层间水分子含量对铜铁水滑石超分子作用力的影响

引用本文: 施炜, 胡军, 倪哲明, 李远, 刘娇. 层间水分子含量对铜铁水滑石超分子作用力的影响[J]. 物理化学学报, 2012, 28(08): 1869-1876. doi: 10.3866/PKU.WHXB201205212 shu

Citation: SHI Wei, HU Jun, NI Zhe-Ming, LI Yuan, LIU Jiao. Influence of Interlayer Water Content on Supermolecular Interaction of Copper-Iron Layered Double Hydroxides[J]. Acta Physico-Chimica Sinica, 2012, 28(08): 1869-1876. doi: 10.3866/PKU.WHXB201205212 shu

层间水分子含量对铜铁水滑石超分子作用力的影响

摘要:

构建铜铁水滑石[Cu₃Fe-LDHs-yH₂O(y=0-2)]周期性计算模型, 采用密度泛函理论(DFT), 选取CASTEP程序模块, 对体系进行几何全优化, 从结构参数、氢键布居、Mulliken电荷布居、逐级水合能等角度研究了层间NO₃^-和H₂O的分布形态及其与水滑石(LDHs)层板的超分子作用, 探究了水分子数目对体系姜-泰勒效应的影响. 结果表明, Cu₃Fe-LDHs-yH₂O主客体间存在着较强的超分子作用力, 主要包括氢键和静电作用, 其中氢键作用在水合过程中起主导作用, 氢键强度的顺序是层板-阴离子(L-A)型＞阴离子-水(A-W)型＞层板-水(L-W)型＞水-水(W-W)型; 随着层间水分子数的增加, 层间距先略微降低后显著升高, Cu₃Fe-LDHs体系的Cu—O八面体被逐渐拉长, 层板Cu²⁺的姜-泰勒畸变程度逐渐增大, 体系的逐级水合能绝对值逐渐降低, 说明Cu₃Fe-LDHs的水合程度不会无限增加, 而是具有一个饱和值. Cu₃Fe-LDHs-1H₂O构型接近理想六方晶胞, 层板金属畸变程度最小, 稳定性最高, 层间距与实验值较吻合, 推测其为实验上合成的Cu₃Fe-LDHs较稳定的构型.

关键词:

English

Influence of Interlayer Water Content on Supermolecular Interaction of Copper-Iron 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: 20 January 2012
Available Online: 10 July 2012

Abstract:

A periodic interaction model was proposed for the copper-iron layered double hydroxides, Cu₃Fe-LDHs-yH₂O(y=0-2). Based on density functional theory, the geometry of Cu₃Fe-LDHs-yH₂O was optimized using the CASTEP program. The distribution of NO₃^- and H₂O in the interlayer and the supermolecular interaction between host and guest was investigated by analyzing the geometric parameters, hydrogen-bonding, charge populations and stepwise hydration energy. Results showed that when NO₃^- and H₂O were inserted into the layers of Cu₃Fe-LDHs, there was strong supramolecular interaction between the host layer and the guest, including hydrogen-bonding and electrostatic interaction. Hydrogen-bonding was superior to the electrostatic interaction in the hydration process. The strength of hydrogen bonding was Layer-Anion(L-A) type hydrogen bonding＞Anion-Water(A-W) type hydrogen bonding＞L-A type hydrogen bonding＞Layer-Water(L-W) hydrogen bonding＞ Water-Water(W-W) type hydrogen bonding. In Cu₃Fe-LDHs-yH₂O, the interlayer distance decreased slightly and then increased significantly with an increase in the number of interlayer water molecules. The Cu-O octahedral forms were stretched gradually, because the Jahn-Teller effect of Cu²⁺ increased. The absolute value for the hydration energy decreased gradually with an increase in the number of water molecules. This suggested that the hydration of Cu₃Fe-LDHs reached a definite saturation state. The geometry parameters of Cu₃Fe-LDHs-1H₂O is close to the ideal hexa nal, the metal distortion of layer is the weakest and the stability is the strongest, interlayer distance matchs with the experimental value, so the Cu₃Fe-LDHs-1H₂O is a stable configuration.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

层间水分子含量对铜铁水滑石超分子作用力的影响

English

Influence of Interlayer Water Content on Supermolecular Interaction of Copper-Iron Layered Double Hydroxides

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层间水分子含量对铜铁水滑石超分子作用力的影响

English

Influence of Interlayer Water Content on Supermolecular Interaction of Copper-Iron Layered Double Hydroxides

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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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