CO<sub>2</sub>在α-U(001)表面的吸附和解离

引用本文: 李赣, 罗文华, 陈虎翅. CO₂在α-U(001)表面的吸附和解离[J]. 物理化学学报, 2011, 27(10): 2319-2325. doi: 10.3866/PKU.WHXB20110936 shu

Citation: LI Gan, LUO Wen-Hua, CHEN Hu-Chi. Adsorption and Dissociation of CO₂on the α-U(001) Surface[J]. Acta Physico-Chimica Sinica, 2011, 27(10): 2319-2325. doi: 10.3866/PKU.WHXB20110936 shu

CO₂在α-U(001)表面的吸附和解离

基金项目:
国防科技重点实验室基金(9140C6601010901) (9140C6601010901)

中国工程物理研究院科学技术基金(2008A0301013)资助项目 (2008A0301013)

摘要: 采用广义梯度密度泛函理论研究了0.25 ML覆盖度下CO₂在α-U(001)表面上的吸附和解离, 得到了CO₂的稳定吸附构型和吸附能, 确定了CO₂的解离过渡态和解离能垒, 探讨了CO₂与表面U原子的相互作用本质. 结果表明, CO₂趋向以C(O)―U多键结合方式在α-U(001)面发生强化学吸附, 吸附能为1.24-1.67 eV; C―O键的活化程度依赖于表面电子向CO₂发生转移的程度. CO₂与表面U原子的相互作用主要来自于U原子电子向CO₂ 最低空轨道(LUMO)2π_u转移, 以及CO₂ 2π_u/1π_g/3σ_u-U 6d 轨道间杂化而生成新的化学键. 以形成3 个C―U键和6 个O―U键模式在穴位1 和穴位2 上发生吸附的CO₂(H1-C₃O₆和H2-C₃O₆)的解离吸附能分别为3.15和3.13 eV, 解离能垒分别为0.26和0.36 eV, 预示着吸附CO₂分子易于解离形成CO分子和O原子.

关键词:

密度泛函理论
/ &
/ alpha
/ -U(001)表面
/ CO₂分子
/ 吸附

English

Adsorption and Dissociation of CO₂on the α-U(001) Surface

1.
1. Key Laboratory for Surface Physics and Chemistry, Mianyang 621907, Sichuan Province, P. R. China;
2. China Academy of Engineering Physics, Mianyang 621900, Sichuan Province, P. R. China
Received Date: 28 April 2011
Available Online: 27 September 2011
Fund Project:
国防科技重点实验室基金(9140C6601010901)

中国工程物理研究院科学技术基金(2008A0301013)资助项目

Abstract: The adsorption and dissociation of CO₂ on the α-U(001) surface at 0.25 monolayer (ML) coverage was studied using density functional theory (DFT) within the generalized gradient approximation (GGA). Stable structures and corresponding energies of CO₂ adsorbed on the α-U(001) surface were obtained while the transition state and corresponding energy barrier for CO₂ dissociation was determined. We discussed the interaction mechanism between CO₂ and the α-U(001) surface. We found that CO₂ strongly chemisorbed onto the α-U(001) surface in a multi-bonding manner with adsorption energies of 1.24-1.67 eV and the degree of C―O bond activation depended on the degree of electron transfer from surface to the adsorbed CO. The interaction between the U atoms and the CO₂ molecules mainly comes from the population of the CO₂ 2π_u lowest unoccupied molecular orbital (LUMO) by U electrons with CO₂ 2π_u/1π_g/3σ_u-U 6d orbital hybridization. The dissociative adsorption energies for the CO₂ adsorbed on the hollow1 and hollow2 sites with three C―U bonds and six O―U bonds (H1-C₃O₆ and H2-C₃O₆ ) are 3.15 and 3.13 eV, respectively. The corresponding dissociation barriers are 0.26 and 0.36 eV, which indicates that the dissociation of adsorbed CO₂ into CO and O occurs easily.

Key words:

1. [1]
  (1) McLean,W.; Colmenares, C. A.; Smith, R. L. Phys. Rev. B 1982, 25, 8. (1) McLean,W.; Colmenares, C. A.; Smith, R. L. Phys. Rev. B 1982, 25, 8.
2. [2]
  (2) uder, T.; Colmenares, C.; Naegele, J. R.; Verbist, J. Surf. Sci. 1989, 235, 280.(2) uder, T.; Colmenares, C.; Naegele, J. R.; Verbist, J. Surf. Sci. 1989, 235, 280.
3. [3]
  (3) Huda, M. N.; Ray, A. K. Int. J. Quantum Chem. 2004, 102, 98.(3) Huda, M. N.; Ray, A. K. Int. J. Quantum Chem. 2004, 102, 98.
4. [4]
  (4) Dholabhai, P. P.; Ray, A. K. J. Alloy. Compd. 2007, 444, 356. (4) Dholabhai, P. P.; Ray, A. K. J. Alloy. Compd. 2007, 444, 356.
5. [5]
  (5) Nie, J. L.; Xiao, H. Y.; Zu, X. T.; Fei, G. J. Phys: Condens. Matter 2008, 20, 445001. (5) Nie, J. L.; Xiao, H. Y.; Zu, X. T.; Fei, G. J. Phys: Condens. Matter 2008, 20, 445001.
6. [6]
  (6) Senanayake, S. D.; Soon, A.; Kohlmeyer, A.; Sohnel, T.; Idriss, H. J. Vac. Sci. Technol. 2005, A23, 1078.(6) Senanayake, S. D.; Soon, A.; Kohlmeyer, A.; Sohnel, T.; Idriss, H. J. Vac. Sci. Technol. 2005, A23, 1078.
7. [7]
  (7) Li, G.; Luo,W. H.; Chen, H. C. Acta Phys. -Chim. Sin. 2010, 26, 1378.(7) Li, G.; Luo,W. H.; Chen, H. C. Acta Phys. -Chim. Sin. 2010, 26, 1378.
8. [8]
  [李赣, 罗文华, 陈虎翅.物理化学学报, 2010, 26, 1378.[李赣, 罗文华, 陈虎翅.物理化学学报, 2010, 26, 1378.
9. [9]
  (8) Blanter, M. S.; Glazkov, V. P.; Somenkov, V. A. The Physics of Metal and Metallography 2006, 101, 153. (8) Blanter, M. S.; Glazkov, V. P.; Somenkov, V. A. The Physics of Metal and Metallography 2006, 101, 153.
10. [10]
  (9) Hohenberg, P.; Kohn,W. Phys. Rev. B 1964, 136, 864. (9) Hohenberg, P.; Kohn,W. Phys. Rev. B 1964, 136, 864.
11. [11]
  (10) Kohn,W.; Sham, L. J. Phys. Rev. A 1965, 140, 1133. (10) Kohn,W.; Sham, L. J. Phys. Rev. A 1965, 140, 1133.
12. [12]
  (11) Delley, B. J. Chem. Phys. 2000, 113, 7756. (11) Delley, B. J. Chem. Phys. 2000, 113, 7756.
13. [13]
  (12) Delley, B. Int. J. Quant. Chem B 1998, 69, 423. (12) Delley, B. Int. J. Quant. Chem B 1998, 69, 423.
14. [14]
  (13) Perdew, J. P.;Wang, Y. Phys. Rev. B 1992, 45, 13244. (13) Perdew, J. P.;Wang, Y. Phys. Rev. B 1992, 45, 13244.
15. [15]
  (14) Monkhorst, H. J.; Pack, J. D. Phys. Rev. B 1976, 13, 5188. (14) Monkhorst, H. J.; Pack, J. D. Phys. Rev. B 1976, 13, 5188.
16. [16]
  (15) Segall, M. D.; Lindan, P. J. D.; Probert, M. J.; Pickard, C. J.; Hasnip, P. J.; Clark, S. J.; Payne, M. C. J. Phys.: Condens. Matter 2002, 14, 2717. (15) Segall, M. D.; Lindan, P. J. D.; Probert, M. J.; Pickard, C. J.; Hasnip, P. J.; Clark, S. J.; Payne, M. C. J. Phys.: Condens. Matter 2002, 14, 2717.
17. [17]
  (16) Vanderbilt, D. Phys. Rev. B 1990, 41, 7892. (16) Vanderbilt, D. Phys. Rev. B 1990, 41, 7892.
18. [18]
  (17) Bell, S.; Crighton, J. S. J. Chem. Phys. 1984, 80, 2464. (17) Bell, S.; Crighton, J. S. J. Chem. Phys. 1984, 80, 2464.
19. [19]
  (18) Fischer, S; Karplus, M. Chem. Phys. Lett. 1992, 194, 252. (18) Fischer, S; Karplus, M. Chem. Phys. Lett. 1992, 194, 252.
20. [20]
  (19) Barett, C. S.; Mueller, M. H.; Hittermann, R. L. Phys. Rev. 1963, 129, 6251.(19) Barett, C. S.; Mueller, M. H.; Hittermann, R. L. Phys. Rev. 1963, 129, 6251.
21. [21]
  (20) S?derlind, P. Phys. Rev. B 2002, 66, 085113. (20) S?derlind, P. Phys. Rev. B 2002, 66, 085113.
22. [22]
  (21) Vitos, L.; Xiao, H. Y.; Gao, F.; Zu, X. T. J. Alloy. Compd. 2008, 476, 675.(21) Vitos, L.; Xiao, H. Y.; Gao, F.; Zu, X. T. J. Alloy. Compd. 2008, 476, 675.
23. [23]
  (22) Lide, D. R. CRC Handbook of Chemistry and Physics; CRC Press:Boca Raton, 2003.(22) Lide, D. R. CRC Handbook of Chemistry and Physics; CRC Press:Boca Raton, 2003.
24. [24]
  (23) Freund, H. J.; Messmer, R. P. Surf. Sci. 1986, 172, 1. (23) Freund, H. J.; Messmer, R. P. Surf. Sci. 1986, 172, 1.
25. [25]
  (24) Storms, E. K.; Haber, A. J. J. Nucl. Mater. 1967, 23, 19. (24) Storms, E. K.; Haber, A. J. J. Nucl. Mater. 1967, 23, 19.
26. [26]
  (25) Wyckoff, R.W. G. Crystal Structures 1; Interscience Press:New York, 1963.(25) Wyckoff, R.W. G. Crystal Structures 1; Interscience Press:New York, 1963.

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沈阳化工大学材料科学与工程学院沈阳 110142

CO₂在α-U(001)表面的吸附和解离

English

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