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 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.展开更多
The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effect...The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effects of solvent triethylamine on these two reactions were also evaluated. It is demonstrated that path B is more preferable than path a due to low barrier height for the rate-determining step.展开更多
基金Supported by the National Natural Science Foundation of China(21476211)the Natural Science Foundation of Zhejiang Province(LY16B060004,LY18B060016)
文摘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.
文摘The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effects of solvent triethylamine on these two reactions were also evaluated. It is demonstrated that path B is more preferable than path a due to low barrier height for the rate-determining step.
