多层组装聚苯胺@硅磁复合物的制备及对磺酸基染料的选择性吸附

doi:10.7503/cjcu20180259

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (10): 2253.doi: 10.7503/cjcu20180259

多层组装聚苯胺@硅磁复合物的制备及对磺酸基染料的选择性吸附

周艳芬, 孟哲(), 王泽岚, 李吉光, 门秀琴, 刘万毅

宁夏大学化学化工学院, 省部共建煤炭高效利用与绿色化工国家重点实验室, 银川 750021

收稿日期:2018-04-04 出版日期:2018-09-10 发布日期:2018-09-10
作者简介:
联系人简介: 孟哲, 女, 博士, 教授, 主要从事功能材料的制备及分离技术方面的研究. E-mail: meng_z@nxu.edu.cn
基金资助:
国家自然科学基金(批准号: 21768003)、西部地区建设一流大学的重大创新项目(批准号: ZKZD2017003)和宁夏国内一流学科建设项目(批准号: NXYLXK2017A04)资助.

Preparation and Selective Adsorption Performance of Polyaniline Silicon Magnetic Composite by Multilayer Assembly for Sulfonic Dye^†

ZHOU Yanfen, MENG Zhe^*(), WANG Zelan, LI Jiguang, MEN Xiuqin, LIU Wanyi

State Key Laboratory of High-efficiency Coal Utilization and Green Chemical Engineering,School of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China

Received:2018-04-04 Online:2018-09-10 Published:2018-09-10
Contact: MENG Zhe E-mail:meng_z@nxu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No. 21768003), the Major Innovations Project for Building First-Class Universities in China’s Western Region(No. ZKZD2017003) and the National First-Rate Discipline Construction Project of Ningxia, China(No. NXYLXK2017A04).

摘要/Abstract

摘要：

以硅磁粒子(Fe₃O₄@SiO₂)为核, 采用低温-原位氧化聚合-共沉淀法制备了多层核壳聚苯胺硅磁复合物(Fe₃O₄@SiO₂@PANI). 通过X射线衍射分析(XRD)、傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等对Fe₃O₄@SiO₂@PANI复合物的结构、形貌和性质进行了表征. 以磺酸基偶氮染料甲基橙、刚果红和蒽醌染料茜素红溶液模拟染料废水, 对其在Fe₃O₄@SiO₂@PANI上的吸附进行了研究, 讨论了pH值、吸附时间、染料初始浓度及吸附剂用量对吸附过程的影响, 优化了吸附条件. 实验结果表明, 弱酸性(pH<6.0)条件下, Fe₃O₄@SiO₂@PANI对甲基橙、刚果红和茜素红具有优异的选择性吸附性能, 其平衡吸附量分别为26.05, 34.0 和69.58 mg/g. 该复合物对染料的吸附过程更接近Langmuir等温吸附的单分子层吸附机理, 其对染料废水的去除率高达96.5%, 易于分离, 且重复使用性能良好.

关键词: 硅磁粒子, 聚苯胺, 磺酸基染料, 选择性吸附

Abstract:

A multi-layer core-shell polyaniline silicon magnetic composite(Fe₃O₄@SiO₂@PANI) via in situ oxidation polymerization-coprecipitation of silicon magnetic particles(Fe₃O₄@SiO₂) as core at low temperature was prepared. The structure, surface morphology and properties of Fe₃O₄@SiO₂@PANI composites were characterized by means of X-ray means of diffraction(XRD), Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM) and transmission electron microscopy(TEM). Using sulfonic azo dyes-methyl orange(MO), congo red(CR), and anthraquinone dye-alizarin red(AR) in aqueous solution, respectively, as an example for dyes in wastewaters, the effects of dyes adsorption pH, adsorption time, dyes concentration and amount of Fe₃O₄@SiO₂@PANI on the adsorption process were studied. The sulfonic dyes was more effective with weakly acidic(pH<6.0). The maximum adsorption capacity of MO, AR and CR on Fe₃O₄@SiO₂@PANI were 26.05, 69.58 and 34.0 mg/g, respectively, under optimized conditions. Analysis of the adsorption results demonstrated that the adsorption was better fit by Langmuir adsorption equation compared to Freundlich adsorption. The results suggested that the shell PANI of Fe₃O₄@SiO₂@PANI composite had good affinity for sulfonic dyes, and the removal efficiency of composites on dye wastewater reached up to 96.5%. In addition, the magnetic composite could be effectively and simply separated by using an external magnetic field and had good repeatability as sorbent of the sulfonic dye wastewater treatment.

Key words: Silicon magnetic particles, Polyaniline, Sulfonic dye, Selective adsorption

中图分类号:

O647

TrendMD:

周艳芬, 孟哲, 王泽岚, 李吉光, 门秀琴, 刘万毅. 多层组装聚苯胺@硅磁复合物的制备及对磺酸基染料的选择性吸附. 高等学校化学学报, 2018, 39(10): 2253.

ZHOU Yanfen,MENG Zhe,WANG Zelan,LI Jiguang,MEN Xiuqin,LIU Wanyi. Preparation and Selective Adsorption Performance of Polyaniline Silicon Magnetic Composite by Multilayer Assembly for Sulfonic Dye^†. Chem. J. Chinese Universities, 2018, 39(10): 2253.

图/表 21

Scheme 1 Synthetic procedure of Fe3O4@SiO2@PANI core-shell microspheres and the adsorption of methyl orange

Fig.1 FTIR spectra of SiO2(a), Fe3O4@SiO2@PANI(b), Fe3O4@SiO2(c) and Fe3O4(d)

Fig.2 XRD patterns of Fe3O4@SiO2@PANI(a),Fe3O4@SiO2(b) and Fe3O4(c)

Fig.3 TG(a) and DSC(b) curves of Fe3O4@SiO2@PANI

Fig.4 Saturation magnetization intensity curves of Fe3O4@SiO2(a) and Fe3O4@SiO2@PANI(b)

Table 1 Structural properties of Fe3O4@SiO2 and Fe3O4@SiO2@PANI

Sample	S_BET/(m²·g^-1)	V_total/(cm³·g^-1)	D/nm
Fe₃O₄@SiO₂	490	0.599	1.94
Fe₃O₄@SiO₂@PANI	64.3	0.074	4.59

Fig.5 SEM images of Fe3O4@SiO2(A) and Fe3O4@SiO2@PANI(B)

Fig.6 TEM images of Fe3O4@SiO2(A) and Fe3O4@SiO2@PANI(B) Insets: magnified image.

Fig.7 UV-Vis absorption spectra obtained for AR(a, b), MO(c, d), CR(e, f) before(a, c, e) and after(b, d, f) absorption on Fe3O4@SiO2@PANI in weakly acidic solution(pH<6.0)

Fig.8 Effects of initial concentration of MO(A), AR(B) and CR(C) on the adsorption capacity

Fig.9 Effects of amount of MO(A), AR(B) and CR(C) on the removal rate(a) and adsorbing capacity(b)

Fig.10 Structural formulas of target dyes

Fig.11 Adsorption capacities of different dyes on Fe3O4@SiO2@PANI(A) and the images of adsorbents before(B) and after(C) adsorption

Fig.12 Adsorbing capacity of MO Fe3O4@SiO2@PANI(a), Fe3O4@SiO2(b) and Fe3O4(c)

Fig.13 Effect of adsorption time on the adsorption capacities of AR(a), CR(b) and MO(c)

Table 2 Pseudo-first order reaction kinetic parameter of adsorption

Sulfonic dye	Equation	k₁/min^-1	R²	Q_e,cal/(mg∙g^-1)	Q_e,exp/(mg∙g^-1)
MO	ln(1-Q_t/Q_e)=-0.0196t-0.2399	0.0195	0.9580	0.78	26.05
AR	ln(1-Q_t/Q_e)=-0.0276t-0.4038	0.0276	0.9412	0.67	69.58
CR	ln(1-Q_t/Q_e)=-0.0077t-0.8598	0.00775	0.8584	0.42	34.00

Table 3 Pseudo-second order reaction kinetic parameter of adsorption

Sulfonic dye	Equation	k₂/(g∙min∙mg^-1)	R²	Q_e,cal/(mg∙g^-1)	Q_e,exp/(mg∙g^-1)
MO	t/Q_t=0.0318t+0.6830	0.0015	0.9956	31.44	26.05
AR	t/Q_t=0.0125t+0.1297	0.0012	0.9987	80.06	69.58
CR	t/Q_t=0.0263t+0.2173	0.0032	0.9992	37.94	34.00

Fig.14 Effects of temperature on the adsorption of MO(A), AR(B) and CR(C) on Fe3O4@SiO2@PANI

Table 4 Correlated parameters of Langmuir and Freundlich isotherm models at 298 K

Sulfonic dye	Langmuir parameter				Freundlich parameter
Sulfonic dye	Equation, c_e/Q_e=(1/Q_max) c_e+ 1/(Q_maxK_L)	R²	Q_m/ (mg·g^-1)	K_L/ (L·mg^-1)	Equation, lnQ_e=(1/n)ln c_e+ lnK_F	R²	K_F/ (L·mg^-1)	n
MO	c_e/Q_e=0.0086c_e+0.0313	0.9991	31.95	3.62	lnQ_e=0.2706lnc_e+2.8389	0.8257	17.08	3.70
AR	c_e/Q_e=0.0157c_e+0.0565	0.9945	63.69	0.28	lnQ_e=1.255lnc_e+1.1768	0.9306	3.24	0.79
CR	c_e/Q_e=0.0210c_e+0.0118	0.9957	47.60	1.78	lnQ_e=1.0766lnc_e+1.4300	0.9084	4.18	0.93

Table 5 Thermodynamic parameters of adsorption

Temperature/K	Sulfonic dye	ΔG/(kJ·mol^-1)	ΔH/(kJ·mol^-1)	ΔS/(J·mol^-1·K^-1)
298	MO	-3.19	45.41	164.49
298	AR	-163.72	167.06	549.95
298	CR	-1.431	58.98	202.72

Fig.15 Reusability of Fe3O4@SiO2@PANI to adsorption of MO

参考文献 37

[1]	Ren N.Q., Zhou X. J., Guo W. Q., Yang S. S., J. Chem. Ind. Eng., 2013, 64(1), 84—94
	(任南琪, 周显娇, 郭婉茜, 杨珊珊. 化工学报, 2013, 64(1), 84—94)
[2]	McMullan G., Meehan C., Conneely A., Kirby N., Robinson T., Nigam P.,Banat I., Marchant R., Smyth W., Appl. Microbiol. Biotechnol., 2001, 56(1/2), 81—87
[3]	Mai J.B., Jiang D., Fan Y. H., Textile Dyeing and Finishing Journal, 2016, 38(2), 58—61
	(麦建波, 江栋, 范远红. 染整技术, 2016, 38(2), 58—61)
[4]	Elmira P., Mokhtar A., Niyaz M.M., Taiwan Inst. Chem. Eng., 2012, 43(2), 282—290
[5]	Shi H.C., Li W. S., Zhong L., Xu C. J., Ind. Eng. Chem. Res., 2014, 53(3), 1108—1118
[6]	Chakraborty S., Purkait M.K., DasGupta S., De S., Basu J. K., Sep. Purif. Technol., 2003, 31(2), 141—151
[7]	Yu S.C., Liu M. H., Ma M., Qi M., Lu Z. H., Gao C. J., J. Membr. Sci., 2010, 350(1/2), 83—91
[8]	Kim T.H., Park C., Yang J., Kim S. Y., J. Hazard. Mater., 2004, 112(1/2), 95—103
[9]	Sekaran G., Karthikeyan S., Boopathy R., Maharaja P., Gupta V.K., Anandan C., Environ. Sci. Pollut. Res., 2014, 21(2), 1489—1502
[10]	Parsa J.B., Merati Z., Abbasi M., J. Ind. Eng. Chem., 2013, 19(4), 1350—1355
[11]	Mohammed F.M., Roberts E. P. L., Hill A., Campen A. K., Brown N. W., Water Res., 2011, 45(10), 3065—3074
[12]	Ju D.J., Byun I. G., Park J. J., Lee C. H., Ahn G. H., Park T. J., Bioresour. Technol., 2008, 99(17), 7971—7975
[13]	Zhan S.H., Zhang Y., Zhu D. D., Qiu M. Y., Yu W. C., Shi Q., Chinese J. Environ. Eng., 2016, 10(1), 1—11
	(展思辉, 张宇, 朱丹丹, 邱明英, 于雯超, 史强. 环境工程学报, 2016, 10(1), 1—11)
[14]	Zheng L.B., Tong J., Wei Y. S., Wang J., Yue Z. G., Wang G., Acta Sci. Circum., 2016, 36(9), 3103—3117
	(郑利兵, 佟娟, 魏源送, 王军, 岳增刚, 王钢. 环境科学学报, 2016, 36(9), 3103—3117)
[15]	Chen X.L., Deng L. C., Wang X. F., Guan S., Chem. J. Chinese Universities, 2014, 35(12), 2510—2515
	(陈晓磊, 邓李川, 王晓峰, 关爽. 高等学校化学学报, 2014, 35(12), 2510—2515)
[16]	Yang M.X., Ma J., Sun Y. R., Chem. J. Chinese Universities, 2014, 35(3), 570—575
	(杨明轩, 马杰, 孙怡然. 高等学校化学学报, 2014, 35(3), 570—575)
[17]	Gao Q., Zheng H.B., Luo D., Ding J., Feng Y. Q., Anal. Chim.Acta, 2012, 720(1), 57—62
[18]	Hajivandi A., Farjadfard S., Ramavandi B., Akbarzadeh S., Data in Brief, 2016, 7, 71—76
[19]	Jing X.B., Wang L. X., Wang X. H., Geng Y. H., Wang F. S., Acta Polym. Sin., 2005, 1(5), 655—663
	(景遐斌, 王利祥, 王献红, 耿延候, 王佛松. 高分子学报, 2005, 1(5), 655—663)
[20]	Song Z., Zhang J.K., Li X. F., Zhang D. H., Chen Y. F., New Chem. Mater., 2018, 46(1), 89—92
	(宋哲, 张婧坤, 李晓飞, 张冬海, 陈运法. 化工新型材料, 2018, 46(1), 89—92)
[21]	Wen R., Sun Y.H., Li C. Y., Chem. Res. Appl., 2016, 28(9), 1237—1242
	(文锐, 孙永华, 李崇瑛. 化学研究与应用, 2016, 28(9), 1237—1242)
[22]	Ding Y., Jin Y., Wang W.X., Li L. C., Kong W. Q., Scientia Sinica Chimica, 2015, 45(2), 202—210
	(丁艳, 金叶, 王伟祥, 李良超, 孔卫秋. 中国科学: 化学, 2015, 45(2), 202—210)
[23]	Gao L., Wang Y.G., Yan T., Cui L. M., Hu L. H., Yan L. G., Wei Q., Du B., New J. Chem., 2015, 39, 2908—2916
[24]	Morel A.L., Nikitenko S. I., Gionnet K., Wattiaux A., Lai-Kee-Him J., Labrugere C., Chevalier B., Deleris G., Petibois C., Brisson A., Simonoff M., ACS Nano, 2008, 2(5), 847—856
[25]	Stjerndahl M., Andersson M., Hall H.E., Pajerowski D. M., Meisel M. W., Duran R. S., Langmuir, 2008, 24(7), 3532—3536
[26]	Chen C., He Y.C., Du Z. P., Yuan H., Wu Y. X., J. Magn. Mater. Dev., 2014, 1(45), 21—24
	(陈成, 贺玉成, 杜治平, 袁华, 吴元欣. 磁性材料及器件, 2014, 1(45), 21—24)
[27]	Sauzedde F., Elaissari A., Pichot C., Coll. Polym. Sci., 1999, 277(9), 846—855
[28]	Sainz R., Benito A.M., Maser W. K., Adv. Mater., 2005, 17(3), 278—281
[29]	Xiong S., Jiang X.P., Li J. M., Li X. H., Chen Y. J., J. Chin. Ceram. Soc., 2015, 43(7), 946—951
	(熊珊, 江向平, 李菊梅, 李小红, 陈云婧. 硅酸盐学报, 2015, 43(7), 946—951)
[30]	Tang S., Chai H.G., Chang Y. P., Lee H. K., Anal. Chem., 2014, 86(22), 11070—11076
[31]	Vidal J.L., Aguilera-Luiz Mdel M., Romero-González R., Frenich A. G., J. Agric. Food Chem., 2009, 57(5), 1760—1767
[32]	Huang W.S., Humphrey B. D., Macdiarmid A. G., J. Chem. Soc. Faraday Trans.1, 1986, 82(8), 2385—2400
[33]	Trivedi D.C., Dhawan S. K., Bull. Electrochem., 1992, 8(11), 548—552
[34]	Liu X.X., Gong W. P., Luo J., Zou C. T., Yang Y., Yang S. J., Appl. Surf. Sci., 2016, 362, 517—524
[35]	Chen S.H., Zhang J., Zhang C. L., Desalination, 2010, 252(1), 149—156
[36]	Chen A.Y., Cheng X., Huang X. R., Sun D. Z., J. Chem. Ind. Eng.(China), 2008, 59(9), 2270—2275
	(陈爱燕, 程翔, 黄新瑞, 孙德智. 化工学报, 2008, 59(9), 2270—2275)
[37]	Kilic M., Yazilcil H., Solak M., Bioresour. Technol., 2008, 100(7), 2130—2137

多层组装聚苯胺@硅磁复合物的制备及对磺酸基染料的选择性吸附

Preparation and Selective Adsorption Performance of Polyaniline Silicon Magnetic Composite by Multilayer Assembly for Sulfonic Dye^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 21

参考文献 37

相关文章 15

编辑推荐

Metrics

本文评价

[1]	杨思娴, 钟文钰, 李超贤, 苏秋瑶, 许炳佳, 何谷平, 孙丰强. 聚苯胺纳米线/SnO₂复合光催化材料的光化学制备与性能[J]. 高等学校化学学报, 2021, 42(6): 1942.
[2]	宋文尧, 周张浪, 杨鑫莉, 陈岚, 葛广路. 介孔二氧化硅对映选择性吸附的手性印迹调控[J]. 高等学校化学学报, 2021, 42(10): 3144.
[3]	任文, 张国立, 闫涵, 胡兴华, 李焜, 王景凤, 李瑞琦. 超疏水聚苯胺/聚四氟乙烯复合膜的制备及油-水乳液分离性能[J]. 高等学校化学学报, 2020, 41(4): 846.
[4]	令旭霞, 龙柱, 王士华, 李志强, 郭帅, 张丹. 聚苯胺表面修饰芳纶浆粕及其纸基材料的导电性能[J]. 高等学校化学学报, 2020, 41(11): 2553.
[5]	王乙涵,尹强,杜凯,殷勤俭. 聚吡咯/聚苯胺二元复合纳米管及其热电性能[J]. 高等学校化学学报, 2020, 41(1): 175.
[6]	王琳, 张艳慧, 阿孜古丽·木尔赛力木, 兰海蝶. 以PS-b-P2VP为模板剂诱导调控聚苯胺形貌、尺寸及电化学性能[J]. 高等学校化学学报, 2019, 40(8): 1748.
[7]	刘小舟, 管新宇, 方千荣, 金永日. 室温离子液体法合成新型三维共价有机骨架材料[J]. 高等学校化学学报, 2019, 40(7): 1341.
[8]	赵宇轩, 陈艳君, 潘顾鑫, 王畅, 彭振博, 孙宗旭, 梁永日, 师奇松. 静电纺丝制备Tb-PEG+Eu-PEG/PANI/PAN荧光导电相变三功能复合纤维[J]. 高等学校化学学报, 2019, 40(4): 824.
[9]	刘奔, 张行颖, 陈韶云, 胡成龙. 一维有序聚苯胺纳米阵列的制备及电化学储能性能[J]. 高等学校化学学报, 2019, 40(3): 498.
[10]	杨倩, 杨璨瑜, 孙孔春, 侯雯清, 吴乐艳, 沈报春. 手性聚苯胺/二氧化硅核/壳复合物的合成及应用[J]. 高等学校化学学报, 2018, 39(7): 1587.
[11]	陈奇丹, 唐俊杰, 方千荣. 高稳定性的含氟多级孔共价有机框架材料[J]. 高等学校化学学报, 2018, 39(11): 2357.
[12]	张龙, 万晓娜, 段文静, 秋虎, 后洁琼, 王晓瑞, 李慧, 杜雪岩. Fe₃O₄@聚吡咯@聚苯胺核壳结构的制备及吸波性能[J]. 高等学校化学学报, 2018, 39(1): 185.
[13]	吕晓静, 于朋飞, 欧阳密, 钱亮, 闫拴马, 金晓强, 张诚. 石墨烯-ITO复合电极对聚苯胺薄膜电致变色性质的影响[J]. 高等学校化学学报, 2017, 38(4): 694.
[14]	李学航, 俞慧涛, 王伟仁, 布林朝克, 辛国祥, 张邦文. 自支撑三维功能化石墨烯/聚苯胺电极材料的制备及超级电容性能[J]. 高等学校化学学报, 2017, 38(12): 2306.
[15]	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[J]. 高等学校化学学报, 2017, 38(11): 2102.

多层组装聚苯胺@硅磁复合物的制备及对磺酸基染料的选择性吸附

Preparation and Selective Adsorption Performance of Polyaniline Silicon Magnetic Composite by Multilayer Assembly for Sulfonic Dye†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 21

参考文献 37

相关文章 15

编辑推荐

Metrics

本文评价

Preparation and Selective Adsorption Performance of Polyaniline Silicon Magnetic Composite by Multilayer Assembly for Sulfonic Dye^†