Preparation and Adsorption Properties of Molybdate Anion Imprinted Ceramic Membrane†

doi:10.7503/cjcu20170143

Abstract

Abstract:

A novel imprinted ceramic membrane(IIP-PVI/CM) for adsorbing selectively molybdate anion[Mo(Ⅵ)] was prepared with surface imprinting technology and graft-polymerization using an alumina ceramic membrane as the supporting material, Mo(Ⅵ) as the template ion, 1-vinylimidazole as the functional monomer and 1,6-dibromohexane as the cross-linking agent. The obtained samples were characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis and scanning electron microscopy. Effect of pH value on adsorption performance of IIP-PVI/CM was investigated. The results indicate that IIP-PVI/CM shows a good adsorption capacity in the pH range of 2—4. The adsorption behaves of IIP-PVI/CM toward Mo(Ⅵ) were studied through adsorption kinetics and thermodynamics. The kinetics curve meets pseudo-second-order model. The adsorption isotherm can be described by Langmuir isotherm model. The selective adsorption experiment for IIP-PVI/CM was carried out at pH of 4.0 and temperature of 30 ℃ by a mixed solution containing 4 mmol/L Mo(Ⅵ) and 4 mmol/L W(Ⅵ). It was found that IIP-PVI/CM has specific selectivity for Mo(Ⅵ), and the selectivity coefficient is 7.48 for Mo(Ⅵ) to W(Ⅵ). A dynamic adsorption experiment was done by a membrane apparatus. The results indicate that IIP-PVI/CM also shows good selectivity for separation of Mo(Ⅵ) and W(Ⅵ). The values of the saturated adsorption time of W(Ⅵ) and Mo(Ⅵ) anions are 24 and 47 min, corresponding to the saturated adsorption amounts of 0.163 mmol/100 g for W(Ⅵ) and 0.672 mmol/100 g for Mo(Ⅵ), respectively. After nine adsorption-desorption cycles, the adsorption capacity of IIP-PVI/CM towards Mo(Ⅵ) still reaches 92% of the initial capacity. The IIP-PVI/CM has good regeneration and recycling performance.

Key words: Ceramic membrane, Molybdate anion, Surface ion-imprinting, Selective adsorption

CLC Number:

O631

TrendMD:

ZENG Jianxian, DONG Zhihui, ZHANG Zhe, LIU Guoqing, ZHOU Hu. Preparation and Adsorption Properties of Molybdate Anion Imprinted Ceramic Membrane^†[J]. Chem. J. Chinese Universities, 2017, 38(11): 2102.

Figures/Tables 15

Scheme 1 Schematic diagram of preparing Mo(Ⅵ) imprinted IIP-PVI/CM(Ⅰ) SiO2 active layer preparation and surface modification of ceramic membrance with coupling agent MPS;(Ⅱ) graft polymerization of Ⅵ on ceramic membrane; (Ⅲ) process of imprinting and crosslinking.

Fig.1 FTIR spectra of raw CM(a), SiO2-CM(b), MPS-CM(c) and PVI-CM(d)(A) and magnifications of curve d(B, C)

Fig.2 Infrared spectrum comparison of IIP-PVI/CM(a) and PVI-CM(b)

Table 1 Surface elemental compositions of various membranes calculated from XPS spectra

Membrane	Atom fraction(%)
Membrane	Al	O	Si	C	N	Mo
CM	38.56	60.68	0.76
SiO₂-CM	32.28	62.27	5.45
MPS-CM	21.08	42.20	3.18	33.54
PVI-CM	22.84	40.51	2.30	27.45	6.90
IIP-PVI/CM	20.93	36.54	2.66	29.26	9.14	1.46

Fig.3 Wide-scan XPS spectra of various membranes(A), C1s core level spectra of MPS-CM(B) and N1s core level spectra of PVI-CM(C)

Fig.4 Thermogravimetry curves of MPS-CM(a) and PVI-CM(b)

Fig.5 SEM images of raw CM(A) and grafted PVI-CM(B)

Fig.6 Effect of pH on Mo(Ⅵ) anions adsorption using IIP-PVI/CM(a) and NIP-PVI/CM(b)

Fig.7 Adsorption kinetics for Mo(Ⅵ) anions using IIP-PVI/CM

Fig.8 Adsorption isotherms of Mo(Ⅵ) on IIP-PVI/CM(A) Experimental data and non-linear modeling by Langmuir and Freundlich isotherms; (B) linear Langmuir isotherm; (C) linear Freundlich isotherm.

Table 2 Langmuir and Freundlich isotherm constants for adsorption of Mo(Ⅵ) on IIP-PVI/CM

Species	Langmuir isotherm				Freundlich isotherm
Species	Q_max/(mmol·100 g^-1)	b	R²	χ²	K_f	n	R²	χ²
Linear	0.72	8.57	0.9976		0.63	3.81	0.74
Non-linear	0.78	5.36	0.95	0.0028	0.61	4.46	0.84	0.009

Fig.9 Selective adsorption of Mo(Ⅵ) and W(Ⅵ) anions on IIP-PVI/CM and NIP-PVI/CM

Table 3 Selective adsorption of Mo(Ⅵ) from multicomponent mixtures by IIP-PVI/CM and NIP-PVI/CM

Membrane type	Adsorption capacity/(mmol/100 g)
Membrane type	Na(Ⅰ)	Ca(Ⅱ)	Cu(Ⅱ)	W(Ⅵ)	Mo(Ⅵ)
IIP-PVI/CM	Neglected	Neglected	0.082	0.151	0.683
NIP-PVI/CM	Neglected	Neglected	0.113	0.184	0.167

Fig.10 Dynamic separation curves of Mo(Ⅵ)(a) and W(Ⅵ)(b) anions on IIP-PVI/CM

Fig.11 Regeneration cycles for IIP-PVI/CM

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