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

doi:10.1016/j.cjche.2018.01.031

Chin.J.Chem.Eng. ›› 2018, Vol. 26 ›› Issue (12): 2542-2548.DOI: 10.1016/j.cjche.2018.01.031

• Catalysis, kinetics and reaction engineering • Previous Articles Next Articles

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 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:2019-01-09 Published:2018-12-28
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).

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 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

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).

Abstract

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

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

Zuojun Wei, Haiyan Liu, Yidong Chen, Dechao Guo, Ruofei Pan, Yingxin Liu. Mechanistic insights into the selective hydrogenation of resorcinol to 1,3-cyclohexanedione over Pd/rGO catalyst through DFT calculation[J]. Chin.J.Chem.Eng., 2018, 26(12): 2542-2548.

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

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

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