Molecular Simulation of Hydrogen Adsorption Performance in Graphene and Carbon Nanotubes

doi:10.3969/j.issn.1006-396X.2022.04.002

Abstract

Abstract:

The adsorption data of hydrogen in graphene,single?walled carbon nanotubes,and multi?walled carbon nanotubes at 293.15 K and 101.30 kPa were measured experimentally.Through the comparison of the data calculated by different force fields under the same conditions, the optimal force fields of the three carbon materials for calculation were selected.On this basis,the hydrogen adsorption data of the three carbon materials at 0~1 000.00 kPa and 77.00~573.15 K were calculated.The results show that the Dreiding force field is the optimal force field to calculate the hydrogen adsorption and storage in graphene,and the Universal force field is the best force field to calculate that in carbon nanotubes.Under given conditions,the hydrogen adsorption and storage capacity of the three materials is ranked as follows:graphene single?walled carbon nanotubes multi?walled carbon nanotubes.The hydrogen storage capacity is closely related to the specific surface area of the material and its weak binding force with hydrogen.The results can provide data and theoretical support for the molecular simulation of hydrogen adsorption and storage in carbon materials as well as hydrogen storage material design.

Key words: Graphene, Carbon nanotubes, Adsorption hydrogen storage performance, Molecular simulation

摘要：

在293.15 K、101.30 kPa的条件下，测定了氢气在石墨烯、单壁碳纳米管和多壁碳纳米管中的储氢密度，对比了同等条件下采用不同力场计算得到的数据，筛选了3种碳材料的最佳计算力场。在此基础上，进一步计算了3种碳材料在0~1 000.00 kPa、77.00~573.15 K条件下的储氢密度。结果表明，Dreiding力场是计算石墨烯吸附储氢密度的最佳力场，Universal力场是计算碳纳米管吸附储氢密度的最佳力场；在给定条件下，3种材料吸附储氢能力强弱排序为石墨烯>单壁碳纳米管>多壁碳纳米管，储氢能力与材料的比表面积及其与氢气的弱结合力紧密相关。该研究结果可为分子模拟碳材料吸附储氢和储氢材料设计提供数据和理论支撑。

关键词: 石墨烯, 碳纳米管, 吸附储氢性能, 分子模拟

CLC Number:

TQ021.2

Mengyao Tang, Tianyi Sun, Jiashu Li, Yan Ding, Jinlong Li. Molecular Simulation of Hydrogen Adsorption Performance in Graphene and Carbon Nanotubes[J]. Journal of Petrochemical Universities, 2022, 35(4): 10-17.

汤梦瑶, 孙天一, 李佳书, 丁延, 李进龙. 石墨烯与碳纳米管氢吸附性能的分子模拟[J]. 石油化工高等学校学报, 2022, 35(4): 10-17.

Figures/Tables 8

Fig.1 Schematic diagram of hydrogen adsorption equilibrium of three carbon?based materials at 293.15 K and 1 000 kPa

Fig.2 Hydrogen adsorption isotherms for three carbon?based materials at 293.15 K and 101.30 kPa

Fig.3 Comparison curves of experimental and simulated values for hydrogen storage and adsorption of three carbon?based materials at 293.15 K and 101.30 kPa

Fig.4 Adsorption isotherms of hydrogen at 77.00 K and 293.15 K

Fig.5 Adsorption isotherms of hydrogen in three carbon?based materials at different temperatures

Table 1 Langmuir and Freundlich adsorption fitting parameters of hydrogen in SWNT at different temperatures

温度/K	Langmuir吸附拟合			Freundlich吸附拟合
温度/K	$q i m$	$K i$	$R 2$	$K F$	$1 n$	$R 2$
77.00	0.978 07	0.660 09	0.544 10	0.765 55	25.342 12	0.922 71
87.00	0.941 92	0.541 09	0.779 28	0.763 90	30.422 88	0.897 58
293.15	0.250 21	0.004 50	0.998 44	0.013 55	2.489 42	0.976 20
373.15	0.215 93	9.573 64×10^-4	0.999 91	9.713 29×10^-4	1.464 43	0.995 43
473.15	0.214 02	2.261 44×10^-4	0.999 89	8.594 98×10^-5	1.125 24	0.999 45
573.15	0.178 90	1.040 03×10^-4	0.999 92	—	—	—

Table 1 Langmuir and Freundlich adsorption fitting parameters of hydrogen in SWNT at different temperatures

温度/K	Langmuir吸附拟合			Freundlich吸附拟合
温度/K	$q i m$	$K i$	$R 2$	$K F$	$1 n$	$R 2$
77.00	0.978 07	0.660 09	0.544 10	0.765 55	25.342 12	0.922 71
87.00	0.941 92	0.541 09	0.779 28	0.763 90	30.422 88	0.897 58
293.15	0.250 21	0.004 50	0.998 44	0.013 55	2.489 42	0.976 20
373.15	0.215 93	9.573 64×10^-4	0.999 91	9.713 29×10^-4	1.464 43	0.995 43
473.15	0.214 02	2.261 44×10^-4	0.999 89	8.594 98×10^-5	1.125 24	0.999 45
573.15	0.178 90	1.040 03×10^-4	0.999 92	—	—	—

Table 2 Langmuir and Freundlich adsorption fitting parameters of hydrogen in MWNT at different temperatures

温度/K	Langmuir吸附拟合			Freundlich吸附拟合
温度/K	$q i m$	$K i$	$R 2$	$K F$	$1 n$	$R 2$
77.00	0.867 51	0.013 23	0.734 10	0.173 37	4.321 89	0.981 73
87.00	0.660 76	0.014 74	0.822 43	0.124 47	4.116 41	0.993 68
293.15	0.520 20	0.001 12	0.997 12	0.003 31	1.553 18	0.999 10
373.15	0.551 97	3.415 38×10^-4	0.999 88	4.226 11×10^-4	1.187 03	0.999 29
473.15	0.992 10	7.595 91×10^-5	0.999 88	9.443 45×10^-5	1.044 70	0.999 87
573.15	1.934 13	2.269 91×10^-5	0.999 95	4.707 59×10^-5	1.013 39	0.999 95

Table 2 Langmuir and Freundlich adsorption fitting parameters of hydrogen in MWNT at different temperatures

温度/K	Langmuir吸附拟合			Freundlich吸附拟合
温度/K	$q i m$	$K i$	$R 2$	$K F$	$1 n$	$R 2$
77.00	0.867 51	0.013 23	0.734 10	0.173 37	4.321 89	0.981 73
87.00	0.660 76	0.014 74	0.822 43	0.124 47	4.116 41	0.993 68
293.15	0.520 20	0.001 12	0.997 12	0.003 31	1.553 18	0.999 10
373.15	0.551 97	3.415 38×10^-4	0.999 88	4.226 11×10^-4	1.187 03	0.999 29
473.15	0.992 10	7.595 91×10^-5	0.999 88	9.443 45×10^-5	1.044 70	0.999 87
573.15	1.934 13	2.269 91×10^-5	0.999 95	4.707 59×10^-5	1.013 39	0.999 95

Fig.6 Isosteric heat of adsorption for hydrogen at 1 000.00 kPa, 77.00 K and 293.15 K

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