Grand Canonical Monte Carlo Simulation Study of Water Adsorption Behavior and Isosteric Adsorption Heat in Carbon Nanotubes

doi:10.19596/j.cnki.1001-246x.8692

Abstract

Abstract:

In this work, water adsorbed in single-walled carbon nanotube (SWCNT) is simulated by the Grand Canonical Monte Carlo (GCMC) method. The effects of pore length, pore size and surface strength on water adsorption behaviors at 298 K are systematically studied, via the characterization of isotherms, local density distribution and isosteric heat. There are hysteresis loops observed for water adsorbed and desorbed in SWCNTs with relatively large pore radii (PR=0.8, 1.0 nm), and the hysteresis loop disappears as the pore radius decreases to 0.55 nm. In addition, the water molecule packing manners are in the arrangement form of single chain, double helix chain and water clusters due to the pore size effects. When the pore length is in the range of 4~8 nm, the initial adsorption pressure becomes smaller and smaller as the pore length increases, but this effect rule gradually disappears with increasing pore length to 10 nm. Finally, the initial pressure of water adsorption decreases with surface strength; and when surface strengths are 20, 28, 32 K, the capillary evaporation phase transitions completed instantaneously. While the surface strength increases to 40 K, the capillary evaporation phase transition is shown gradually desorbed steps. As surface strengths increased from 20 K to 40 K, the isosteric adsorption heat at the pressure points of capillary condensation phase transition is 127.47, 117.98, 84.04, 59.16 kJ·mol^-1, respectively.

Key words: carbon nanotubes, adsorption, Monte Carlo simulation, isosteric adsorption heat, phase change

CLC Number:

TQ021.2

Chen LIU, Zhongjun LIU, Minghui ZHAO, Qingbo AO. Grand Canonical Monte Carlo Simulation Study of Water Adsorption Behavior and Isosteric Adsorption Heat in Carbon Nanotubes[J]. Chinese Journal of Computational Physics, 2024, 41(2): 203-213.

Figures/Tables 9

Fig.1 Schematic diagram of adsorption system

Table 1 Potential model parameters used in the GCMC simulations

Molecule		Molecule Parameters
Carbon^[23]		σ/nm	(ε/k_B)/k	ρ_s/nm^-2
Carbon^[23]		0.34	28.0	38.2
Water^[21]		σ/nm	(ε/k_B)/k	q/e
	O	0.316 6	78.23	-0.847 6
	H			0.423 8
		R_OM/nm	R_OH/nm	∠_HOH/°
		0.0	0.1	109.47

Fig.2 (a) Isotherms of water adsorption and desorption in SWCNTs with pore radius of 1.0 nm and different pore lengths at 298 K; (To ease visualization, the isotherms of PL=6, 8, 12, 16 nm are shifted up by 45, 90, 135, 180, respectively.) (b) local density distributions of water adsorbed in 1.0 nm SWCNT with pore length of 12 nm at 298 K

Fig.3 (a) Isotherms of water adsorption and desorption in SWCNTs with different pore radii and the pore length of 4 nm at 298 K; (For easy observation, SWCNT with PR=0.4, 0.44, 0.46, 0.48 and 0.5 nm only gives the isotherms of the adsorption branch.) (b) relations between pore densities of water adsorption and the pore radii of SWCNT at a series of pressures at 298 K

Fig.4 (a) Local density distributions of water adsorbed in SWCNTs with different pore radii and pore length of 4 nm at 298 K; (b) the snapshots of water adsorption corresponding to the adsorption conditions in (a) (The pore radius is 0.4, 0.44, 0.46, 0.48, 0.5, 0.55, 0.8, and 1.0 nm from top to bottom.)

Fig.5 Isosteric heats versus accessible pore density for water adsorption at 298 K in SWCNT with different pore radius (a) PR=0.4 nm; (b) PR=0.44 nm; (c) PR=0.46 nm; (d) PR=0.48 nm; (e) PR=0.5 nm; (f) PR=0.55 nm; (g) PR=0.8 nm; (h) PR=1.0 nm

Fig.6 (a) Isotherms of water adsorbed in tubes with pore radius of 1.0 nm, pore length of 4 nm and different surface strengths of 20, 28 (SWCNT), 32, 40 K at 298 K; (To ease visualization, the isotherms of SWCNT, εss=32, 40 K are shift up by 45, 90, 135 respectively.) (b) local density distributions of water adsorbed in pores with the surface strength of 40 K

Fig.7 Isosteric heats at the pressures corresponding to the denoted points shown in 6(a) with the surface strength of 40 K at 298 K

Fig.8 Isosteric heats for water adsorption in cylindrical pores with different surface strengths at 298 K (a) εss=20 K; (b) SWCNT; (c) εss=32 K; (d) εss=40 K

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