To improve the mechanical strength and separation performance of sulfonated polysulfone (SPSf) ultrafiltration membranes, Tröger's base (TB) polymer was blended into the casting solution. An acid-base crosslinking structure between the sulfonic acid groups of SPSf and tertiary amine groups in TB would contribute to their good compatibility and influence the membrane formation process, morphology and properties. The formation of acid-base pairs was confirmed by the existence of quaternary amine groups in the X-ray photoelectron spectra of SPSf/TB blend membranes. According to the pore structure analysis of ultrafiltration membranes, the blending of TB polymer into SPSf enhanced the surface and total porosities, and reduced the top layer thickness. In addition, the finger-like pores became more regular and vertically interconnected. The SPSf/TB blend membrane showed a higher water contact angle than SPSf membrane due to the addition of hydrophobic TB polymer and formation of acid-base crosslinking structure. The SPSf/TB blend membranes showed higher pure water fluxes (127.4–342.7 L m −2 h −1 ) than the SPSf membrane (51.6 L m −2 h −1 ). All membranes showed similar retention factor for bovine serum albumin (BSA), a model protein foulant. In static experiments, the amount of BSA adsorbed by the SPSf/TB blend membranes was much lower than that of the pristine SPSf membrane because the enhanced charge of the blend membranes (ζ = −72.46 ~ −79.17 mV) strengthened the electrostatic repulsion between membrane surface and BSA. The flux recovery ratio after three ultrafiltration cycles using SPSf/TB blend membranes was lower than that of SPSf membrane because pore blockage and irreversible pollution occurred more easily under a high flux, larger average pore size, and lower hydrophilicity. The introduction of TB polymer enhanced the mechanical strength of the ultrafiltration membrane due to the formation of acid-base crosslinking structure between TB polymer and SPSf.
Yin Jiulong,Tang Hai,Liu Di,Huang Tingting,Zhu Lei
High-performance sulfonated polysulfone (SPSf) mixed-matrix membranes (MMMs) were fabricated via a nonsolvent-induced phase separation (NIPS) method using zeolitic imidazolate frameworks-67 (ZIF-67) as a crosslinker. Acid-base crosslinking occurred between the sulfonic acid groups of SPSf and the tertiary amine groups of the embedded ZIF-67, which improved the dispersion of ZIF-67 and simultaneously improved the membrane strzcture and permselectivity. The dispersion of ZIF-67 in the MMMs and the acid-base crosslinking reaction were verified by energy-dispersive X-ray spectroscopy (EDX), X-ray diffractometry (XRD), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The pore structure analysis of MMMs indicated that filling ZIF-67 into SPSf enhanced the average surface pore sizes, surface porosities and more micropore in cross-sections. The crossflow filtrations showed the MMMs have higher pure water fluxes (57 to 111 L m −2 h −1 ) than the SPSf membrane (55 L m −2 h −1 ) but also higher bovine serum albumin (BSA) rejection rate of 93.9–95.8%, a model protein foulant. The MMMs showed a higher water contact angle than the SPSf membrane due to the addition of hydrophobic ZIF-67 and acid-base crosslinking, and also maintained high thermal stability evidenced by the thermogravimetric analysis (TGA) results. At the optimal ZIF-67 concentration of 0.3 wt%, the water flux of the SPSf-Z67-0.3 membrane was 82 L m −2 h −1 with a high BSA rejection rate of 95.3% at 0.1 MPa and better antifouling performance (FRR = 70%). An SPSf-matrix ultrafiltration (UF) membrane was developed by blending with hydrophobic ZIF-67. ZIF-67 has good dispersibility and compatibility with SPSf of weak acid-base interaction. Simultaneous enhancement in the permeability and selectivity of the MMMs.
危险品化学品经营许可证（带存储）