氧化石墨烯吸附亚甲基蓝的分子动力学模拟

doi:10.7503/cjcu20190392

摘要/Abstract

摘要：

采用分子动力学方法研究了亚甲基蓝在不同氧化度的氧化石墨烯表面的吸附行为及其动力学性质, 从微观角度讨论了亚甲基蓝由体相到氧化石墨烯表面的吸附过程及主要作用机制, 并通过亚甲基蓝分子动力学性质解释了氧化石墨烯的氧化度和含氧官能团类型对吸附行为的影响. 结果表明, 吸附过程中, 亚甲基蓝主要受氧化石墨烯表面含氧官能团的静电作用, 以近似垂直氧化石墨烯表面的方向进入, 并以平行的方式吸附于氧化石墨烯表面; 亚甲基蓝不易脱离高氧化度氧化石墨烯的吸附位点; 吸附平衡过程中, 相对于低氧化度的氧化石墨烯, 高氧化度氧化石墨烯对亚甲基蓝的束缚性更强, 同时与亚甲基蓝间相互作用更强; 含氧官能团中的环氧基与亚甲基蓝间的作用势能更强, 且羟基能够与亚甲基蓝间形成氢键结构, 共同保障了亚甲基蓝吸附层的稳定性.

关键词: 氧化石墨烯, 亚甲基蓝, 吸附机制, 分子动力学

Abstract:

The adsorption distribution and kinetic properties of methylene blue on graphene oxide surfaces with different oxidation degrees were studied by molecular dynamics method. The adsorption process and main mechanism of methylene blue from aqueous solution to graphene oxide surface were proposed from the trajectory displacement of methylene blue, and the reasons for the adsorption stability were explained. In the adsorption process, methylene blue is mainly attracted by the electrostatic attraction of oxygen-containing functional groups on the graphene oxide surface and enters the graphene oxide surface vertically, and is concentra-ted on the surface of the graphene oxide in a parallel manner firstly. Methylene blue is not easily desorbed from the adsorption site of high oxidation degree graphene oxide secondly. In the adsorption equilibrium process, comparing with the low oxidation degree graphene oxide, the interaction between the high oxidation degree graphene oxide and methylene blue is enhanced and more hydrogen bonds are formed to bind the methylene blue molecules movement in the adsorption layer, so that the interface between the graphene oxide and the methy-lene blue solution forms a stable adsorption layer.

Key words: Graphene oxide, Methylene blue, Adsorption mechanism, Molecular dynamics

中图分类号:

O641

TrendMD:

马莹,王恬,张恒. 氧化石墨烯吸附亚甲基蓝的分子动力学模拟. 高等学校化学学报, 2019, 40(12): 2534.

Ying MA,Tian WANG,Heng ZHANG. Molecular Dynamics Simulation of Adsorption of Methylene Blue by Graphene Oxide ^†. Chem. J. Chinese Universities, 2019, 40(12): 2534.

图/表 11

Table 1 Force field parameters for graphene oxide and methylene blue used in this work*

Site	Graphene oxide			Site	Methylene blue
Site	σ/nm	ε/(kJ·mol^-1)	q/e	Site	σ/nm	ε/(kJ·mol^-1)	q/e
C(graphene)	0.355	0.293	0	N(in N—CH₃)	0.325	0.711	0.216
C(—COO^-)	0.375	0.439	0.700	C(in N—CH₃)	0.380	0.209	-0.323
O(—COO^-)	0.296	0.879	-0.900	H(in N—CH₃)	0.250	0.125	0.137
C(—C—O—)	0.350	0.276	0.196	S	0.355	1.046	-0.689
O(^-O^-)	0.290	0.586	-0.393	N(in middle)	0.325	0.711	-0.226
O(—OH)	0.307	0.711	-0.592
H(—OH)	0	0	0.329

Fig.1 Chemical structures of methylene blue(A), GO20 structure diagram(B) and simulation system initial model on let panel(C)

Fig.2 Adsorption of methylene blue on graphene oxide of GO10(A), GO20(B) and GO30(C) systems The water molecules in the system are removed for clarity.

Fig.3 Trajectory displacement of methylene blue in the z direction changes with time evolution(A), local amplifications of trajectory displacement (A)(B) and the change of potential energy between amino groups of methylene blue and GO30 graphene oxide with time evolution(C)

Fig.4 Side view of partial enlargements of the trajectory displacement of a methylene blue in the z direction(A), the opposite side view of a diagram(B), three-dimensional spatial coordinates of a methylene blue adsorption process change with time of GO10(C), GO20(D) and GO30(E) systems

Table 2 Diffusion coefficient(D) and residence time(τr) of methylene blue near graphene oxide surface

System	10⁵D/(cm²·s^-1)	τ_r/ns
GO10	0.03±0.01	3.31
GO20	0.007±0.005	4.94
GO30	0.0057±0.004	6.16

Fig.5 MSD-time curves(A) and the residence time correlation functions(B) of methylene blue near graphene oxide surface

Fig.6 Potential energy between methylene blue and graphene oxide after adsorption stabilization

Fig.7 Hydrogen bond number distribution between methylene blue and graphene oxide in adsorption layer Inset: the microscopic structure of hydrogen bonds.

Fig.8 Adsorption of methylene blue on graphene oxide of GO20-O(A), GO20-OH(B) and GO20-COO system(C) The water molecules in the system are removed for clarity.

Fig.9 Potential energy between methylene blue and graphene oxide with different oxygen-containing functional groups after adsorption stabilization

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