碱土金属Mg外掺杂硼笼B40Mg6的储氢性能

doi:10.7503/cjcu20180780

摘要/Abstract

摘要：

对外掺杂碱土金属Mg的B₄₀硼笼的储氢性能进行了密度泛函理论研究. 结果表明, B₄₀笼含有2个六元环与4个七元环. 多个Mg原子对B₄₀笼进行外掺杂时不会发生成簇现象, 有利于进一步储氢. Mg原子外掺杂的B₄₀笼对H₂分子的平均吸附能介于物理吸附与化学吸附之间(0.1~0.8 eV). 体系的储氢密度达到7.60%(质量分数). 储氢结构能在常温常压下释放H₂分子, 因此, Mg原子外掺杂的B₄₀笼比Mg合金具有更好的储氢性能.

关键词: B₄₀, B₄₀Mg, 储氢, 密度泛函理论

Abstract:

The density functional theory(DFT) was used to study the hydrogen storage capacity of alkaline earth metal Mg exohedral doped B₄₀ cage structure. There are two B₆ hexagon rings and four B₇ heptagon rings in the B₄₀ cage. The clustering of the Mg atoms on the surface of the B₄₀ cage can be effectively avoided, which should be benefit for the further hydrogen storage. The average adsorption energy of H₂ molecules is intermediate between physical adsorption and chemisorption. The hydrogen gravimetric density of B₄₀Mg₆ is 7.60%(mass fraction), which far exceed the target of 5.5%(mass fraction) by the year 2017 specified by the US Department of Energy. The hydrogen adsorbed structure tends to desorb hydrogen under the near-ambient conditions. Therefore, the Mg atom exohedral doped B₄₀ cage has better hydrogen storage capacity than Mg alloy. This research can provide a very important theoretical basis for the development of hydrogen storage materials.

Key words: B₄₀, B₄₀Mg, Hydrogen storage, Density functional theory(DFT)

中图分类号:

O641.3

周晓锋, 周彦冰, 唐春梅. 碱土金属Mg外掺杂硼笼B₄₀Mg₆的储氢性能[J]. 高等学校化学学报, 2019, 40(3): 473-480.

ZHOU Xiaofeng,ZHOU Yanbing,TANG Chunmei. Hydrogen Storage Capacity of the Alkaline Earth Metal Mg Exohedral Doped Boron Cage B₄₀M $g 6 †$ [J]. Chemical Journal of Chinese Universities, 2019, 40(3): 473-480.

图/表 8

Fig.1 Cage structure of B40H-1 and H-2 represent hexagonal ring and heptagonal ring, respectively.

Fig.2 Mg atom located at H-1-inside, H-2-inside, the cage center, H-1-outside, H-2-outside and the structure of B40Mg6

Fig.3 Initial and optimized structures of the B40 cage adsorbed by 2—4 Mg atoms outside of the hexagonal ring and heptagonal ring

Table 1 Eab of the Mg atom outside of the hexagonal ring(H-1-outside) and the heptagonal ring(H-2-outside) of the B40 cage

Site	E_ab/eV
Site	B₄₀Mg	B₄₀Mg₂	B₄₀Mg₃	B₄₀Mg₄
H-1-outside	4.84	1.86	1.62	1.55
H-2-outside	3.81	1.93	1.63	1.52

Fig.4 Structures of B40Mg and B40Mg-nH2(n=1—5) with the Mg atom outside of the hexagonal ring(A) and heptagonal ring(B) and B40(Mg-4H2)6 structure with each Mg atom adsorbing four H2 molecules(C)

Table 2 Eb of the Mg atom to the hexagonal ring(H-1-outside) and the heptagonal ring(H-2-outside) of the B40 cage and the Ead of B40Mg-nH2(n=1—5)

Site	E_b/eV	E_ad/eV					E_r/eV
Site	E_b/eV	1H₂	2H₂	3H₂	4H₂	5H₂	1H₂	2H₂	3H₂	4H₂	5H₂
H-1-outside	2.58	0.25	0.17	0.16	0.15	0.10	0.15	0.16	0.16	0.16	0.02
H-2-outside	2.57	0.26	0.24	0.22	0.20	0.08	0.16	0.15	0.16	0.17	0.01

Fig.5 PDOS of H2 in B40Mg-H2(A) and B40Mg-2H2(B)

Fig.6 Dynamic structure B40Mg-4H2 with the Mg atom located outside of the hexagonal ring and heptagonal ring of B40 after 5 ps at 77 and 300 K

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碱土金属Mg外掺杂硼笼B₄₀Mg₆的储氢性能

Hydrogen Storage Capacity of the Alkaline Earth Metal Mg Exohedral Doped Boron Cage B₄₀M $g 6 †$

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