二维金属-六亚氨基苯框架材料的气体吸附效应

doi:10.7503/cjcu20180768

摘要/Abstract

摘要：

利用密度泛函理论研究了气体分子(NH₃, H₂O, H₂S, NO₂)吸附在二维M₃(HIB)₂(M=Ni, Cu; HIB为六亚氨基苯)薄膜上体系的几何结构和电子结构的变化. 结果表明, 2种薄膜对气体分子的响应不同. 其中NH₃, H₂O和H₂S在M₃(HIB)₂薄膜表面的吸附较弱, 主要与薄膜的亚氨基形成氢键, 吸附能均小于-0.36 eV, 吸附对体系电子性质的影响很小. 但是 NO₂分子在薄膜表面形成化学吸附, 吸附能在-0.65~-1.72 eV范围内. 吸附NO₂分子使其电子结构发生明显改变, 如Cu₃(HIB)₂在费米能级处打开带隙, 由金属性质转变为半导体性质. 这是由于NO₂分子的p_z轨道与金属原子$d_{z}^{2}$ 轨道发生了强烈的轨道杂化. 此外, 研究发现高浓度的NO₂分子吸附能够使Ni₃(HIB)₂薄膜由非磁性变为磁性体系, 由普通金属性质变为半金属性质; 而高浓度的NO₂分子使Cu₃(HIB)₂薄膜由金属性质变为半导体性质, 薄膜电导率降低.

关键词: 金属有机框架材料, 表面吸附, 电子结构, 半金属

Abstract:

The effects of gas molecules(NH₃, H₂O, H₂S, and NO₂) adsorption on two-dimensional M₃(HIB)₂(M=Ni, Cu; HIB=hexaiminobenzene) surfaces on the geometric structure and electronic structure were studied via the first-principles theory. The results show that there are different responses of two thin films to four gas molecules. The adsorptions of NH₃, H₂O and H₂S on the surface of M₃(HIB)₂ thin films are weak and the gas molecules tend to form hydrogen bond with the imino group of the film with an adsorption energy that is less than -0.36 eV. These weak adsorptions just slightly affect the electronic properties of the adsorbed films. In contrast, NO₂ molecules are strongly chemisorbed on the two films with adsorption energy in the region of -0.65—-1.72 eV. The adsorption of NO₂ molecules evidently changes the electronic structures of the film. For instance, there is a band gap opening at the Fermi level for Cu₃(HIB)₂ film and it changes from metal to semiconductor. This feature originates from the strong orbital hybridization between NO₂ p_z and metal $d_{z}^{2}$ orbitals. Furthermore, when NO₂ molecules with a high concentration are adsorbed on M₃(HIB)₂ surface, the Ni₃(HIB)₂ film transits from nonmagnetic to magnetic states and changes from metallic to half-metallic property, while the Cu₃(HIB)₂ film converts to semiconductor, suggesting a potential application of M₃(HIB)₂ films in gas sensing.

Key words: Metal-organic framework, Surface adsorption, Electronic structure, Half-metal

中图分类号:

O647

TrendMD:

孙国栋, 王雪, 江国亮, 徐之勇, 刘洪梅. 二维金属-六亚氨基苯框架材料的气体吸附效应. 高等学校化学学报, 2019, 40(5): 995.

SUN Guodong,WANG Xue,JIANG Guoliang,XU Zhiyong,LIU Hongmei. Effects of Gas Adsorption on Two Dimensional Metal-hexaiminobenzene Frameworks^†. Chem. J. Chinese Universities, 2019, 40(5): 995.

图/表 9

Fig.1 Lattice structure(A) of 2D M3(HIB)2 films(M=Ni, Cu) and the side views of Ni3(HIB)2 (B) and Cu3(HIB)2(C)

Fig.2 Band structures(A, C) and the projected density of states(PDOS)(B, D) of free-standing Ni3(HIB)2(A, B) and Cu3(HIB)2(C, D) films along the high symmetry directionsThe Fermi level is marked by dashed lines.

Fig.3 Top(A1—F1) and side(A2—F2) views of the adsorption structures of four molecules on Ni3(HIB)2 surfaceFour adsorption sites are denoted byⅠ, Ⅱ, Ⅲ, and Ⅳ in (A1). ⅢNi—O and ⅢNi—N denote that metal Ni binds with O or N atom in NO2 molecule. The hydrogen bonds are noted by red dotted lines. (A1, A2) NH3; (B1, B2) H2O; (C1, C2) H2S; (D1, D2) NO2; (E1, E2) NO2(ⅢNi—O); (F1, F2) NO2(ⅢNi—N).

Table 1 Distance dH—X between the hydrogen atom and the adsorbed atoms X(X=N for NH3, O for H2O, O for NO2)*

Species	d_H—X/nm	E_ads/eV	ΔQ/e
NH₃(Ⅱ)	0.247	-0.35	-0.011
H₂O(Ⅰ)	0.229	-0.36	0.005
H₂S(Ⅰ)	0.259	-0.27	0.008
NO₂(Ⅰ)	0.179	-1.72	0.847
NO₂(Ⅲ_Ni—O)	—	-0.83	0.544
NO₂(Ⅲ_Ni—N)	—	-0.73	0.468

Fig.4 Band structures(A—E) of the gas-adsorbed Ni3(HIB)2 films and PDOS of NO2-adsorbed Ni3(HIB)2 film with ⅢNi—O configuration(F) (A) NH3; (B) H2O; (C) H2S; (D) NO2(Ⅰ); (E) NO2(ⅢNi—O). The Fermi level is marked by dashed lines.

Fig.5 Top(A1—F1) and side(A2—F2) views of the adsorption structures of four molecules on Cu3(HIB)2 surface(A1, A2) NH3; (B1, B2) H2O; (C1, C2) H2S; (D1, D2) NO2; (E1, E2) NO2(ⅢCu—O) ; (F1, F2) NO2(ⅢCu—N). Four adsorption sites are denoted by Ⅰ, Ⅱ, Ⅲ, and Ⅳ in (A). ⅢCu—O and ⅢCu—N denote the adsorption configurations that Cu binds with O or Ni atom in NO2 molecule. The hydrogen bonds are noted by red dotted lines.

Table 2 Distance dH—X between the hydrogen atom and the adsorbed atoms X(X=N for NH3, O for H2O, O for NO2)*

Species	d_H—X/nm	E_ads/eV	ΔQ/e
NH₃(Ⅰ)	0.249	-0.32	-0.010
H₂O(Ⅱ)	0.245	-0.34	0.008
H₂S(Ⅱ)	0.279	-0.27	0.010
NO₂(Ⅰ)	0.183	-1.41	0.806
NO₂(Ⅲ_Cu—O)	—	-0.71	0.573
NO₂(Ⅲ_Cu—N)	—	-0.65	0.504

Fig.6 Band structures(A—E) of the gas-adsorbed Cu3(HIB)2 film and PDOS(F) of NO2-adsorbed Cu3(HIB)2 film with ⅢCu—O configuration (A) NH3; (B) H2O; (C) H2S; (D) NO2(Ⅰ); (E) NO2(ⅢCu—O); (F) NO2(ⅢCu—O). The Fermi level is marked by dashed lines.

Fig.7 Band structures(A, C) and PDOS(B, D) of the NO2-adsorbed Ni3(HIB)2(A, B) and Cu3(HIB)2(C, D)

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