SCI和EI收录∣中国化工学会会刊

Chinese Journal of Chemical Engineering ›› 2018, Vol. 26 ›› Issue (12): 2542-2548.DOI: 10.1016/j.cjche.2018.01.031

• Catalysis, Kinetics and Reaction Engineering • 上一篇    下一篇

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

Zuojun Wei1, Haiyan Liu1, Yidong Chen2, Dechao Guo1, Ruofei Pan1, Yingxin Liu2   

  1. 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 Catalytic Hydrogenation, College of Pharmaceutical Science, Zhejiang University of Technology, 18 Chaowang Road, Xiacheng District, Hangzhou 310014, China
  • 收稿日期:2017-11-17 修回日期:2018-01-07 出版日期:2018-12-28 发布日期:2019-01-09
  • 通讯作者: Yingxin Liu
  • 基金资助:

    Supported by the National Natural Science Foundation of China (21476211) and the Natural Science Foundation of Zhejiang Province (LY16B060004, LY18B060016).

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

Zuojun Wei1, Haiyan Liu1, Yidong Chen2, Dechao Guo1, Ruofei Pan1, Yingxin Liu2   

  1. 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 Catalytic Hydrogenation, College of Pharmaceutical Science, Zhejiang University of Technology, 18 Chaowang Road, Xiacheng District, Hangzhou 310014, China
  • Received:2017-11-17 Revised:2018-01-07 Online:2018-12-28 Published:2019-01-09
  • Contact: Yingxin Liu
  • Supported by:

    Supported by the National Natural Science Foundation of China (21476211) and 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.

关键词: Catalysis, 1, 3-Cyclohexanedione, Density functional theory, Hydrogenation, Pd@reduced graphene oxide, Resorcinol

Abstract: 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.

Key words: Catalysis, 1,3-Cyclohexanedione, Density functional theory, Hydrogenation, Pd@reduced graphene oxide, Resorcinol