Enhanced Water Permeability and Antifouling Property of Coffee-Ring-Textured Polyamide Membranes by In Situ Incorporation of a Zwitterionic Metal-Organic Framework.

Modulation of the polyamide structure is critically important for the reverse-osmosis performance of thin-film composite (TFC) membranes in the field of water reuse and desalination. Herein, zwitterionic nanoparticles of zeolitic imidazolate framework-8 (PZ@ZIF-8) were fabricated and incorporated into the polyamide active layer through the interfacial polymerization method. A hydrophilic, zwitterionic coffee-ring structure was formed on the surface of polyamide thin-film nanocomposite (TFN) membranes due to the adjusted diffusion rate of m-phenylenediamine (MPD) from the aqueous phase into the organic phase during the interfacial polymerization process. Surface characterization demonstrated that the coffee-ring structure increased the amounts of water transport channels on the membrane surface and the intrinsic pores of PZ@ZIF-8 maintained the salt rejection. Antifouling and bactericidal activities of TFN membranes were enhanced remarkably owing to the bacterial-"defending" and bacterial-"attacking" behaviors of hydrophilic and zwitterionic groups from PZ@ZIF-8 nanoparticles. This work would provide a promising method for the application of MOFs to enhance the bio-/organic-fouling resistance of TFN membranes with high water permeation and salt rejection.

Strong improvement of nanofiltration performance on micropollutant removal and reduction of membrane fouling by hydrolyzed-aluminum nanoparticles.

Increasing attention has been focused on the removal of micropollutants from contaminated drinking source water. However, low rejection efficiency and membrane fouling still inhibit further application of nanofiltration membrane in this field. Interesting results were found that the residual hydrolyzed-aluminum nanoparticles from supernatant after coagulation and sedimentation strongly improved the nanofiltration performance for micropollutant removal. A simulated raw water containing humic acids, micropollutants and kaolinite clay was employed to investigate the factors of water matrix affecting the nanoparticle-enhanced nanofiltration for micropollutant removal. Results of experiments showed that these hydrolyzed-aluminum nanoparticles easily induced the aggregation of bisphenol-A (BPA) and humic acids in the supernatant. The enhancement of BPA removal was mainly attributed to the repelling interaction between the Al-BPA-DOC complexity and in situ-modified membrane surface during nanofiltration. 'This in situ surface modification by the hydrolyzed-aluminum nanoparticles improved membrane hydrophilicity, roughness and positively-charging capacity. For the treatment of River Songhua water spiked with micropollutant, the percentage removal of BPA was improved to be 88.5%, much more than the case of single nanofiltration without coagulation (60.7%). Meanwhile, the membrane fouling was reduced by 2.13 times than the case of single nanofiltration without the dynamically deposited-layer of nanoparticles. This in situ modification of nanofiltration membrane by hydrolyzed-aluminum nanoparticles achieved excellent removal efficiency for micropollutants from River Songhua water background.

Strong improvement of reverse osmosis polyamide membrane performance by addition of ZIF-8 nanoparticles: Effect of particle size and dispersion in selective layer.

Metal-organic frameworks (MOFs) addition into membranes is able to improve water flux without jeopardizing selectivity, which enhance the performance of reverse osmosis (RO) processes owing to its intrinsic physical and chemical properties, such as porosity structure and high compatibility with the polymer matrix. However, there were few studies about influences of nanoparticle size on MOFs-incorporated thin film nanocomposite (TFN) membranes. Here ZIF-8 particles with different average sizes (50, 150 and 400 nm) were synthesized and incorporated into organic monomer solution to fabricate TFN membranes for water desalination to investigate the membrane performance changed by nanomaterial size. Dispersion of ZIF-8 in selective layer during interfacial polymerization process was affected by particle size. The apparent morphology, roughness, and hydrophilicity of ZIF-8 modified TFN membranes were changed subsequently, which affected the water permeability, salt rejection and fouling resistance performance of the TFN membranes correspondingly. Our results showed that the TFN membrane comprising ZIF-8 with particle size of 50 nm had the best performance due to the highest dispersion in polyamide layer, revealing the importance of MOFs particle size in further investigation of MOFs-incorporated TFN membranes.

CDs@ZIF-8 Modified Thin Film Polyamide Nanocomposite Membrane for Simultaneous Enhancement of Chlorine-Resistance and Disinfection Byproducts Removal in Drinking Water.

Reverse osmosis (RO) is an emerging membrane technology for disinfection byproducts (DBPs) removal. However, the chlorine-resistance and DBPs removal performance of thin film composite (TFC) polyamide membranes should be simultaneously improved when used in chlorinated drinking water. This study was dedicated to synthesize a novel nanoparticle of ZIF-8 with carbon dots (CDs@ZIF-8) and then modify thin film nanocomposite (TFN) membranes to enhance their performance in removing four trihalomethanes (THMs), four haloacetonitriles (HANs), and two haloketones (HKs) in chlorinated drinking water. The fabricated CDs@ZIF-8 nanoparticles and TFN membranes were characterized by FESEM, AFM, XPS, water contact angle, membrane surface potential, and a three-dimensional excitation-emission matrix (EEM) to investigate the influences of CDs@ZIF-8 on TFN membranes. After chlorination, percentage reduction in salt rejection of the CDs@ZIF-8 TFN membranes was lower than that of the TFC membranes due to hydrogen bonding between CDs and polyamide, replacing amidic hydrogen with chlorine, rendering the membrane less susceptible to chlorine attack and enhancing chlorine-resistance. Results also showed that the rejection of DBPs in chlorinated drinking water by CDs@ZIF-8 TFN membranes was more than 95%. The large surface area and abundant oxygen-containing groups of CDs@ZIF-8 made the nanoparticle act as a nanocarbon filler with high adsorption capacity of DBPs. The enhanced performances of chlorine-resistance and DBPs removal by CDs@ZIF-8 TFN membranes determined in this study provided valuable insights on the DBPs control in chlorinated drinking water by RO membranes.