Reaction mechanism of methyl nitrite dissociation during co catalytic coupling to dimethyl oxalate: A density functional theory study

doi:10.1016/j.cjche.2015.06.007

Abstract

Abstract: Dissociation of methyl nitrite is the first step during CO catalytic coupling to dimethyl oxalate followed by hydrogenation to ethyl glycol in a typical coal to liquid process. In this work, the first-principle calculations based on density functional theory were performed to explore the reaction mechanism for the non-catalytic dissociation of methyl nitrite in the gas phase and the catalytic dissociation of methyl nitrite on Pd(111) surface since palladium supported on alpha-alumina is the most effective catalyst for the coupling. For the non-catalytic case, the calculated results show that the CH₃O-NO bond will break with a bond energy of 1.91 eV, and the produced CH₃O radicals easily decompose to formaldehyde, while the further dissociation of formaldehyde in the gas phase is difficult due to the strong C-H bond. On the other hand, the catalytic dissociation of methyl nitrite on Pd(111) to the adsorbed CH₃O andNOtakes place with a small energy barrier of 0.03 eV. The calculated activation energies along the proposed reaction pathways indicate that (i) at lowcoverage, a successive dehydrogenation of the adsorbed CH₃O to CO and H is favored while (ii) at high coverage, hydrogenation of CH₃O to methanol and carbonylation of CH₃O to methyl formate are more preferred. On the basis of the proposed reaction mechanism, two meaningfulways are proposed to suppress the dissociation of methyl nitrate during the CO catalytic coupling to dimethyl oxalate.

Key words: Methyl nitrite, Catalytic, Non-catalytic, Dissociation, Density functional theory

摘要： Dissociation of methyl nitrite is the first step during CO catalytic coupling to dimethyl oxalate followed by hydrogenation to ethyl glycol in a typical coal to liquid process. In this work, the first-principle calculations based on density functional theory were performed to explore the reaction mechanism for the non-catalytic dissociation of methyl nitrite in the gas phase and the catalytic dissociation of methyl nitrite on Pd(111) surface since palladium supported on alpha-alumina is the most effective catalyst for the coupling. For the non-catalytic case, the calculated results show that the CH₃O-NO bond will break with a bond energy of 1.91 eV, and the produced CH₃O radicals easily decompose to formaldehyde, while the further dissociation of formaldehyde in the gas phase is difficult due to the strong C-H bond. On the other hand, the catalytic dissociation of methyl nitrite on Pd(111) to the adsorbed CH₃O andNOtakes place with a small energy barrier of 0.03 eV. The calculated activation energies along the proposed reaction pathways indicate that (i) at lowcoverage, a successive dehydrogenation of the adsorbed CH₃O to CO and H is favored while (ii) at high coverage, hydrogenation of CH₃O to methanol and carbonylation of CH₃O to methyl formate are more preferred. On the basis of the proposed reaction mechanism, two meaningfulways are proposed to suppress the dissociation of methyl nitrate during the CO catalytic coupling to dimethyl oxalate.

关键词: Methyl nitrite, Catalytic, Non-catalytic, Dissociation, Density functional theory

Chen Fan, Man Luo, Wende Xiao. Reaction mechanism of methyl nitrite dissociation during co catalytic coupling to dimethyl oxalate: A density functional theory study[J]. Chin.J.Chem.Eng., 2016, 24(1): 132-139.

Chen Fan, Man Luo, Wende Xiao. Reaction mechanism of methyl nitrite dissociation during co catalytic coupling to dimethyl oxalate: A density functional theory study[J]. Chinese Journal of Chemical Engineering, 2016, 24(1): 132-139.

References

[1] L. Zhao, Y. Zhao, S. Wang, H. Yue, B. Wang, J. Lv, X. Ma, Hydrogenation of dimethyl oxalate using extruded Cu/SiO₂ catalysts: Mechanical strength and catalytic performance, Ind. Eng. Chem. Res. 51 (43) (2012) 13935-13943.

[2] Z. Meng, J. Sun, J. Wang, J. Zhang, Z. Fu, W. Cheng, X. Zhang, An efficient and stable ionic liquid system for synthesis of ethylene glycol via hydrolysis of ethylene carbonate, Chin. J. Chem. Eng. 18 (6) (2010) 962-966.

[3] H. Zhou, S. Zhang, F. Gao, X. Bai, Z. Sha, Solubility of ammonia in ethylene glycol between 303 K and 323 K under low pressure from 0.030 to 0.101 MPa, Chin. J. Chem. Eng. 22 (2) (2014) 181-186.

[4] X.Ma, H. Chi, H. Yue, Y. Zhao, Y. Xu, J. Lv, S.Wang, J. Gong, Hydrogenation of dimethyl oxalate to ethylene glycol over mesoporous Cu-MCM-41 catalysts, AIChE J. 59 (7) (2013) 2530-2539.

[5] S.Y. Peng, Z.N. Xu, Q.S. Chen, Y.M. Chen, J. Sun, Z.Q. Wang, M.S. Wang, G.C. Guo, An ultra-low Pd loading nanocatalyst with high activity and stability for CO oxidative coupling to dimethyl oxalate, Chem. Commun. 49 (51) (2013) 5718-5720.

[6] Z.N. Xu, J. Sun, C.S. Lin, X.M. Jiang, Q.S. Chen, S.Y. Peng, M.S. Wang, G.C. Guo, Highperformance and long-lived Pd nanocatalyst directed by shape effect for CO oxidative coupling to dimethyl oxalate, ACS Catal. 3 (2) (2013) 118-122.

[7] G.L. Zhuo, X.Z. Jiang, An attractive synthetic approach tomethyl formate frommethanol via methyl nitrite, Catal. Lett. 80 (3-4) (2002) 171-174.

[8] G.L. Zhuo, X.Z. Jiang, Catalytic decomposition of methyl nitrite over supported palladium catalysts in vapor phase, React. Kinet. Catal. Lett. 77 (2) (2002) 219-226.

[9] J.W. Peck, D.E. Beck, D.I. Mahon, Methyl nitrite adsorption as a novel route to the surface methoxy intermediate, J. Phys. Chem. B 102 (18) (1998) 3321-3323.

[10] J.W. Peck, D.I.Mahon, D.E. Beck, B. Bansenaur, B.E. Koel, TPD, HREELS and UPS study of the adsorption and reaction of methyl nitrite (CH₃ONO) on Pt(111), Surf. Sci. 410 (2-3) (1998) 214-227.

[11] Y. He, W.A. Sanders, M.C. Lin, Thermal decomposition of methyl nitrite: Kinetic modeling of detailed product measurements by gas-liquid chromatography and Fourier-transform infrared spectroscopy, J. Phys. Chem. 92 (19) (1988) 5474-5481.

[12] Y. Ji, Study of Catalyst, Mechanism, and Intrinsic Kinetics of CO Catalytic Coupling to Dimethyl Oxalate (DMO)(Ph. D thesis) East China University of Science and Technology (ECUST), Shanghai, 2010.

[13] J.R.B. Gomes, F. Illas, The adsorption of methyl nitrite on the Au(111) surface, Catal. Lett. 71 (1-2) (2001) 31-35.

[14] Z.X. Chen, K.M. Neyman, K.H. Lim, N. Rösch, CH₃O decomposition on PdZn(111), Pd(111), and Cu(111). A theoretical study, Langmuir 20 (19) (2004) 8068-8077.

[15] Z.X. Chen, K.H. Lim, K.M. Neyman, N. Rösch, Effect of steps on the decomposition of CH₃O at PdZn alloy surfaces, J. Phys. Chem. B 109 (10) (2005) 4568-4574.

[16] R. Jiang, W. Guo, M. Li, D. Fu, H. Shan, Density functional investigation of methanol dehydrogenation on Pd(111), J. Phys. Chem. C 113 (10) (2009) 4188-4197.

[17] R. Jiang, W. Guo, M. Li, X. Lu, J. Yuan, H. Shan, Dehydrogenation of methanol on Pd(100): comparison with the results of Pd(111), PCCP 12 (28) (2010) 7794-7803.

[18] K.H. Lim, Z.X. Chen, K.M. Neyman, N. Rösch, Comparative theoretical study of formaldehyde decomposition on PdZn, Cu, and Pd surfaces, J. Phys. Chem. B 110 (30) (2006) 14890-14897.

[19] G. Kresse, J. Furthmüller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Comput. Mater. Sci. 6 (1) (1996) 15-50.

[20] G. Kresse, J. Furthmüller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B 54 (16) (1996) 11169-11186.

[21] G. Kresse, J. Hafner, Ab initio molecular dynamics for liquid metals, Phys. Rev. B 47 (1) (1993) 558-561.

[22] G. Kresse, J. Hafner, Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium, Phys. Rev. B 49 (20) (1994) 14251-14269.

[23] P.E. Blöchl, Projector augmented-wave method, Phys. Rev. B 50 (24) (1994) 17953-17978.

[24] G. Kresse, D. Joubert, From ultrasoft pseudopotentials to the projector augmentedwave method, Phys. Rev. B 59 (3) (1999) 1758-1775.

[25] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77 (18) (1996) 3865-3868.

[26] H.J. Monkhorst, J.D. Pack, Special points for Brillouin-zone integrations, Phys. Rev. B 13 (12) (1976) 5188-5192.

[27] M.Methfessel, A.T. Paxton, High-precision sampling for Brillouin-zone integration in metals, Phys. Rev. B 40 (6) (1989) 3616-3621.

[28] D.R. Lide, CRC Handbook of Chemistry and Physics, 79th ed. CRC Press, Boca Raton, Florida, 1998.

[29] D. Loffreda, D. Simon, P. Sautet, Dependence of stretching frequency on surface coverage and adsorbate-adsorbate interactions: a density-functional theory approach of CO on Pd (111), Surf. Sci. 425 (1) (1999) 68-80.

[30] Z.H. Zeng, J.L.F. Da Silva, W.X. Li, Density functional theory and ab initio molecular dynamics study of NO adsorption on Pd(111) and Pt(111) surfaces, Phys. Rev. B 81 (8) (2010).

[31] C. Fan, W.D. Xiao, Origin of site preference of CO and NO adsorption on Pd(111) at different coverages: a density functional theory study, Comput. Theor. Chem. 1004 (2013) 22-30.

[32] G. Henkelman, H. Jonsson, A dimermethod for finding saddle points on high dimensional potential surfaces using only first derivatives, J. Chem. Phys. 111 (15) (1999) 7010-7022.

[33] D. Sheppard, R. Terrell, G. Henkelman, Optimization methods for finding minimum energy paths, J. Chem. Phys. 128 (13) (2008) 134106.

[34] A. Fernández-Ramos, E. Martínez-Núñez,M.A. Ríos, J. Rodríguez-Otero, S.A. Vázquez, C.M. Estévez, Direct dynamics study of the dissociation and elimination channels in the thermal decomposition of methyl nitrite, J. Am. Chem. Soc. 120 (30) (1998) 7594-7601.

[35] J.L. Davis, M.A. Barteau, Polymerization and decarbonylation reactions of aldehydes on the Pd(111) surface, J. Am. Chem. Soc. 111 (5) (1989) 1782-1792.

[36] Z.P. Liu, S.J. Jenkins, D.A. King, Car exhaust catalysis from first principles: Selective NO reduction under excess O₂ conditions on Ir, J. Am. Chem. Soc. 126 (34) (2004) 10746-10756.