A density functional theory （DFT） study has been carried out for [Zn-1AI（OH2）n＋6（OH）2n-2]^3＋ （n=3-6） and [Znn-1AI（OH2）2n-2（OH）2n-2]^3＋ （n = 7） clusters, which include the basic structural information ...A density functional theory （DFT） study has been carried out for [Zn-1AI（OH2）n＋6（OH）2n-2]^3＋ （n=3-6） and [Znn-1AI（OH2）2n-2（OH）2n-2]^3＋ （n = 7） clusters, which include the basic structural information of the brucite-like lattice structure of Zn/Al layered double hydroxides （LDHs） with Zn/AI molar ratio （R） in the range 2-6, in order to understand the effect of the Zn/Al ratio on the structure and stability of binary Zn/Al LDHs. Based on systematic calculations of the geometric parameters and formation energies of the cluster models, it was found that it is possible for Zn^2＋ and Al^3＋ cations to replace Mg^2＋ isomorphously in the brucite-like structure with different R values, resulting in differences in microstructure of the clusters and unit cell parameter a of the Zn/Al LDHs. Analysis of the geometry and bonding around the trivalent Al^3＋ or divalent Zn^2＋ cations reveals that Al^3＋ plays a more significant role than Zn^2＋ in determining the microstructure properties, formation and bonding stability of the corresponding ZnRAl clusters when R〈5, while the influence of Zn^2＋ becomes the dominant factor in the case of R〉 5. These findings are in good agreement with experiments. This work provides a detailed electronic-level understanding of how the composition of cations affects the microstructure and stability of Zn-containing binary LDH layers.展开更多
基金supported by the National Natural Science Foundation of China and the Program for Changjiang Scholars and Innovative Research Teams in Universities (Grant No.IRT0406)
文摘A density functional theory （DFT） study has been carried out for [Zn-1AI（OH2）n＋6（OH）2n-2]^3＋ （n=3-6） and [Znn-1AI（OH2）2n-2（OH）2n-2]^3＋ （n = 7） clusters, which include the basic structural information of the brucite-like lattice structure of Zn/Al layered double hydroxides （LDHs） with Zn/AI molar ratio （R） in the range 2-6, in order to understand the effect of the Zn/Al ratio on the structure and stability of binary Zn/Al LDHs. Based on systematic calculations of the geometric parameters and formation energies of the cluster models, it was found that it is possible for Zn^2＋ and Al^3＋ cations to replace Mg^2＋ isomorphously in the brucite-like structure with different R values, resulting in differences in microstructure of the clusters and unit cell parameter a of the Zn/Al LDHs. Analysis of the geometry and bonding around the trivalent Al^3＋ or divalent Zn^2＋ cations reveals that Al^3＋ plays a more significant role than Zn^2＋ in determining the microstructure properties, formation and bonding stability of the corresponding ZnRAl clusters when R〈5, while the influence of Zn^2＋ becomes the dominant factor in the case of R〉 5. These findings are in good agreement with experiments. This work provides a detailed electronic-level understanding of how the composition of cations affects the microstructure and stability of Zn-containing binary LDH layers.
