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. 2022 May 23;12(5):544.
doi: 10.3390/membranes12050544.

Ultrafiltration Membranes Functionalized with Copper Oxide and Zwitterions for Fouling Resistance

Cannon Hackett  1 , Mojtaba Abolhassani  1 , Lauren F Greenlee  2 , Audie K Thompson  1
Affiliations

Ultrafiltration Membranes Functionalized with Copper Oxide and Zwitterions for Fouling Resistance

Cannon Hackett et al. Membranes (Basel). .

Abstract

Polymeric membrane fouling is a long-standing challenge for water filtration. Metal/metal oxide nanoparticle functionalization of the membrane surface can impart anti-fouling properties through the reactivity of the metal species and the generation of radical species. Copper oxide nanoparticles (CuO NPs) are effective at reducing organic fouling when used in conjunction with hydrogen peroxide, but leaching of copper ions from the membrane has been observed, which can hinder the longevity of the CuO NP activity at the membrane surface. Zwitterions can reduce organic fouling and stabilize NP attachment, suggesting a potential opportunity to combine the two functionalizations. Here, we coated polyethersulfone (PES) ultrafiltration membranes with polydopamine (PDA) and attached the zwitterionic compound, thiolated 2-methacryloyloxyethyl phosphorylcholine (MPC-SH), and CuO NPs. Functionalized membranes resulted in a higher flux recovery ratio (0.694) than the unfunctionalized PES control (0.599). Copper retention was high (>96%) for functionalized membranes. The results indicate that CuO NPs and MPC-SH can reduce organic fouling with only limited copper leaching.

Keywords: anti-fouling; copper oxide; polydopamine; ultrafiltration; zwitterion.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
MPC-SH synthesis from 1,10-decanedithiol and MPC.
Figure 2
Figure 2
Possible structures of functionalized membrane top layer. In structure (A), CuO NPs are covalently bonded to the central sulfur atoms in MPC-SH. In structure (B), CuO NPs are adsorbed on top of the MPC-SH.
Figure 3
Figure 3
XRD spectra of CuO nanoparticles.
Figure 4
Figure 4
TEM image of CuO NP suspension at 500,000× magnification.
Figure 5
Figure 5
XPS spectra of nanoparticle and membrane samples. (a) CuO NPs spectra show peaks in the Cu 2p and O 1s regions consistent with copper (II) oxide. (b) CuO/MPC NPs spectra contain Cu2p1/2 and Cu2p3/2 peaks that are shifted to lower binding energy due to Cu-S bonds formed between the CuO NPs and MPC-SH. O 1s region peaks are from the C-O and C=O bonds in MPC-SH and an N 1s peak is from the alkyl ammonium group in MPC-SH. S 2p region peaks arise from oxidized sulfur (S5), C-S-C bonds (S6 and S7) and Cu-S bonds between CuO NPs and MPC-SH (S8). (c) PES/PDA/MPC/CuO membrane spectra contain peaks at virtually the same positions in the Cu 2p and O 1s regions as for CuO NPs and have no apparent peaks in the N 1s or S 2p regions, indicating that the CuO NPs cover the surface.
Figure 6
Figure 6
SEM image of the top surface of a PES membrane (A), PES/PDA membrane (B), PES/PDA/MPC membrane (C), and PES/PDA/MPC/CuO membrane (D) at 20,000× magnification.
Figure 7
Figure 7
Elemental composition of top surface of functionalized PES/PDA/MPC/CuO membrane, as determined by EDX.
Figure 8
Figure 8
FTIR spectra of PES, PES/PDA/MPC, and PES/PDA/MPC/CuO membranes and pure MPC-SH. The peak visible at 1730 cm−1 is from the carbonyl group in MPC-SH. Peaks at 3030 cm−1 and 2853 cm−1 are C-H stretching peaks. These peaks occur in spectra of MPC-SH, PES/PDA/MPC, and PES/PDA/MPC/CuO, but not PES.
Figure 9
Figure 9
Water contact angles for membranes at various stages of functionalization.
Figure 10
Figure 10
Dead-end filtration flux for PES and functionalized membranes. “Func.” results are for functionalized PES/PDA/MPC/CuO membranes.
See this image and copyright information in PMC

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