Abstract

High-performance thin film nanocomposite (TFN) hollow fiber (HF) membranes, with MIL-101(Cr) MOF nanoparticles (52 ± 13 nm) embedded, have been synthesized with the polyamide layer formed either on the outer or inner surface of a polysulfone HF (250 and 380 μm ID and OD, respectively). The TFN_out membrane was developed using the conventional interfacial polymerization method, typically applied to obtain TFN flat membranes (MOF particles added to the thin layer by deposition). This membrane gave a water permeance value of 1.0 ± 0.7 L·m–2·h–1·bar–1 and a rejection of 90.9 ± 1.2% of acridine orange (AO, 265 Da). In contrast, the TFN_in membrane was synthesized by microfluidic means and gave a significantly higher water permeance of 2.8 ± 0.2 L·m–2·h–1·bar–1 and a slightly lower rejection of 87.4 ± 2.5% of the same solute. This remarkable increase of flux obtained with small solute AO suggests that the HF membranes developed in this work would exhibit good performance with other typical solutes with higher molecular weight than AO. The differences between the performances of both TFN_in and TFN_out membranes lay on the distinct superficial physicochemical properties of the support, the synthesis method, and the different concentrations of MOF present in the polyamide films of both membranes. The TFN_in is more desirable due to its potential advantages, and more effortless scalability due to the microfluidic continuous synthesis. In addition, the TFN_in membrane needs much fewer quantities of reactants to be synthesized than the TFN_out or the flat membrane version.

Highlights

  • Nanofiltration is a process that aims at separating different mixtures that involve water and organic solvents, as well as ionic solutes and organic molecules with molecular weights between 200 to 1000 gꞏmol-1, by economic and efficient means

  • The Thermo-gravimetric analysis (TGA) curve shows the total activation of the MIL-101(Cr) in agreement with the lack of mass losses previous to the degradation temperature, except for a 7% lost at the beginning of the curve, probably due to the well-known hydrophilicity of this MOF.[6]

  • Even if the current work is focused on only one type of support, especially suitable due to its commercial application and availability, the influence of the support on the synthesis of thin film composite (TFC) membranes has been addressed by several authors from the point of view of porosity and hydrophobicity.25,x One of the key issues deals with its chemical composition, while for water nanofiltration applications PSf are suitable, in case of organic solvent nanofiltration, solvent resistant polymers submitted to crosslinking are applied.[2,3]

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Summary

Introduction

Nanofiltration is a process that aims at separating different mixtures that involve water and organic solvents, as well as ionic solutes and organic molecules with molecular weights between 200 to 1000 gꞏmol-1, by economic and efficient means. Many researchers from several countries have studied and suggested different membrane structures, among which the thin film composite (TFC) and nanocomposite (TFN) membranes are two of the most successful types.[1] The structure of these membranes, which consists of an asymmetric support with a selective thin layer of polyamide (PA) on top, allowed to change the physicochemical properties of each layer separately.[2] For this reason, many combinations of polymers have been studied,[3] several of them available as commercial membranes. In 2013, Sorribas et al.[6] developed metalorganic framework (MOF) embedded TFN membranes for organic solvent nanofiltration (OSN) with enhanced separation properties, because of the high specific surface areas, narrow porosity, and inorganic-organic character of these nanostructures (MIL-101(Cr), ZIF-8, MIL-53(Al) and NH2-MIL-53(Al)) for good compatibility with polymers. Several authors studied the effect of other MOF NPs (MIL-68(Al) and ZIF-11,7 and UiO-66, ZIF-8 and ZIF-93,8 and the simultaneous combination of two complementary MOFs (ZIF-11 and MIL-101(Cr)9) in the performance of TFN membranes for OSN

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