Mechanistic insights into the selective hydrogenation of resorcinol to 1,3-cyclohexanedione over Pd/rGO catalyst through DFT calculation  

作　　者：Zuojun Wei Haiyan Liu Yidong Chen Dechao Guo Ruofei Pan Yingxin Liu 

机构地区：[1]Key Laboratory of Biomass Chemical Engineering of the Ministry of Education,College of Chemical and Biological Engineering,Zhejiang University,38 Zheda Road,Xihu District,Hangzhou 310027,China [2]Research and Development Base of Catalytc Hydrogenation,College of Pharmaceutcal Science,Zhejiang University of Technology,18 Chaowang Road,Xiacheng District,Hangzhou 310014,China

出　　处：《Chinese Journal of Chemical Engineering》2018年第12期2542-2548,共7页中国化学工程学报（英文版）

基　　金：Supported by the National Natural Science Foundation of China(21476211);the Natural Science Foundation of Zhejiang Province(LY16B060004,LY18B060016)

摘　　要：In our previous work, graphene-supported Pd catalyst(Pd/rGO) exhibited higher activity and selectivity for the liquid phase selective hydrogenation of resorcinol to 1,3-cyclohexanedione compared with other catalysts. In the present study, further experimental and theoretical investigations were conducted to reveal the reaction mechanism and the catalytic mechanism of Pd/rGO for resorcinol hydrogenation. The effects of graphene nanosheet and the solvent on the reaction were investigated, and the pathway for resorcinol hydrogenation was proposed supported by density functional theory(DFT) calculations. The results showed that the excellent selectivity of Pd/rGO to 1,3-cyclohexanedione was attributed to the strong π–π and p–π interactions between the graphene nanosheet and the benzene ring as well as hydroxyl in resorcinol molecule, which was in agreement with our previous speculation. In weak polar aprotic solvents, solvation free energy had less impact to the π–π and p–π interactions mentioned above. In strong polar aprotic solvents and polar protic solvents,however, the influence of solvation free energy was much greater, which led to the decrease in the conversion of resorcinol and the selectivity to 1,3-cyclohexanedione.In our previous work, graphene-supported Pd catalyst(Pd/rGO) exhibited higher activity and selectivity for the liquid phase selective hydrogenation of resorcinol to 1,3-cyclohexanedione compared with other catalysts. In the present study, further experimental and theoretical investigations were conducted to reveal the reaction mechanism and the catalytic mechanism of Pd/rGO for resorcinol hydrogenation. The effects of graphene nanosheet and the solvent on the reaction were investigated, and the pathway for resorcinol hydrogenation was proposed supported by density functional theory(DFT) calculations. The results showed that the excellent selectivity of Pd/rGO to 1,3-cyclohexanedione was attributed to the strong π–π and p–π interactions between the graphene nanosheet and the benzene ring as well as hydroxyl in resorcinol molecule, which was in agreement with our previous speculation. In weak polar aprotic solvents, solvation free energy had less impact to the π–π and p–π interactions mentioned above. In strong polar aprotic solvents and polar protic solvents,however, the influence of solvation free energy was much greater, which led to the decrease in the conversion of resorcinol and the selectivity to 1,3-cyclohexanedione.

关 键 词：CATALYSIS 1 3-CYCLOHEXANEDIONE Density functional theory HYDROGENATION Pd@reduced graphene oxide RESORCINOL 

分 类 号：TQ[化学工程]