混合改性PAN纳米纤维铁配合物的吸附-催化双功能在有机染料去除中的应用

doi:10.7503/cjcu20170281

摘要/Abstract

摘要：

将静电纺丝法制备的聚丙烯腈(PAN)纳米纤维膜用不同比例的盐酸羟胺和水合肼混合溶液改性, 再与Fe³⁺离子进行配位反应, 制备了5种不同表面结构的改性PAN纳米纤维铁配合物; 考察了水合肼加入量对纤维铁配合物的制备及对偶氮染料活性红195去除能力的影响. 结果表明, 随着水合肼加入量的增大, 改性PAN纳米纤维的直径减小且其铁配合物表面的铁离子配合量降低; 3种混合改性PAN纳米纤维铁配合物均对活性红195具有优良的吸附和光催化降解功能, 可通过2种功能之间的协同效应实现快速去除水溶液中染料分子的目的.

关键词: 聚丙烯腈纳米纤维, 混合改性, Fenton反应, 染料降解, 吸附-催化

Abstract:

Polyacrylonitrile nanofibrous(n-PAN) membrane were prepared by electrospun method and modified with different molar ratios of hydroxylamine(HA) and/or hydrazine hydrate(HH). The resulting modified n-PANs were then coordinated with Fe³⁺ ions to fabricate five modified n-PAN Fe complexes with different surface structures. The effect of HH addition on the complex preparation and its removal performance of azo dye Reactive red 195 from water were investigated and compared. The results indicated that the modified n-PAN fibrous diameter and Fe content of its Fe complex decreased as the addition of HH increased. This lead to a better adsorption and photocatalytic degradation capacities of three hybrid modified n-PAN Fe complexes. Thus, the rapid removal of dye molecules from aqueous solution was obtained through combination of both functions of the complexes mentioned above.

Key words: Polyacrylonitrile nanofibers, Hybrid modification, Fenton reaction, Dye degradation, Adsorption-catalysis

中图分类号:

O643
TS190

TrendMD:

李甫, 董永春, 程博闻, 康卫民. 混合改性PAN纳米纤维铁配合物的吸附-催化双功能在有机染料去除中的应用. 高等学校化学学报, 2018, 39(1): 115.

LI Fu, DONG Yongchun, CHENG Bowen, KANG Weimin. Application of Hybrid Modified PAN Nanofibrous Membrane Fe Complexes with Adsorption-photocatalysis Bifunctions for Removal of Organic Dye from Water^†. Chem. J. Chinese Universities, 2018, 39(1): 115.

图/表 10

Fig.1 Modification of PAN with HH and/or HA

Fig.2 SEM images of mix-modified n-PAN Fe complexes(A) n-PAN; (B) Fe-HH-n-PAN; (C) Fe-M-n-PAN1; (D) Fe-M-n-PAN2; (E) Fe-M-n-PAN3; (F) Fe-HA-n-PAN.

Table 1 Variation of ΔW and dm values with different molar ratios of HH/HA for n-PAN and conventional PAN fiber after modification and coordination

n(HH):n(HA)	n-PAN				PAN fiber
	ΔW(%)	d_m/nm		Q_Fe/	ΔW(%)	d_m/μm		Q_Fe/
		Modification	Coordination	(mmol·g^-1)		Modification	Coordination	(mmol·g^-1)
1:0	2.45±0.26	252±19	279±21	1.20±0.22	2.12±0.32	19.37±0.21	19.39±0.18	0.94±0.15
3:1	45.62±1.15	295±22	355±19	5.97±0.18	32.25±1.13	22.58±0.19	23.96±0.20	4.64±0.21
1:1	56.71±1.35	303±25	347±24	6.69±0.19	44.42±1.47	26.69±0.22	27.73±0.16	5.31±0.18
1:3	57.81±1.25	312±21	348±20	7.22±0.20	42.29±1.33	27.71±0.21	28.06±0.17	6.15±0.17
0:1	63.89±1.05	ND	ND	8.08±0.14	64.52±1.51	53.63±0.14	53.61±0.14	7.74±0.12

Fig.3 FTIR spectra of the modified n-PAN and their Fe complexes(A) a. n-PAN; b. HH-n-PAN; c. M-n-PAN2; d. HA-n-PAN; (B) a. HH-n-PAN; b. Fe-HH-n-PAN; c. M-n-PAN2; d. Fe-M-n-PAN.

Fig.4 Effect of the molar ratios of HH/HA on the adsorption ability of Fe complexes prepared with modified n-PAN(A) or conventional PAN fiber(B)(A) a. Fe-HH-n-PAN; b. Fe-M-n-PAN1; c. Fe-M-n-PAN2; d. Fe-M-n-PAN3; e. Fe-HA-n-PAN; f. n-PAN.(B) a. Fe-HH-PAN; b. Fe-M-PAN1; c. Fe-M-PAN2; d. Fe-M-PAN3; e. Fe-HA-PAN; f. PAN.

Fig.5 SEM images of conventional PAN fiber(A) and HA-PAN(B)

Fig.6 Dark adsorption and visible-driven photocatalytic degradation curves for different modified n-PAN Fe complexes

Table 2 Adsorption and photocatalytic degradation kinetic model parameters for different modified n-PAN Fe complexes*

Complex	Q_Fe/ (mmol·g^-1)	Adsorption			Photocatalytic degradation
Complex	Q_Fe/ (mmol·g^-1)	D_e(%)	k_a/(g·min^-1·mg^-1)	$R a 2$	D_e(%)	k_p/(g·min^-1·mg^-1)	$R p 2$
Fe-HH-n-PAN	1.20±0.11	8.98	9.63×10^-3	0.9990	9.81	ND	ND
Fe-M-n-PAN₁	1.21±0.08	28.72	3.56×10^-3	0.9987	98.01	1.12×10^-2	0.9990
Fe-M-n-PAN₂	1.19±0.10	34.71	2.60×10^-3	0.9984	98.32	1.43×10^-2	0.9997
Fe-M-n-PAN₃	1.20±0.05	35.45	2.31×10^-3	0.9971	99.06	2.53×10^-2	0.9997
Fe-HA-n-PAN	1.20±0.07	0.82	2.93×10	0.9974	12.49	9.65×10^-3	0.8938

Table 2 Adsorption and photocatalytic degradation kinetic model parameters for different modified n-PAN Fe complexes*

Complex	Q_Fe/ (mmol·g^-1)	Adsorption			Photocatalytic degradation
Complex	Q_Fe/ (mmol·g^-1)	D_e(%)	k_a/(g·min^-1·mg^-1)	$R a 2$	D_e(%)	k_p/(g·min^-1·mg^-1)	$R p 2$
Fe-HH-n-PAN	1.20±0.11	8.98	9.63×10^-3	0.9990	9.81	ND	ND
Fe-M-n-PAN₁	1.21±0.08	28.72	3.56×10^-3	0.9987	98.01	1.12×10^-2	0.9990
Fe-M-n-PAN₂	1.19±0.10	34.71	2.60×10^-3	0.9984	98.32	1.43×10^-2	0.9997
Fe-M-n-PAN₃	1.20±0.05	35.45	2.31×10^-3	0.9971	99.06	2.53×10^-2	0.9997
Fe-HA-n-PAN	1.20±0.07	0.82	2.93×10	0.9974	12.49	9.65×10^-3	0.8938

Fig.7 Pseudo-second-order plots for the adsorption(A) and photocatalytic degradation(B) of RR 195 in the presence of different modified n-PAN Fe complexes

Fig.8 Variation in D values of RR 195 degradation catalyzed by Fe complexes prepared with modified n-PAN(A) or conventional PAN fibers(B)

参考文献 25

[1]	Bethi B., Sonawane S. H., Bhanvase B. A., Gumfekar S. P., Chem. Eng. Process., 2016, 109, 178—189
[2]	Wu W., Wu C. C., Zhao Y. P., Environ. Sci. Technol., 2010, 33(6), 99—104
	(吴伟, 吴程程, 赵雅萍.环境科学与技术, 2010, 33(6), 99—104)
[3]	Yan C. Q., Liu B., Lu G. X., Li Y. X., Yang Q. B., Song Y., Chem. J. Chinese Universities, 2016, 37(1), 189—194
	(闫春秋, 刘斌, 鲁冠秀, 李耀先, 杨清彪, 宋岩.高等学校化学学报, 2016, 37(1), 189—194)
[4]	Xing G., Fibers Polym., 2016, 17(2), 194—198
[5]	Baseri S., J. Text. Inst., 2016, 13(5), 1—11
[6]	Wu Z. C., Tao T. X., Wang X. Q., Spectrosc. Spectral Anal., 2004, 24(4), 440—443
	(吴之传, 陶庭先, 汪学骞.光谱学与光谱分析, 2004, 24(4), 440—443)
[7]	Han Z. B., Dong Y. C., Dong S. M., Mater. Des., 2010, 31(6), 2784—2789
[8]	Han Z. B., Dong Y. C., Ma B., Du F., Liu C. Y., Acta Energ. Sol. Sin., 2011, 32(3), 408—415
	(韩振邦, 董永春, 马斌, 杜芳, 刘春燕.太阳能学报, 2011, 32(3), 408—415)
[9]	Han Z. B., Dong Y. C., Du F., J. Tianjin Polytech. Univ., 2008, 27(5), 93—96
	(韩振邦, 董永春, 杜芳.天津工业大学学报, 2008, 27(5), 93—96)
[10]	Han Z. B., Dong Y. C., Liu C. Y., Chem. J. Chinese Universities, 2010, 31(5), 986—993
	(韩振邦, 董永春, 刘春燕.高等学校化学学报, 2010, 31(5), 986—993)
[11]	Cheng M. M., Ma W. H., Li J., Huang Y. P., Zhao J. C., Environ. Sci. Technol., 2004, 38(5), 1569—1575
[12]	Mezohegyi G., van der Zee F. P., Font J., Fortuny A., Fabregat A., J. Environ. Manage., 2012, 102(14), 148—164
[13]	Wang L., Yao Y. Y., Zhang Z. H., Sun L. J., Lu W. Y., Chen W. X., Chen H. X., Chem. Eng. J., 2014, 251, 348—354
[14]	Dong Y. C., Wang Q. F., Dun M. N., Zhu H. X., Chin. J. Process Eng., 2007, 7(4), 668—673
	(董永春, 王秋芳, 顿咪娜, 朱红星.过程工程学报, 2007, 7(4), 668—673)
[15]	Pan G., Liu Y. Y., Environ. Chem., 2006, 25(1), 11—15
	(潘纲, 刘媛媛.环境化学, 2006, 25(1), 11—15)
[16]	Ishtchenko V. V., Huddersman K. D., Vitkovskaya R. F., Appl. Catal. A, 2003, 242(1), 123—127
[17]	Kin’ya O., Nobuko T., Bull. Chem. Soc. Jpn., 1966, 39, 227—272
[18]	Chen W. J., Xin B. J., Wu X. J., J. Ind. Text., 2014, 44(1), 159—179
[19]	Dong Y. C., Han Z. B., Liu C. Y., Du F., Sci. Total Environ., 2010, 408(10), 2245—2253
[20]	Lin W. P., Lu Y., Zeng H. M., Ion Exch. Adsorpt., 1991, 7(5), 364—370
	(林伟平, 陆耘, 曾汉民.离子交换与吸附, 1991, 7(5), 364—370)
[21]	Karaivanova S., Badev A., Angew. Makromol. Chem., 1986, 140, 1—32
[22]	Wang X. P., Feng Y. F., Shen Z. Q., Chem. J. Chinese Universities, 2000, 21(10), 1598—1602
	(王新平, 封云芳, 沈之荃.高等学校化学学报, 2000, 21(10), 1598—1602)
[23]	Zhu S.Y., Coordination Chemistry Introductory Tutorial, Tianjin Science and Technology Press, Tianjin, 1990
	(朱声逾. 配位化学简明教程, 天津: 天津科学技术出版社, 1990)
[24]	Deng S. B., Bai R. B., Chen J. P., Langmuir, 2003, 19(12), 5058—5064
[25]	Hsieh C. T., Fan W. S., Chen W. Y., Lin J. Y., Sep. Purif. Technol., 2009, 67, 312—318