CeO<sub>2</sub>(100)极性面结构与活性的密度泛函理论研究

引用本文: 钟素红, 卢冠忠, 龚学庆. CeO₂(100)极性面结构与活性的密度泛函理论研究[J]. 催化学报, 2017, 38(7): 1138-1147. doi: 10.1016/S1872-2067(17)62843-2 shu

Citation: SuHong Zhong, Guanzhong Lu, XueQing Gong. A DFT+U study of the structures and reactivities of polar CeO₂(100) surfaces[J]. Chinese Journal of Catalysis, 2017, 38(7): 1138-1147. doi: 10.1016/S1872-2067(17)62843-2 shu

CeO₂(100)极性面结构与活性的密度泛函理论研究

a 华东理工大学, 化学与分子工程学院, 计算化学中心, 结构可控先进功能材料及其制备教育部重点实验室, 上海 200237;
b 华东理工大学, 化学与分子工程学院, 工业催化研究所, 结构可控先进功能材料及其制备教育部重点实验室, 上海 200237
基金项目:
国家自然科学基金（21421004，21573067）.

摘要: CeO₂是一类使用非常广泛的稀土氧化物催化材料，在许多重要的催化反应过程，如机动车尾气净化、水汽转换、石油裂解等，表现出很高的活性.大量研究表明，CeO₂的高活性来源于其表面晶格氧，正是由于这些晶格氧能够直接参与氧化反应，同时反应留下的氧空位又能够被气相氧分子吸附填补，因而体现出很好的储放氧催化性能.目前多数研究采用CO氧化为模型反应，研究了CeO₂常见的（111）和（110）晶面的晶格氧活性，但对于其另外一种重要低指数晶面（100）的结构和活性研究却非常有限.需要指出的是，CeO₂（100）是一种极性表面，这给该表面的模型构建和理论研究带来了困难.为了深入了解这种极性表面的结构稳定性和催化活性，本文运用在位库仑力校正的密度泛函理论（DFT+U）方法系统研究了CeO₂（100）极性面的可能结构及相关稳定性，并且深入分析了CO在该表面上的吸附和反应.
本文首先利用板层模型尝试构建稳定的CeO₂（100）极性面结构，方法是在保证整个板层化学计量配比完整的前提下，在表层或体相去除氧原子，同时使得整个板层上下对称不存在极性以利于计算.通过计算发现，在CeO₂（100）表层分布氧空位的结构比体相中分布氧空位的结构要稳定，同时，氧空位的分布越接近表面，CeO₂（100）面的结构稳定性就会越高，其最稳定的结构是将表层满覆盖氧离子移除一半.
对CeO₂（100）面不同结构的稳定性及相关电子结构分析表明，CeO₂（100）表层满覆盖的氧离子间存在很强的相互排斥作用，因此倾向于降低表面氧浓度来提高表面的稳定性.另外，这种相互作用会降低相邻氧离子的价态，并能引起体相铈离子在整体表面维持完整的化学计量比的情况下，仍能出现局域4ƒ电子而被还原为三价铈.
随后我们研究了CO在CeO₂（100）最稳定和次稳定表面上的氧化反应.发现CO在不同CeO₂（100）表面的氧空位处吸附较强，另外，CO在CeO₂（100）最稳定结构上可与表面晶格氧反应形成吸附的CO₂中间物种，中间物种可直接解离成气相CO₂，也可以继续与表面晶格氧反应形成碳酸盐.而在CeO₂（100）次稳定表面上，CO很难与表面晶格氧形成吸附的CO₂中间态，而直接产生气态CO₂.

关键词:

English

A DFT+U study of the structures and reactivities of polar CeO₂(100) surfaces

a Key Laboratory for Advanced Materials, Centre for Computational Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China;
b Key Laboratory for Advanced Materials, Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China
Received Date: 28 February 2017
Revised Date: 17 April 2017
Fund Project:
This work was supported the National Natural Science Foundation of China (21421004, 21573067).

Abstract: Density functional theory calculations corrected by on-site Coulomb interactions were carried out to study the structures of polar CeO₂(100) surfaces as well as activities during catalytic CO oxida-tion. The stabilities of various CeO₂(100) termination structures are discussed, and calculated ener-getics are presented. The most stable CeO₂(100) surface was obtained by removing half the outer-most full layer of oxygen and the surface stability was found to decrease as the exposed oxygen concentration was increased. Assessing the reaction pathways leading to different final products during CO oxidation over the most stable CeO₂(100) surface, we determined that the formation of carbonate species competed with CO₂ desorption. However, during CO oxidation on the less stable CeO₂(100) surfaces having more exposed oxygen, the CO is evidently able to react with surface oxygen, leading to CO₂ formation and desorption. The calculation results and electronic analyses reported herein also indicate that the characteristic Ce 4ƒ orbitals are directly involved in deter-mining the surface stabilities and reactivities.

Key words:

Cerium dioxide(100)
/ Density functional theory calculations corrected by on-site Coulomb interactions
/ Polar surface
/ Carbon monoxide oxidation
/ Electron localization

1. [1] K. Otswka, Y. Wang, E. Sunada, I. Yamanaka, J. Catal., 1998, 175, 152-160.
2. [2] S. Hilaire, X. Wang, T. Luo, R. Gorte, J. Wagner, Appl. Catal. A, 2001, 25, 271-278.
3. [3] Q. Fu, H. Soltsburg, M. Flytzani-Stephanopoulos, Science, 2003, 301, 935-938.
4. [4] I. I. Soykal, H. Sohn, U. S. Ozkan, ACS Catal., 2012, 2, 2335-2348.
5. [5] Z. Cheng, B. J. Sherman, C. S. Lo, J. Chem. Phys., 2013, 138, 014702/1-014702/12.
6. [6] G. Dutta, A. Gupta, U. Waghmare, M. S. Hedge, J. Chem. Sci., 2011, 123, 509-516.
7. [7] H. Y. Kim, G. Henkelman, J. Phys. Chem. Lett., 2012, 3, 2194-2199.
8. [8] G. E. Murgida, V. Ferrai, M. Veronica. Ganduglia-Pirovano, A. M. Llois, Phys. Rev. B, 2014, 90, 115120/1-115120/12.
9. [9] F. Esch, S. Fabris, L. Zhou, T. Montini, C. Africh, P. Fornasiero, G. Comelli, R. Rosei, Science, 2005, 309, 752-755.
10. [10] S. Torbrugge, M. Reichling, A. Ishiyama, S. Morita, O. Custance, Phys. Rev. Lett., 2007, 99, 056101/1-056101/4.
11. [11] D. C. Grinter, R. Ithnin, C. L. Pang, G. Thorton, J. Phys. Chem. C, 2010, 114, 17036-17041.
12. [12] J. F. Jerratsch, X. Shao, N. Nilius, H. J. Freund, C. Popa, M. V. Ganduglia-Pirovano, A. M. Burow, J. Sauer, Phys. Rev. Lett., 2011, 106, 246801/1-246801/4.
13. [13] H. Wilkens, O. Schuckmann, R. Oellke, S. Gevers, A. Schaefer, M. Baumer, M. H. Zoellner, T. Schroeder, J. Wollschlager, Appl. Phys. Lett., 2013, 102, 111602/1-111602/3.
14. [14] T. Duchon, F. Dvorak, M. Aulicka, V. Stetsovych, M. Vorokhta, D. Mazur, K. Veltruska, T. Skala, J. Myslivecek, I. Matolınova, V. Matolın, J. Phys. Chem. C, 2014, 118, 357-365.
15. [15] M. V. Ganduglia-Pirovano, A. Hofmann, J. Sauer, Surf. Sci. Rep., 2007, 62, 219-270.
16. [16] J. Paier, C. Penschke, J. Sauer, Chem. Rev., 2013, 113, 3949-3985.
17. [17] C. J. Zhang, A. Michaelides, D. A. King, S. J. Jenkins, Phys. Rev. B, 2009, 79, 075433/1-075433/11.
18. [18] A. P. Amrute, C. Mondelli, M. Moser, G. Novell-Leruth, N. Lopez, D. Rosenthal, R. Farra, M. E. Schuster, D. Teschner, T. Schmidt, J. Pe-rez-Ramirez, J. Catal., 2012, 286, 287-297.
19. [19] G. E. Murgida, M. V. Ganduglia-Pirovano, Phys. Rev. Lett., 2013, 110, 246101/1-246101/5.
20. [20] M. Nolan, S. C. Parker, G. W. Watson, Surf. Sci., 2005, 595, 223-232.
21. [21] M. Nolan, G. W. Watson, J. Phys. Chem. B, 2006, 110, 16600-16606.
22. [22] M. Nolan, J. Phys. Chem. C, 2009, 113, 2425-2432.
23. [23] L. Cheng, D. H. Mei, Q. F. Ge, J. Phys. Chem. C, 2009, 113, 18296-18303.
24. [24] B. T. Teng, S. Y. Jia, X. W. Guo, J. H. Yuan, M. F. Luo, Acta Chim. Sin., 2009, 25, 2765-2772.
25. [25] P. W. Tasker, J. Phys. C-Solid State Phys., 1979, 12, 4977-4984.
26. [26] J. Soria, A. Martinez-Arias, J. C. Conesa, J. Chem. Soc. Faraday Trans., 1995, 91, 1669-1678.
27. [27] K. B. Zhou, X. Wang, X. M. Sun, Q. Peng, Y. D. Li, J. Catal., 2005, 229, 206-212.
28. [28] E. Aneggi, J. Llorca, M. Boaro, A. Trovarelli, J. Catal., 2005, 234, 88-95.
29. [29] H. Y. Kim, H. M. Lee, G. Henkelman, J. Am. Chem. Soc., 2012, 134, 1560-1570.
30. [30] H. F. Wang, X. Q. Gong, Y. L. Guo, Y. Guo, G. Z. Lu, P. Hu, J. Phys. Chem. C, 2009, 113, 10229-10232.
31. [31] Z. Yang, T. K. Woo, K. Hermansson, J. Chem. Phys., 2006, 124, 224704/1-224704/7.
32. [32] W. Song, E. J. M. Hensen, ACS Catal., 2014, 4, 1885-1892.
33. [33] S. M. Kozlov, K. M. Neyman, Phys. Chem. Chem. Phys., 2014, 16, 7823-7829.
34. [34] W. L. Cen, Y. Liu, Z. B. Wu, H. Q. Wang, X. L. Weng, Phys. Chem. Chem. Phys., 2012, 14, 5769-5777.
35. [35] N. J. Casteuani, M. M. Branda, N. C. Hernandez, J. F. Sanz, F. Illas, J. Phys. Chem. C, 2009, 113, 4948-4954.
36. [36] M. M. Branda, R. M. Ferullo, M. Causa, F. Illas, J. Phys. Chem. C, 2011, 115, 3761-3721.
37. [37] J. Zhang, X. Q. Gong, G. Z. Lu, J. Catal., 2014, 35, 1305-1317.
38. [38] G. Kresse, J. Hafner, Phys. Rev. B, 1993, 48, 13115-13118.
39. [39] G. Kresse, J. Furthmuller, Comp. Mater. Sci., 1996, 6, 15-50.
40. [40] G. Kresse, D. Joubert, Phys. Rev. B, 1999, 59, 1758-1775.
41. [41] M. Gajdos, K. Hummer, G. Kresse, J. Furthmuller, F. Bechstedt, Phys. Rev. B, 2006, 73, 045112/1-045112/9.
42. [42] D. O. Scanlon, N. M. Galea, B. J. Morgan, G. W. Watson, J. Phys. Chem. C, 2009, 113, 11095-11103.
43. [43] M. Huang, S. Fabris, J. Phys. Chem. C, 2008, 112, 8643-8648.
44. [44] C. Loschen, J. Carrasco, K. M. Neyman, F. Illas, Phys. Rev. B, 2007, 75, 035115/1-035115/8.
45. [45] H. J. Monkhorst, J. D. Pack, Phys. Rev. B, 1976, 13, 5188-5192.
46. [46] M. Baudin, M. Wojcik, K. Hermansson, Surf. Sci., 2000, 468, 51-61.
47. [47] Y. Pan, N. Nilius, C. Stiehler, H. J. Freund, J. Goniakowski, C. Nogue-ra, Adv. Mater. Interfaces, 2014, 1, 1400404/1-1400404/6.
48. [48] M. Capdevila-Cortada, N. Lopez, Nat. Mater., 2017, 16, 328-334.
49. [49] Z. L. Wu, M. J. Li, S. H. Overbury, J. Catal., 2012, 285, 61-73.
50. [50] F. Chen, D. Liu, J. Zhang, P. Hu, X. Q. Gong, G. Z. Lu, Phys. Chem. Chem. Phys., 2012, 14, 16573-16580.
51. [51] Y. L. Song, L. L. Yin, J. Zhang, P. Hu, X. Q. Gong, G. Z. Lu, Surf. Sci., 2013, 618, 140-147.
52. [52] J. Zhang, X. Q. Gong, G. Z. Lu, Surf. Sci., 2015, 632, 164-173.

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沈阳化工大学材料科学与工程学院沈阳 110142

CeO₂(100)极性面结构与活性的密度泛函理论研究

English

A DFT+U study of the structures and reactivities of polar CeO₂(100) surfaces

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CeO2(100)极性面结构与活性的密度泛函理论研究

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A DFT+U study of the structures and reactivities of polar CeO₂(100) surfaces

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