聚砜/钌纳米簇杂化膜的制备及其性能研究

Preparation and properties of polysulfone/ruthenium nanocluster hybrid membrane

以乙二醇为溶剂和还原剂,聚乙烯吡咯烷酮(PVP)为保护剂,RuCl_3·nH_2O为前体盐[n(PVP)∶n(Ru^(3+))=10∶1],还原制备了高分子稳定的Ru纳米簇。通过TEM、XRD表征发现,制得的钌粒径在2.5 nm左右;通过控制钌的负载量制备了一系列聚砜/钌纳米簇杂化膜,通过SEM、XPS、TG、透气性能和孔隙率测试对杂化膜的结构及性能进行表征。结果发现,由于Ru和聚砜中的S、O元素存在着配位作用而使得杂化膜热稳定性提高,透气选择性明显提高;杂化前后,膜的孔隙率由21%增大到52%左右,而负载量的变化对膜的孔隙率影响不大。基于以上基础研究,通过干湿法纺丝制得PSF/2%Ru杂化中空纤维膜并经费托测试发现,在190℃时,产物中C_1~C_4质量分数达到6.3%左右,对费托反应起到一定的催化作用。

The polymer stabled Ru nano-cluster is prepared by using ethylene glycol as solvent and reducing agent,PVP as protect agent,Rucl3·nH2O as salt precursor [n（ PVP） ∶ n（ Ru^3＋） = 10 ∶ 1]. The diameter of ruthenium is determined as around 2. 5 nm by TEM and XRD. By controlling the loading of ruthenium,a series of polysulfone（ PSF） /ruthenium（ Ru） hybrid membranes are prepared. The structure and performance of hybrid membranes are characterized by SEM,XPS,TGA,permselectivity and porosity test. The results show that the addition of ruthenium can improve the thermal stability and permselectivity of the PSF/Ru hybrid membrane in a certain extent through the coordination between Ru and O,S atoms in PSF. In comparison with pristine PSF membrane,the porosity of PSF/Ru can be increase from 21%to about 52% after doping of ruthenium. Moreover,the porosity is only slightly affected by changing the amount of Ru.Based on these fundamental researches,PSF/2% Ru hybrid hollow fiber membranes are prepared by dry-wet spinning and tested in Fischer-Tropsch synthesis. It is found that the PSF/Ru hybrid fiber membrane exhibits catalytic capability in Fischer-Tropsch Synthesis and the mass fraction of C1- C4 in products is about 6. 3% at 190℃.