乙醇在Co(111)表面脱氢反应机理的第一性原理研究

doi:10.6023/A19010020

摘要/Abstract

采用密度泛函理论和周期平板模型相结合的方法针对Co（111）表面上乙醇脱氢反应的反应机理进行了细致的研究，同时，对反应过程中涉及到的各个物种在表面上不同吸附位（顶位（top），桥位（bridge），三重空穴位（fcc和hcp））的吸附模型进行了结构优化以及相关能量的计算，确定了各物种的最佳吸附位点.研究结果表明，CH₃CH₂OH在Co（111）表面的脱氢反应可具体描述为三条反应路径：反应路径I为CH₃CH₂OH逐步脱氢经由中间体CH₃CHO，最终生成CH₄和CO的反应；反应路径Ⅱ为CH₃CH₂OH脱氢产生的CH₃CH₂O基和CH₃CHO相互作用通过CH₃COOH分子最终生成CH₄和CO₂的反应；反应路径Ⅲ为CH₃CH₂O基和CH₃CO基作用生成CH₃COOC₂H₅的过程，其中，反应路径I为最优路径（CH₃CH₂OH→CH₃CH₂O→CH₃CHO→CH₃CO→CH₃+CO→CH₂→CH→CH₄+CO+C+H），该反应路径中的CH₃CH₂O基脱氢生成CH₃CHO为速控步骤，反应能垒为1.61 eV.

关键词: 第一性原理, 乙醇, Co(111)表面, 脱氢, 吸附

The detailed reaction mechanism of ethanol dehydrogenation on Co(111) surface was studied using the density functional theory (DFT) and slab periodic model. The structures and energies of the species involved in the reaction adsorbed on different adsorption sites (top, fcc, hcp and bridge sites) of the surface were calculated and compared. The calculated results show that ethanol adsorbs weakly on the Co(111) surface. CH₃CH₂O, CH and C prefer hcp sites with adsorption energies of -2.72, -6.85, and -6.92 eV, respectively. CH₃CHO adsorbs weakly at the bridge-η¹(O)-η¹(C^α) site with adsorption energy of -0.47 eV. CH₃CO and CH₂ adsorb stably on Co(111) surface through their unsaturated C atoms with binding energies of -2.31 and -3.90 eV, respectively. CH₃ and CH₄ prefer to locate at top sites through the C atom with adsorption energies of -1.95 and -0.12 eV, respectively. CO and H are bind stably at fcc sites with binding energies of -1.62 and -2.77 eV, respectively. Due to the complexity of the decomposition of ethanol, the scissions of O-H, C-H, C-O and C-C bonds of CH₃CH₂OH were examined. The results show that ethanol decomposition on Co(111) surface starts with the scission of the O-H bond, and the dehydrogenation reaction of ethanol on Co(111) surface can be described as three reaction pathways:Path I is the gradual dehydrogenation of CH₃CH₂OH via intermediate CH₃CHO, which ultimately produces CH₄ and CO; Path Ⅱ is the reaction of CH₃CH₂O and CH₃CHO which were generated by dehydrogenation of ethanol, to form CH₄ and CO₂ via CH₃COOH intermediate; Path Ⅲ is the process of CH₃CH₂O reacts with CH₃CO to generate CH₃COOC₂H₅. On the basis of our computational results, Path I (CH₃CH₂OH→CH₃CH₂O→CH₃CHO→CH₃CO→CH₃+CO→CH₂→CH→CH₄+CO+C+H) is more favorable than Paths Ⅱ and Ⅲ and the dehydrogenation of CH₃CH₂O to CH₃CHO is the rate-determining step with a reaction energy barrier of 1.61 eV.

Key words: first principle, ethanol, Co(111) surface, dehydrogenation, adsorption

引用此文

付雯雯, 李严, 梁长海. 乙醇在Co(111)表面脱氢反应机理的第一性原理研究[J]. 化学学报, 2019, 77(6): 559-568.

Fu Wenwen, Li Yan, Liang Changhai. Dehydrogenation Mechanism of Ethanol on Co(111) Surface: A First-principles Study[J]. Acta Chim. Sinica, 2019, 77(6): 559-568.

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参考文献

[1] Dunn, S. Int. J. Hydrogen Energy 2002, 27, 235.
[2] Navarro, R. M.; Peña, M. A.; Fierro, J. L. G. Chem. Rev. 2007, 107, 3952.
[3] Song, C. S. Catal. Today 2006, 115, 2.
[4] Öhgren, K.; Rudolf, A.; Galbe, M.; Zacchi, G. Biomass Bioenergy 2006, 30, 863.
[5] Rao, L.; Jiang, Y. X.; Zhang, B. W.; You, L. X.; Li, Z. H.; Sun, S. G. Prog. Chem. 2014, 26, 727(in Chinese). (饶路, 姜艳霞, 张斌伟, 游乐星, 李崭红, 孙世刚, 化学进展, 2014, 26, 727.)
[6] Rodríguez, L. A.; Toro, M. E.; Vazquez, F.; Correa-Daneri, M. L.; Gouiric, S. C.; Vallejo, M. D. Int. J. Hydrogen Energy 2010, 35, 5914.
[7] Lamy, C.; Belgsir, E. M.; Léger, J. M. J. Appl. Electrochem. 2001, 31, 799.
[8] Llorca, J.; Homs, N.; Sales, J.; de la Poscina, P. R. J. Catal. 2002, 209, 306.
[9] Meng, C.; Wang, H.; Wu, Y. B.; Fu, X. Z.; Yuan, R. S. Acta Chim. Sinica 2017, 75, 508(in Chinese). (孟超, 王华, 吴煜斌, 付贤智, 员汝胜, 化学学报, 2017, 75, 508.)
[10] Wu, K. H.; Zhou, Y. W.; Ma, X. Y.; Ding, C.; Cai, W. B. Acta Chim. Sinica 2018, 76, 292(in Chinese). (吴匡衡, 周亚威, 马宪印, 丁辰, 蔡文斌, 化学学报, 2018, 76, 292.)
[11] Van Der Laan, G. P.; Beenackers, A. A. C. M. Catal. Rev. 1999, 41, 255.
[12] Shekhar, R.; Barteau, M. A. Catal. Lett. 1995, 31, 221.
[13] Bowker, M.; Holroyd, R. P.; Sharpe, R. G.; Corneille, J. S.; Francis, S. M.; Goodman, D. W. Surf. Sci. 1997, 370, 113.
[14] Lee, A. F.; Naughton, J. N.; Liu, Z.; Wilson, K. ACS Catal. 2012, 2, 2235.
[15] Lee, A. F.; Gawthrope, D. E.; Hart, N. J.; Wilson, K. Surf. Sci. 2004, 548, 200.
[16] Vigier, F.; Coutanceau, C.; Hahn, F.; Belgsir, E. M.; Lamy, C. J. Electroanal. Chem. 2004, 563, 81.
[17] Gates, S. M.; Russell Jr, J. N.; Yates Jr, J. T. Surf. Sci. 1986, 171, 111.
[18] Resini, C.; Montanari, T.; Barattini, L.; Ramis, G.; Presto, S.; Riani, P.; Costantino, U. Appl. Catal., A 2009, 355, 83.
[19] Tian, Z. J.; Wei, X. M.; Zhai, R. S.; Ren, S. Z.; Liang, D. B.; Lin, L. W. Chem. Res. Chin. Univ. 1997, 7, 1158.
[20] Vicente, J.; Montero, C.; Ereña, J.; Azkoiti, M. J.; Bilbao, J.; Gayubo, A. G. Int. J. Hydrogen Energy 2014, 39, 12586.
[21] Wachs, I. E.; Madix, R. J. Appl. Surf. Sci. 1978, 1, 303.
[22] Zhang, M.; Yao, R.; Jiang, H.; Li, G. RSC Adv. 2017, 7, 1443.
[23] Qiu, C. W.; Wu, B. S.; Meng, S. C.; Li, Y. W. Acta Chim. Sinica 2015, 73, 690(in Chinese). (邱成武, 吴宝山, 孟劭聪, 李永旺, 化学学报, 2015, 73, 690.)
[24] Sun, Y. H.; Chen, J. G.; Wang, J. G.; Jia, L. T.; Hou, B.; Li, D. B.; Zhang, J. J. Chin. Catal. 2010, 31, 919(in Chinese). (孙予罕, 陈建刚, 王俊刚, 贾丽涛, 侯博, 李德宝, 张娟, 催化学报, 2010, 31, 919.)
[25] Dry, M. E. Catal. Today 2002, 71, 227.
[26] Liu, J. X.; Su, H. Y.; Sun, D. P.; Zhang, B. Y.; Li, W. X. J. Am. Chem. Soc. 2013, 135, 16284.
[27] Xu, L. S.; Ma, Y. S.; Zhang, Y. L.; Chen, B.; Wu, Z.; Jiang, Z.; Huang, W. J. Phys. Chem. C 2010, 114, 17023.
[28] Lv, B. L.; Chen, G. Q.; Zhou, W. L.; Su, H. Comput. Mater. Sci. 2013, 68, 206.
[29] Balakrishnan, N.; Joseph, B.; Bhethanabotla, V. R. Surf. Sci. 2012, 606, 634.
[30] van Helden, P.; van den Berg, J. A.; Weststrate, C. J. ACS Catal. 2012, 2, 1097.
[31] Pour, A. N.; Keyvanloo, Z.; Izadyar, M.; Modaresi, S. M. Int. J. Hydrogen Energy 2015, 40, 7064.
[32] Swart, J. C. W.; Ciobîcä, L. M.; van Santen, R. A.; van Steen, E. J. Phys. Chem. C 2008, 112, 12899.
[33] Kitakami, O.; Sato, H.; Shimada, Y.; Sato, F.; Tanaka, M. Phys. Rev. B 1997, 56, 13849.
[34] Ashok, A.; Kumar, A.; Bhosale, R.; Saad, M. A. S.; AlMomani, F.; Tarlochan, F. Int. J. Hydrogen Energy 2017, 42, 23464.
[35] Kresse, G.; Furthmuller, J. Phys. Rev. B:Condens. Matter 1996, 54, 11169.
[36] Kresse, G.; Hafner, J. Phys. Rev. B:Condens. Matter Mater. Phys. 1994, 49, 14251.
[37] Kresse, G.; Hafner, J. Phys. Rev. B:Condens. Matter Mater. Phys. 1993, 48, 13115.
[38] Kresse, G.; Hafner, J. Phys. Rev. B:Condens. Matter Mater. Phys. 1993, 47, 558.
[39] Kresse, G.; Furthmuller, J. Comput. Mater. Sci. 1996, 6, 15.
[40] Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865.
[41] Blöchl, P. E. Phys. Rev. B:Condens. Matter 1994, 50, 17953.
[42] Kresse, G.; Joubert, D. Phys. Rev. B:Condens. Matter Mater. Phys. 1999, 59, 1758.
[43] Monkhorst, H. J.; Pack, J. D. Phys. Rev. B 1976, 13, 5188.
[44] Häglund, J.; Guillermet, A. F.; Grimvall, G.; Körling, M. Phys. Rev. B 1993, 48, 11685.
[45] Chen, C.; Wang, Q.; Wang, G.; Hou, B.; Jia, L.; Li, D. J. Phys. Chem. C 2016, 120, 9132.
[46] Henkelman, G.; Uberuaga, B. P.; Jónsson, H. J. Chem. Phys. 2000, 113, 9901.
[47] Henkelman, G.; Jónsson, H. J. Chem. Phys. 2000, 113, 9978.
[48] CRC Handbook of Chemistry and Physics, 3rd electronic ed., Ed.:Lide, D. R., CRC Press, Boca Raton, Florida, 2000, Chapter 9, p. 31.
[49] Li, M.; Guo, W. Y.; Jiang, R. B.; Zhao, L. M.; Lu, X. Q.; Zhu, H. Y.; Fu, D. L.; Shan, H. H. J. Phys. Chem. C 2010, 114, 21493.
[50] Li, M. R.; Chen, J.; Wang, G. C. J. Phys. Chem. C 2016, 120, 14198.
[51] Christmann, K.; Demuth, J. E. J. Chem. Phys. 1982, 76, 6308.
[52] Davis, J. L.; Barteau, M. A. J. Am. Chem. Soc. 1989, 111, 1782.
[53] Luo, W. J.; Asthagiri, A. J. Phys. Chem. C 2014, 118, 15274.
[54] Zhong, W. H.; Zhang, D. J. Catal. Commun. 2012, 29, 82.
[55] Park, S.; Xie, Y.; Weaver, M. J. Langmuir 2002, 18, 5792.
[56] O?uz, I. C.; Mineva, T.; Guesmi, H. J. Chem. Phys. 2018, 148, 024701.
[57] Liu, J.; Fan, X. F.; Sun, C. Q.; Zhu, W. G. Appl. Surf. Sci. 2018, 441, 23.
[58] Liang, Y. Y.; Chen, L. T.; Ma, C. A. Surf. Sci. 2017, 656, 7.
[59] Ma, C. A.; Liu, T.; Chen, L. T. Appl. Surf. Sci. 2010, 256, 7400.
[60] Ding, Q. Y.; Xu, W. B.; Sang, P. P.; Xu, J.; Zhao, L. M.; He, X. L.; Guo, W. Y. Appl. Surf. Sci. 2016, 369, 257.
[61] Qi, Y.; Yang, J.; Duan, X.; Zhu, Y. A.; Chen, D.; Holmen, A. Catal. Sci. Technol. 2014, 4, 3534.
[62] van Helden, P.; van den Berg, J. A.; Weststrate, C. J. ACS Catal. 2012, 2, 1097.
[63] Hyman, M. P.; Vohs, J. M. Surf. Sci. 2011, 605, 383.
[64] Llorca, J.; Homs, N.; de la Piscina, P. R. J. Catal. 2004, 227, 556.
[65] Wang, H. F.; Liu, Z. P. J. Am. Chem. Soc. 2008, 130, 10996.
[66] Kitchin, J. R.; Nørskov, J. K.; Barteau, M. A.; Chen, J. G. Catal. Today 2005, 105, 66.
[67] Wei, Z. Z.; Li, D. C.; Pang, X. Y.; Lv, C. Q.; Wang, G. C. Chem-CatChem 2012, 4, 100.