eAQ is suggested to be more favorable than that of eAQ owing to a higher adsorption energy of the reactant (H4eAQ), lower barrier of activation energy, and smaller desorption energy of the target product (2‐ethyl‐5,6,7,8‐tetrahydro‐9,10‐anthrahydroquinone, H4eAQH2). 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 Pd6H2 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 Pd6H2 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). |
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| Keywords: | anthraquinone derivative density functional calculations electron transfer hydrogenation palladium cluster |
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