Selective Permeation of Gas Molecules through a Two-Dimensional Graphene Nanopore

Citation: SUN Chengzhen, BAI Bofeng. Selective Permeation of Gas Molecules through a Two-Dimensional Graphene Nanopore[J]. Acta Physico-Chimica Sinica, 2018, 34(10): 1136-1143. doi: 10.3866/PKU.WHXB201801301 shu

气体分子在二维石墨烯纳米孔中的选择性渗透特性

孙成珍 ,
白博峰 ^,

.
西安交通大学动力工程多相流国家重点实验室，西安 710049

通讯作者: 白博峰, bfbai@mail.xjtu.edu.cn

基金项目:
国家自然科学基金青年项目(51506166), 国家杰出青年科学基金项目(51425603)和中国博士后科学基金特别资助项目(2016T90915)

国家杰出青年科学基金项目 51425603

中国博士后科学基金特别资助项目 2016T90915

国家自然科学基金青年项目 51506166

摘要: 二维石墨烯纳米孔中气体分子的选择性渗透对多孔石墨烯分离膜非常重要。本文采用分子动力学方法研究了气体分子在氮氢修饰石墨烯纳米孔中的渗透特性，从分子的大小和结构、纳米孔的构型以及分子与石墨烯之间的作用强度等角度阐明了分子出现选择性渗透的原因。结果表明，不同分子的渗透率不同，即H₂O＞H₂S＞CO₂＞N₂＞CH₄。渗透率跟分子的质量和直径以及分子在石墨烯表面上的吸附密度有关；根据气体分子动理学理论，渗透率跟分子质量成反比关系；而分子在石墨烯表面上的高吸附密度对渗透起促进作用。对于H₂O和CH₄分子，分子直径起主导作用；H₂O分子直径最小，其渗透率最大；同理，CH₄分子的渗透率最小。对于H₂S和CO₂分子，H₂S分子的直径较大，但其与石墨烯之间的作用强度较大(吸附密度较高)，导致渗透率较高；对于CO₂和N₂分子，CO₂分子的直径较小，并且与石墨烯之间的作用强度较大，渗透率较高。同时发现，分子在纳米孔中的渗透使得其在石墨烯表面的密度分布极不均匀。纳米孔左右两侧的功能化氮原子使CH₄分子容易从孔两侧区域穿过，而其它分子由于直径较小在纳米孔中心区域穿过的概率最大。分子与石墨烯之间的作用越强，导致分子在石墨烯表面区域内停留的时间越长，最终使其在渗透纳米孔的过程中所经历的时间越长。本文所采用的氮氢修饰石墨烯纳米孔中，分子渗透速率达到~10^-3 mol·s^-1·m^-2·Pa^-1，并且其它分子相对于CH₄分子的选择性也很高，说明基于该类型纳米孔的多孔石墨烯分离膜在天然气处理等工业气体分离领域具有很好的应用前景。

关键词:

English

Selective Permeation of Gas Molecules through a Two-Dimensional Graphene Nanopore

SUN Chengzhen ,
BAI Bofeng ^,

State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an 710049, P. R. China

Corresponding author: BAI Bofeng, bfbai@mail.xjtu.edu.cn

Received Date: 18 December 2017
Accepted Date: 26 January 2018
Revised Date: 15 January 2018
Available Online: 15 October 2018
Fund Project:
The project was supported by the National Natural Science Foundation of China (51506166), China National Funds for Distinguished Young Scientists (51425603) and National Science Foundation for Post-doctoral Scientists of China (2016T90915)

Abstract: Selective molecular permeation through two-dimensional nanopores is of great importance for nanoporous graphene membranes. In this study, we investigate the selective permeation characteristics of gas molecules through a nitrogen-and hydrogen-modified graphene nanopore using molecular dynamics simulations. We reveal the mechanisms of selective molecular permeation from the aspects of molecular size and structure, pore configuration, and interactions between gas molecules and graphene. The results show that the permeances of different molecules are different, and the following order is observed in our study: H₂O > H₂S > CO₂ > N₂ > CH₄. Molecular permeance is related to the molecular size, mass, and molecular density on the graphene surface. The molecular permeation rate is inversely proportional to the molecular mass based on gas kinetic theory, while the molecular density on the graphene surface exerts a positive effect on molecular permeation. The permeance of H₂O molecules is the highest owing to their smallest diameter, while the permeance of CH₄ molecules is the lowest owing to their biggest diameter; in these cases, the molecular size is a dominating factor. For H₂S and CO₂ molecules, the diameters of H₂S molecules are larger than those of CO₂ molecules, but the interactions between H₂S molecules and graphene are stronger, resulting in a stronger permeation ability of H₂S molecules. Between CO₂ and N₂ molecules, CO₂ molecules show higher permeation rates owing to smaller diameters and stronger interactions with graphene. The graphene surface also shows nonuniform molecular density distribution owing to molecular permeation through graphene nanopores. Because of the doped nitrogen atoms, the CH₄ molecules prefer to permeate from the left and right sides of the graphene nanopore, while the other molecules prefer to permeate from the center of the nanopore owing to their small diameters. For the molecules that show stronger interactions with graphene, the molecular density on the graphene surface is higher; accordingly, the residence time on the graphene surface is longer and the experience time period during permeation is also longer. The mechanisms identified in this study can provide theoretical guidelines for the application of graphene-based membranes. In addition, the permeance of gas molecules in the graphene nanopore adopted in this study is on the order of 10^-3 mol·s^-1·m^-2·Pa^-1, and the selectivity of other molecules relative to CH₄ molecules is also high, showing that the membranes based on this type of nanopore can be employed in natural gas processing and other separation industries.

Key words:

1. [1]
  Geim, A. K.; Novoselov, K. S. Nat. Mater. 2007, 6, 183. doi: 10.1038/nmat1849
2. [2]
  Lee, C.; Wei, X. D.; Kysar, J. W.; Hone, J. Science 2008, 321, 385. doi: 10.1126/science.1157996
3. [3]
  雷广平, 刘朝, 解辉.物理化学学报, 2015, 31, 660. doi: 10.3866/PKU.WHXB201501291Lei, G. -P.; Liu, C.; Xie, H. Acta Phys. -Chim. Sin. 2015, 31, 660. doi: 10.3866/PKU.WHXB201501291
4. [4]
  赵胜君, 张伟, 邓会宁, 刘伟.物理化学学报, 2016, 32, 723. doi: 10.3866/PKU.WHXB201512141Zhao, S. -J.; Zhang, W.; Deng, H. -N.; Liu, W. Acta Phys. -Chim. Sin. 2016, 32, 723. doi: 10.3866/PKU.WHXB201512141
5. [5]
  Jiang, D. E.; Cooper, V. R.; Dai, S. Nano Lett. 2009, 9, 4019. doi: 10.1021/nl9021946@proofing
6. [6]
  Kim, H. W.; Yoon, H. W.; Yoon, S. -M.; Yoo, B. M.; Ahn, B. K.; Cho, Y. H.; Shin, H. J.; Yang, H.; Paik, U.; Kwon, S.; et al. Science 2013, 342, 91. doi: 10.1126/science.1236098
7. [7]
  Koenig, S. P.; Wang, L. D.; Pellegrino, J.; Bunch, J. S. Nat. Nanotechnol. 2012, 7, 728. doi: 10.1038/nnano.2012.162
8. [8]
  Li, H.; Song, Z.; Zhang, X.; Huang, Y.; Li, S.; Mao, Y.; Ploehn, H. J.; Bao, Y.; Yu, M. Science 2013, 342, 95. doi: 10.1126/science.1236686
9. [9]
  Sun, C.; Wen, B.; Bai, B. Sci. Bull. 2015, 60, 1807. doi: 10.1007/s11434-015-0914-9
10. [10]
  温伯尧, 孙成珍, 白博峰.物理化学学报, 2015, 31, 261. doi: 10.3866/PKU.WHXB201411271Wen, B. Y.; Sun, C. Z.; Bai, B. F. Acta Phys. -Chim. Sin. 2015, 31, 261. doi: 10.3866/PKU.WHXB201411271
11. [11]
  Sun, C.; Wen, B.; Bai, B. Chem. Eng. Sci. 2015, 138, 616. doi: 10.1016/j.ces.2015.08.049
12. [12]
  Du, H. L.; Li, J. Y.; Zhang, J.; Su, G.; Li, X. Y.; Zhao, Y. L. J. Phys. Chem. C 2011, 115, 23261. doi: 10.1021/jp206258u
13. [13]
  Schrier, J. ACS Appl. Mater. Interf. 2012, 4, 3745. doi: 10.1021/am300867d
14. [14]
  Shan, M.; Xue, Q.; Jing, N.; Ling, C.; Zhang, T.; Yan, Z.; Zheng, J. Nanoscale 2012, 4, 5477. doi: 10.1039/C2NR31402A
15. [15]
  Drahushuk, L. W.; Strano, M. S. Langmuir 2012, 28, 16671. doi: 10.1021/la303468r
16. [16]
  Sun, C.; Boutilier, M. S. H.; Au, H.; Poesio, P.; Bai, B.; Karnik, R.; Hadjiconstantinou, N. G. Langmuir 2014, 30, 675. doi: 10.1021/la403969g
17. [17]
  Wen, B.; Sun, C.; Bai, B. Phys. Chem. Chem. Phys. 2015, 17, 23619. doi: 10.1039/c5cp03195h
18. [18]
  Liu, H.; Dai, S.; Jiang, D. Nanoscale 2013, 5, 9984. doi: 10.1039/c3nr02852f
19. [19]
  Wu, T.; Xue, Q.; Ling, C.; Shan, M.; Liu, Z.; Tao, Y.; Li, X. J. Phys. Chem. C 2014, 118, 7369. doi: 10.1021/jp4096776
20. [20]
  Hauser, A. W.; Schwerdtfeger, P. Phys. Chem. Chem. Phys. 2012, 14, 13292. doi: 10.1039/c2cp41889d
21. [21]
  Celebi, K.; Buchheim, J.; Wyss, R. M.; Droudian, A.; Gasser, P.; Shorubalko, I.; Kye, J. -I.; Lee, C.; Park, H. G. Science 2014, 344, 289. doi: 10.1126/science.1249097
22. [22]
  Stuart, S. J.; Tutein, A. B.; Harrison, J. A. J. Chem. Phys. 2000, 112, 6472. doi: 10.1063/1.481208
23. [23]
  Lei, G.; Liu, C.; Xie, H.; Song, F. Chem. Phys. Lett. 2014, 599, 127. doi: 10.1016/j.cplett.2014.03.040
24. [24]
  Chae, K.; Violi, A. J. Chem. Phys. 2011, 134, 044537. doi: 10.1063/1.3512918
25. [25]
  Jorgensen, W. L.; Chandrasekhar, J.; Madura, J. D.; Impey, R. W.; Klein, M. L. J. Chem. Phys. 1983, 79, 926. doi: 10.1063/1.445869
26. [26]
  Liu, H.; Chen, Z.; Dai, S.; Jiang, D. -E. J. Solid State Chem. 2015, 224, 2. doi: 10.1016/j.jssc.2014.01.030
27. [27]
  http://www.wiredchemist.com/chemistry/data/bond_energies_lengths.html(accessed on May 3, 2017).
28. [28]
  Harris, J. G.; Yung, K. H. J. Phys. Chem. 1995, 99, 12021. doi: 10.1021/j100031a034
29. [29]
  Kamath, G.; Lubna, N.; Potoff, J. J. J. Chem. Phys. 2005, 123, 124505. doi: 10.1063/1.2049278
30. [30]
  Sun, C.; Bai, B. Phys. Chem. Chem. Phys. 2017, 19, 3894. doi: 10.1039/c6cp06267a
31. [31]
  Sun, C.; Bai, B. Appl. Therm. Eng. 2017, 116, 724. doi: 10.1016/j.applthermaleng.2017.02.002

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

气体分子在二维石墨烯纳米孔中的选择性渗透特性

通讯作者: 白博峰, bfbai@mail.xjtu.edu.cn

English

Selective Permeation of Gas Molecules through a Two-Dimensional Graphene Nanopore

Corresponding author: BAI Bofeng, bfbai@mail.xjtu.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

气体分子在二维石墨烯纳米孔中的选择性渗透特性

通讯作者: 白博峰, bfbai@mail.xjtu.edu.cn

English

Selective Permeation of Gas Molecules through a Two-Dimensional Graphene Nanopore

Corresponding author: BAI Bofeng, bfbai@mail.xjtu.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

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