Harnessing the power of metal-organic frameworks to develop microplastic

fouling resistant forward osmosis membranes

Mitra Golgoli1, Javad Farahbakhsh1, Abdul Hannan Asif1, Mehdi Khiadani1, Amir
Razmjou1,2,3, Michael L. Johns4, and Masoumeh Zargar*1,3

1
School of Engineering, Edith Cowan University, 270 Joondalup Drive, Joondalup, Perth, WA, 6027,
Australia
2
UNESCO Centre for Membrane Science and Technology, School of Chemical Engineering,
University of New South Wales, Sydney, NSW 2052, Australia
3
Mineral Recovery Research Center (MRRC), School of Engineering, Edith Cowan University,
Joondalup, Perth, WA6027, Australia
4
Fluid Science & Resources Division, Department of Chemical Engineering, The University of
Western Australia, Crawley, WA 6009, Australia

* Corresponding author: m.zargar@ecu.edu.au

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Schematic of the Forward osmosis (FO) setup

A schematic of the FO system used in this work is presented in Fig. S1.

Fig. S1- Schematic of the FO system

Concentration of Microplastics (MPs)

In this study, the concentration of MPs was determined based on data adapted from a recent
investigation of MPs in three different wastewater treatment plants (WWTPs) at different
stages [3]. Since the FO system in this study is proposed as a tertiary treatment strategy, the
total number of MPs (microbeads and fragments) before the tertiary treatments were averaged
based on the data reported in Table 1 of the reference paper; that was found to be 2934
MPs/L. In addition, the average size of the detected microbead and fragment MPs in the
previous study was averaged (based on the data reported in Table S3 of the reference paper)
to estimate the size of MPs which was found to be 197 µm.

Table S1- Number and size of MPs in the effluent of the secondary treatment stages of 3 different WWTPs. All
data are adapted from [3] and averaged to estimate an average concentration of MPs.

WWTP-
WWTPs WWTP - B WWTP - C
A
Number of microbead MPs in S3 (after secondary treatment stage) 570 7748 198
Number of fragment MPs in S3 (after secondary treatment stage) 65 20 203
Total Number of microbead and fragments MPs (MP/L) 635 7768 401
Average Number of microbead and fragments MPs (MP/L) 2934
Average size of microbead MPs 53.17 64.01 26.58
Average size of fragment MPs 400.83 390.09 247.67

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 Average size of microbead and fragments MPs (µm) 197

By using Equation S.1, the average mass concentration of MPs was calculated to be
approximately 10 ppm. The average density of MPs was 0.93 gr/cm3.

Concentration of MPs= Volume of 1 MP * Density * Number of MPs/L (Equation S.1)

Characterization of MPs

The morphology of MPs was analyzed using Hitachi SU3500 SEM. The sample was sputter-
coated with 10 nm silver using an RF magnetron sputtering system (Korea vacuum tech., Ltd)
before SEM imaging was conducted. The SEM image of MPs is shown in Fig. S2. The FTIR
spectra of MPs were investigated using a Perkin Elmer spectrometer and the result is
presented in Fig. S3. The peaks at 718, 731, 1462, and 1472 are attributed to CH 2 bonding,
and the peaks at 2848 and 2914 are correlated to CH bonding [4]. The zeta potential of MPs
solution was measured via a ZEN3600 Zetasizer (Malvern Instruments Co., Ltd., U.K.). The
result showed a zeta potential of −32.49 ± 3.701.

Fig. S2- SEM image of used polyethylene (PE) MPs in this study.

1
The standard deviation was calculated from five independent samples each with 3 measurements of 10 runs.

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 Fig. S3- FTIR spectra of used PE MPs in this study.

Characterization of MIL-53 (Fe)

The size range of MOF particles was determined using a ZEN3600 Zetasizer (Malvern
Instruments Co., Ltd., U.K.) through dynamic light scattering (DLS) measurement. The result
is presented in Fig. S4. The reported data is an average of three independent samples, each
measured three times during 10 runs.

Fig. S4- (A) SEM image and (B) DLS size measurement of the as-prepared MIL-53(Fe) (with a polydispersity
index (PDI) of 0.61 and an average size of 1083 nm)

Images of control and modified substrates

The images of the control (PSf0) and modified (PSf4; with MIL-53(Fe) loading of 0.5 wt.%)
substrates are presented in Fig. S5. The modified substrate appears to have an orange color,
which is attributed to the presence of MIL-53(Fe).

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 Fig. S5- Images of control (PSf0) and modified (PSf4; MIL-53(Fe) loading of 0.5 wt.%) substrates.

Cross section SEM images of substrates

The high magnification cross-section SEM images of the control (PSf0) and modified (PSf4;
with MIL-53(Fe) loading of 0.5 wt.%) substrates are presented in Fig. S6. It is evident that
the modified substrates have several microcellular-like structures due to the rapid
solvent/non-solvent exchange during the phase inversion.

Fig. S6- Cross-section SEM images of control (PSf0) and modified (PSf4; MIL-53(Fe) loading of 0.5 wt.%)
substrates at a magnification of 2.5 kx.

S5
The cross-section SEM images of the modified membrane (PSf4; with MIL-53(Fe) loading of
0.5 wt.%) is presented in Fig. S7.

Fig. S7- Cross-section SEM images of the PSf4 substrate (MIL-53(Fe) loading of 0.5 wt.%).

Washburn Equation
The contact angle and porosity of a membrane surface are related according to the Washburn
Equation [5]:
W [ ( cr ) ω ( π R ) ] ρ σ Cosθ
2 2 2 2
=
t 2η
(Equation S.2)
Where W is the weight of the penetrating liquid, c is a constant to estimate the tortuous path
of the capillaries, r is the radius of the capillary, ω is relative porosity, R is the inner radius of
the measuring tube, 𝜌 is the density of measuring liquid, 𝜎 is the surface tension of the liquid,
𝜃 is advancing contact angle and 𝜂 is the viscosity of the liquid. According to this equation,
the advancing contact angle (𝜃) can be calculated:

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 2
W 2η
Cosθ= (Equation S.3)
[ ( cr ) ω ( π R2 ) ]ρ 2 σ t
2

EDS mapping of the modified substrate

The elemental mapping of the top surface and cross-section of the PSf4 substrate (MIL-53
(Fe) loading of 0.5 wt.%) as the representative of the modified substrates are presented in Fig.
S8. The results confirmed the presence and uniform distribution of Fe element across the
membrane.

Fig. S8- EDS mapping of the top surface and cross-section of PSf4 (MIL-53(Fe) loading of 0.5 wt.%) as the
representative of modified substrates.

Initial water flux data for each group of foulants

The initial water flux data for each group of foulants (i.e., MPs, BSA and combined BSA and
MPs) are presented in Table S2.

Table S2- Initial water flux data of fouling experiments for each group of foulants; Standard deviations are the
average of two replicates of fouling experiments.

Initial water flux (LMH)

FS TFC0 TFC3

MPs 5.24±0.29 10.3±1.3

BSA 5.78±0.48 10.81±0.6

BSA+MP
s 5.92±0.1 11.16±0.12

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