Application of Hybrid Modified PAN Nanofibrous Membrane Fe Complexes with Adsorption-photocatalysis Bifunctions for Removal of Organic Dye from Water†

doi:10.7503/cjcu20170281

Abstract

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

CLC Number:

O643
TS190

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2018, 39(1): 115.

Figures/Tables 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)

References 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