Ordered Self-assembly of Gemini Molecules in Mesoporous Silica Channels Constructing Normal Micelles to Assist the Migration of OH-†

doi:10.7503/cjcu20160596

Abstract

Abstract:

Using assembly properties of Gemini surfactants[maleic alkylene group diethyl bis(octyl dimethyl chloro/bromide), abbreviated as G_8-2-8], the normal wormlike micelles, on which were full of quaternary ammonium groups, were orderly assembled in the mesoporous silica channels by the induction of sodium salicylate(NaSal). The above mentioned normal wormlike micelles and the Si hydroxyl groups, which were in the inner wall of the porous silicon, function together as annular water chambers to construct the orderly and efficient transmission channels of OH^-. The study of the G_8-2-8/NaSal micelle systems’ rheological properties suggested that the G_8-2-8/NaSal micelle network systems have been formed. Under the same experimental conditions, the formation process of G_8-2-8/NaSal micelle network systems was introduced into polysulfone system to prepare the high alkaline-resistant anion exchange membranes, which with orderly, efficient OH^- transmission channels. The characterization results indicated that ion conductivities, water uptake and ion exchange capacity showed a rising trend with the increasing mass fraction of G_8-2-8, especially under the condition which the ion exchange capacity and water uptake were not highlevel, but the migration efficiency of OH^- had improved significantly. The 400 h high temperature alkaline-resistant test indicated that the largest decline of ion conducti-vity was only round about 1.5%, and no obvious changes on morphology, which showed excellent alkaline resistance stability.

Key words: Gemini surfactant, Wormlike micelle, Migration efficiency of OH^-, Rheological property, Anionic exchange membrane, Mesoporous silica channels

CLC Number:

O631.5

TrendMD:

WANG Yifu, DONG Jinxin, WANG Jilin, WANG Lulu, FENG Ruijiang. Ordered Self-assembly of Gemini Molecules in Mesoporous Silica Channels Constructing Normal Micelles to Assist the Migration of OH-†[J]. Chem. J. Chinese Universities, 2017, 38(1): 141.

Figures/Tables 15

Scheme 1 Structure of the Pw-X anion exchange membrane

Fig.1 Effect of NaSal concentration on steady rheology(A) and zero-shear viscosity η0(B) of 100 mmol/L G8-2-8 solution c(NaSat)/(mmol·L-1): a. 2; b. 5; c. 10; d. 15; e. 20.

Fig.2 Frequency sweeps obtained at 25 ℃ in linear viscoelastic regime of 100 mmol/L G8-2-8 solutionsInset is Cole-Cole of G″ vs. G'.

Fig.3 N2 adsorption-desorption isotherms(A) and pore size distribution(B)(unloaded)

Fig.4 N2 adsorption-desorption isotherms(A) and pore size distribution(B)(loaded)

Table 1 N2 adsorption-desorption results of NaSal-loaded and NaSal-unloaded SiO2 nanoparticles

Sample	BET surface area/(m²·g^-1)	Pore volume/(cm³·g^-1)	Small mean pore/nm	Large mean pore/nm
G_8-2-8/NaSal-unloaded	948.1	1.34	3.8	9.8
G_8-2-8/NaSal-loaded	282.1	0.34	3.8	9.5

Table 2 Anionic conductivity and IEC of Pw-X anion exchange membranes before and after adding NaSal

Sample	10³ Conductivity/(S·cm^-1)		IEC/(mmol·g^-1)
	30 ℃	80 ℃	Experimental	Theoretical
	NaSal(No NaSal)	NaSal(No NaSal)	NaSal(No NaSal)
PSF	0(0)	0(0)	0(0)	0
Pw-5	3.29(2.21)	5.20(2.91)	0.14±0.02(0.15)	0.16
Pw-10	4.04(2.43)	5.86(3.44)	0.30±0.03(0.31)	0.32
Pw-15	4.52(2.60)	6.37(4.19)	0.46±0.04(0.46)	0.48
Pw-20	5.68(3.65)	7.02(4.62)	0.61±0.04(0.62)	0.64

Table 3 IEC and conductivity values reported in the literature for different AEMs

Membrane material	Ionic group	IEC/(mmol·g^-1)	10³ Conductivity/ (S·cm^-1)	Con/IEC	Ref.
PSF/ G_8-2-8	QA	0.15	3.29(30 ℃)	21.93	This research
PSF/G_8-2-8	QA	0.15	5.20(80 ℃)	34.66	This research
Poly(tetrafluoroethene-co-hexafluoropropylene)	Q $A TMA d$	0.72	20(25 ℃)	27.7	[32]
Poly(MMA-co-BA-co-VBC)^a	QA_TMA	0.66—1.25	5.2—13.5(80 ℃)	7.8—10.8	[33]
PVBC grafted FEP^b	QA_TMA	0.92—1.10	11—16(25 ℃)	11.9—14.5	[34]
ETFE grafted with VBC	QA_TMA	1.03±0.11	27±5(20 ℃)	26.2	[35]
Poly(arylene ether sulfone)	QA_TMA	1.47—2.62	15-65(80 ℃)	10.2—24.8	[36]
Cardo polyetherketone	QA_TMA	0.11	1.6(20 ℃)	14.5	[37]
SEBS^c	QA_TMA	0.3	5(30 ℃)	16.6	[38]
Polyepichlorydrin	Q $A Dabco e$	1.3	2.5(20 ℃)	1.9	[39]
Silica/poly(2,6-dimethyl-1,4-phenylene oxide)	QA_TEA	2.01	12(30 ℃)	5.9	[40]
Polystyrene(ethylene utylenes) polystyrene	QA_TEA	0.57	0.69(30 ℃)	1.21	[41]
Poly(arylene ether sulfone)	Guanidinium	0.79—1.89	5—45(20 ℃)	6.3—23.8	[42]

Table 3 IEC and conductivity values reported in the literature for different AEMs

Membrane material	Ionic group	IEC/(mmol·g^-1)	10³ Conductivity/ (S·cm^-1)	Con/IEC	Ref.
PSF/ G_8-2-8	QA	0.15	3.29(30 ℃)	21.93	This research
PSF/G_8-2-8	QA	0.15	5.20(80 ℃)	34.66	This research
Poly(tetrafluoroethene-co-hexafluoropropylene)	Q $A TMA d$	0.72	20(25 ℃)	27.7	[32]
Poly(MMA-co-BA-co-VBC)^a	QA_TMA	0.66—1.25	5.2—13.5(80 ℃)	7.8—10.8	[33]
PVBC grafted FEP^b	QA_TMA	0.92—1.10	11—16(25 ℃)	11.9—14.5	[34]
ETFE grafted with VBC	QA_TMA	1.03±0.11	27±5(20 ℃)	26.2	[35]
Poly(arylene ether sulfone)	QA_TMA	1.47—2.62	15-65(80 ℃)	10.2—24.8	[36]
Cardo polyetherketone	QA_TMA	0.11	1.6(20 ℃)	14.5	[37]
SEBS^c	QA_TMA	0.3	5(30 ℃)	16.6	[38]
Polyepichlorydrin	Q $A Dabco e$	1.3	2.5(20 ℃)	1.9	[39]
Silica/poly(2,6-dimethyl-1,4-phenylene oxide)	QA_TEA	2.01	12(30 ℃)	5.9	[40]
Polystyrene(ethylene utylenes) polystyrene	QA_TEA	0.57	0.69(30 ℃)	1.21	[41]
Poly(arylene ether sulfone)	Guanidinium	0.79—1.89	5—45(20 ℃)	6.3—23.8	[42]

Fig.5 Water uptakes of the Pw-X anion exchange membranes

Fig.6 Water absorption rate and swelling ratio(inset) of the Pw-X anion exchange membranes

Fig.7 Anionic conductivity of Pw-X anion exchange membranesa. Pw-5; b. Pw-10; c. Pw-15; d. Pw-20.

Fig.8 Arrhenius plots for the Pw-X anion exchange membranesEa: activation energy of the ions transport (arrow represents the trend).

Fig.9 SEM images of the PSF(A, B) and Pw-20(C, D) anion exchange membranes

Fig.10 Alkaline resistance stability of Pw-X membranes after immersion in 3 mol/L NaOH solution at 60 ℃ for 400 h

Table 4 Mechanical properties and IEC values of Pw-20 membranes after immersion in 3 and 10 mol/L NaOH solution at 60 ℃

c(NaOH)/(mol·L^-1)	Time/h	Tensile strength/MPa	Young modulus/GPa	Elongation at break(%)	IEC^*/(mmol·g^-1)
0	0	15.52±0.45	2.91±0.08	3.59±0.26	0.65±0.02
3	24	14.45±0.39	2.51±0.13	3.18±0.13	0.61±0.04
3	48	13.63±0.31	2.23±0.11	3.43±0.12	0.64±0.03
3	72	12.07±0.67	2.09±0.07	4.11±0.34	0.58±0.05
3	96	7.84±0.98	1.82±0.09	4.57±0.24	0.65±0.02
3	120	6.98±0.61	1.11±0.15	5.21±0.36	0.68±0.03
3	240	6.29±0.36	0.98±0.05	5.64±0.22	0.61±0.02
3	400	5.79±0.32	1.04±0.03	5.53±0.23	0.63±0.04
10	48	6.88±0.45	2.15±0.12	2.16±0.19	0.59±0.05
10	72	6.67±1.14	2.10±0.14	3.51±0.21	0.62±0.05

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