碱土金属Mg外掺杂硼笼B40Mg6的储氢性能

doi:10.7503/cjcu20180780

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (3): 473.doi: 10.7503/cjcu20180780

碱土金属Mg外掺杂硼笼B₄₀Mg₆的储氢性能

周晓锋, 周彦冰, 唐春梅()

河海大学理学院, 南京 210098

收稿日期:2019-11-19 出版日期:2019-01-15 发布日期:2019-01-15
作者简介:
联系人简介: 唐春梅, 女, 博士, 教授, 主要从事纳米材料的物理化学特性研究. E-mail: tcmnj@163.com
基金资助:
中央高校基本科研业务费专项资金(批准号: 2016B01914, 2018B19414)、江苏省水利科技创新项目(批准号: 20155087)、江苏省自然科学基金(批准号: BK20161501)和江苏省六大人才高峰项目(批准号: 2015-XCL-010) 资助.

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

ZHOU Xiaofeng, ZHOU Yanbing, TANG Chunmei^*()

College of Science, Hohai Univeisity, Nanjing 210098, China

Received:2019-11-19 Online:2019-01-15 Published:2019-01-15
Contact: TANG Chunmei E-mail:tcmnj@163.com
Supported by:
† Supported by the Fundamental Research Funds for the Central Universities, China(Nos.2016B01914, 2018B19414), the Water Science Innovation Project of Jiangsu Province, China(No.20155041612), the Natural Science Foundation of Jiangsu Province, China(No.BK20161501) and the Six Talent Peaks Project in Jiangsu Province, China(No.2015-XCL-010).

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

TrendMD:

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. 高等学校化学学报, 2019, 40(3): 473.

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

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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