Effects of Gas Adsorption on Two Dimensional Metal-hexaiminobenzene Frameworks†

doi:10.7503/cjcu20180768

Abstract

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

CLC Number:

O647

TrendMD:

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

Figures/Tables 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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