Adsorption of Phenolic Organic Pollutants on Graphene Oxide: Molecular Dynamics Study

doi:10.15541/jim20190377

Abstract

Abstract:

In this work, molecular dynamics (MD) simulations were applied to address the major concerns about the independent and competitive adsorption processes of phenolic organic pollutants (POPs) on the graphene oxide (GO) in aqueous solution. Phenol, α-naphthol and 4-octyl-phenol were adopted as representatives of POPs and their adsorption energies were calculated, which followed an order of 4-octyl-phenol (41.34 kJ/mol)>α-naphthol (33.23 kJ/mol)> phenol (19.31 kJ/mol). The simulation results showed that hydrophobic properties of POPs were recognized as the driving force for their adsorption behaviors. Moreover, van der Waals interaction, electrostatic interaction, as well as hydrogen bonds, may also improve the adsorption capacity of GO towards POPs. The competitive adsorption process revealed that in addition to the direct adsorption onto the GO surface, the molecular aggregation may be another indirect adsorption way existed in the mixed system. Understanding the interaction between GO and POPs in aqueous solution is critical to the design and application of graphene-based materials and our findings are believed to contribute further theoretical basis to the engineering treatment of POPs-containing waste water.

Key words: phenolic organic pollutants, graphene oxide, competitive adsorption, molecular dynamics simulation

CLC Number:

X703

ZHAO Chaofeng, JIN Jiaren, HUO Yingzhong, SUN Lu, AI Yuejie. Adsorption of Phenolic Organic Pollutants on Graphene Oxide: Molecular Dynamics Study[J]. Journal of Inorganic Materials, 2020, 35(3): 277-283.

Figures/Tables 11

Fig. 1 (a) GO model, (b) structures of phenol, α-naphthol and 4-octyl-phenol molecules in MD simulations, and (c) initial configuration of phenol (green), α-naphthol (purple) and 4-octyl-phenol (yellow) molecules in the competitive system

Fig. 2771 Initial configurations of (a) phenol, (b) α-naphthol and (c) 4-octyl-phenol molecules in the independent system

Fig. 2 Equilibrium structures of (a) phenol, (b) α-naphthol and (c) 4-octyl-phenol molecules adsorbed on GO surface

Fig. 3 Snapshots of competitive system from simulation process at different time Phenol, α-naphthol and 4-octyl-phenol molecules are shown as green, purple and yellow molecules, respectively. Water molecules are not shown to highlight the configuration

Fig. 4 Distances of centers of mass between GO and each (a) phenol, (b) α-naphthol and (c) 4-octyl-phenol molecule, as function of time

Fig. 5 (a) Interaction energies between different POPs molecules in competitive system; The maximal cluster size of POPs in (b) independent and (c) competitive systems, respectively; The radial distribution functions (g(r)) and coordination numbers (n(r)) of POPs in (d) independent and (e) competitive systems, respectively

Fig. 6 (a) Potential of mean force of POPs molecules; The interaction energies between GO and POPs molecules in (b) independent and (c) competitive systems, respectively; The hydrophobic areas of POPs molecules in (d) independent and (e) competitive systems, respectively; The hydrogen bonds between GO and POPs molecules in (f) independent and (g) competitive systems, respectively

Table S1 Interaction energies between GO and POPs molecules in independent system at different periods

Time/ns	Phenol/(kJ•mol^-1)			α-naphthol/(kJ•mol^-1)			4-octyl-phenol/(kJ•mol^-1)
Time/ns	Coulomb interaction	L-J Potential	Total	Coulomb interaction	L-J Potential	Total	Coulomb interaction	L-J Potential	Total
20	-44.10	-866.02	-910.12	-317.12	-1172.76	-1489.87	-195.98	-1311.17	-1507.15
40	-174.71	-877.44	-1052.16	-388.46	-1276.89	-1665.35	-162.60	-1359.01	-1521.60
60	-124.19	-897.25	-1021.45	-405.37	-1243.64	-1649.01	-96.07	-1340.12	-1436.19
80	-167.61	-864.44	-1032.05	-358.80	-1313.62	-1672.42	-125.83	-1454.64	-1580.47
100	-237.23	-880.63	-1117.87	-251.36	-1338.97	-1590.33	-62.78	-1344.93	-1407.71

Table S2 Interaction energies between GO and POPs molecules in competitive system at different periods

Time/ns	Phenol/(kJ•mol^-1)			α-naphthol/(kJ•mol^-1)			4-octyl-phenol/(kJ•mol^-1)
Time/ns	Coulomb interaction	L-J Potential	Total	Coulomb interaction	L-J Potential	Total	Coulomb interaction	L-J Potential	Total
20	-160.11	-448.40	-608.51	-235.85	-914.54	-1150.38	-71.34	-980.56	-1051.90
40	-240.86	-533.62	-774.48	-288.30	-960.43	-1248.73	-182.74	-928.42	-1111.16
60	-334.12	-573.27	-907.39	-354.11	-993.34	-1347.46	-152.72	-1013.83	-1166.55
80	-215.40	-672.38	-887.78	-363.20	-959.82	-1323.02	-201.10	-912.11	-1113.20
100	-214.74	-674.05	-888.79	-305.51	-1069.33	-1374.84	-179.30	-918.63	-1097.92

Fig. S2 SASAs of (a) phenol, (b) α-naphthol and (c) 4-octyl-phenol molecules in the independent system

Fig. S3 SASAs of (a) phenol, (b) α-naphthol and (c) 4-octyl-phenol molecules in the competitive system

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