钼酸根阴离子印迹陶瓷膜的制备与吸附性能

doi:10.7503/cjcu20170143

摘要/Abstract

摘要：

以三氧化二铝陶瓷膜为载体, 以钼酸根阴离子为模板离子, 1-乙烯基咪唑为功能单体, 1,6-二溴己烷为交联剂, 采用表面印迹和接枝聚合方法制备了能选择性吸附Mo(Ⅵ)的新型印迹陶瓷膜(IIP-PVI/CM). 采用红外光谱、 X射线光电子能谱、热重分析及扫描电子显微镜等方法对陶瓷膜进行结构表征. 研究了pH值对吸附性能的影响, 当pH值范围为2~4时, IIP-PVI/CM具有良好吸附能力; 动力学和热力学结果表明, IIP-PVI/CM对Mo(Ⅵ)的吸附符合准二级动力学模型和Langmuir吸附模型; 当pH=4.0和温度为30 ℃时, IIP-PVI/CM对Mo(Ⅵ) 具有良好选择性, Mo(Ⅵ)对W(Ⅵ)的选择性系数高达7.48; 动态吸附结果表明, IIP-PVI/CM对W(Ⅵ)和Mo(Ⅵ)的吸附饱和时间分别为24和47 min, 饱和吸附量分别为0.163和0.672 mmol/100 g, 动态吸附时IIP-PVI/CM亦具有良好选择性; 经9次吸附与解吸后, IIP-PVI/CM对Mo(Ⅵ)吸附容量仍可达到初始值的92%, 再生和循环使用性能良好.

关键词: 陶瓷膜, 钼酸根阴离子, 表面离子印迹, 选择性吸附

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

中图分类号:

O631

TrendMD:

曾坚贤, 董志辉, 张哲, 刘国清, 周虎. 钼酸根阴离子印迹陶瓷膜的制备与吸附性能. 高等学校化学学报, 2017, 38(11): 2102.

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

图/表 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

参考文献 35

[1]	Namasivayam C., Sangeetha D., Bioresour Technol., 2006, 97(10), 1194-2000
[2]	Moret A., Rubio J., Miner. Eng., 2003, 16(8), 715-722
[3]	Yousefi T., Khanchi A. R., Ahmadi S. J., Rofouei M. K., Yavari R., Davarkhah R., Myanji B., J. Hazard. Mater., 2012, 215/216(10), 266-271
[4]	Xu S., Chen L., Li J., Guan Y., Lu H., J. Hazard. Mater., 2012, 237/238, 347-354
[5]	Zhang Y., Zheng J., Wang J., Guo M. D., Chem. J. Chinese Universities,2010, 31(5), 860-866
	(张燕, 郑晶, 王娟, 郭满栋. 高等学校化学学报, 2016, 37(5), 860-866)
[6]	Wu Y. L., Zhao J., Wang C., Lu J. , Meng M. J., Dai X. H., Yan Y. S., Li C. X., Chem. Eng. J., 2016, 306, 492-503
[7]	Rao W., Yin Y. L., Long F., Zhang Z. H., Chem. J. Chinese Universities,2010, 31(3), 449-455
	(饶维, 尹玉立 , 龙芳 , 张朝晖. 高等学校化学学报, 2015, 36(3), 449-455)
[8]	Su T. T., Liu J. B., Tang S. S., Jin R. F., Chem. J. Chinese Universities,2010, 31(10), 2146-2155
	(苏婷婷, 刘俊渤, 唐珊珊, 靳瑞发. 高等学校化学学报, 2014, 35(10), 2146-2155)
[9]	Wei X., Husson S. M., Ind. Eng. Chem. Res., 2007, 46(7), 2117-2124
[10]	Yin J., Cui Y., Yang G., Wang H., Chem. Commun., 2010, 46(41), 7688-7690
[11]	An F. Q., Gao B. J., Li G., Acta Polym. Sin., 2007, 4, 366-373
	(安富强, 高保娇, 李刚. 高分子学报, 2007, 4, 366-373)
[12]	Berengere C., Cecile V., Karsten H., Philippe M., Chem. J. Chinese Universities,2010, 31(2), 180-185
[13]	Hou H., Yu D., Hu G., Langmuir,2015, 31(4), 1376-1384
[14]	Bessbousse H., Rhlalou T., Verchère J. F., Lebrun L., Chem. J. Chinese Universities,2010, 31, 8588-8598
[15]	Sun D., Zhu Y., Meng M., Qiao Y., Yan Y., Li C., Sep. Purif. Technol., 2017, 175, 19-26
[16]	Zeng J. X., Zhang Z., Dong Z. H., Ren P. F., Li Y., Liu X., React. Funct. Polym., 2017, 115, 1-9
[17]	Deng H., Gao L., Zhang S., Yuan J., Ind. Eng. Chem. Res., 2012, 51, 14018-14025
[18]	Vatanpour V., Madaeni S. S., Zinadini S., Rajabi H. R., J. Membr. Sci., 2011, 373(1/2), 36-42
[19]	He J., Liu A., Chen J. P., J. Colloid Interf. Sci., 2015, 439, 162-169
[20]	Gao B. J. , Li D. , Lei Q. J., J. Polym. Res., 2011, 18, 1519-1526
[21]	Zeng J. X., Chen H. J., Yuan X. K., Guo Q. N., Yu X., Desalin. Water Treat., 2015, 55(5), 1229-1239
[22]	Cao X. Z., Zhang T. Z., Nguyen Q. T., Zhang Y. Y., Ping Z. H., J. Membr. Sci., 2008, 312, 15-22
[23]	Gao B. J., Chen Y. X., Zhang Z. G., Appl. Surf. Sci., 2010, 257(1), 254-260
[24]	Zhao X. T., Su Y. L., Chen W. J., Peng J. M., Jiang Z. Y., J. Membr. Sci., 2011, 382(1/2), 222-230
[25]	Kim S., Choi Y. E., Yun Y. S., J. Hazard. Mater., 2016, 313, 29-36
[26]	Bayramoglu G., Arica M. Y., J. Hazard. Mater., 2011, 187(1/3), 213-221
[27]	You Q. P., Peng M. J., Zhang Y. P., Guo J. F., Shi S. Y., Anal. Bioanal. Chem., 2013, 406(3), 831-839
[28]	Courtens E., Szke A., Chem. J. Chinese Universities,2010, 31(1), 42-48
[29]	Repo E., Warchol J. K., Kurniawan T. A., Sillanp M. E. T., Chem. Eng. J., 2010, 161(1/2), 73-82
[30]	Ho Y. S., McKay G., Process Biochem., 1999, 34(5), 451-465
[31]	Ersöz A., Say R., Denizli A., Chem. J. Chinese Universities,2010, 31, 91-97
[32]	Say R., Ersöz A., Türk H., Denizli A., Sep. Purif. Technol., 2004, 40, 9-14
[33]	Araki K., Maruyama T., Kamiya N., Goto M., Chem. J. Chinese Universities,2010, 31, 141-145
[34]	Kuchen W., Schram J., Angew. Chem. Int. Edit., 1988, 27(12), 1695-1697
[35]	Rao Z., Feng K., Tang B. B., Wu P. Y., Chem. J. Chinese Universities,2010, 31(3), 2594-2605