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

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 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 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/Abstract

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

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]. Chinese Journal of Chemical Engineering, 2018, 26(12): 2542-2548.

参考文献

[1] S. Molchanov, A. Gryff-Keller, Inhibition of 4-hydroxyphenylpyruvate dioxygenase by 2-[2-nitro-4-(trifluoromethyl)benzoyl]-1,3-cyclohexanedione, Acta Biochim. Pol. 56(3) (2009) 447-454.

[2] C. Zhang, W. Lv, Q.H. Yang, Y. Liu, Graphene supported nano particles of Pt-Ni for CO oxidation, Appl. Surf. Sci. 258(20) (2012) 7795-7800.

[3] D. Kalpogiannaki, C.-I. Martini, A. Nikopoulou, J.A. Nyxas, V. Pantazi, L.P. Hadjiarapoglou, Fused dihydrofurans from the one-pot, three-component reaction of 1,3-cyclohexanedione, iodobenzene diacetate and alkenes, Tetrahedron 69(5) (2013) 1566-1575.

[4] R.W. Lewis, J.W. Botham, A review of the mode of toxicity and relevance to humans of the triketone herbicide 2-(4-methylsulfonyl-2-nitrobenzoyl)-1, 3-cyclohexanedione, Crit. Rev. Toxicol. 43(3) (2013) 185-199.

[5] P. Zhou, D.Z. Li, S.W. Jin, S.H. Chen, Z.H. Zhang, Catalytic transfer hydrogenation of nitro compounds into amines over magnetic graphene oxide supported Pd nanoparticles, Int. J. Hydrog. Energy 41(34) (2016) 15218-15224.

[6] W.H. Muller, Process for preparing 1,3-cyclohexanedione, USA Pat., 3922307, 1975.

[7] W.H. Muller, T. Weil, Process for manufacture of 1,3-cyclohexanedione, USA Pat., 4028417, 1977.

[8] J.B. Heather, P.D. Milano, Process for the production of acylated 1,3-dicarbonyl compounds, USA Pat., 4695673, 1987.

[9] J.C. Sircar, A.I. Meyers, A convenient method for preparation of 1,3-cyclohexanedione, J. Org. Chem. 30(9) (1965) 3206-3207.

[10] V. Elango, M.U. Norwood, R. Sakamuri, R.I.U. Warwick, A new process for the manufacture of 1,3-cyclohexanedione, Europe Pat., 0822173(A1), 1998.

[11] Y.X. Hou, L.B. Xu, Z.J. Wei, Y.X. Liu, X.H. Li, S.G. Deng, Reaction process and kinetics of the selective hydrogenation of resorcinol into 1,3-cyclohexanedione, J. Taiwan Inst. Chem. Eng. 45(4) (2014) 1428-1434.

[12] R.B. Thompson, Dihydroresorcinol-1,3-Cyclohexanedione, Org. Synth. 27(1947) 21-23.

[13] D.I. Enache, G.J. Hutchings, S.H. Taylor, R. Natividad, S. Raymahasay, J.M. Winterbottom, et al., Experimental evaluation of a three-phase downflow capillary reactor, Ind. Eng. Chem. Res. 44(16) (2005) 6295-6303.

[14] Z. Xu, Z.H. Hu, D. Xu, A method for preparing 1,3-cyclohexanedione, China Pat., 1680247 A, 2005.

[15] S. Zhang, One kind of 1,3-cyclohexanedione industrial production methods, China Pat., 101381294, 2006.

[16] D.I. Enache, G.J. Hutchings, S.H. Taylor, S. Raymahasay, J.M. Winterbottom, M.D. Mantle, et al., Multiphase hydrogenation of resorcinol in structured and heat exchange reactor systems influence of the catalyst and the reactor configuration, Catal. Today 128(1-2) (2007) 26-35.

[17] R.B. Thompson, Dihydroresorcinol, Org. Synth. 3(1955) (2-&).

[18] P. Makowski, R.D. Cakan, M. Antonietti, F. Goettmann, M.M. Titirici, Selective partial hydrogenation of hydroxy aromatic derivatives with palladium nanoparticles supported on hydrophilic carbon, Chem. Commun. (8) (2008) 999-1001.

[19] Z. Wei, R. Pan, Y. Hou, Y. Yang, Y. Liu, Graphene-supported Pd catalyst for highly selective hydrogenation of resorcinol to 1, 3-cyclohexanedione through giant pi-conjugate interactions, Sci. Rep. 5(2015) https://doi.org/10.1038/srep 15664.

[20] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, et al., Gaussian 09, Gaussian, Inc., Wallingford, CT, 2009.

[21] R.K. Dennington, T., J. Millam, GaussView, Semichem Inc., Shawnee Mission, KS, 2009.

[22] L. Tian, F. Chen, Quantitative analysis of molecular surface based on improved Marching Tetrahedra algorithm, J. Mol. Graphics Modell. 38(9) (2012) 314-323.

[23] T. Lu, F. Chen, Multiwfn:A multifunctional wavefunction analyzer, J. Comput. Chem. 33(5) (2012) 580-592.

[24] W. Humphrey, A. Dalke, K. Schulten, VMD:Visual molecular dynamics, J. Mol. Graph. 14(1) (1996) 33-38.

[25] R.F.W. Bader, Atoms in Molecules:A Quantum Theory, Oxford University Press, New York, 1994.

[26] P.C. Harihara, J.A. Pople, Influence of polarization functions on molecular-orbital hydrogenation energies, Theor. Chim. Acta 28(3) (1973) 213-222.

[27] B.J. Lynch, Y. Zhao, D.G. Truhlar, Effectiveness of diffuse basis functions for calculating relative energies by density functional theory, J. Phys. Chem. A 107(9) (2003) 1384-1388.

[28] C.T. Lee, W.T. Yang, R.G. Parr, Development of the Colle-Salvetti correlation-energy formula into a functional of the electron-density, Phys. Rev. B 37(2) (1988) 785-789.

[29] A.D. Becke, Density-functional thermochemistry. 3. The role of exact exchange, J. Chem. Phys. 98(7) (1993) 5648-5652.

[30] P.J. Stephens, F.J. Devlin, C.F. Chabalowski, M.J. Frisch, Ab-initio calculation of vibrational absorption and circular-dichroism spectra using density-functional force-fields, J. Phys. Chem. 98(45) (1994) 11623-11627.

[31] J. Sirijaraensre, J. Limtrakul, Hydrogenation of CO₂ to formic acid over a Cu-embedded graphene:A DFT study, Appl. Surf. Sci. 364(2016) 241-248.

[32] M.D. Esrafili, F. Sharifi, L. Dinparast, Catalytic hydrogenation of CO₂ over Pt-and Ni-doped graphene:A comparative DFT study, J. Mol. Graphics Modell. 77(2017) 143-152.

[33] K. Balamurugan, V. Subramanian, Adsorption of chlorobenzene onto (5,5) armchair single-walled carbon nanotube and graphene sheet:Toxicity versus adsorption strength, J. Phys. Chem. C 117(41) (2013) 21217-21227.

[34] J. Ho, A. Klamt, M.L. Coote, Comment on the correct use of continuum solvent models, J. Phys. Chem. A 114(51) (2010) 13442-13444.

[35] F. Li, B. Cao, W.X. Zhu, H. Song, K.L. Wang, C.Q. Li, Hydrogenation of phenol over Pt/CNTs:The effects of Pt loading and reaction solvents, Catalysts 7(5) (2017) 145.

[36] B. Chan, L. Radom, Base-catalyzed hydrogenation:Rationalizing the effects of catalyst and substrate structures and solvation, J. Am. Chem. Soc. 127(8) (2005) 2443-2454.

[37] J.F. Espinal, T.N. Truong, F. Mondragon, Mechanisms of NH₃ formation during the reaction of H-2 with nitrogen containing, carbonaceous materials, Carbon 45(11) (2007) 2273-2279.

[38] G. Zhong, B. Chan, L. Radom, Hydrogenation of simple aromatic molecules:A computational study of the mechanism, J. Am. Chem. Soc. 129(4) (2007) 924-933.

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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