Preparation of Porous Polyacrylonitrile Fibrous Membranes and Their Properties for Oil/Water Separation
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摘要: 首先采用静电纺丝制备聚丙烯腈/聚乙烯吡咯烷酮（PAN/PVP）纤维膜，再经水浸渍处理获得多孔聚丙烯腈（PPAN）纤维膜。通过傅里叶变换红外（FT-IR）光谱、热重分析（TGA）探究纤维成孔机理，以X射线光电子能谱（XPS）研究多孔纤维膜中PAN与PVP分子间相互作用力；同时探究PAN与PVP质量比对多孔纤维膜形貌、比表面积、润湿性、力学性能、油/水分离性能的影响，并确定最佳配比。当m（PAN）/m（PVP）=1∶2时，PPAN纤维膜具有较高的力学性能；对正己烷/水混合物的分离通量高达46318 ± 3879 L/（m2·h·bar），效率为（96.01 ± 0.38）%；还实现了对不同种类油/水混合物的高效分离。此外，该PPAN纤维膜表现出优异的循环分离性能，经10次循环分离，通量损失率仅为8.9%。Abstract: First, polyacrylonitrile/polyvinyl pyrrolidone (PAN/PVP) fibrous membrane was prepared by electrospinning, and then polyacrylonitrile porous (PPAN) fibrous membrane was obtained by water impregnation. Fourier transform infrared (FT-IR) spectra and thermogravimetric analysis (TGA) were used to explore the mechanism of fiber pore-forming, and X-ray photoelectron spectroscopy (XPS) was used to study the interaction between PAN and PVP molecules in the porous fibrous membrane. At the same time, the effects of mass ratio of PAN to PVP on the morphology, surface area, wettability, mechanical properties, and oil/water separation performance of porous fibrous membrane were investigated, and the optimal mass ratio was determined. When m(PAN)/m(PVP) was 1∶2, PPAN fibrous membrane showed higher mechanical properties. The separation flux of the n-hexane/water mixture was (46318 ± 3879) L/(m2·h·bar), and the efficiency was (96.01 ± 0.38)%. It also realized the efficient separation of different kinds of oil/water mixtures. In addition, PPAN fibrous membrane showed excellent cyclic separation performance, and the flux loss rate was only 8.9% after ten cycles of separation.
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图 4 纤维膜的（a）FT-IR光谱和（b）TGA曲线
Figure 4. (a) FT-IR spectra and (b) TGA curves of fibrous membranes
图 5 （a）不同纤维的N2吸附-脱附等温曲线；（b）不同纤维膜的BJH孔径分布
Figure 5. (a) N2 adsorption-desorption isotherms of different fibers; (b) BJH pore size distribution of different fibrous membranes
图 6 （a）PAN纤维膜、PPAN2纤维膜的XPS宽扫光谱；（b）PAN纤维膜与（c）PPAN2纤维膜的C1 s窄扫光谱
Figure 6. (a) XPS wide sweep spectra of PAN and PPAN2 fibrous membranes; C1 s narrow sweep spectrum of (b) PAN fibrous membrane and (c) PPAN2 fibrous membrane
图 7 纤维膜的（a）水接触角与润湿时间（b）水下正己烷接触角；（c）PPAN2纤维膜的水下不同油接触角与（d）水下超疏油示意图
Figure 7. (a) Water contact angle, wetting time, and (b) underwater n-hexane contact angle of fibrous membranes; (c) Contact angle for different oils underwater and (d) schematic diagram of underwater superoleophobic of PPAN2 fibrous membrane
图 8 纤维膜的（a）应力-应变曲线和（b）拉伸强度
Figure 8. (a) Stress-strain curve and (b) tensile strength of fibrous membrane
图 9 （a）不同纤维膜对正己烷/水混合物的分离性能；（b）PPAN2纤维膜对不同油/水混合物的分离性能；PPAN2纤维膜10次循环分离的（c）通量和（d）效率
Figure 9. (a) Separation performance of different fibrous membranes for n-hexane/water mixture; (b) Separation performance of PPAN2 fibrous membrane for different oil/water mixtures; (c) Flux and (d) efficiency of 10 cycles separation of PPAN2 fibrous membrane
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