铜锌镁铝四元水滑石的微观结构及其姜-泰勒畸变

引用本文: 王力耕, 施炜, 姚萍, 倪哲明, 李远, 刘娇. 铜锌镁铝四元水滑石的微观结构及其姜-泰勒畸变[J]. 物理化学学报, 2012, 28(01): 58-64. doi: 10.3866/PKU.WHXB20122858 shu

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

铜锌镁铝四元水滑石的微观结构及其姜-泰勒畸变

摘要: 采用密度泛函理论(DFT), 选取CASTEP程序模块, 对铜锌镁铝四元水滑石[(M)-IV-LDHs (M=Cu, Zn,Mg, Al)]周期性模型进行几何全优化, 从各体系的结构参数、电子排布、Mulliken 电荷布居、结合能、氢键等方面, 研究了体系中的姜-泰勒效应、氯离子位置对层板畸变及体系稳定性的影响. 优化结果表明, 姜-泰勒效应不仅存在于d 轨道未排满的Cu²⁺中, 也存在于理论上d 轨道排满的Zn²⁺与p 轨道未排满的Mg²⁺中. 氯离子排在金属上方的体系, 其金属畸变程度大于氯离子排在非金属上方的体系. 同时, 对于本文选取的8个CuAl-IV-LDHs体系, 结合能绝对值按照1-8号逐渐降低, 体系的稳定性下降, 最终转变为不稳定的压扁的八面体构型. 这有助于从理论上对含铜四元水滑石的姜-泰勒效应进一步认识.

关键词:

English

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: 05 September 2011
Available Online: 29 December 2011

Abstract: 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.

Key words:

Copper-containing quaternary hydrotalcite
/ Density functional theory
/ Jahn-Teller effect

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沈阳化工大学材料科学与工程学院沈阳 110142

铜锌镁铝四元水滑石的微观结构及其姜-泰勒畸变

English

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

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中国化学会秘书处

铜锌镁铝四元水滑石的微观结构及其姜-泰勒畸变

English

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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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