Molecular Dynamics Simulation of Adsorption of Methylene Blue by Graphene Oxide †

doi:10.7503/cjcu20190392

Abstract

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

CLC Number:

O641

TrendMD:

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

Figures/Tables 11

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

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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