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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

Postal Subscription Code 80-973

2018 Impact Factor: 3.883

Front. Environ. Sci. Eng.    2022, Vol. 16 Issue (4) : 40    https://doi.org/10.1007/s11783-021-1474-7
RESEARCH ARTICLE
Tuning the primary selective nanochannels of MOF thin-film nanocomposite nanofiltration membranes for efficient removal of hydrophobic endocrine disrupting compounds
Ruobin Dai1, Hongyi Han1, Yuting Zhu2, Xi Wang2, Zhiwei Wang1()
1. State Key Laboratory of Pollution Control and Resource Reuse, Shanghai Institute of Pollution Control and Ecological Security, School of Environmental Science and Engineering, Tongji University, Shanghai 200092, China
2. Tongji Architectural Design (Group) Co., Ltd., Environmental Engineering Branch, Shanghai 200092, China
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Abstract

• PA layer properties tune the primary nanochannels in MIL-101(Cr) TFN NF membranes.

• The dense PA layer induced transition of primary nanochannels of TFN NF membranes.

• Nanochannels around MOF contributed to the improved flux with a loose PA structure.

• Nanochannels in MOFs dominated the separation performance with a dense PA structure.

Metal organic framework (MOF) incorporated thin-film nanocomposite (TFN) membranes have the potential to enhance the removal of endocrine disrupting compounds (EDCs). In MOF-TFN membranes, water transport nanochannels include (i) pores of polyamide layer, (ii) pores in MOFs and (iii) channels around MOFs (polyamide-MOF interface). However, information on how to tune the nanochannels to enhance EDCs rejection is scarce, impeding the refinement of TFN membranes toward efficient removal of EDCs. In this study, by changing the polyamide properties, the water transport nanochannels could be confined primarily in pores of MOFs when the polyamide layer became dense. Interestingly, the improved rejection of EDCs was dependent on the water transport channels of the TFN membrane. At low monomer concentration (i.e., loose polyamide structure), the hydrophilic nanochannels of MIL-101(Cr) in the polyamide layer could not dominate the membrane separation performance, and hence the extent of improvement in EDCs rejection was relatively low. In contrast, at high monomer concentration (i.e., dense polyamide structure), the hydrophilic nanochannels of MIL-101(Cr) were responsible for the selective removal of hydrophobic EDCs, demonstrating that the manipulation of water transport nanochannels in the TFN membrane could successfully overcome the permeability and EDCs rejection trade-off. Our results highlight the potential of tuning primary selective nanochannels of MOF-TFN membranes for the efficient removal of EDCs.

Keywords Porous metal organic framework      Thin-film nanocomposite membrane      Primary selective nanochannels      Nanofiltration      Endocrine disrupting compounds     
Corresponding Author(s): Zhiwei Wang   
Issue Date: 13 July 2021
 Cite this article:   
Ruobin Dai,Hongyi Han,Yuting Zhu, et al. Tuning the primary selective nanochannels of MOF thin-film nanocomposite nanofiltration membranes for efficient removal of hydrophobic endocrine disrupting compounds[J]. Front. Environ. Sci. Eng., 2022, 16(4): 40.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-021-1474-7
https://academic.hep.com.cn/fese/EN/Y2022/V16/I4/40
Fig.1  Characterization of the synthesized MIL-101(Cr): (a) SEM image, (b) measured XRD pattern and simulated pattern using Diamond 3.2, (c) FTIR spectrum with vertical lines showing bands at 3428, 1613, 1510, and 1394 cm−1, and (d) N2 adsorption-desorption curves. All characterization techniques for the MIL-101(Cr) were conducted after activation by overnight vacuum-drying at 120°C.
Fig.2  SEM characterization of (a–d) the TFC and (e–h) MOF-TFN membranes synthesized at four PIP monomer concentrations (corresponding to C1, C2, C3 and C4). All membranes before SEM characterization were sputter coated with Au and Pd. The accelerating voltage for the measurements is 5 kV.
Fig.3  ATR-FTIR (a) and XPS spectra (b) of TFC membranes, and ATR-FTIR (c) and XPS spectra (d) of TFN membranes synthesized with the four different monomer concentrations. Vertical lines in Figs. 3(a) and (c) show bands at 1404 cm−1. Elemental chromium was detected in the XPS spectra of TFN membranes, whose peak was highlighted in Fig. 3(d).
Membrane PIP concentration C (%) N (%) O (%) Cr (%) O/Na O/Nb Cross-linking degree (%)
TFC C1 77.28 13.86 8.87 / 1.56 1.56 34.4
C2 76.43 14.18 9.39 / 1.51 1.51 39.0
C3 76.76 13.57 9.67 / 1.4 1.4 50.0
C4 78.62 12.79 10.38 / 1.23 1.23 69.1
TFN C1 74.05 15.77 9.81 0.41 1.61 1.48 42.4
C2 74.55 15.00 10.03 0.42 1.50 1.33 57.5
C3 73.37 15.06 11.13 0.44 1.35 1.23 69.7
C4 74.12 14.65 10.93 0.40 1.34 1.22 70.3
Tab.1  Elemental ratios and cross-linking degrees of TFC and TFN membranes based on XPS results. Before calculation of cross-linking degrees of TFN membranes, the interference of MOF on O/N was excluded according to the chemical formula of MIL-101(Cr)
Fig.4  Zeta potentials of (a) the TFC and (b) TFN membranes, (c) schematic of polyamide layer structural changes with increasing monomer concentrations. Water contact angles of (d) the TFC and (e) TFN membranes under the four different monomer concentrations, and (f) a chemical reaction describing interfacial polymerization. Note: The zeta potential of MIL-101(Cr) is also presented in the Fig. 4(b) for comparison, and membrane characterizations were performed in triplicate.
Fig.5  GNPs-TEM characterization and corresponding schematics of primary water transport pathways of MOF-TFN membranes with different monomer concentrations: (a) C1 of 0.5 wt%, (b) C2 of 1.0 wt%, (c) C3 of 1.5 wt% and (d) C4 of 2.0 wt% PIP in water. The GNP solution (1.0 × 1012 particles/mL) was dosed into a dead-end filtration cell for dynamic filtration under 5.0 bar pressure. The accelerating voltage of TEM characterization is 120 kV.
Fig.6  Pure water permeability of (a) the TFC and (b) TFN membranes, rejection of multiple salts of (c) the TFC and (d) TFN membranes, and dextrose rejection of (e) the TFC and (f) TFN membranes across the four monomer concentrations. The cross-flow velocity for all performance evaluations was 20 cm/s. The water temperature and applied pressure was 25°C and 8 bar, respectively. The salt concentration in the feed was 10 mmol/L and the dextrose concentration was 40 mg/L (as TOC). All experiments were performed in triplicate.
Fig.7  (a) Incremental factors calculated from data of Fig. 6, (b) schematic of multiple water transport pathways, and (c) schematic of water transport and resistance changes for TFN membranes across the increase in monomer concentrations. W1, W2 and W3 denote water transport nanochannels of polyamide (W1), inside MIL-101(Cr) (W2) and around MIL-101(Cr) (W3), respectively, while R1, R2 and R3 indicate the resistance of the corresponding nanochannels (W1, W2 and W3).
Fig.8  EDCs rejection rates of (a) the TFC and (b) TFN membranes across four monomer concentrations. The cross-flow velocity for all performance evaluations was 20 cm/s. The water temperature and applied pressure was 25°C and 8 bar, respectively. The EDCs concentration in the feed was 200 μg/L. All experiments were performed in triplicate.
Fig.9  EDCs sorption by (a) the TFC and (b) TFN membranes across four monomer concentrations. The EDCs sorption was measured by extracting EDCs from membranes after a cross-filtration test using a 50% methanol solution. All experiments were performed in triplicate.
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[1] FSE-21057-OF-DRB_suppl_1 Download
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