电纺zein-SLS纤维膜的制备及其离子吸附性能研究

doi:10.11949/0438-1157.20191063

摘要/Abstract

摘要：

选用玉米醇溶蛋白（zein）作为鞘层包裹材料、木质素磺酸钠（SLS）作为芯层强化材料，采用同轴电纺技术制备了可有效吸附重金属离子的zein-SLS纤维膜。优化了膜制备工艺条件，确定纺丝电压适宜为14 kV，芯鞘层进料速率比适宜为1∶1。TEM证实，SLS被成功包埋于zein纤维膜中，但其负载量、包埋率和流失率受溶液pH的影响。离子吸附测试结果表明，SLS的加入可强化zein纤维膜对三种金属离子Ni²⁺、Zn²⁺、Cd²⁺的吸附效果，其中对Zn²⁺吸附能力的强化效果最为显著，上述吸附过程符合准二级吸附动力学模型。同时，在酸性条件下，随着pH的上升，zein纤维膜对Ni²⁺、Zn²⁺、Cd²⁺的吸附能力逐渐提高。

关键词: 同轴电纺, 玉米醇溶蛋白, 木质素磺酸钠, 膜, 制备, 重金属离子, 吸附

Abstract:

In order to fabricate nanofiber film with enhanced adsorption capacity for heavy metal ions, the coaxial electrospinning was utilized to embed sodium lignosulfonate (SLS) in electrospun zein fibers. The process parameters were optimized, i.e. the electrospinning voltage is 14 kV and the core-to-sheath flow rate ratio is 1∶1. The TEM results indicated that SLS was embedded in electrospun zein films successfully. However, its loading capacity, encapsulation efficiency and loss ratio were influenced by the pH of solution. The results of metal ion adsorption tests indicated that SLS enhanced adsorption capacity of Ni²⁺, Zn²⁺ and Cd²⁺, among which Zn²⁺ is the most significant. The pseudo-second-order model was more suitable to describe the adsorption. Furthermore, the adsorption capacity of these three metal ions increased with increasing pH of the solution under acidic conditions.

Key words: coaxial electrospinning, zein, sodium lignosulfonate, film, preparation, heavy metal ions, adsorption

中图分类号:

TQ 341.5

武君媛, 霍伟智, 李志强, 曾嘉恒, 江燕斌. 电纺zein-SLS纤维膜的制备及其离子吸附性能研究[J]. 化工学报, 2020, 71(S1): 252-260.

Junyuan WU, Weizhi HUO, Zhiqiang LI, Jiaheng ZENG, Yanbin JIANG. Preparation of coaxial electrospun zein nanofiber film embedding sodium lignosulfonate for enhanced adsorption of heavy metal ions[J]. CIESC Journal, 2020, 71(S1): 252-260.

图/表 10

图1 不同纺丝电压下zein-SLS同轴纤维SEM

Fig.1 SEM images of zein-SLS coaxial fibers under different electrospinning voltages

图2 不同进料速率比下的zein-SLS同轴纤维扫描电镜图

Fig.2 SEM images of zein-SLS coaxial fibers under different core-to-sheath flow rate ratios

图3 三种zein电纺纤维膜的实物外观照片

Fig.3 Photographs of electrospun zein films with different core materials obtained by spinning

图4 三种电纺纤维的SEM

Fig.4 SEM images of electrospun fibers with different core materials

图5 三种电纺纤维的TEM

Fig.5 TEM images of electrospun fibers with different core materials

图6 SLS改性强化前后zein纤维膜的力学性能

Fig.6 Mechanical properties of electrospun zein films with different core materials

图7 不同pH下zein-SLS纤维膜的负载量和包埋率(a)及流失率(b)

Fig.7 Loading capacity and encapsulation efficiency (a), and loss ratio (b) of electrospun zein-SLS film at different pH

图8 三种纤维膜对Ni2+、Zn2+ 和Cd2+的吸附量与吸附时间的关系

Fig.8 Effect of time on adsorption of Ni2+, Zn2+ and Cd2+ on electrospun films with different core materials

表1 两种动力学模型的拟合参数

Table 1 Parameters of pseudo-first-order model and pseudo-second-order model

离子种类	纤维膜种类	相关系数平方R²
离子种类	纤维膜种类	准一级模型	准二级模型
Ni²⁺	zein-zein	0.9731	0.9962
	zein-0	0.9079	0.9948
	zein-SLS	0.8401	0.9906
Zn²⁺	zein-zein	0.9129	0.9949
	zein-0	0.9709	0.9875
	zein-SLS	0.9451	0.9895
Cd²⁺	zein-zein	0.9370	0.9781
	zein-0	0.8521	0.9886
	zein-SLS	0.9097	0.9885

图9 不同pH下三种纤维膜对Ni2+、Zn2+ 和Cd2+的平衡吸附量

Fig.9 Equilibrium adsorption capacity of Ni2+, Zn2+ and Cd2+ on electrospun films with different core materials at different pH

参考文献 31

1	Sun X Q, Peng B, Ji Y, et al. Chitosan(chitin)/ cellulose composite biosorbents prepared using ionic liquid for heavy metal ions adsorption[J]. AIChE Journal, 2009, 55(8): 2062-2069.
2	Wen Y, Tang Z R, Chen Y, et al. Adsorption of Cr(Ⅵ) from aqueous solutions using chitosan-coated fly ash composite as biosorbent[J]. Chemical Engineering Journal, 2011, 175: 110-116.
3	周婷. 木质素磺酸盐的化学改性及其对金属离子络合性能的研究[D]. 广州: 华南理工大学, 2013.
	Zhou T. Study on the chemical modification of lignosulfonates and its complexing capacity with metal ions[D]. Guangzhou: South China University of Technology, 2013.
4	Liu D G, Li Z H, Li W, et al. Adsorption behavior of heavy metal ions from aqueous solution by soy protein hollow microspheres[J]. Industrial & Engineering Chemistry Research, 2013, 52(32): 11036-11044.
5	Shukla R, Cheryan M. Zein: the industrial protein from corn[J]. Industrial Crops and Products, 2001, 13(3): 171-192.
6	Liu G J, Pang J F, Huang Y N, et al. Self-assembled nanospheres of folate-decorated zein for the targeted delivery of 10-hydroxycamptothecin [J]. Industrial & Engineering Chemistry Research, 2017, 56(30): 8517-8527.
7	Wei D W, Huo W Z, Li G M, et al. The combined effects of lysozyme and ascorbic acid on microstructure and properties of zein-based films [J]. Chinese Journal of Chemical Engineering, 2018, 26(3): 648-656.
8	Kim S, Xu J. Aggregate formation of zein and its structural inversion in aqueous ethanol[J]. Journal of Cereal Science, 2008, 47(1): 1-5.
9	Panchapakesan C, Sozen N, Dogan H, et al. Effect of different fractions of zein on the mechanical and phase properties of zein films at nano-scale[J]. Journal of Cereal Science, 2012, 55(2): 174-182.
10	Fu J X, Wang H J, Zhou Y Q, et al. Antibacterial activity of ciprofloxacin-loaded zein microsphere films[J]. Materials Science & Engineering C-Biomimetic and Supramolecular Systems, 2009, 29(4): 1161-1166.
11	Yoshino T, Isobe S, Maekawa T. Physical evaluation of pure zein films by atomic force microscopy and thermal mechanical analysis[J]. Journal of the American Oil Chemists Society, 2000, 77(7): 699-704.
12	Padgett T, Han I Y, Dawson P L. Incorporation of food-grade antimicrobial compounds into biodegradable packaging films[J]. Journal of Food Protection, 1998, 61(10): 1330-1335.
13	Liu Y H, Nie W, Mu Y B, et al. A synthesis and performance evaluation of a highly efficient ecological dust depressor based on the sodium lignosulfonate-acrylic acid graft copolymer[J]. RSC Advances, 2018, 8(21): 11498-11508.
14	Li Z L, Ge Y Y, Wan L. Fabrication of a green porous lignin-based sphere for the removal of lead ions from aqueous media[J]. Journal of Hazardous Materials, 2015, 285: 77-83.
15	Liang F B, Song Y L, Huang C P, et al. Synthesis of novel lignin-based ion-exchange resin and its utilization in heavy metals removal[J]. Industrial & Engineering Chemistry Research, 2013, 52(3): 1267-1274.
16	王珏珏. 吸附重金属水凝胶的制备及其在冶金污泥资源化中的应用[D]. 武汉: 武汉工程大学, 2017.
	Wang J J. Adsorption of heavy metal in the preparation of hydrogels and its application in metallurgical sludge[D]. Wuhan: Wuhan Institute of Technology, 2017.
17	王文栋, 张健伟, 郑积烽, 等. 三聚氰胺改性木质素的制备及银离子吸附性能[J]. 化工学报, 2013, 64(4): 1478-1484.
	Wang W D, Zhang J W, Zheng J F, et al. Preparation of melamine-modified lignin and its adsorption performance for silver ion[J]. CIESC Journal, 2013, 64(4): 1478-1484.
18	丁春立, 林帝出, 王德武, 等. 电纺及疏水改性制备CA/SiNPs-FAS超疏水复合膜及膜蒸馏脱盐研究[J]. 化工学报, 2018, 69(4): 1774-1782.
	Ding C L, Lin D C, Wang D W, et al. Preparation of superhydrophobic CA/SiNPs-FAS electrospun nanofibrous membranes for direct contact membrane distillation [J]. CIESC Journal, 2018, 69(4): 1774-1782.
19	汪怀远, 肖博, 王池嘉, 等. 静电纺丝法制备氧化钛-氧化石墨复合载体的加氢脱硫性能[J]. 化工学报, 2015, 66(7): 2514-2520.
	Wang H Y, Xiao B, Wang C J, et al. Hydrodesulfurization performance of TiO₂-graphene oxide composite support prepared by electro-spinning[J]. CIESC Journal, 2015, 66(7): 2514-2520.
20	Song J, Zhang B W, Lu Z H, et al. Hierarchical porous poly(L‑lactic acid) nanofibrous membrane for ultrafine particulate aerosol filtration[J]. ACS Applied Materials & Interfaces, 2019, 11: 46261-46268.
21	Liao Y, Loh C H, Tian M, et al. Progress in electrospun polymeric nanofibrous membranes for water treatment: fabrication, modification and applications[J]. Progress in Polymer Science, 2018, 77: 69-94.
22	Wen H F, Yang C, Yu D G, et al. Electrospun zein nanoribbons for treatment of lead-contained wastewater[J]. Chemical Engineering Journal, 2016, 290: 263-272.
23	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.
24	Li J J, Feng H T, He J M, et al. Coaxial electrospun zein nanofibrous membrane for sustained release[J]. Journal of Biomaterials Science, Polymer Edition, 2013, 24(17): 1923-1934.
25	Lin J T, Li C H, Zhao Y, et al. Co-electrospun nanofibrous membranes of collagen and zein for wound healing[J]. ACS Applied Materials & Interfaces, 2012, 4(2): 1050-1057.
26	Yu D G, Chian W, Wang X, et al. Linear drug release membrane prepared by a modified coaxial electrospinning process[J]. Journal of Membrane Science, 2013, 428: 150-156.
27	中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会. 塑料拉伸性能的测定: GB/T 1040—2006[S]. 北京: 中国标准出版社, 2006.
	General Administration of Quality Supervision, Inspection and Quarantine of the People s Republic of China, Standardization Administration of the People s Republic of China. Plastics—determination of tensile properties: GB/T 1040—2006[S]. Beijing: Standards Press of China, 2006.
28	中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会. 水质镍的测定火焰原子吸收分光光度法: GB/T 11912—1989[S]. 北京: 中国标准出版社, 1989.
	General Administration of Quality Supervision, Inspection and Quarantine of the People s Republic of China, Standardization Administration of the People s Republic of China. Water quality—determination of nickel—flame atomic absorption spectrometric method: GB/T 11912—1989[S]. Beijing: Standards Press of China, 1989.
29	中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会. 水质铜、锌、铅、镉的测定原子吸收分光光度法: GB 7475—1987[S]. 北京: 中国标准出版社, 1987.
	General Administration of Quality Supervision, Inspection and Quarantine of the People s Republic of China, Standardization Administration of the People s Republic of China. Water quality—determination of copper, zinc, lead and cadmium—atomic absorption spectrometry: GB 7475—1987[S]. Beijing: Standards Press of China, 1987.
30	Chang F C, Chan K K, Chang C Y. The effect of processing parameters on formation of lignosulfonate fibers produced using electrospinning technology[J]. Bioresources, 2016, 11(2): 4705-4717.
31	Pakravan M, Heuzey M C, Ajji A. Core-shell structured PEO-chitosan nanofibers by coaxial electrospinning[J]. Biomacromolecules, 2012, 13(2): 412-421.

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