Citation: WANG Li-Geng, SHI Wei, YAO Ping, NI Zhe-Ming, LI Yuan, LIU Jiao. Microstructure and Jahn-Teller Effect of Cu-Zn-Mg-Al Layered Double Hydroxides[J]. Acta Physico-Chimica Sinica, ;2012, 28(01): 58-64. doi: 10.3866/PKU.WHXB20122858 shu

Microstructure and Jahn-Teller Effect of Cu-Zn-Mg-Al Layered Double Hydroxides

1.
Laboratory of Advanced Catalytic Materials, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032, P. R. China

Received Date: 5 September 2011
Available Online: 24 October 2011

We propose a periodic interaction model for layered double hydroxides, CuZnMgAl quaternary hydrotalcites [(M)-IV-LDHs (M=Cu, Zn, Mg, Al)]. Based on density functional theory the geometries of CuZnMgAl quaternary hydrotalcites were optimized using the CASTEP program. The impacts of the Jahn-Teller effect and the location of chlorine over the layer distortion and stability were investigated by analyzing the geometric parameters, the electronic arrangement, charge populations, binding energies, and hydrogen-bonding. The optimization results showed that the Jahn-Teller effect does not only exist in Cu²⁺ when its d orbital is partially filled but it also exists in Zn²⁺ when its d orbital is full as well as in Mg²⁺ when its p orbital is partially filled. Systems where the chloride is located above the metal show greater metal distortion than systems with anions located above non-metals. Eight systems (Nos. 1-8) were chosen for our work and their absolute binding energy values were found to decrease gradually while the stability of the systems became worse. Finally, the systems became unstable and were found to be flattened octahedral forms. These results help us to better understand the Jahn-Teller effect in copper-containing IV-LDHs from theory.
- Copper-containing quaternary hydrotalcite,
- Density functional theory,
- Jahn-Teller effect
1. [1]
  (1) Cavani, F.; Trifiro, F.; Vaccari, A. Catal. Today 1991, 11, 173.
2. [2]
  (2) Duan, X.; Zhang, F. Z. Intercalation and Assembly Chemistry of Inorganic Supramolecular Materials; Science Press: Beijing, 2009. [段雪, 张法智. 无机超分子材料的插层组装化学. 北京: 科学出版社, 2009.]
3. [3]
  (3) Yan, H.; Lu, J.;Wei, M.; Ma, J.; Li, H.; He, J.; Evans, D. G.; Duan, X. J. Mo1 . Struct . -Theochem 2008, 866, 34.
4. [4]
  (4) Becke, A. D. Chem. Phys. 1993, 98, 5648.
5. [5]
  (5) Lee, C.; Yang,W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
6. [6]
  (6) Yan, H.;Wei, M.; Ma, J.; Li, F.; Evans, D. G.; Duan, X. J. Phys. Chem. A 2009, 113, 6133.
7. [7]
  (7) Feng, Y. J.; Li, D. Q.; Li, C. X.;Wang, Z. G. Acta Chimica Sinica 2003, 61, 78. [冯拥军, 李殿卿, 李春喜, 王子镐. 化学学报, 2003, 61, 78.]
8. [8]
  (8) Wu, J. S.; Xiao, Y. K.; Lin, Y. P.; Liang, H. Q.; Li, C. Y.; He, H. Y. Journal of Synthetic Crystals 2010, 39, 817. [吴健松, 肖应凯, 林意萍, 梁海群, 李春银, 何海英. 人工晶体学报, 2010, 39, 817.]
9. [9]
  (9) Wang, X. P.; Yu, J. J.; Cheng, J.; Hao, P. Z.; Xu, P. Z. Environ. Sci. Technol. 2008, 42, 614.
10. [10]
  (10) Zhang, J.; Zhao, N.;Wei,W.; Sun, Y. H. The Research on Using Quaternary Hydrotalcites for the Partial Qxidation of Methane. In The Proceedings of The Seventh National Conference on Catalysis Science and Technology, The Seventh National Conference on Catalysis Science and Technology, Taiyuan, 2009; pp 319-321. [张军, 赵宁, 魏伟, 孙予罕. 新型四元水滑石在甲烷部分氧化中的应用研究. 第七届全国催化剂制备科学与技术研讨会会议论文集, 第七届全国催化剂制备科学与技术研讨会, 太原, 2009: 319-321.]
11. [11]
  (11) Heermann, D.W. Computer Simulation Methods in Theoretical Physics; Springer-Verlag Press: Heidelberg, 1990; pp 387-439.
12. [12]
  (12) Leach, A. R. Molecular Modelling: Principles and Applications; AddisonWesley Longman Limitted Press: Essex, 2001; pp 26-454.
13. [13]
  (13) Ni, Z. M.; Yao, P.; Liu, X. M.;Wang, Q. Q.; Xu, Q. Chem. J. Chin. Univ. 2010, 31, 2438. [倪哲明, 姚萍, 刘晓明, 王巧巧, 胥倩. 高等学校化学学报, 2010, 31, 2438.]
14. [14]
  (14) Tang, J. Y.; Jiang, H. F.; Deng, G. H.; Zhou, L. Chin. J. Org. Chem. 2005, 25, 1503. [唐金玉, 江焕峰, 邓国华, 周磊. 有机化学, 2005, 25, 1503.]
15. [15]
  (15) Suresh, I.; Vinay, V. T. J. Mol. Catal. A: Chem. 2000, 157, 275.
16. [16]
  (16) Matthew, D. J.; Christine, J. C.; Mary, F. M.; Paul, R. R.; David, A.; Joann,W.; David, C. J. Mol. Catal. A: Chem. 2010, 325, 8.
17. [17]
  (17) Surapas, E. R. Catal Lett. 2011, 141, 784.
18. [18]
  (18) Xu, J. H.; Man, Q. S.; Lin, Y. C.; Li, Y. Y.; Feng, Y. S. Chin. J. Org. Chem. 2010, 30, 9. [许建华, 蔄秋实, 林义成, 李源源, 冯乙巳. 有机化学, 2010, 30, 9.]
19. [19]
  (19) Xu, Q.; Ni, Z. M.; Mao, J. H. J. Mol. Struct: Theochem. 2009, 915, 122.
20. [20]
  (20) Xu, Q.; Ni, Z. M.; Pan, G. X.; Chen, L. T.; Liu, T. Acta Phys. -Chim. Sin. 2008, 24, 601. [胥倩, 倪哲明, 潘国祥, 陈丽涛, 刘婷. 物理化学学报, 2008, 24, 601.]
21. [21]
  (21) Segall, M. D.; Linda, P.; Probert, M.; Pickard, C.; Hasnip, P.; Clark, S.; Payne, M. J . Phys . -Condes . Matter. 2002, 14, 2717.
22. [22]
  (22) Ceperley, D. M.; Aider, B. J. Phys. Rev. Lett. 1980, 45, 566.
23. [23]
  (23) Vanderbilt, D. Phys. Rev. B 1990, 41, 7892.
24. [24]
  (24) Kresse, G.; Furthmiiller, J. Phys. Rev. B 1996, 54, 11169.
25. [25]
  (25) Pan, D. K.; Zhao, C. D.; Zheng, Z. X. The Structure of Matter; Higher Education Press: Beijing, 1989; pp 329-330. [潘道皑, 赵成大, 郑载兴. 物质结构. 北京: 高等教育出版社, 1989: 329-330.]
26. [26]
  (26) Mulliken, R. S. J. Chem. Phys. 1955, 23, 1833.
27. [27]
  (27) Scheiner, S. Hydrogen Bonding; Oxford University Press: New York, 1997.
28. [28]
  (28) Jeffrey, G. A. An Introduction to Hydrogen Bond; Oxford University Press: New York, 1997.
29. [29]
  (29) Desiraju, G.; Steiner, T. The Weak Hydrogen Bond; Oxford University Press: New York, 1999.
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沈阳化工大学材料科学与工程学院沈阳 110142