A Theoretical Study of the Hydrogenation of CO over Co2Cu2 Bimetallic Catalyst Supported on MgO(200) by Means of Density Functional Theory Part 2: Reaction Mechanism
Main Article Content
Abstract
This paper investigates the hydrogenation of carbon monoxide (CO) over Co2Cu2 bimetallic catalyst supported on MgO (200) using a combination of density functional theory (DFT) and a climbing image nudged elastic band (CI-NEB) module. In the study, a reaction mechanism for the formation of methane, methanol and ethanol was proposed. The proposed mechanism consisted of 28 reaction steps (per surface type) and three different reaction positions were included. Reaction energy and activation energy for the overall steps involved in the reaction process were calculated and analyzed. The results show that the CoCu mixed sites reduced the activation energy of the CO insertion process into CH3, resulting in the formation of products with a larger number of carbon atoms.
Keywords:
Syngas, ethanol, methanol, bimetallic Co2Cu2, DFT, CI-NEB, reaction mechanisms.
References
[1] Min Ao, P.G. Hung Jaka Sunarso, Moses Tade, Shaomin Liu, Active Centers of Catalysts for Higher Alcohol Synthesis from Syngas: A Review, ACS Catalysis 8 (8) (2018) 7025 -7050.
[2] Ho Ting Luk, Cecilia Mondelli, Daniel Curulla Ferré, Joseph A. Stewart and Javier Pérez-Ramírez, Status and prospects in higher alcohols synthesis from syngas, Chem. Soc. Rev. 46 (2017) 1358-1426.
[3] Sharif Zaman, Kevin Smith, A Review of Molybdenum Catalysts for Synthesis Gas Conversion to Alcohols: Catalysts, Mechanisms and Kinetics, Cat. Rev. 54(1) (2012) 41-132.
[4] N. Zhao, R. Xu, W. Wei, Y. Sun, Cu/Mn/ZrO2 catalyst for alcohol synthesis by Fischer-Tropsch modified elements, React. Kinet. Catal. Lett. 75 (2002) 297-304.
[5] R. Xu, W. Wei, W. Li, T. Hu, Y. Sun, Fe modified CuMnZrO2 catalyst for higher alcohols synthesis from syngas: Effect of calcination temperature, J. Mol. Catal. A: Chem. 234 (2005) 75-83.
[6] He, Ming, A Computational Approach for the Rational Design of Bimetallic Clusters for Ethanol Formation from Syn-gas, All Dissertation (2013) 1175.
[7] M.J.P. Zurita, M. Cifarelli, M.L. Cubeiro, J.A. M.Goldwasser, E. Pietri, L. Garcia, A. Aboukais, J.F. Lamonier, Palladium-based catalyst for the synthesis of alcohol, J. Mol. Catal. A: Chem. 206 (2003) 339-351.
[8] H.L. Jin, K.R. Hariprasad, S.J. Jae, Y. Eun-Hyeok, J.M. Dong, Role of support on higher alcohol synthesis from syngas, Applied Catalysis A: General 480 (2014) 128 -133.
[9] N.B. Long, N.T.T. Ha, P.T. Lan, L.M. Cam, N.N. Ha. A Theoretical Study on the Hydrogenation of CO Over Co2Cu2 Bimetallic Catalyst Supported on MgO (200) by Means of Density Functional Theory Part 1: Adsorption and Activation Stages, VNU Journal of Science: Natural Sciences and Technology 36 (1) (2020) 81-89. https://doi.org/ 10.25073/2588-1140/vnunst.4995.
[10] Perdew, John and Burke, Kieron and Ernzerhof, Matthias, Generalized Gradient Approximation Made Simple, Phys. Rev. Let. 77(18) (1996) 3865-3868.
[11] D.R. Hamann, M. Schlüter, C. Chiang, Norm-conserving pseudopotentials, Phys. Rev. Lett. 43 (1979) 1494–1497.
[12] José Soler, Emilio Artacho, Julian Gale, Alberto García, Javier Junquera, Pablo Ordejón, Daniel Sánchez-Portal, The SIESTA method for ab initio order-N materials simulation, J. Phys. Cond. Matt. 14 (2002) 2745-2779.
[13] G. Henkelman, B.P. Uberuaga, H. Jónsson, A climbing image nudged elastic band method for finding saddle points and minimum energy paths, J. Chem. Phys.133 (2000) 9901 - 9904.
[14] N.B. Long, N.T.T. Ha, L.M. Cam, P.T. Lan, N.N. Ha. Theoretical study of CO hydrogenation reaction on Ni2Cu2 bimetallic catalytic system on MgO carrier (200) by density function method. Journal of chemistry 57 (2019) 108-114.
[2] Ho Ting Luk, Cecilia Mondelli, Daniel Curulla Ferré, Joseph A. Stewart and Javier Pérez-Ramírez, Status and prospects in higher alcohols synthesis from syngas, Chem. Soc. Rev. 46 (2017) 1358-1426.
[3] Sharif Zaman, Kevin Smith, A Review of Molybdenum Catalysts for Synthesis Gas Conversion to Alcohols: Catalysts, Mechanisms and Kinetics, Cat. Rev. 54(1) (2012) 41-132.
[4] N. Zhao, R. Xu, W. Wei, Y. Sun, Cu/Mn/ZrO2 catalyst for alcohol synthesis by Fischer-Tropsch modified elements, React. Kinet. Catal. Lett. 75 (2002) 297-304.
[5] R. Xu, W. Wei, W. Li, T. Hu, Y. Sun, Fe modified CuMnZrO2 catalyst for higher alcohols synthesis from syngas: Effect of calcination temperature, J. Mol. Catal. A: Chem. 234 (2005) 75-83.
[6] He, Ming, A Computational Approach for the Rational Design of Bimetallic Clusters for Ethanol Formation from Syn-gas, All Dissertation (2013) 1175.
[7] M.J.P. Zurita, M. Cifarelli, M.L. Cubeiro, J.A. M.Goldwasser, E. Pietri, L. Garcia, A. Aboukais, J.F. Lamonier, Palladium-based catalyst for the synthesis of alcohol, J. Mol. Catal. A: Chem. 206 (2003) 339-351.
[8] H.L. Jin, K.R. Hariprasad, S.J. Jae, Y. Eun-Hyeok, J.M. Dong, Role of support on higher alcohol synthesis from syngas, Applied Catalysis A: General 480 (2014) 128 -133.
[9] N.B. Long, N.T.T. Ha, P.T. Lan, L.M. Cam, N.N. Ha. A Theoretical Study on the Hydrogenation of CO Over Co2Cu2 Bimetallic Catalyst Supported on MgO (200) by Means of Density Functional Theory Part 1: Adsorption and Activation Stages, VNU Journal of Science: Natural Sciences and Technology 36 (1) (2020) 81-89. https://doi.org/ 10.25073/2588-1140/vnunst.4995.
[10] Perdew, John and Burke, Kieron and Ernzerhof, Matthias, Generalized Gradient Approximation Made Simple, Phys. Rev. Let. 77(18) (1996) 3865-3868.
[11] D.R. Hamann, M. Schlüter, C. Chiang, Norm-conserving pseudopotentials, Phys. Rev. Lett. 43 (1979) 1494–1497.
[12] José Soler, Emilio Artacho, Julian Gale, Alberto García, Javier Junquera, Pablo Ordejón, Daniel Sánchez-Portal, The SIESTA method for ab initio order-N materials simulation, J. Phys. Cond. Matt. 14 (2002) 2745-2779.
[13] G. Henkelman, B.P. Uberuaga, H. Jónsson, A climbing image nudged elastic band method for finding saddle points and minimum energy paths, J. Chem. Phys.133 (2000) 9901 - 9904.
[14] N.B. Long, N.T.T. Ha, L.M. Cam, P.T. Lan, N.N. Ha. Theoretical study of CO hydrogenation reaction on Ni2Cu2 bimetallic catalytic system on MgO carrier (200) by density function method. Journal of chemistry 57 (2019) 108-114.