Citation: LIU Jiao, YAO Ping, NI Zhe-Ming, LI Yuan, SHI Wei. Jahn-Teller Effect of Cu-Mg-Al Layered Double Hydroxides[J]. Acta Physico-Chimica Sinica, ;2011, 27(09): 2088-2094. doi: 10.3866/PKU.WHXB20110923 shu

Jahn-Teller Effect of Cu-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: 9 May 2011
Available Online: 15 July 2011

We propose a periodic interaction model for the layered double hydroxides, Cu_xMg_3-xAl-LDHs (x=0-3). Based on density functional theory, the geometries of Cu_xMg_3-xAl-LDHs(x=0-3) were optimized using the CASTEP program. The Jahn-Teller effect and the stability were investigated by analyzing the geometric parameters, electronic arrangement, hydrogen-bonding, charge populations, and binding energies. The results show that the Jahn-Teller effect exists in the unfilled Cu²⁺ d orbital and also exists in the unfilled Mg²⁺ p orbital. The two orbitals affect the Jahn-Teller distortion of the metal ions. In Cu_xMg_3-xAl-LDHs(x=0-3), both aluminum and magnesium exist in stabilized octahedral forms. With an increase of Cu²⁺ in the layer the octahedral of copper changes from a flat configuration to a stable elongated configuration and the Jahn-Teller stabilization energy of the system gradually increases. In general, with an increase of Cu²⁺ in the layer the distortion caused by the Jahn-Teller effect weakens hydrogen-bonding and the electrostatic interactions between the host layer and the guest. The absolute value of the binding energy decreases and the chemical stability of the system decreases as well. This allows us to theoretically understand the Jahn-Teller effect better for the synthesis of copper-containing LDHs.
- Layered double hydroxide,
- Jahn-Teller effect,
- Density functional theory,
- Binding energy,
- Mulliken population
1. [1]
  (1) Kovanda, F.; Jirátová, K.; Rymes, J.; Kolousek, D. Appl. Clay Sci. 2001, 18, 71.
2. [2]
  (2) Centi, G.; Fornasari, G.; bbi, C.; Livi, M.; Trifiro, F.; Vaccari, A. Catal. Today 2002, 73, 287.
3. [3]
  (3) Busca, G.; Costantino, U.; Marmottini, F.; Montanari, T.; Patrono, P.; Pinzari, F.; Ramis, G. Appl. Catal. A-Gen. 2006, 310, 70.
4. [4]
  (4) Xie, X. M.; An, X.; Yan, K.;Wu, X.; Song, J. L.;Wang, Z. Z. J. Nat. Gas Chem. 2010, 19, 77.
5. [5]
  (5) Liu, H. B.; Jiao, Q. Z.; Zhao, Y.; Li, H. S.; Sun, C. B.; Li, X. F.; Wu, H. Y. Mater. Lett. 2010, 64, 1698.
6. [6]
  (6) Bridier, B.; Lopez, N.; Perez-Ramirez, J. J. Catal. 2010, 269, 80.
7. [7]
  (7) Bridier, B.; Hevia, M. A. G.; Lopez, N.; Perez-Ramirez, J. J. Catal. 2011, 278, 167.
8. [8]
  (8) Velu, S.; Swamy, C. S. Appl. Catal. A-Gen. 1996, 145, 141.
9. [9]
  (9) Velu, S.; Suzuki, K.; Osaki, T. Catal. Lett. 1999, 62, 159.
10. [10]
  (10) Morpur , S.; Jacono, M. L.; Porta, P. J. Solid State Chem. 1996, 122, 324.
11. [11]
  (11) Lu, R. Q.; Zhang, N. N. J. Nat. Gas Chem. 2010, 19, 179.
12. [12]
  (12) Yan, H.; Lu, J.;Wei, M.; Ma, J.; Li, H.; He, J.; Evans, D. G.; Duan, X. J. Mol . Struct . -Theochem 2008, 866, 34.
13. [13]
  (13) Becke, A. D. Chem. Phys. 1993, 98, 5648.
14. [14]
  (14) Lee, C.; Yang,W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
15. [15]
  (15) Yan, H.;Wei, M.; Ma, J.; Li, F.; Evans, D. G.; Duan, X. J. Chem. Phys. A 2009, 113, 6133.
16. [16]
  (16) Vanderbilt, D. Phys . Rev . B 1990, 41, 7892.
17. [17]
  (17) 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.]
18. [18]
  (18) Xu, Q.; Ni, Z. M.; Mao, J. H. J. Mol. Struct . -Theochem 2009, 915, 122.
19. [19]
  (19) Yan, H.;Wei,W.; Ma, J.; Evans, D. G.; Duan, X. J. Phys. Chem. A 2010, 114, 7369.
20. [20]
  (20) 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.]
21. [21]
  (21) Liu, Y. H.; Guo, Y. H.;Wu, J. Y.; Liu, L. Y.; He, J.; Chen, B. H.; Pu, M. Chem. J. Chin. Univ. 2008, 29, l171. [刘亚辉, 郭玉华, 吴静怡, 刘灵燕, 何静, 陈标华, 蒲敏. 高等学校化学学报, 2008, 29, l171.]
22. [22]
  (22) Luo, Q. S.; Li, L.;Wang, Z. X.; Duan, X. Chin. J. Inorg. Chem. 2001, 17, 835. [罗青松, 李蕾, 王作新, 段雪. 无机化学学报, 2001, 17, 835.]
23. [23]
  (23) Cavani, F.; Trifiro, F.; Vaccari, A. Catal. Today 1991, 11, 173.
24. [24]
  (24) Yao, P.; Ni, Z. M.; Xu, Q.; Mao, J. H.; Liu, X. M.;Wang, Q. Q. Acta . Phys. -Chim. Sin. 2010, 26, 175. [姚萍, 倪哲明, 胥倩, 毛江洪, 刘晓明, 王巧巧. 物理化学学报, 2010, 26, 175.]
25. [25]
  (25) Segall, M. D.; Linda, P.; Probert, M.; Pickard, C.; Hasnip, P.; Clark, S.; Payne, M. J . Phys . -Condes . Matter 2002, 14, 2717.
26. [26]
  (26) Ceperley, D. M.; Aider, B. J. Phys. Rev. Lett. 1980, 45, 566.
27. [27]
  (27) Kresse, G.; Furthmiiller, J. Phys. Rev. B 1996, 54, 11169.
28. [28]
  (28) Duan, X.; Zhang, F. Z. Assembly and Function of Intercalative Materials; Chemical Industry Press: Beijing, 2007; p 93. [段雪, 张法智. 插层组装与功能材料. 北京: 化学工业出版社, 2007: 93.]
29. [29]
  (29) 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.]
30. [30]
  (30) Mulliken, R. S. J. Chem. Phys. 1955, 23, 1833.
1. [1]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
2. [2]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
3. [3]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
4. [4]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
5. [5]
  Xiaochen Zhang , Fei Yu , Jie Ma . 多角度数理模拟在电容去离子中的前沿应用. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-. doi: 10.3866/PKU.WHXB202311026
6. [6]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
7. [7]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
8. [8]
  Tongtong Zhao , Yan Wang , Shiyue Qin , Liang Xu , Zhenhua Li . New Experiment Development: Upgrading and Regeneration of Discarded PET Plastic through Electrocatalysis. University Chemistry, 2024, 39(3): 308-315. doi: 10.3866/PKU.DXHX202309003
9. [9]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
10. [10]
  Zhengkun QIN , Zicong PAN , Hui TIAN , Wanyi ZHANG , Mingxing SONG . A series of iridium(Ⅲ) complexes with fluorophenyl isoquinoline ligand and low-efficiency roll-off properties: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1235-1244. doi: 10.11862/CJIC.20240429
11. [11]
  Yaping Li , Sai An , Aiqing Cao , Shilong Li , Ming Lei . The Application of Molecular Simulation Software in Structural Chemistry Education: First-Principles Calculation of NiFe Layered Double Hydroxide. University Chemistry, 2025, 40(3): 160-170. doi: 10.12461/PKU.DXHX202405185
12. [12]
  Nengmin ZHU , Wenhao ZHU , Xiaoyao YIN , Songzhi ZHENG , Hao LI , Zeyuan WANG , Wenhao WEI , Xuanheng CHEN , Weihai SUN . Preparation of high-performance CsPbBr₃ perovskite solar cells by the aqueous solution solvent method. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1131-1140. doi: 10.11862/CJIC.20240419
13. [13]
  Kun Rong , Cuilian Wen , Jiansen Wen , Xiong Li , Qiugang Liao , Siqing Yan , Chao Xu , Xiaoliang Zhang , Baisheng Sa , Zhimei Sun . Hierarchical MoS₂/Ti₃C₂T_x heterostructure with excellent photothermal conversion performance for solar-driven vapor generation. Acta Physico-Chimica Sinica, 2025, 41(6): 100053-. doi: 10.1016/j.actphy.2025.100053
14. [14]
  Yaling Chen . Basic Theory and Competitive Exam Analysis of Dynamic Isotope Effect. University Chemistry, 2024, 39(8): 403-410. doi: 10.3866/PKU.DXHX202311093
15. [15]
  Qiqi Li , Su Zhang , Yuting Jiang , Linna Zhu , Nannan Guo , Jing Zhang , Yutong Li , Tong Wei , Zhuangjun Fan . 前驱体机械压实制备高密度活性炭及其致密电容储能性能. Acta Physico-Chimica Sinica, 2025, 41(3): 2406009-. doi: 10.3866/PKU.WHXB202406009
16. [16]
  Ying Zhang , Fang Ge , Zhimin Luo . AI-Driven Biochemical Teaching Research: Predicting the Functional Effects of Gene Mutations. University Chemistry, 2025, 40(3): 277-284. doi: 10.12461/PKU.DXHX202412104
17. [17]
  Yuena Yang , Xufang Hu , Yushan Liu , Yaya Kuang , Jian Ling , Qiue Cao , Chuanhua Zhou . The Realm of Smart Hydrogels. University Chemistry, 2024, 39(5): 172-183. doi: 10.3866/PKU.DXHX202310125
18. [18]
  Chao Liu , Huan Yu , Jiaming Li , Xi Yu , Zhuangzhi Yu , Yuxi Song , Feng Zhang , Qinfang Zhang , Zhigang Zou . Facile synthesis of hierarchical Ti₃C₂/Bi₁₂O₁₇Br₂ Schottky heterojunction with photothermal effect for solar-driven antibiotics photodegradation. Acta Physico-Chimica Sinica, 2025, 41(7): 100075-. doi: 10.1016/j.actphy.2025.100075
19. [19]
  Wen YANG , Didi WANG , Ziyi HUANG , Yaping ZHOU , Yanyan FENG . La promoted hydrotalcite derived Ni-based catalysts: In situ preparation and CO₂ methanation performance. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 561-570. doi: 10.11862/CJIC.20230276
20. [20]
  Yanglin Jiang , Mingqing Chen , Min Liang , Yige Yao , Yan Zhang , Peng Wang , Jianping Zhang . Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone. Acta Physico-Chimica Sinica, 2025, 41(2): 100012-. doi: 10.3866/PKU.WHXB202309027

Get Citation

PDF

XML

Metrics

PDF Downloads(1289)
Abstract views(3839)
HTML views(242)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142