TiO2/PVDF共混微滤膜的制备及其吸附胆红素的研究

doi:10.11949/0438-1157.20200081

摘要/Abstract

摘要：

胆红素是一种内源性毒素，当人体肝脏系统受损或代谢受阻时，则在体内累积，引起高胆红素血症，其具有神经毒性，严重时甚至会危及生命。无机纳米材料作为胆红素吸附剂越来越受到关注，但也存在因团聚而吸附效率降低、因颗粒过小而容易泄漏的问题。以聚偏氟乙烯(PVDF)为基膜原料，掺杂纳米TiO₂颗粒，DMAc为溶剂、PVP为致孔剂，通过干湿相转化法，制得TiO₂/PVDF共混微滤膜。当铸膜液中PVDF浓度为10%(质量)、TiO₂含量为1%(质量)、PVP含量为6%(质量)时，制备的TiO₂/PVDF共混微滤膜的胆红素特异性吸附显著。电镜照片及EDX能谱发现，该膜内部及孔隙中均匀分布TiO₂颗粒，颗粒无团聚现象。实验还考察了胆红素初始浓度、吸附时间、吸附温度、pH等吸附条件的影响。

关键词: 纳米粒子, 聚合物, 共混膜, 吸附, 胆红素

Abstract:

Bilirubin is an endogenous toxin, and accumulated in the body when hepatic injure is happened and excretion is hindered. The high level of bilirubin in the body, i.e., hyperbilirubinemia, manifests neurotoxicity, and threatens life even in serious case. Inorganic nanomaterials have attracted more and more attention as bilirubin adsorbents. However, some problems in bilirubin adsorption with using nanomaterials exist such as a decreasing adsorption efficiency due to agglomeration, and easy leakage because of small particle size. In this paper, TiO₂/PVDF blend microfiltration membrane was prepared by dry-wet phase inversion, which the polyvinylidene fluoride (PVDF) as a matrix material, blended with nano-TiO₂ particles, DMAc as solvent and PVP as porogen. When PVDF concentration was 10%(mass), TiO₂ content was 1%(mass) and PVP content was 6%(mass), the prepared TiO₂/PVDF blend microfiltration membrane showed significantly specific adsorption for bilirubin. SEM and EDX showed that TiO₂ particles were evenly distributed in the membrane and in the pores without agglomeration. The effects of initial bilirubin concentration, adsorption time, adsorption temperature, pH and other adsorption conditions were also investigated.

Key words: nanoparticles, polymers, blend membranes, adsorption, bilirubin

中图分类号:

Q 658

鞠佳, 祁文旭, 孔鹏飞, 汤佳玉, 梁飞雪, 张晓欣, 贺高红, 杨磊. TiO₂/PVDF共混微滤膜的制备及其吸附胆红素的研究[J]. 化工学报, 2020, 71(6): 2705-2712.

Jia JU, Wenxu QI, Pengfei KONG, Jiayu TANG, Feixue LIANG, Xiaoxin ZHANG, Gaohong HE, Lei YANG. Preparation of TiO₂/PVDF blend microfiltration membrane and its adsorption of bilirubin[J]. CIESC Journal, 2020, 71(6): 2705-2712.

图/表 11

图1 胆红素分子结构

Fig.1 Molecular structure of bilirubin

图2 TiO2/PVDF共混微滤膜的制备示意图

Fig.2 Schematic diagram of preparation of TiO2/PVDF blend microfiltration membrane

图3 TiO2含量对TiO2/PVDF共混微滤膜对胆红素吸附量的影响(胆红素浓度2.5 mg/ml，pH 10.9，25℃，吸附2 h)

Fig.3 Effect of TiO2 content on bilirubin adsorption capacity of TiO2/PVDF blend microfiltration membrane(bilirubin concentration 2.5 mg/ml, pH 10.9, 25℃, adsorption time 2 h)

图4 TiO2/PVDF共混微滤膜的微观结构

Fig.4 Microstructure of TiO2/PVDF blend microfiltration membrane

表1 微滤膜性能的比较

Table 1 Comparison of properties of microfiltration membranes

膜

J /

(ml/(cm²·min))

θ/

(°)

W₁/

W₂/

V_M/

cm²

ε /

图5 PVDF-10-1膜断面的SEM图和EDX能谱图

Fig.5 SEM image and EDX spectra of cross section of PVDF-10-1 membrane

图6 吸附温度和时间对TiO2/PVDF共混微滤膜的胆红素吸附量的影响(胆红素浓度2.5 mg/ml，pH 10.9)

Fig.6 Effects of adsorption temperature and time on bilirubin adsorption capacity of TiO2/PVDF blend microfiltration membrane(bilirubin concentration 2.5 mg/ml, pH 10.9)

图7 胆红素初始浓度对TiO2/PVDF共混微滤膜的胆红素吸附量的影响(pH 10.9，37℃，吸附2 h)

Fig.7 Effect of initial bilirubin concentration on bilirubin adsorption capacity of TiO2/PVDF blend microfiltration membrane(pH 10.9, 37℃, adsorption time 2 h)

图8 胆红素Freundlich等温吸附机理

Fig.8 Freundlich isothermal adsorption mechanism of bilirubin

图9 胆红素溶液pH对TiO2/PVDF共混微滤膜吸附胆红素的影响(胆红素浓度2.4 mg/ml，37℃，吸附2 h)

Fig.9 Effect of bilirubin solution pH on bilirubin adsorption capacity of TiO2/PVDF blend microfiltration membrane(bilirubin concentration 2.4 mg/ml, 37℃, adsorption time 2 h)

表2 TiO2/PVDF复合膜与其他吸附材料的吸附性能比较

Table 2 Comparison of adsorption performance of TiO2/PVDF composite membrane with other adsorption materials

吸附剂	胆红素饱和吸附量/ (mg/g membrane)	文献
TiO₂纳米晶体膜	17.1	[20]
Procion Blue H-5R担载纤维素膜	26.0	[29]
聚(吡咯-3-羧酸)氧化铝复合膜	40.7	[30]
β-环糊精改性聚醚砜中空纤维膜	51.0	[31]
TiO₂颗粒	2.4	本文
TiO₂/PVDF复合膜	49.5	本文

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TiO₂/PVDF共混微滤膜的制备及其吸附胆红素的研究

Preparation of TiO₂/PVDF blend microfiltration membrane and its adsorption of bilirubin

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