Preparation of Small-Pore Ultrafiltration Membranes with High Surface Porosity by In Situ CO2 Nanobubble-Assisted NIPS

The fabrication of ultrafiltration (UF) membranes with a small pore size (<20 nm) and high surface porosity is still a great challenge. In this work, a nanobubble-assisted nonsolvent-induced phase separation (BNIPS) technique was developed to prepare high-performance UF membranes by adding a tiny amount of CaCO3 nanoparticles into the casting solution. The phase inversion occurred in a dilute-acid coagulation bath to simultaneously generate CO2 nanobubbles, which regulated the membrane structure. The effects of the nano-CaCO3 content in the casting solution on the structure and performance of poly(ethersulfone)/sulfonated polysulfone (PES/SPSf) UF membranes were studied. The UF membrane prepared from a casting solution with 0.3% nano-CaCO3 achieved a surface porosity of 12%, a pore diameter of 10.2 nm, and a skin-layer thickness of 80.3 nm. The superior structure of the UF membrane was mainly attributed to the in situ generation of CO2 nanobubbles because the CO2 nanobubbles were amphiphobic to water and solvents to delay the phase inversion time and acted as nanosize porogens. The produced membrane showed an unprecedented separation performance, achieving a pure water permeance of up to 1128 L·m-2·h-1·bar-1, 2.5 fold that of the control membrane. Similarly, a high bovine serum albumin rejection of above 99.0% was obtained. The overall permeability and selectivity were better than those of commercial and other previously reported UF membranes. This work provides insight toward a simple and cost-effective technique to address the trade-off between pure water permeance and solute rejection of UF membranes.