Dielectric Constant of Confined Water in a Bilayer Graphene Oxide Nanosystem

doi:10.7503/cjcu20210614

Abstract

Abstract:

The properties of the dielectric constant of water in confined systems vary greatly， which has a significant impact on its applications in electrochemistry， membrane treatment and energy storage. For example， in graphene pores， the physical properties are affected by factors such as membrane pore size and degree of oxidation， but few studies have been conducted in this regard. Therefore， in order to further understand the influence of pore size and oxidation degree on the dielectric properties， molecular dynamics simulation method was used to explore the dielectric behavior of water in the double-layer graphene nanochannels with different pore size and oxidation degree. At the same time， as a local diagonal tensor in a constrained system， the dielectric constant can be defined in two directions parallel to and orthogonal to the wall. The experimental results show that water molecules exhibit a greater spatial and orientation order in a narrow environment， and the dielectric constant of confined water decreases with the decrease of the space of the nanochannels. With the increase of oxidation degree， the influence of the wider spacing on the dielectric constant is greater than that of the narrower nanochannel. For the widest channels（d=1.2 nm）， the dielectric constant of the graphene bilayer decreased with the increase of oxidation degree， while for the relatively narrow channels（d=0.6 nm， 0.9 nm）， the dielectric behavior showed a non-monotonic trend. To understand the physics behind this， we calculated the number of hydrogen bonds in the three nanochannels. The results showed that the number of hydrogen bonds and the dynamic stability（corresponding to the fastest decay rate） were the lowest at 1.2 nm， indica?ting that the water molecules were more unstable and disordered in the large nanoscale than in the 0.6 nm and 0.9 nm nanoscale. This work emphasizes the significant importance of regulating the interlamellar distance for understanding the permeance of water and its transport mechanism and provides fundamental theories for the preparation of advanced materials based on graphene oxide（GO） and their application in water treatment.

Key words: Graphene oxide, Dielectric constant, Hydrogen bond dipole wave, Molecular dynamics simulation

CLC Number:

O647.11

TrendMD:

HU Bo, ZHU Haochen. Dielectric Constant of Confined Water in a Bilayer Graphene Oxide Nanosystem[J]. Chem. J. Chinese Universities, 2022, 43(2): 20210614.

Figures/Tables 7

Fig.1 3D image of a nanochannel formed by two layers of graphene flanked by two storage poolsThe O and H atoms are represented by yellow and blue spheres, respectively.

Table 1 LJ potential and charge of the atoms used in the simulation*

Atom	σ/nm	ε/（kJ?mol^-1）	q/e
O_w	0.3159	3.2436	0
H_w	0	0	0.5564
O_h	0.3070	0.7116	-0.585
H_h	0	0	0.435
C（C—C）	0.3851	0.4395	0
C_h	0.3550	0.2930	0.150

Fig.2 Distribution of the ratio of the radial permittivity[ε(r)] of confined aqueous solution to that of water in the bulk system with the degree of oxidation in the double?layer graphene channels with d=0.6 nm(A), 0.9 nm(B) and 1.2 nm(C), the ratio of their mean radial permittivity(εavg) to εbw with the degree of oxidation(D)

Fig.3 Radial profile of the water density as a function of various oxidation concentration in the double?layer graphene channels with d=0.6 nm(A), 0.9 nm(B) and 1.2 nm(C)

Fig.4 Probability of angular distribution of water molecules for PG nanochannels(A) and GO nanochannels with a size of 0.6 nm(B), 0.9 nm(C) and 1.2 nm(D)

Fig.5 Schematic diagram of angle(θ) between the dipole vector of water molecules(μ?H2O) and the normal of the graphene surface plane(N?)

Table 2 Number of hydrogen bond per water molecule between GO substrate and water and their corresponding dipolar relaxation time(τHB) for both PG and GO nanochannels with various oxidation degree

d/nm	PG		GO?10%		GO?20%		GO?30%		GO?35%		GO?40%
d/nm	n_HB/H₂O	τ_HB/ps	n_HB/H₂O	τ_HB/ps	n_HB/H₂O	τ_HB/ps	n_HB/H₂O	τ_HB/ps	n_HB/H₂O	τ_HB/ps	n_HB/H₂O	τ_HB/ps
0.6	0.25	3.23	0.37	4.12	0.33	3.71	0.51	5.14	0.53	5.25	0.55	5.35
0.9	0.10	1.21	0.23	1.84	0.30	2.79	0.42	3.58	0.38	3.33	0.44	3.98
1.2	0.04	0.72	0.10	1.21	0.24	2.10	0.30	2.75	0.35	3.19	0.39	3.71

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