偕胺肟化聚丙烯腈-β-环糊精纳米纤维膜的制备及其吸附性能

刘兰; 林晓艳; 梁力丽; 龚红英; 罗学刚

doi:10.13801/j.cnki.fhclxb.20210514.002

偕胺肟化聚丙烯腈-β-环糊精纳米纤维膜的制备及其吸附性能

doi: 10.13801/j.cnki.fhclxb.20210514.002

刘兰^{1, 2,},
林晓艳^{1, 2, ,},
梁力丽^{1, 2,},
龚红英^{1, 2,},
罗学刚¹

1.
西南科技大学　生物质材料教育部工程研究中心，绵阳 621010
2.
西南科技大学　材料科学与工程学院，绵阳 62010

基金项目: 国家核设施退役及放射性废物治理科研重点项目(14ZG6101)

详细信息

通讯作者:
林晓艳，博士，教授，博士生导师，研究方向为生物质材料　E-mail：lxy20100205@163.com

中图分类号: X703；TQ340.64；TQ424
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- 被引次数: 0
出版历程
- 收稿日期: 2021-03-04
- 修回日期: 2021-04-26
- 录用日期: 2021-05-06
- 网络出版日期: 2021-05-14
- 刊出日期: 2022-02-01

Synthesis of amidoxime-modifide polyacrylonitrile-β- cyclodextrin nanofiber membranes and its adsorption properties

LIU Lan^{1, 2
,},
LIN Xiaoyan^{1, 2
, ,},
LIANG Lili^{1, 2
,},
GONG Hongying^{1, 2
,},
LUO Xuegang¹

1.
School of Materials Science and Engineering, Southwest University of Science and Technology, Mianyang 621010, China
2.
Engineering Research Center of Biomass Materials, Ministry of Education, Southwest University of Science and Technology, Mianyang 621010, China

摘要

摘要: 利用聚丙烯腈(PAN)和β-环糊精(β-CD)原料，采用盐酸羟胺原位偕胺肟改性和静电纺丝技术，一步合成制备出偕胺肟聚丙烯腈(AOPAN)-β-CD纳米纤维膜。以纤维膜的形貌和对铀的吸附量为评价指标，优化了改性制备工艺条件。通过SEM、FTIR、表面张力仪等对纤维的形貌、组成和性能进行表征。结果表明，当氰基与羟胺摩尔比为1∶1、改性时间为2 h时，AOPAN-β-CD纳米纤维膜的形态及纤维直径分布更均匀，纤维直径约为230 nm，纤维膜的吸附容量最大，达到78.62 mg/g。
- 偕胺肟化 /
- 膜 /
- 吸附性能 /
- 铀 /
- 聚丙烯腈 /
- β-环糊精
Abstract: Amidoxime polyacrylonitrile (AOPAN)-β-cyclodextrin (β-CD) nanofiber membranes were synthesized in one step using polyacrylonitrile (PAN) and β-CD as raw materials by in-situ amidoxime modification with hydroxylamine hydrochloride and then electrospinning technology. Evaluating by morphology and adsorption capacity, the preparation condition of modification was optimized. The morphology, composition and properties of the membranes were characterized by SEM, FTIR and surface tension meter. The results show that under the optimized modification process conditions, which the molar ratio of cyanogroup to hydroxylamine is 1∶1 and the modification time is 2 h, the morphology distribution of AOPAN-β-CD nanofiber membrane is more uniform and the fiber diameter is about 230 nm, and the adsorption capacity of the fiber membrane reaches 78.62 mg/g.
- amidoximation /
- membranes /
- adsorption characteristic /
- uranium /
- PAN /
- β-CD

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图 1 聚丙烯腈(PAN)偕胺肟化反应原理

Figure 1. Reaction of hydroxylamine hydrochloride with polyacrylonitrile (PAN)

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图 2 偕胺肟聚丙烯腈(AOPAN)-β-环糊精(β-CD)纳米纤维膜制备及吸附铀机制示意图

Figure 2. Schematic diagram of amidoxime polyacrylonitrile (AOPAN)-β-cyclodextrin (β-CD) nanofiber membranes formation and adsorption mechanism for uranium

AOPAN-β-CD-U—AOPAN-β-CD after the adsorption of uranium

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图 3 不同氰基:羟胺摩尔比下AOPAN-β-CD纤维膜SEM图像

Figure 3. SEM images of AOPAN-β-CD nanofiber membranes with different molar ratios of cyanogroup to hydroxylamine

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图 4 不同改性时间下AOPAN-β-CD纤维膜SEM图像

Figure 4. SEM images of AOPAN-β-CD nanofiber membranes with different modification time

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图 5 氰基/羟胺摩尔比 (a) 和改性时间 (b) 对AOPAN-β-CD纳米纤维膜铀吸附性能的影响

Figure 5. Effect of cyanogroup to hydroxylamine (a) and modification time (b) on the adsorption of uranium by AOPAN-β-CD membrane

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图 6 β-CD浓度对AOPAN-β-CD纳米纤维膜铀吸附性能的影响

Figure 6. Effect of the content of β-CD on the adsorption of uranium by AOPAN-β-CD membrane

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图 7 AOPAN-β-CD的脱附再生循环

Figure 7. Adsorption-desorption cycle of AOPAN-β-CD

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图 8 PAN(a)和AOPAN-β-CD(b)的水接触角

Figure 8. Water contact angles of PAN (a) and AOPAN-β-CD (b)

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图 9 PAN-β-CD (a)、AOPAN-β-CD (b)的 SEM图像以及AOPAN-β-CD吸附前后的SEM图像 ((c)、(d)) 和EDX图谱 ((e)、(f))

Figure 9. SEM images of PAN-β-CD (a) and AOPAN-β-CD (b), and SEM images ((c), (d)) and EDX spectra ((e), (f)) of AOPAN-β-CD membrane before and after adsorption

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图 10 PAN、β-CD和AOPAN-β-CD的FTIR图谱

Figure 10. FTIR spectra of PAN, β-CD and AOPAN-β-CD

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图 11 PAN (a)、PAN-β-CD (b)、AOPAN (c )和AOPAN-β-CD (d)纳米纤维膜的热重分析

Figure 11. TGA analysis of PAN (a), PAN-β-CD (b), AOPAN (c) and AOPAN-β-CD (d) nanofibers

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表 1 改性条件对AOPAN-β-CD溶液的可纺性影响

Table 1. Effect of modified condition on the spinnability of AOPAN-β-CD solution

	Spinnability
Modification time/h	2	4	6	8	10
Modification time/h	+	+	+	+	+
n_{hydroxylamine}∶n_KOH	1∶0.15	1∶0.25	1∶0.35	1∶0.45
n_{hydroxylamine}∶n_KOH	+	+	×	×
n_cyano∶n_{hydroxylamine}	3∶1	2∶1	1∶1	1∶2	1∶3
n_cyano∶n_{hydroxylamine}	+	+	+	+	-
Notes：“+”—Easy to electrospinning; “-”—Electrospinning is difficult; “×”—Electrospinning is not possible; n_i∶n_j—Molar ratio.

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表 2 氰基/羟胺摩尔比对AOPAN-β-CD溶液性质及纤维直径的影响

Table 2. Effect of molar ratios of cyanogroup to hydroxylamine on properties of AOPAN-β-CD solution and fiber diameter (Mole ratio of n_{hydroxylamine}∶ n_KOH is 1∶0.25 and modification time is 6 h)

n_cyano∶n_{hydroxylamine}	Viscosity/(mPa·s)	Conductivity/(mS·cm⁻¹)	Surface Tension/(mN·m⁻¹)	Average diameter/nm
3∶1	446.68	719	35.74	400
2∶1	395.57	858	35.91	467
1∶1	426.98	897	30.52	598
1∶2	433.45	1143	36.50	222

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表 3 改性时间对AOPAN-β-CD溶液性质及纤维直径的影响

Table 3. Effect of modification time on properties of AOPAN-β-CD solution and fiber diameter (Mole ration of n_{hydroxylamine}∶n_KOH is 1∶0.25 and n_cyano∶ n_{hydroxylamine} is 1∶1)

Time/h	Viscosity/(mPa·s)	Conductivity/(mS·cm⁻¹)	Surface tension/(mN·m⁻¹)	Average diameter/nm
2	512.64	900	34.90	238
4	339.57	1090	30.18	239
8	381.60	964	36.65	494
10	485.61	913	36.41	433

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表 4 PAN, AOPAN和AOPAN-β-CD纤维膜的力学性能

Table 4. Mechanical properities of PAN, AOPAN and AOPAN-β-CD

Name	Width of membrane/mm	Average thickness/mm	Tensile strength/MPa
PAN	20	0.102	8.673
AOPAN	19	0.065	3.222
AOPAN-β-CD	20	0.125	3.006

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参考文献(22)

[1]	胡鄂明, 邵二言, 赵静. 含铀废水处理技术研究进展[J]. 湖南生态科学学报, 2016, 3(1):42-48. doi: 10.3969/j.issn.1671-6361.2016.01.008 HU Eming, SHAO Eryan, ZHAO Jing. A study on the research progress in treatment of uranium bearing wastewater[J]. Journal of Hunan Ecological Science,2016,3(1):42-48(in Chinese). doi: 10.3969/j.issn.1671-6361.2016.01.008
[2]	邓冰, 刘宁, 王和义, 等. 铀的毒性研究进展[J]. 中国辐射卫生, 2010, 19(1):113-116. DENG Bing, LIU Ning, WANG Heyi, et al. Research progress of the toxicity of uranium[J]. Chinese Journal of Radiological Health,2010,19(1):113-116(in Chinese).
[3]	董辉阳. 功能高分子膜的制备及其对海水中铀的吸脱附过程的研究[D]. 青岛: 青岛科技大学, 2010. DONG Huiyang. Preparation of functional film and study on the process of adsorption-desorption of uranium from seawater[D]. Qingdao: Qingdao University of Science and Technology, 2010. (in Chinese).
[4]	GAO B, GAO Y, LI Y. Preparation and chelation adsorption property of composite chelating material poly (amidoxime)/SiO₂ towards heavy metal ions[J]. Chemical Engi-neering Journal,2010,158(3):542-549. doi: 10.1016/j.cej.2010.01.046
[5]	FENG Q, WANG X, WEI A, et al. Surface modified ployacrylonitrile nanofibers and application for metal ions chelation[J]. Fibers And Polymers,2011,12(8):1025-1029. doi: 10.1007/s12221-011-1025-0
[6]	NEGHLANI P K, RAFIZADEH M, TAROMI F A. Preparation of aminated-polyacrylonitrile nanofiber membranes for the adsorption of metal ions: Comparison with microfibers[J]. Journal of Hazardous Materials,2011,186(1):182-189. doi: 10.1016/j.jhazmat.2010.10.121
[7]	HUANG F, XU Y, LIAO S, et al. Preparation of amidoxime polyacrylonitrile chelating nanofibers and their application for adsorption of metal ions[J]. Materials,2013,6(3):969-980. doi: 10.3390/ma6030969
[8]	REN J, YAN C, LIU Q, et al. Preparation of amidoxime-modified polyacrylonitrile nanofibrous adsorbents for the extraction of copper(II) and lead(II) ions and dye from aqueous media[J]. Journal of Applied Polymer Science,2018,135:456973.
[9]	武丁胜, 凤权, 魏安方, 等. AOPAN纳米纤维膜的制备及其固定化漆酶研究[J]. 东华大学学报(自然科学版), 2016, 42(5):693-698. WU Dingsheng, FENG Quan, WEI Anfang, et al. Study on preparation of AOPAN nanofibrous membrane and its immobilized laccase[J]. Journal of Donghua University (Natural Science),2016,42(5):693-698(in Chinese).
[10]	YAN C, LIU B, LU G, et al. Preparation of AOPAN/PA-66 composite nanofibers and its adsorption of metal ions[J]. Chemical Journal of Chinese Universities-Chinese,2016,37(1):189-194.
[11]	任晶, 王书刚, 李延春, 等. AOPAN@PAN同轴纳米纤维的制备及吸附性能[J]. 高等学校化学学报, 2018, 39(4):825-831. REN Jing, WANG Shugang, LI Yanchun, et al. Preparation of AOPAN@PAN coaxial nanofiber membrane and it's adsorption property[J]. Chemical Journal of Chinese Universities,2018,39(4):825-831(in Chinese).
[12]	XIE S, LIU X, ZHANG B, et al. Electrospun nanofibrous adsorbents for uranium extraction from seawater[J]. Journal of Materials Chemistry A,2015,3(6):2552-2558. doi: 10.1039/C4TA06120A
[13]	虎龙, 潘智勇, 陈虹, 等. 环糊精功能化聚丙烯腈纳米纤维膜的制备[J]. 合成纤维, 2020, 49(10):25-28. HU Long, PAN Zhiyong, CHEN Hong, et al. Preparation of cyclodextrin functionalized polyacrylonitrile fiber membrane[J]. Synthetic Fiber in China,2020,49(10):25-28(in Chinese).
[14]	赵晟锌, 康晶, 陈忠林, 等. β-环糊精及其衍生物处理水中重金属的研究进展[J]. 水处理技术, 2016, 42(9):1-9. ZHAO Shengxin, KANG Jing, CHEN Zhonglin, et al. Progress in β-cyclodextrin and its derivatives in water treatment[J]. Technology of Water Treatment,2016,42(9):1-9(in Chinese).
[15]	韩叶强, 周文杰, 沈海民, 等. 固载化β-环糊精吸附环境污染物的研究进展[J]. 有机化学, 2016, 36(2):248-257. doi: 10.6023/cjoc201508002 HAN Yeqiang, ZHOU Wenjie, SHEN Haimin, et al. Progress in the immobilization of β-cyclodextrin and their application in adsorption of environmental pollutants[J]. Chinese Journal of Organic Chemistry,2016,36(2):248-257(in Chinese). doi: 10.6023/cjoc201508002
[16]	管迎梅, 张强. 聚丙烯腈纤维碱法部分水解机理研究[J]. 舰船防化, 2007(1):8-12. GUAN Yingmei, ZHANG Qiang. Study on the mechanism for alkaline partial hydrolysis of polyacrylonitrile fiber[J]. Chemical Defence on Ships,2007(1):8-12(in Chinese).
[17]	周建华, 陈锋, 丁玎. 静电纺丝技术制备纳米纤维的影响参数研究进展[J]. 科技与创新, 2019(16):34-35. ZHOU Jianhua, CHEN Feng, DING Ding. Progress in the influence parameters of nanofibers prepared by electrospinning technology[J]. Science and Technology & Innovation,2019(16):34-35(in Chinese).
[18]	邹爽, 赵金松, 陈驰. 静电纺丝技术的影响因素及应用研究综述[J]. 河南科技, 2019(5):75-77. doi: 10.3969/j.issn.1003-5168.2019.05.030 ZOU Shuang, ZHAO Jinsong, CHEN Chi. Review on the influence factors and application of electrostatic spinning technology[J]. Henan Science and Technology,2019(5):75-77(in Chinese). doi: 10.3969/j.issn.1003-5168.2019.05.030
[19]	ZHANG B, GUO X, XIE S, et al. Synergistic nanofibrous adsorbent for uranium extraction from seawater[J]. RSC Advances,2016,6(85):81995-82005. doi: 10.1039/C6RA18785D
[20]	张凡, 汪滨, 王娇娜, 等. AOPAN@Mg(OH)₂多层次电纺纤维膜的制备及除铬性能[J]. 高等学校化学学报, 2016, 37(11):2117-2124. doi: 10.7503/cjcu20160217 ZHANG Fan, WANG Bin, WANG Jiaona, et al. Preparation of hierarchically structured AOPAN@Mg(OH)₂ composite nanofibrous membrane and Cr(VI)-removal capacity[J]. Chemical Journal of Chinese Universities,2016,37(11):2117-2124(in Chinese). doi: 10.7503/cjcu20160217
[21]	何丽凯, 王琳, 张志宾, 等. 偕胺肟功能化水热碳微球对铀的吸附性能[J]. 核化学与放射化学, 2016, 38(2):116-122. HE Likai, WANG Lin, ZHANG Zhibin, et al. Adsorption of U(VI) in aqueous solution by amidoxime-functionalized hydrothermal carbon spheres[J]. Journal of Nuclear and Radiochemistry,2016,38(2):116-122(in Chinese).
[22]	史冬峰. 氧化石墨烯基复合材料吸附铀(VI)的性能与机理试验研究[D]. 衡阳: 南华大学, 2016. SHI Dongfeng. Adsorption characteristics and mechanism experimental study of uranium(VI) by graphene oxide composites[D]. Hengyang: University of South China, 2016. (in Chinese).