Subscriber access provided by UNIVERSITY OF SASKATCHEWAN LIBRARY

Energy, Environmental, and Catalysis Applications

Biomimetic Durable Multifunctional Self-Cleaning Nanofibrous
Membrane with Outstanding Oil/water Separation, Photodegradation
of Organic Contaminants, and Antibacterial Performances
Wenjing Ma, Yuansheng Li, Mengjie Zhang, Shuting Gao, Jiaxin Cui, Chaobo Huang, and Guo-Dong Fu
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.0c09059 • Publication Date (Web): 14 Jul 2020
Downloaded from pubs.acs.org on July 15, 2020

Just Accepted

“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a service to the research community to expedite the dissemination
of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in
full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully
peer reviewed, but should not be considered the official version of record. They are citable by the
Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore,
the “Just Accepted” Web site may not include all articles that will be published in the journal. After
a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web
site and published as an ASAP article. Note that technical editing may introduce minor changes
to the manuscript text and/or graphics which could affect content, and all legal disclaimers and
ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or
consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W.,

Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the
course of their duties.
Page 1 of 31 ACS Applied Materials & Interfaces

1
2
3
4 Biomimetic Durable Multifunctional Self-cleaning Nanofibrous
5
6
7 Membrane with Outstanding Oil/water Separation, Photodegradation
8
9 of Organic Contaminants, and Antibacterial Performances
10
11
12 Wenjing Ma1, Yuansheng Li 2, Mengjie Zhang2, Shuting Gao2, Jiaxin Cui2, Chaobo
13
14
Huang2, * and Guodong Fu1, *
15
16
17 1. College of Chemistry and Chemical Engineering, Southeast University (SEU),
18
19
20 Nanjing, 211189, P. R. China
21
22 2. College of Chemical Engineering, Jiangsu Provincial Key Lab for the Chemistry
23
24
25 and Utilization of Agro-forest Biomass, Jiangsu Key Lab of Biomass-based Green
26
27
28
Fuels and Chemicals, Nanjing Forestry University (NFU), Nanjing, 210037, P. R.
29
30 China
31
32
33 *Corresponding authors
34
35 Tel: +86-25-85427532; Fax: +86-25-85427532; Email: Chaobo.Huang@njfu.edu.cn
36
37
38 (Chaobo Huang);
39
40
41
Tel.: +86-25-52090625; Fax: +86-25-52090625; Email: 101010855@seu.edu.cn
42
43 (Guodong Fu)
44
45
46 Abstract
47
48 Wastewater pollution has always been one of the most sever worldwide environmental
49
50 problems. In addition, in light of the frequent oil spills that have occurred in recent
51
52 years, the treatment of oily wastewater is particularly important. In this work, a novel
53
54 zeolitic imidazolate framework-8@thiolated graphene (ZIF-8@GSH) composites-
55
56 based polyimide (PI) nanofibrous membrane was developed via a facile electrospinning
57
58 and in-situ hydrothermal synthesis approaches for effective purification of oily
59
60 wastewater. The membrane showed superhydrophobicity/superoleophilicity and high
1

ACS Paragon Plus Environment

 ACS Applied Materials & Interfaces Page 2 of 31

1
2
3
4 separation efficiency (>99.9%) for a wide range of oil/water mixtures and water-in-oil
5
6 emulsions. Besides, the membrane demonstrated excellent photocatalytic dye
7
8 degradation, antibacterial, self-cleaning, and mechanochemical durable abilities,
9
10 showing high potential in oily wastewater treatment and water remediation.
11
12
Keywords: Durable, zeolitic imidazolate framework-8@thiolated graphene,
13
14
nanofibrous membrane, self-cleaning, oil/water separation, photodegradation of
15
organic contaminants, antibacterial
16
17
18 Introduction
19
20 The severe shortage of the clean water poses significant challenges for our modern
21
22 societies.1-3 Water pollution including oil, organic solvents, and dyes has become a
23
24 major environmental concern, which led to severe environmental problems, threatened
25
26 human health and affected the sustainable development of society.4-5 However, there
27
28 are challenges related to the traditional approaches, including mechanical removal,
29
30 controlled burning, and photocatalysis, for water remediation in single-material
31
32 systems for sustainable development.6-9 Consequently, the development of
33
34 multifunctional material which can effectively separate oils and organic solvents,
35
36 simultaneously degrade these pollutants from water is highly desirable.
37
38
39
40
The present technologies for oil-spill cleaning are categorized into filtration and
41
adsorption.10 Compared with adsorption, filtration attracts intensive attentions owing to
42
43
its high efficiency, simplicity, and cost-effectiveness.11 Additionally, many materials
44
45 have been developed to separate oil from water, including aerogel,12 monolith,13
46
47 microsphere14 and membrane.15 Compared to the others, membrane filtration offers
48
49 several advantages such as lower energy input, no need for extraneous chemicals and
50
51 continuous operation.3, 16-17 These advantages, coupled with the ability of membranes
52
53 to reject other pollutants present in the feed, make membranes separation a promising
54
55 technology to treat a variety of oily wastewater. Various methods have been exploited
56
57 to prepare membranes for oily wastewater treatment, such as electrospinning, self-
58
59 assembly, and phase separation. Among those approaches, electrospinning seems to be
60
2

ACS Paragon Plus Environment

Page 3 of 31 ACS Applied Materials & Interfaces

1
2
3
4 the most versatile and straightforward technique for generating membranes. The most
5
6 noticeable feature associated with electrospinning membranes is the relatively uniform
7
8 fiber diameter, large porosity, and a high surface area to volume ratio. 15, 18-19 Recently,
9
10 inspired by lotus leaf and butterfly wings, electrospun fibrous membrane with
11
12
superhydrophobicity and superoleophilicity have been developed and show promising
13
14
applications for oily wastewater treatment.20 However, despite the fact that
15
superhydrophobic membranes have been intensively investigated, current methods still
16
17
suffer from problems with respect to expensive components and complex experimental
18
19 procedures. In addition, most superhydrophobic/superoleophilic membranes lost their
20
21 superhydrophobic performance when exposed to harsh environments. Furthermore, to
22
23 achieve superhydrophobicity, post-treatment was usually required to increase the
24
25 surface roughness by introduction of nanoparticles. However, the particle could easily
26
27 detach from the fibers due to the weak bonding between the nanofibers and
28
29 nanoparticles, which results in a gradual loss of superhydrophobicity.21 These
30
31 associated concerns may limit their application in real oily wastewater treatment. From
32
33 a practical point of view, cost-effective and facile fabrication of robust,
34
35 superhydrophobic electrospun fibrous membranes are urgently needed.
36
37
38
39 In this regard, metal-organic framework (MOF) materials have been the recent focus as
40
41 related nanodevices and molecular sieve membranes.22-24 On account of its
42
43 straightforward synthesis and low cost, the zeolitic imidazolate framework-8 (ZIF-8)
44
45 has been extensively investigated for its various applications in water treatment,
46
47 adsorption of organic pollutants, and photocatalysis.25-27 For another, a drastically risen
48
49 interest in graphene-based materials have witnessed in the past few years .28-29 Inspired
50
51
by the hydrophobic nature and two-dimensional structure, some researchers begun to
52
53
use graphene-related materials to develop superhydrophobic materials for the
54
separation of oil-water mixture.30-31 For instance, Nguyen et al. reported a dip-coating
55
56
method to fabricate graphene coated sponge as a highly efficient oil absorbent.32 By in-
57
58 situ reduction, Liu et al. fabricated the superhydrophobic reduced graphene oxide
59
60
3

ACS Paragon Plus Environment

 ACS Applied Materials & Interfaces Page 4 of 31

1
2
3
4 functionalized polyurethane sponge with high oil absorption capacity.33 In another
5
6 study, Zhou and co-workers prepared superhydrophobic graphene/polyurethane (PU)
7
8 sponge using a dip-coating and a solvothermal route for oil-water separation.34 Whereas,
9
10 as far as we know, the widely studied superhydrophobic graphene-based materials are
11
12
restricted to graphene and derivative compounds like reduced graphene oxide, silane
13
14
functionalized graphene oxide, and so forth. Recently, Kolleboyina Jayaramulu et al.
15
generated superhydrophobic and superoleophilic hybrid material based on ZIF-8
16
17
intercalated between highly fluorinated graphene oxide (HFGO), which displayed high
18
19 sorption selectivity and good absorbencies for oils from water.31 Unfortunately, the use
20
21 of fluorine-containg of HFGO presents plenty of disadvantages, especially its
22
23 expensive and toxic, preventing their further large-scale application and may causing
24
25 severe environmental concerns after application.
26
27
28
29 Inspired by the self-cleaning lotus leaf,13 here we report facile electrospinning and in-
30
31 situ hydrothermal synthesis strategies to obtain a ZIF-8@thiolated graphene
32
33 composites-based PI nanofibrous membrane with superhydrophobicity based on the
34
35 synergistical effect of the inherent hydrophobic nature of ZIF-8 and GSH and porous
36
37 micro/nanostructure of the nanofibrous membrane. Owing to the surface decorated with
38
39 novel designed ZIF-8@GSH nanohybrids, the obtained membrane features
40
41 superhydrophobicity with a large water contact angle (WCA ≈ 153.25o) like lotus leaves
42
43 as well as self-cleaning ability. The coated PI membrane owns ultra-high anti-stain,
44
45 excellent reusability and durability, which can effectively separate not only oil/water
46
47 mixtures, but also highly stabilized water-in-oil emulsions. Additionally, the prepared
48
49 membrane exhibited high photocatalytic dye degradation performance and high
50
51
antibacterial activity against Escherichia coli and Bacillus subtilis. Furthermore, the as-
52
53
prepared membrane endows with excellent chemical and mechanical stabilities. These
54
promising properties render ZIF-8@GSH/PI membrane a potential material for
55
56
complex wastewater treatment.
57
58
59
60
4

ACS Paragon Plus Environment

Page 5 of 31 ACS Applied Materials & Interfaces

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Scheme. 1. Schematic illustration of the fabrication routine of ZIF-8@GSH/PI
26
27
nanofibrous membrane
28 2. Experimental section
29
2.1. Materials
30
31 Biphenyl tetracarboxylic dianhydride (BPDA, C16H6O6), phenylenediamine (PDA,
32
33 C6H8N2), graphite powder, thiourea (CH4N2S), and sodium hydroxide (NaOH), sodium
34
35 chloride (NaCl), sodium sulphate (Na2SO4), 2-methylimidazole (2-MI, C4H6N2), zinc
36
37 nitrate hexahydrate (Zn(NO3)2·6H2O), 5,5-dimethyl-1-pyrroline-N-oxide (DMPO,
38
39 C6H11NO), petroleum ether (PE, C5H12), n-hexane (C6H14), N, N-Dimethylformamide
40
41 (DMF, C3H7NO ), ethyl acetate (EA, CH3COOCH2CH3), ethanol (C2H5OH), dimethyl
42
43 sulfoxide (DMSO, C2H6OS) (C6H14), oil red O (C26H24N4O), methylene blue (MB,
44
45 C16H18N3ClSIUPAC), kerosene, and paraffin were all purchased from Aladdin
46
47 (Shanghai, China). Sulfuric acid (H2SO4), hydrogen peroxide (H2O2, 30%),
48
49 hydrochloric acid (HCl, 37%), ethanol (C2H5OH), dichloromethane (C2H2Cl2),
50
51
trichloromethane (CH3Cl), bromobenzene (C6H5Br), carbon tetrachloride (CCl4),
52
53
dichloroethane (C₂H₄Cl₂), and potassium permanganate (KMnO4) were supplied by
54
Sinopharm Chemical Reagent (Shanghai, China).
55
56
57
2.2. Synthesis of thiolated graphene (GSH)
58
59
60
5

ACS Paragon Plus Environment

 ACS Applied Materials & Interfaces Page 6 of 31

1
2
3
4 The synthesis of thiolated graphene was carried out as follows. 24 mL HBr was added
5
6 into 300 mL graphene oxide (GO) suspension (synthesized in Supporting
7
8 Information, 1mg/mL, containing about 0.3 g GO). After stirring for 2 h at room
9
10 temperature, thiourea (20 g) was introduced and the mixture was reacted at 80
11 o
12 C for 20 h. Then, NaOH (20 g) was added into the above solution and stirring
13
14
vigorously for 10 min. The resulting mixtures was cooled down to room
15
16
temperature. After filtration and washing with water and ethanol, the product was dried
17
in vacuum.
18
19
20 2.3. Preparation of the ZIF-8@GSH/PI nanofibrous membrane
21
22
23 The PI membrane was prepared following the previous study19 and presented in
24
25 supporting information. First, PI nanofibrous membrane was ultrasonically rinsed in
26
27 acetone and deionized water, respectively. Then cleaned PI membrane (M0) was
28
29 immersed into the GSH aqueous dispersion (1mg/ml) and sonicated for 24 h. The GSH
30
31 coated PI membrane (denoted as: GSH/PI (M1)) was dried in vacuum for 2 h at 80 oC.
32
33 To optimize the hydrophobicity of the GSH/PI membrane, the GSH concentration
34
35 varied from 0.1 mg/mL to 2 mg/mL.
36
37
38 220 mg Zn (NO3)2·6H2O and 4220 mg 2-MI were each dissolved in 50 ml DI water (i.e.
39
40 the 2-methylimidazole and the zinc nitrate concentration in water were fixed at a
41
42 concentration of 42.2 and 2.2 g/L). And a homogenous solution was obtained after
43
44 mixing the above solutions and stirring for 5 min. Then, the GSH/PI membrane was
45
46 dipped into the mixed solution and the reaction was allowed to proceed for 1 h at 50 °C
47
48 for ZIF-8 growth. Subsequently, the as-fabricated ZIF-8@GSH/PI membrane (M3) was
49
50 washed with deionized water for three times. The membrane was finally immersed in
51
52 methanol and heated in vacuum at 70 °C overnight.
53
54
55
In addition, the pure PI membrane with only growth of ZIF was also fabricated.
56
57
(denoted as ZIF-8/PI (M2)). For comparison, GSH concentration was set to be 1 mg/mL,
58
the 2-methylimidazole and zinc concentrations were systematically adjusted to
59
60
6

ACS Paragon Plus Environment

Page 7 of 31 ACS Applied Materials & Interfaces

1
2
3
4 different. Specially, the 2-methylimidazole and the zinc nitrate concentrations in water
5
6 84.4 and 4.4 g/L, as well as 21.1 and 1.1 g/L, respectively, were used to construct ZIF-
7
8 8@GSH/PI membrane (marked as ZIF-8-2@GSH/PI (M4) and ZIF-8-1@GSH/PI (M5)).
9
10 The content of GSH and ZIF-8 in the different membranes was presented in Figure S1.
11
12
13
2.4. Antibacterial activity testing
14
15
The antibacterial test was implemented by two typical pathogen, bacillus subtilis (B.
16
sub, Gram-positive) and Escherichia coli (E. coli, Gram-negative). The membranes
17
18
were cut into circles with a diameter of 8 mm. All the solution’s glassware and
19
20 membranes were autoclaved sterilization. Briefly, B. sub and E. coli were pre-cultured
21
22 and diluted with nutrient broth to get the desired test inoculum. Subsequently, 0.3 mL
23
24 of the test inoculum was spread on the agar plates uniformly, followed by the placing
25
26 of membrane samples. The Petri dishes were incubated for 24 h at 37 °C. The diameter
27
28 was measured for the area around the disc where no bacterial growth, called the
29
30 inhibition zone, which characterizes the bacteriostatic effect of membranes. No UV
31
32 light irradiation was conducted in the whole test process.
33
34 2.5. Characterization
35
36 The surface morphology of the samples was determined by a JSM-7600F field emission
37
38 scanning electron microscope (FESEM), working in high-vacuum mode with an
39
40 accelerating voltage of 10.0 kV, equipped with an energy-dispersive spectroscope
41
42 (EDS). Fourier transform infrared (FTIR) spectroscopy was performed with a Nicolet
43
44 7000 spectrometer to investigate the characteristic of the samples. For measurement,
45
46 the samples were mixed with potassium bromide (KBr) and pressed as pellets. The
47
48 scans (32 scans) were recorded between 4000 and 400 cm−1 at a resolution of 4 cm−1.15
49
50 The electron paramagnetic resonance (EPR) spectra was obtained using a Bruker A300
51
52
electron paramagnetic resonance spectrometer with DMPO as the spin trapping agent.
53
54
X-ray photoelectron spectroscopy (XPS) data was attained with a K-Alpha electron
55
spectrometer (Thermo Fisher, USA). Topographical surface images of the samples
56
57
were examined by a noncontact optical profilometry using an interferometer profile
58
59 (KLA-Toncor, MicroXam100, USA). The X-ray diffraction (XRD) pattern was
60
7

ACS Paragon Plus Environment

 ACS Applied Materials & Interfaces Page 8 of 31

1
2
3
4 collected with Rigaku Ultima IV instrument with 2θ ranging from 5° to 80° at a scan
5
6 step of 5°. The contact angles (CA) were measured using a JC2000D1 contact angle
7
8 system (ZhongChen, Shanghai) with 2 μL droplets. The average CA values were
9
10 obtained by testing three different regions of the sample. An optical microscope (E200,
11
12
Nikon, Japan) was employed to observe the emulsions and filtrates, while the emulsion
13
14
droplet size distribution was analyzed by dynamic light scattering using a laser particle
15
size analyzer (Malvern Zetasizer Nano ZS, Malvern, UK). The procedure involved 2ml
16
17
of each of the emulsion sample (before and after separation) being put into a small
18
19 cuvette and inserted into the analyzer. Each analysis was conducted three times (n = 3).
20
21
22 UV-vis spectra of the samples were recorded using a UV-2450 spectrophotometer
23
24 (Shimadzu, Japan). N2 adsorption/desorption isotherms were measured with a
25
26 Quantachrome analyzer at 353.15 K. Pore size distribution was plotted via the Barret-
27
28 Joyner-Halenda (BJH) method.
29
30
31 3. Results and discussion
32
33
34 3.1. Characterization of ZIF-8@GSH/PI electrospun fibrous membrane
35
36
37 The fabrication procedure of ZIF-8@GSH/PI membrane is illustrated in Scheme. 1. In
38
39 this study, PI nanofibrous was utilized as substrate owing to its high mechanical
40
41
strength, low-cost and durability.19, 35-36 The decoration of oxygen functionalities onto
42
43
the surface of GSH enabled excellent loading and chemical functionalization
44
capabilities, thus promoting the growth of a well intergrown selective layer on its
45
46
surface attributed to the formation of strong covalent and noncovalent bonds.37
47
48 Additionally, ZIF-8 is usually unstable in the presence of water, the great chemical
49
50 stability of GSH can protect the hydrophobic coating in harsh environment when
51
52 considering the fact that GSH coated PU sponges have been used for oil/water
53
54 separation.38 The synergetic properties of GSH and ZIF-8 with its micro/nanoscale
55
56 hierarchical structure considerably affect the wettability of the obtained GSH@ZIF-8
57
58 hybrid and endow it with remarkable superhydrophobicity and superoleophilicity
59
60 (Figure S2a-c).
8

ACS Paragon Plus Environment

Page 9 of 31 ACS Applied Materials & Interfaces

1
2
3
4 The morphologies of membranes are shown in Figure 1a-c and Figure S2d-f. The
5
6 surface of pristine PI nanofibers is quite smooth with an average diameter of around
7
8 300 nm (Figure 1a). After further in-site growth of ZIF-8, the PI membrane is covered
9
10 by continuous ZIF-8@GSH, which is ascribed to the fact that the GSH is beneficial for
11
12
anchoring ZIF-8 layer on account of preserving some oxygen-containing groups.
13
14
Specially, the oxygen containing groups of GSH along with noncovalent π–π stacking
15
interactions can anchor Zn2+ from the surrounding solution through coordination
16
17
bonding.37 Additionally, the Zn2+ will serve as the nucleation node for ZIF-8 formation
18
19 after the introduction of ligand (2-methylimidazole) solution.39-40 Hence, the ZIF-8 can
20
21 be formed densely and relatively uniformly on the GSH surface (Figure 1c). Meanwhile,
22
23 the inside structure of the GSH/PI, ZIF-8/PI and ZIF-8@GSH/PI membranes were not
24
25 completely similar with each other. (Figure S2d-f). The existence of ZIF-8 on GSH
26
27 could further enhance the superhydrophobicity and surface roughness of the as-
28
29 designed membrane. (Figure S2g-i)
30
31
32 In order to identify the existence of GSH@ZIF-8 on the PI membrane, FT-IR and XRD
33
34 spectra of PI, GSH/PI, ZIF-8@GSH/PI and ZIF-8 were compared. As displayed in
35
36 Figure 1d, in comparison with GO, after thiolation, the C=O and C-OH stretching
37
38 vibrations peaks at 1710 and 1060 cm−1 disappeared. Additionally, the peak appears at
39
40 2750-3000 cm−1 for the GSH coated PI membrane, which is attributed to the S-H
41
42 vibrational. Also, the signs of the function groups of imidazole moiety (1146, 1310,
43
44 1350-1500 cm−1) in the ZIF-8 are clearly seen in the FT-IR spectra of ZIF-8@GSH/PI
45
46 membrane,41 demonstrating that the GSH@ZIF-8 are successfully coated on the PI
47
48 nanofibrous mats. Figure 1e shows the XRD pattern of the samples. The GO curve
49
50 indicates a sharp diffraction peak centered at 10.48°, which corresponds to reflection
51
52
from the plane of GO. It manifests that the graphite was successfully oxidized into GO.
53
54
In contrast, a broad diffraction peak centered at 24.57° is observed for GSH, which
55
attributes to the reflection from the plane of GSH. Pristine PI membrane does not
56
57
display a diffraction peak, while typical diffraction peaks of ZIF-8 were identified in
58
59 ZIF-8@GSH/PI membrane. It is also noted that the representative characteristic peaks
60
9

ACS Paragon Plus Environment

 ACS Applied Materials & Interfaces Page 10 of 31

1
2
3
4 of GSH at around 25o was not observed, which can be result from the relatively low
5
6 peak intensity and overlapping with the ZIF-8. In addition, the existence of the well
7
8 coated GSH layer and ZIF-8@GSH were further verified by Raman spectra, EDS
9
10 spectra, EDS mappings and XPS spectra (See Figure S3 and Figure S4). Figure 1f
11
12
shows the high-resolution C 1s XPS spectra of GO, GSH/PI, and ZIF-8@GSH/PI. In
13
14
contrast to GO, the peak intensity of O-C=O and C-O of GSH was decreased, ascribed
15
to the nucleophilic substitution reaction of hydroxyl groups and ring-opening on
16
17
epoxide groups, which was consistent with the results of Raman and FTIR observations
18
19 (Figure 1d and Figure S3a). For ZIF-8@GSH/PI, new peak can be seen at 291.2 eV,
20
21 belonging to C–N groups.42 Results further confirms that ZIF-8@GSH coating layer
22
23 has been successfully formed on the surface of PI membrane. To examine the pore
24
25 structure of the ZIF-8@GSH composites-based materials, nitrogen
26
27 adsorption/desorption isotherms of the resultant membranes were obtained (Figure. S5).
28
29 Obviously, all the membranes possess a large number of meso- and macro-pores,
30
31 exhibiting a broad pore size distribution, which suggests the as-prepared membranes
32
33 have hierarchical pore structure.
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
Figure 1 SEM micrographs of (a) PI nanofibrous membrane, (b) GSH/PI nanofibrous
57
58
membrane, and (c) ZIF-8@GSH/PI nanofibrous membrane. (d) FTIR spectra, (e) XRD
59
60
10

ACS Paragon Plus Environment

Page 11 of 31 ACS Applied Materials & Interfaces

1
2
3
4 patterns of ZIF-8, GO, GSH, pristine PI, GSH/PI and as-prepared ZIF-8@GSH/PI
5
6 membrane. (f) High resolution of the C1s XPS spectra of GO, GSH/PI, and ZIF-
7
8 8@GSH/PI membrane.
9
10
11 3.2. Wettability and self-cleaning property of ZIF-8@GSH/PI electrospun fibrous
12
13
membrane
14
15
16
Membrane wetting behavior is a key issue in causing separation performance in oily
17
wastewater treatment. To evaluate the wettability, both water contact angle and oil
18
19
contact angle were obtained. As exhibited in Figure S6a, water contact angle on the PI
20
21 membrane in air is 82°. However, it increased to 135.6° and 130.64o after GSH or ZIF-
22
23 8 coated, implying that the GSH/PI surface is more hydrophobic than ZIF/PI, but none
24
25 of them achieved the superhydrophobicity. Interestingly, we note that the GSH/PI
26
27 membrane after in-situ growth the ZIF-8 shows improved hydrophobic behavior with a
28
29 water contact angle of 153.25°, because the increased roughness of the membrane can
30
31 enhance the hydrophobicity.43 Moreover, the water droplet can maintain a spherical
32
33 shape on the membrane for 180 s (Figure 2a), indicates good stability.
34
35
36 Several simple experiments were conducted to show the wettability changes of PI
37
38 nanofibrous membrane materials. As displayed in Figure 2b, a water droplet was readily
39
40 adsorbed by the PI membrane, by contrast, a spherical water droplet formed on the ZIF-
41
42 8@GSH/PI and could be entirely adsorbed by using filter paper. In addition, when such
43
44 ZIF-8@GSH/PI was immersed into water, a typical silver-mirror-like reflection can be
45
46 observed (Figure 2c), which should be ascribed that plenty air bubbles trapped in the
47
48 nanofibrous membrane.44 The above results illustrated that the hydrophilic PI
49
50 nanofibrous membrane had been greatly transformed into superhydrophobic. Besides,
51
52 the water droplet contact-depart experiment was conducted (Figure 2d, top), evidencing
53
54
the remarkable water repellence of ZIF-8@GSH/PI membrane.
55
56
57
The oil wettability of ZIF-8@GSH/PI membrane were also investigated in Figure 2d,
58
bottom. It can be observed that the oil droplet (kerosene) spread out quickly within 2 s
59
60
11

ACS Paragon Plus Environment

 ACS Applied Materials & Interfaces Page 12 of 31

1
2
3
4 with a near-zero contact angle when it contacted the membrane, which was indicative
5
6 of superoleophilicity. Benefiting from the superhydrophobicity and superoleophilicity,
7
8 the as-prepared ZIF-8@GSH/PI membrane can extract hexadecane and
9
10 dichloromethane (dyed red) quickly (Figure S6b-c). More interestingly, the superior
11
12
oil-wettability of the ZIF-8@GSH/PI is observed for various oils (Figure S6d). Notably,
13
14
the hydrophobicity of the membrane is significantly affected by the concentration of
15
GSH and ZIF-8 (Figure S7).
16
17
18
The outstanding anti-wettability for water of the as-fabricated ZIF-8@GSH/PI
19
20 membrane is capable of repelling dust and stain liquids. By taking tannic acid powder
21
22 as dust, self-cleaning property was demonstrated in Figure S8a. The phenomenon that
23
24 dust placed on the membrane surface was quickly carried away by the moving water
25
26 droplets demonstrated good self-cleaning ability of the ZIF-8@GSH/PI membrane in
27
28 air. In addition, the anti-fouling property was also assessed by distributing the tannic
29
30 acid power on the as-prepared membrane in oil (Figure S8b). It can be observed that
31
32 tannic acid powder also could be easily washed away by running water droplets,
33
34 demonstrating an excellent anti-fouling capability in oil. Besides tannic acid powder,
35
36 the as-prepared membrane also exhibited self-cleaning behavior to Fe3O4 nanoparticle
37
38 and SiO2 nanoparticle both in air and in oil (Figure S8).
39
40
41 Besides pure water repellence, the anti-fouling ability with respect to other common
42
43 water-based liquids would also drastically enhance the possible applications of the as-
44
45 fabricated membrane. Stain liquids including coffee, milk, soy sauce, and wine were
46
47 observed to form a nearly spherical shapes on the membrane surface and it can be seen
48
49 in Figure 2e. In addition, when these stain liquids were dispensed toward a slightly
50
51 titled sample surface, they rolled down either in air or when immersed in oil, indicating
52
53
successful repellency of all the test liquids. Additionally, the contact angles and sliding
54
55
angles for the four stain droplets are all higher than 150 ° and lower than 10° (Figure
56
2f). These results revealed very low adhension of the membrane. Therefore, the
57
58
resultant superhydrophobic membrane is a very promising candidate for advanced
59
60
12

ACS Paragon Plus Environment

Page 13 of 31 ACS Applied Materials & Interfaces

1
2
3
4 engineering materials with antifouling ability.
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27 Figure 2 (a) Photographs showing the stable superhydrophobicity of the membrane. (b)
28
29 The residue of the dyed water on the surface of the pristine PI membrane, and the quasi-
30
31 spherical water droplet on the surface of the ZIF-8@GSH/PI membrane. This water
32
33 droplet can be removed by a piece of filter paper without any residual dye. (c)
34
35 Immersing ZIF-8@GSH/PI membrane in water. (d) Dynamic contact-detach water-
36
37 repellence test of ZIF-8@GSH/PI membrane (top) and an oil droplet spreading on the
38
39 membrane within 2 s (bottom). (e) Stain drops standing on the as-prepared membrane
40
41 with nearly spherical shapes and these could move away quickly, and (f) the contact
42
43 angles and sliding angles of stain liquids.
44
45
46 3.3. Durability and Stability of ZIF-8@GSH/PI membrane
47
48
49 As mentioned above, ZIF-8 is usually unstable. Especially, there are no reports for the
50
51 stability of the ZIF-8@GSH hybrid coating. In addition, most reported
52
53 superhydrophobic materials have poor durability under harsh conditions, such as strong
54
55
light, chemical oxidation, or physical rubbing.45 For those reasons, it is necessary to
56
57
assess the stability of the as-prepared membrane for practical applications. The
58
chemical stability was investigated via immersing the membrane into corrosive
59
60
13

ACS Paragon Plus Environment

 ACS Applied Materials & Interfaces Page 14 of 31

1
2
3
4 solutions (acidic, alkaline, organic solution ((e.g. petroleum ether, DMF, ethyl acetate,
5
6 n-hexane, DMSO) or salt solutions (e.g. 0.1 M NaCl, 0.1 M Na2SO4)) for 24 h. As
7
8 presented in Figure 3a and Figure 3b, the WCAs of the modified membrane were almost
9
10 unchanged and remained larger than 150°. These results indicated the membrane
11
12
possessed extraordinary superhydrophobicity towards corrosive solutions. Additional
13
14
test also evidenced that the as-prepared ZIF-8@GSH/PI membrane resist high
15
temperature treatment and air storage, even after 400 °C of high temperature heated and
16
17
300 days of air exposure (Figure S9a-b).
18
19
20 Mechanical durability of the membrane was estimated by a sandpaper abrasion (Figure S9c)
21
22 and ultrasonic cleaning. The WCAs variation on the membrane with abrasion cycles was
23
24 shown in Figure 3c. It is found that the as-prepared membrane maintained high
25
26 hydrophobicity even after 10 cycles of abrasion. More importantly, it should note that
27
28 these surface morphologies were similar as that before the test (Figure S9d-f). Figure
29
30 3d presents the results of the ultrasonic treatment test. It can be observed that the
31
32 superhydrophobicity just slightly decreased with continuous ultrasonic treatment, but
33
34 the modified membrane still sustained high hydrophobic with a WCA of greater than
35
36 150o after a 500 min test. The phenomenon could be explained by the fact that the ZIF-
37
38 8@GSH is very stable and firmly adhered to the surface of PI membrane (Inset Figure
39
40 3d). The improved stability of ZIF-8@GSH coating may be due to the fact that GSH
41
42 feature generates strong π–π and ionic interactions with ZIF-8 as well as the van der
43
44 Waals interaction with PI.37, 46 Moreover, the formation of hydrogen bonding between
45
46 the oxygen groups of GSH and imine groups of PI further enhanced the adhesion of
47
48 GSH layer on PI membrane.47 These results demonstrated that the as-obtained
49
50 membrane has excellent durability and stability.
51
52
53
54
55
56
57
58
59
60
14

ACS Paragon Plus Environment

Page 15 of 31 ACS Applied Materials & Interfaces

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30 Figure 3. Variations in WCA of the ZIF-8@GSH/PI membrane as a function of (a) pH,
31
32 (b) organic solvent/salt solution. (c) Water contact angles change with abrasion cycles.
33
34 Inset: the picture displayed water (blue) and oil (red) droplets on the membrane after
35
36 10 cycles of abrasion test. (d) WCA variations of the as-designed membrane with
37
38
ultrasound time. Inset: SEM image after various conditions treatment.
39
40
3.5. Oil-water separation application of the ZIF-8@GSH/PI membrane
41
42
The permeate flux of composite membrane was strongly depended on the morphology
43
44
and micro-structure of membrane. The effect of different concentration ZIF-8@GSH
45
46 on separation performance of nanofibrous composite membranes was shown in Figure.
47
48 4a (Take chloromethane as an example). It can be seen that the flux for GSH/PI
49
50 membrane (M1) is 2743.85 L m-2 h-1, and that of the ZIF-8/PI (M2) up to 2587.26 L m-
51
52 2
h-1. The higher flux for GSH/PI membrane was attributed to the higher WCA values
53
54 for GSH/PI membrane. Obviously, the flux was significantly enhanced by growth of
55
56 ZIF-8 on GSH due to the significantly increased in hydrophobicity of composite
57
58 membrane. As the content of ZIF-8 increased to 7.98 wt%, permeate flux of
59
60 nanofibrous composite membrane (ZIF-8@GSH/PI, M3) was increased to 5632.98 m-2
15

ACS Paragon Plus Environment

 ACS Applied Materials & Interfaces Page 16 of 31

1
2
3
4 h-1, exhibiting 2 times higher than that of composite membrane without ZIF-8. Clearly,
5
6 the as-prepared fibrous membranes have a high separation efficiency. Typically, the
7
8 increase in flux and high separation efficiency may due to the newly constructed micro-
9
10 /nano-sized hierarchical structures and improved hydrophobicity after deposition of
11
12
ZIF-8, which have also been proposed by our previously studies.19 However, further
13
14
increasing content of ZIF-8@GSH would cause the decrease of flux for nanofiber
15
composite membrane (ZIF-8-2@GSH/PI, M4). In this case, the increased thickness of
16
17
composite membrane enhanced the mass transfer resistance and prolonged the passage
18
19 of oil molecules through composite membranes. Besides, the high content of ZIF-
20
21 8@GSH would cause the aggregation of ZIF-8.
22
23 Figure 4b and Figure 4c presents the separation performance of membrane for different
24
25 oil/water mixtures. The results showed that the ZIF-8@GSH/PI membrane still
26
27 maintained a high flux after twenty cycles of separation. Specially, the highest oil
28
29 permeation flux of 5625 L m−2 h−1 was obtained for dichloromethane/water mixture.
30
31 Besides, the fluxes are 5043, 4613, 4835 and 4196 L m−2 h−1, respectively, for
32
33 trichloromethane, dichloroethane, chlorobenzene, tetrachloromethane/water mixtures
34
35 (Figure 4b). Meanwhile, the separation efficiency was all higher than 99% for the tested
36
37 oil/water mixtures (Figure 4c), which are better than previously reported for other
38
39 membranes.48-49 In addition, the separation process further demonstrated that the as-
40
41 prepared ZIF-8@GSH/PI membrane can effectively separate oil/water mixture (Figure
42
43 S10a).
44
45
46 Compared with oil/water mixtures, the surfactant-stabilized emulsions (SSEs) are more
47
48 difficult to be separated. The detail process for the preparation of water-in-oil emulsions
49
50 could be found in supporting information S1.4. Interestingly, it is noted that the
51
52
emulsions can remain stable without demulsification or stratification even after one
53
54
week (Figure S10b-c). The results of water content and separation efficiency of the ZIF-
55
8@GSH/PI membrane for different surfactant-stabilized water-in-oil emulsions are
56
57
given in Figure 4d. It can be seen that the as-prepared membrane can separate these
58
59 emulsions with separation efficiencies of 99.96% for water-in-kerosene, 99.94 % for
60
16

ACS Paragon Plus Environment

Page 17 of 31 ACS Applied Materials & Interfaces

1
2
3
4 water-in-toluene, 99.89% for water-in-n-hexane and 99.88 % for water-in-petroleum
5
6 ether. Additionally, the separation performances were further assessed in detail by
7
8 optical microscope and particle analyzer, which are displayed in Figure 4e and Figure
9
10 S10b. Obviously, the milky pristine emulsion (water-in-kerosene emulsion) changed
11
12
from opaque to transparent after filtration. Moreover, from the optical microscopy
13
14
images, one can observe that the SSEs contained massive water droplets, while no water
15
droplets were observed after the separation process (Figure 4e). Besides, the droplet
16
17
size distribution results revealed that abundant micro/nano-sized water droplets in the
18
19 pristine emulsion disappear after passing through the ZIF-8@GSH/PI membrane, and
20
21 the size distribution shifted to 1-10 nm in the filtrate, demonstrating the high efficiency
22
23 of the as-prepared membrane for purifying emulsions (Figure S10d). Significantly, the
24
25 membrane surface morphology was well maintained after the separation (Figure S10e).
26
27 More importantly, the water droplet size distribution analyses of the water-in-kerosene,
28
29 toluene, n-hexane, and petroleum ether emulsions show similar results (Figure S11).
30
31 Additionally, the cycle stability was also assessed by investigating the separation
32
33 efficiency in each cycle of water-in-kerosene emulsion separation. As observed in
34
35 Figure 4f, the exceptional separation efficiency (> 99%) and low water content (< 100
36
37 ppm) of ZIF-8@GSH/PI were maintained throughout the cycle test, which indicated
38
39 the favorable recyclability of the as-obtained membrane. Based on the discussion above,
40
41 it is obvious that the ZIF-8@GSH/PI membrane can effectively separate various water-
42
43 in-oil emulsions.
44
45
46 Figure 4g illustrates the hypothetical schematic diagram to describe the separation
47
48 process for oil/water mixture and water-in-oil emulsion of the ZIF-8@GSH/PI
49
50 membrane. As for the separation of oil/water mixtures, the water droplets dropped onto
51
52
the membrane surface are in cassia state and can be easily repelled as a consequence of
53
54
the outstanding superhydrophobic behavior of the membrane. While the oil droplets
55
will gradually wet the membrane and permeate into the grooves part of the
56
57
micro/nanoscale structure resulting from superoleophilicity of the membrane.
58
59 Consequently, the separation of oil/water mixtures is successfully achieved. Whereas
60
17

ACS Paragon Plus Environment

 ACS Applied Materials & Interfaces Page 18 of 31

1
2
3
4 for surfactant-stabilized water-in-oil emulsions, the stability of emulsion could be
5
6 seriously disrupted once they touch the membrane surface on account of the
7
8 superhydrophobic and superoleophilic properties of the membrane50-51. Meanwhile, the
9
10 existence of surfactant could prevent the water droplets aggregated and the membrane
11
12
readily interrupt the micro/nano-sized water droplets wrapped in oils originally. Hence,
13
14
the oils would be rapidly captured and spread out under capillary effect. Then, a solid-
15
liquid-gas interface was formed, which can be elucidated by Eq. (5).52
16
17 cos 𝜃𝑓 = 𝑓𝑆𝐿 cos 𝜃𝑜 + 𝑓𝑆𝐿 − 1 (5)
18
19 where 𝑓𝑆𝐿 is the fraction of the projected area of the solid surface that is wetted by the
20
21 liquid. 𝜃𝑜 and 𝜃𝑓 are CA on the smooth and rough surfaces, respectively. In this study,
22
23 𝜃𝑓 =153.25° (Figure S6), θ0= 82o (Figure S6) and 𝑓𝑆𝐿 = 0.094, indicating that only about
24
25 9.4% of areas of the water drop could be contacted with the ZIF-8@GSH/PI membrane.
26
27 Thus, superhydrophobicity and low adhesive can be observed (Figure 2). In addition, a
28
29 model was proposed to better understand the oil-water separation process. (Inset Figure
30
31 4g) The theoretical intrusion pressure (𝑃𝑡ℎ𝑒𝑜 ) is described as:53
32
33 2𝛾 𝑙γ cos 𝜃𝐴
34
𝑃𝑡ℎ𝑒𝑜 = =− (6)
𝑅 𝐴
35
36 Where 𝛾 is the surface tension, 𝜃𝐴 represents the water contact angle on the
37
38 membrane surface, R is the meniscus’s radius, 𝑙 is the membrane pore’s perimeter, A
39
40
is the pore’s area. When the ZIF-8@GSH/PI nanofibrous membrane contacted with oil
41
before oil/water separation, it was firstly wetted by oil, and the micro/nano-sized
42
43
hierarchical structures would be occupied by oil, thus strengthening the repellent force
44
45 between water and the membrane. Therefore, 𝜃𝐴 is obviously above 90°, and ∆P > 0,
46
47 means the ZIF-8@GSH/PI nanofibrous membrane can sustain water pressure to some
48
49 extent. Consequently, water cannot pass through and being retained on the membrane.
50
51 Thus, SSEs can be separated successfully through the membrane. For comparison, the
52
53 corresponding experimental intrusion pressure of water that the membrane can support
54
55 were also measured (See supporting information S4).
56
57
58
59
60
18

ACS Paragon Plus Environment

Page 19 of 31 ACS Applied Materials & Interfaces

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33 Figure 4 (a) Separation performance of the resultant membranes. (b, c) Cycle
34
35 separation ability of ZIF-8@GSH/PI membrane for various oil/water mixtures. (d)
36
37 Water content and separation efficiency of the ZIF-8@GSH/PI membrane for various
38
39 water-in-oil emulsions. (e) Optical microscope images of the water-in-kerosene
40
41 emulsion before and after filtration. The inset in (e) are the corresponding photographs.
42
43 (f) The cycle separation efficiency of the membrane for various water-in-oil emulsions.
44
45 (g) Hypothetical schematic diagram for the separation of oil/water mixture and water-
46
47 in-oil emulsion.
48
49 3.6. Photocatalytic Application of ZIF-8@GSH/PI membrane
50
51
52 Most of the reports on graphene material for dye adsorption were based on aerogels,
53
54 the photocatalytic degradation of organic dyes using nanofibrous membrane have rarely
55
56 been reported. Except for that, the detoxification of sustainable photocatalytic
57
58 degradation processes is more significant compared to traditional adsorption
59
60 processes.54 Here, we chose MB as model organic pollutant to explore the
19

ACS Paragon Plus Environment

 ACS Applied Materials & Interfaces Page 20 of 31

1
2
3
4 photocatalytic performance for our ZIF-8@GSH/PI membrane (the detail process was
5
6 displayed in supporting information S.1.5). After 60 min stirring without light
7
8 irradiation, MB can absorb onto all the tested materials (Figure 5a). The PI membrane
9
10 can only absorb about 10% MB and no photocatalytic performance was found. About
11
12
15% of MB dyes were adsorbed for the GSH/PI and ZIF-8/PI membrane, whereas the
13
14
ZIF-8@GSH/PI membrane showed improved absorption capacity for approximately
15
25%. The concentration of MB only reduced by 56% and 65% for GSH/PI and ZIF-
16
17
8/PI membrane after dark adsorption and subsequent 120 min UV irradiation. Whereas,
18
19 it was rapidly reduced to about 8.4% of the original concentration when ZIF-
20
21 8@GSH/PI membrane present, evidencing superior photocatalytic activity compared
22
23 with GSH/PI, ZIF-8/PI membranes and other up-to-date ZIF-8-based photocatalysts
24
25 reported.55 This phenomenon is most likely caused by high electron mobility and π-
26
27 conjugated of the GSH, which effectively inhibits the recombination of electron-hole
28
29 pairs.56 Consequently, higher degradation performance can be obtained for ZIF-
30
31 8@GSH/PI than that of GSH/PI or ZIF-8/PI. Interestingly, as for self-degradation, no
32
33 obviously photodegradation of MB is observed, which indicates the MB molecular is
34
35 stable under UV illumination (Figure S12). More importantly, the as-prepared
36
37 membrane can be reused for ten cycles (Figure 5b). The slightly reduction of
38
39 degradation rate could be assigned to the unavoidable loss of the negligible coated ZIF-
40
41 8@GSH in recycling process. Furthermore, it should note that the microstructure of the
42
43 ZIF-8@GSH/PI membrane is hardly affected (insets Figure 5b), implying the
44
45 outstanding reusability of the ZIF-8@GSH/PI membrane and stable modification of
46
47 ZIF-8@GSH.
48
49
50 The plausible mechanism for photocatalytic degradation process of MB using ZIF-
51
52
8@GSH/PI nanofibrous membrane is displayed in Figure 5c. Under UV light
53
54
irradiation, ZIF-8 nanoparticles generate electron (e−)-hole (h+) pairs. Then, because of
55
the highly efficient link between ZIF-8 and GSH, excited electrons (e−) of ZIF-8
56
57
transferred from the value band (VB) to the conduction band (CB) through the
58
59 conductive GSH sheets. After that, the e− in the CB of ZIF-8 react with the adsorbed O2
60
20

ACS Paragon Plus Environment

Page 21 of 31 ACS Applied Materials & Interfaces

1
2
3
4 and H2O on the surface of ZIF-8@GSH/PI to produce superoxide radicals of ·O2– on
5
6
7 the ZIF-8 surface and subsequently partial ·O2– reacts with H+ to form H2O2, which
8
9 further generate hydroxyl radicals of ·OH. Meanwhile, photoinduced holes (h+) on the
10
11
12 VB of ZIF-8 also easily react with H2O2 to produce more ·OH. The ·OH and ·O2– are
13
14 responsible for the oxidization the MB dye molecules into CO2 and H2O, attribute to
15
16 their high oxidation ability.57 (The reaction described the photoinduced degradation
17
18 process for an organic pollutant is presented in S3.) Furthermore, the DMPO spin-
19
20 trapping EPR technique was used to detect the production of ·OH and ·O2– (Figure
21
22
23 S13). Characteristic peaks of DMPO-·OH and DMPO-·O2– were obviously observed
24
25
26 in ZIF-8@GSH/PI suspension under UV irradiation, while no ·OH and ·O2– was
27
28 detected in dark, suggesting that ·OH and ·O2– were the main reactive species in the
29
30
photocatalytic process. Thus, the resultant rapid decolourization of MB dye is attributed
31
32 to these synergistic effects of the two ways. It is worth mentioning that the method used
33
34 to immobilize the ZIF-8@GSH to PI membrane is simple, economical, and no toxic
35
36 solvent. From the perspective of environmental protection, the ZIF-8@GSH/PI
37
38 nanofibrous membrane is a promising candidate in application of wastewater treatment.
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
21

ACS Paragon Plus Environment

 ACS Applied Materials & Interfaces Page 22 of 31

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32 Figure 5 (a) Photodegradation of MB solution under UV light by different samples. (b)
33
34 Recycled photodegradation rate of the MB solution by ZIF-8@GSH/PI. Insert: SEM of
35
36 the superhydrophobic ZIF-8@GSH/PI before and after several degradation processes.
37
38 (c) Schematic illustration of the mechanism of photocatalytic degradation process of
39
40 MB dye using ZIF-8@GSH/PI membrane.
41
42
43 3.7. Antibacterial activity of the ZIF-8@GSH/PI nanofibrous membrane
44
45
46 In addition to organic fouling, biofouling is also one of the major obstacles limiting the
47
48 membrane applications in wastewater treatment.58 The antibacterial activity of the
49
50 membrane was evaluated by inhibition zone method, with B. sub and E. coli as the
51
52 model microorganisms. As shown in Figure 6a, an obvious clear zone of inhibition was
53
54 observed around the ZIF-8/PI (M2), and ZIF-8@GSH/PI (M3) membranes. In contrast,
55
56 no such inhibition zone was presented around pristine PI membrane (M0) and GSH
57
58 coated PI (GSH/PI, M1) membranes. The results indicated that the pristine PI and
59
60 GSH/PI membrane can barely remove biofouling by E. coli and B. sub. In addition, no
22

ACS Paragon Plus Environment

Page 23 of 31 ACS Applied Materials & Interfaces

1
2
3
4 antimicrobial activity was found for GSH/PI membrane. While the ZIF-8 can be
5
6 exposed on the surface of membrane benefit from its stereo structure, thus endowing
7
8 the ZIF-8/PI membranes with improved antimicrobial activity in comparison to GSH/PI
9
10 membrane. Moreover, as shown in Figure 6b, the ZIF-8@GSH/PI membrane displayed
11
12
larger inhibition zones as compared to ZIF-8/PI membrane, indicating higher
13
14
antibacterial activity. The possible mechanism of ZIF-8@GSH/PI antimicrobial
15
membrane is given in Figure 6c. The Zn2+ ions released from ZIF-8 can react with the
16
17
cell membrane proteins or directly act as a microbial reactant through the disruption of
18
19 liposomes, which damaged the structure of bacteria, subsequently causing leakage of
20
21 intracellular molecules and then the death of cells.59-61 Briefly, cellular internalization,62
22
23 reactive oxygen species generation, and plasma membrane disorganization caused by
24
25 the released Zn2+ contribute to its bactericidal performance.63
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
23

ACS Paragon Plus Environment

 ACS Applied Materials & Interfaces Page 24 of 31

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35 Figure 6 (a) Zone of inhibition tests for membranes against E. coil (left) and B. sub
36
37 (right). M0: unmodified PI membrane, M1: GSH/PI, M2: ZIF-8/PI, and M3: ZIF-
38
39
8@GSH/PI. (b) Average diameter of the bacteria inhibition zones for different
40
41
membranes. (c) Schematic diagrams for the antimicrobial mechanism of ZIF-
42
8@GSH/PI membrane.
43
44
4. Conclusions
45
46
47 In conclusion, we have successfully fabricated a superhydrophobic ZIF-8@GSH/PI
48
49 nanofibrous membrane by the combination of a facile electrospinning and in-situ
50
51 hydrothermal synthesis technologies. In this preparation process, the strong interaction
52
53 between oxygen functional groups of GSH and ZIF-8 ensures the direct growth of ZIF-
54
55 8 on the surface of GSH. The synergetic properties of ZIF-8, GSH, nanoscale roughness
56
57 and hierarchical structure produce a composite ZIF-8@GSH/PI membrane, which
58
59 exhibited outstanding oil/water separation performance with excellent separation
60
24

ACS Paragon Plus Environment

Page 25 of 31 ACS Applied Materials & Interfaces

1
2
3
4 efficiency of 99.9% for various oil/water mixture and water-in-oil emulsions. In
5
6 addition, the resulted membrane showed remarkable stability of ZIF-8@GSH coating
7
8 and PI substrate material, and could keep the superhydrophobicity in various harsh
9
10 conditions, including acid, alkaline, salinity, corrosive organic solvent, high
11
12
temperature and mechanical abrasion, ultrasonic treatment. The excellent
13
14
comprehensive performances including oil-water separation, stain repellency,
15
antibacterial, mechanochemical robustness and good photocatalytic degradation
16
17
abilities made the membrane a valuable candidate to be used for a range of industrial
18
19 fields.
20
21
22 ASSOCIATED CONTENT
23
24
25 Supporting information
26
27
28 Preparation of PI nanofibrous membrane, GO and water-in-oil emulsions. Oil/water
29
30 separation experiment. Photocatalytic activity test for MB degradation. Durability
31
32 testing. Content of GSH or ZIF-8. SEM micrographs, optical profilometry images, EDS
33
34 spectra, and XPS spectra. nitrogen adsorption–desorption isotherms and the
35
36 corresponding pore width of the resultant membranes. Wettability of the resultant
37
38 membranes. Self-cleaning experiment. Durability and separation performance of the
39
40 ZIF-8@GSH/PI membrane. Stability of water-in-oil emulsions. The absorbance of MB
41
42 solution after different irradiation time in the presence of different membranes. DMPO
43
44 spin-trapping EPR spectra. Degradation process for MB. Comparison of theoretical
45
46 maximum pressures and experimental values.
47
48
49 AUTHOR INFORMATION
50
51
52 Corresponding Author
53
54
55 Tel: +86-25-85427532; Fax: +86-25-85427532; Email: Chaobo.Huang@njfu.edu.cn
56
57
(Chaobo Huang);
58
59
60
Tel.: +86-25-52090625; Fax: +86-25-52090625; Email: 101010855@seu.edu.cn
25

ACS Paragon Plus Environment

 ACS Applied Materials & Interfaces Page 26 of 31

1
2
3
4 (Guodong Fu)
5
6
7 ORCID
8
9
10 Chaobo Huang: 0000-0003-3484-0545
11
12
13 Guodong Fu: 0000-0001-7571-9675
14
15
16
Declaration of competing interest
17
18
19
There are no conflicts to declare
20
Acknowledgement
21
22
23
This work was supported by National Natural Science Foundation of China under the
24
25 Grant 21774060, 21274020 and 21304019. This work was also supported by the
26
27 Fundamental Research Funds for the Central Universities under the Grant
28
29 2242017K41030.
30
31
32
33
34 References
35
36
37 (1) Wang, C.-C.; Li, J.-R.; Lv, X.-L.; Zhang, Y.-Q.; Guo, G. Photocatalytic Organic
38 Pollutants Degradation in Metal-Organic Frameworks. Energy Environ. Sci. 2014, 7 (9),
39 2831-2867.
40
41 (2) Shannon, M. A.; Bohn, P. W.; Elimelech, M.; Georgiadis, J. G.; Marinas, B. J.;
42 Mayes, A. M. Science and Technology for Water Purification in the Coming Decades.
43 In Nanoscience and technology: a collection of reviews from nature Journals; World
44
45 Scientific: 2010; pp 337-346.
46 (3) Shi, Z.; Zhang, W.; Zhang, F.; Liu, X.; Wang, D.; Jin, J.; Jiang, L. Ultrafast
47 Separation of Emulsified Oil/Water Mixtures by Ultrathin Free‐Standing Single‐Walled
48
49
Carbon Nanotube Network Films. Adv. Mater. 2013, 25 (17), 2422-2427.
50 (4) Howarth, A. J.; Katz, M. J.; Wang, T. C.; Platero-Prats, A. E.; Chapman, K. W.;
51 Hupp, J. T.; Farha, O. K. High Efficiency Adsorption and Removal of Selenate and
52 Selenite From Water Using Metal-Organic Frameworks. J. Am. Chem. Soc. 2015, 137
53
54 (23), 7488-7494.
55 (5) Zhang, D.; Su, C.; Li, H.; Pu, X.; Geng, Y. Synthesis and Enhanced
56 Piezophotocatalytic Activity of Ag2O/K0.5Na0.5NbO3 Composites. J. Phys. Chem.
57
58 Solids 2020, 139, 109326.
59 (6) Tang, Y.; Zhang, X.; Ma, Y.; Wang, X.; Su, C.; Zhang, D.; Pu, X.; Geng, Y. One-
60 Dimensional Core-Shell Zn0.1Cd0.9S/Snln4S8 Heterojunction for Enhanced Visible
26

ACS Paragon Plus Environment

Page 27 of 31 ACS Applied Materials & Interfaces

1
2
3
Light Photocatalytic Degradation. Sep. Purif. Technol. 2020, 230, 115896.
4
5 (7) Ge, M.; Li, Q.; Cao, C.; Huang, J.; Li, S.; Zhang, S.; Chen, Z.; Zhang, K.; Al‐Deyab,
6 S. S.; Lai, Y. One‐Dimensional TiO2 Nanotube Photocatalysts for Solar Water Splitting.
7 Adv. Sci. 2017, 4 (1), 1600152.
8
9 (8) Ussia, M.; Mauro, A. D.; Mecca, T.; Cunsolo, F.; Nicotra, G.; Spinella, C.; Cerruti,
10 P.; Impellizzeri, G.; Privitera, V.; Carroccio, S. ZnO–pHEMA Nanocomposites: An
11 Ecofriendly and Reusable Material for Water Remediation. ACS Appl. Mater. Interfaces
12
13
2018, 10 (46), 40100-40110.
14 (9) Gao, S.; Li, X.; Li, L.; Wei, X. A Versatile Biomass Derived Carbon Material for
15 Oxygen Reduction Reaction, Supercapacitors and Oil/water separation. Nano Energy
16
2017, 33, 334-342.
17
18 (10) Gaaseidnes, K.; Turbeville, J. Separation of Oil and Water in Oil Spill Recovery
19 Operations. Pure Appl. Chem. 1999, 71 (1), 95-101.
20 (11) Darmanin, T.; Guittard, F. Recent Advances in the Potential Applications of
21
22 Bioinspired Superhydrophobic Materials. J. Mater. Chem. A 2014, 2 (39), 16319-16359.
23 (12) Zhang, Y.-G.; Zhu, Y.-J.; Xiong, Z.-C.; Wu, J.; Chen, F. Bioinspired Ultralight
24 Inorganic Aerogel for Highly Efficient Air Filtration and Oil-Water Separation. ACS
25
26
Appl. Mater. Interfaces 2018, 10 (15), 13019-13027.
27 (13) Jiang, L.; Zhao, Y.; Zhai, J. A Lotus‐Leaf‐Like Superhydrophobic Surface: a
28 Porous Microsphere/Nanofiber Composite Film Prepared by Electrohydrodynamics.
29
Angew. Chem.-Int. Edit. 2004, 43 (33), 4338-4341.
30
31 (14) Gao, J.; Song, X.; Huang, X.; Wang, L.; Li, B.; Xue, H. Facile Preparation of
32 Polymer Microspheres and Fibers with a Hollow Core and Porous Shell for Oil
33 Adsorption and Oil/Water Separation. Appl. Surf. Sci. 2018, 439, 394-404.
34
35 (15) Ma, W.; Samal, S. K.; Liu, Z.; Xiong, R.; De Smedt, S. C.; Bhushan, B.; Zhang,
36 Q.; Huang, C. Dual pH-and Ammonia-Vapor-Responsive Electrospun Nanofibrous
37 Membranes for Oil-Water Separations. J. Membr. Sci. 2017, 537, 128-139.
38
39
(16) Kota, A. K.; Kwon, G.; Choi, W.; Mabry, J. M.; Tuteja, A. Hygro-Responsive
40 Membranes for Effective Oil-Water Separation. Nat. Commun. 2012, 3, 1025.
41 (17) Zhang, W.; Liu, N.; Cao, Y.; Lin, X.; Liu, Y.; Feng, L. Superwetting Porous
42
Materials for Wastewater Treatment: From Immiscible Oil/Water Mixture to Emulsion
43
44 Separation. Adv. Mater. Interfaces 2017, 4 (10), 1600029.
45 (18) Ma, W.; Zhang, Q.; Hua, D.; Xiong, R.; Zhao, J.; Rao, W.; Huang, S.; Zhan, X.;
46 Chen, F.; Huang, C. Electrospun Fibers for Oil-Water Sseparation. RSC Adv. 2016, 6
47
48 (16), 12868-12884.
49 (19) Ma, W.; Guo, Z.; Zhao, J.; Yu, Q.; Wang, F.; Han, J.; Pan, H.; Yao, J.; Zhang, Q.;
50 Samal, S. K. Polyimide/Cellulose Acetate Core/Shell Electrospun Fibrous Membranes
51
52
for Oil-Water Separation. Sep. Purif. Technol. 2017, 177, 71-85.
53 (20) Feng, L.; Li, S.; Li, Y.; Li, H.; Zhang, L.; Zhai, J.; Song, Y.; Liu, B.; Jiang, L.; Zhu,
54 D. Super‐hydrophobic Surfaces: From Natural To Artificial. Adv. Mater. 2002, 14 (24),
55
1857-1860.
56
57 (21) Qing, W.; Shi, X.; Deng, Y.; Zhang, W.; Wang, J.; Tang, C. Y. Robust
58 Superhydrophobic-Superoleophilic Polytetrafluoroethylene Nanofibrous Membrane
59 for Oil/Water Separation. J. Membr. Sci. 2017, 540, 354-361.
60
27

ACS Paragon Plus Environment

 ACS Applied Materials & Interfaces Page 28 of 31

1
2
3
(22) Shekhah, O.; Liu, J.; Fischer, R.; Wöll, C. MOF Thin Tilms: Existing and Future
4
5 Applications. Chem. Soc. Rev. 2011, 40 (2), 1081-1106.
6 (23) Shilun, Q.; Ming, X.; Guangshan, Z. Metal-Organic Framework Membranes: From
7 Synthesis To Separation Application. Chem. Soc. Rev. 2014, 43 (16), 6116-6140.
8
9 (24) Talin, A. A.; Centrone, A.; Ford, A. C.; Foster, M. E.; Stavila, V.; Haney, P.; Kinney,
10 R. A.; Szalai, V.; El Gabaly, F.; Yoon, H. P. Tunable Electrical Conductivity in Metal-
11 Organic Framework Thin-Film Devices. Science 2014, 343 (6166), 66-69.
12
13
(25) Chen, B.; Yang, Z.; Zhu, Y.; Xia, Y. Zeolitic Imidazolate Framework Materials:
14 Recent Progress in Synthesis and Applications. J. Mater. Chem. A 2014, 2 (40), 16811-
15 16831.
16
(26) Brown, A. J.; Brunelli, N. A.; Eum, K.; Rashidi, F.; Johnson, J.; Koros, W. J.; Jones,
17
18 C. W.; Nair, S. Interfacial Microfluidic Processing of Metal-Organic Framework
19 Hollow Fiber Membranes. Science 2014, 345 (6192), 72-75.
20 (27) Zhu, Q.; Li, Y.; Wang, W.; Sun, G.; Yan, K.; Wang, D. High Performance HKUST-
21
22 1@PVA- co -PE/PVA Hybrid Hydrogel with Enhanced Selective Adsorption. Compos.
23 Commun. 2018, 10, 36-40.
24 (28) Stankovich, S.; Dikin, D. A.; Dommett, G.; Kohlhaas, K.; Zimney, E.; Stach, E.
25
26
A.; Piner, R. D.; Nguyen, S. T.; Ruoff, R. S. Graphene-Based Composite Materials.
27 Nature 2006, 442 (7100), 282-286.
28 (29) Dikin, D. A.; Sasha, S.; Zimney, E. J.; Piner, R. D.; Dommett, G. H. B.; Guennadi,
29
E.; Nguyen, S. B. T.; Ruoff, R. S. Preparation and Characterization of Graphene Oxide
30
31 Paper. Nature 2015, 448 (7152), 457-460.
32 (30) Feng, C.; Yi, Z.; She, F.; Gao, W.; Peng, Z.; Garvey, C. J.; Dumée, L. F.; Kong, L.
33 Superhydrophobic and Superoleophilic Micro-Wrinkled Reduced Graphene Oxide as a
34
35 Highly Portable and Recyclable Oil Sorbent. ACS Appl. Mater. Interfaces 2016, 8 (15),
36 9977-9985.
37 (31) Jayaramulu, K.; Datta, K. K. R.; Rösler, C.; Petr, M.; Otyepka, M.; Zboril, R.;
38
39
Fischer, R. A. Biomimetic Superhydrophobic/Superoleophilic Highly Fluorinated
40 Graphene Oxide and ZIF‐8 Composites for Oil-Water Separation. Angew. Chem.-Int.
41 Edit. 2016, 55 (3), 1178-1182.
42
(32) Nguyen, D. D.; Tai, N.-H.; Lee, S.-B.; Kuo, W.-S. Superhydrophobic and
43
44 Superoleophilic Properties of Graphene-Based Sponges Fabricated Using a Facile Dip
45 Coating Method. Energy Environ. Sci. 2012, 5 (7), 7908-7912.
46 (33) Liu, Y.; Ma, J.; Wu, T.; Wang, X.; Huang, G.; Liu, Y.; Qiu, H.; Li, Y.; Wang, W.;
47
48 Gao, J. Cost-Effective Reduced Graphene Oxide-Coated Polyurethane Sponge as a
49 Highly Efficient and Reusable Oil-Absorbent. ACS Appl. Mater. Interfaces 2013, 5 (20),
50 10018-10026.
51
52
(34) Zhou, S.; Hao, G.; Zhou, X.; Jiang, W.; Wang, T.; Zhang, N.; Yu, L. One-Pot
53 Synthesis of Robust Superhydrophobic, Functionalized Graphene/Polyurethane
54 Sponge for Effective Continuous Oil-Water Separation. Chem. Eng. J. 2016, 302, 155-
55
162.
56
57 (35) Liaw, D.-J.; Wang, K.-L.; Huang, Y.-C.; Lee, K.-R.; Lai, J.-Y.; Ha, C.-S. Advanced
58 Polyimide Materials: Syntheses, Physical Properties and Applications. Prog. Polym. Sci.
59 2012, 37 (7), 907-974.
60
28

ACS Paragon Plus Environment

Page 29 of 31 ACS Applied Materials & Interfaces

1
2
3
(36) Chen, L.; Xu, Z.; Wang, F.; Duan, G.; Xu, W.; Zhang, G.; Yang, H.; Liu, J.; Jiang,
4
5 S. A Flame-Retardant and Transparent Wood/Polyimide Composite with Excellent
6 Mechanical Strength. Compos. Commun. 2020.10335
7 (37) Bonakala, S.; Lalitha, A.; Shin, J. E.; Moghadam, F.; Semino, R.; Park, H. B.;
8
9 Maurin, G. Understanding of the Graphene Oxide/Metal-Organic Framework Interface
10 at the Atomistic Scale. ACS Appl. Mater. Interfaces 2018, 10 (39), 33619-33629.
11 (38) Lin, Z.; Li, H.; Lai, X.; Su, X.; Tao, L.; Zeng, X. Thiolated Graphene-Based
12
13
Superhydrophobic Sponges for Oil-Water Separation. Chem. Eng. J. 2017, 316
14 (Complete), 736-743.
15 (39) Kim, D.; Kim, D. W.; Hong, W. G.; Coskun, A. Graphene/ZIF-8 Composites with
16
Tunable Hierarchical Porosity and Electrical Conductivity. J. Mater. Chem. 2016, 4 (20),
17
18 7710-7717.
19 (40) Yang, L.; Tang, B.; Wu, P. Metal–Organic Framework–Graphene Oxide
20 Composites: a Facile Method to Highly Improve the Proton Conductivity of PEMs
21
22 Operated Under Low Humidity. J. Mater. Chem. 2015, 3 (31), 15838-15842.
23 (41) Song, Q.; Nataraj, S.; Roussenova, M. V.; Tan, J. C.; Hughes, D. J.; Li, W.;
24 Bourgoin, P.; Alam, M. A.; Cheetham, A. K.; Al-Muhtaseb, S. A. Zeolitic Imidazolate
25
26
Framework (ZIF-8) Based Polymer Nanocomposite Membranes for Gas Separation.
27 Energy Environ. Sci. 2012, 5 (8), 8359-8369.
28 (42) Miao, W.; Zhang, Y.; Li, H.; Zhang, Z.; Li, L.; Yu, Z.; Zhang, W. ZIF-8/ZIF-67-
29
derived 3D Amorphous Carbon-Encapsulated CoS/NCNTs Supported on CoS-Coated
30
31 Carbon Nanofibers as an Advanced Potassium-Ion Battery Anode. J. Mater. Chem.
32 A 2019, 7 (10), 5504-5512.
33 (43) Patankar, N. A. On the Modeling of Hydrophobic Contact Angles on Rough
34
35 Surfaces. Langmuir 2003, 19 (4), 1249-1253.
36 (44) Chen, X.; Wu, Y.; Su, B.; Wang, J.; Song, Y.; Jiang, L. Terminating Marine
37 Methane Bubbles by Superhydrophobic Sponges. Adv. Mater. 2012, 24 (43), 5884-5889.
38
39
(45) Wang, H.; Xue, Y.; Ding, J.; Feng, L.; Wang, X.; Lin, T. Durable, Self‐Healing
40 Superhydrophobic and Superoleophobic Surfaces from Fluorinated‐Decyl Polyhedral
41 Oligomeric Silsesquioxane and Hydrolyzed Fluorinated Alkyl Silane. Angew. Chem.-
42
Int. Edit. 2011, 50 (48), 11433-11436.
43
44 (46) Perreault, F.; Tousley, M. E.; Elimelech, M. Thin-Film Composite Polyamide
45 Membranes Functionalized with Biocidal Graphene Oxide Nanosheets. Environ. Sci.
46 Technol. Lett. 2013, 1 (1), 71-76.
47
48 (47) Ha, H. W.; Choudhury, A.; Kamal, T.; Kim, D.-H.; Park, S.-Y. Effect of Chemical
49 Modification of Graphene on Mechanical, Electrical, and Thermal Properties of
50 Polyimide/Graphene Nanocomposites. ACS Appl. Mater. Interfaces 2012, 4 (9), 4623-
51
52
4630.
53 (48) Gu, J.; Xiao, P.; Chen, J.; Zhang, J.; Huang, Y.; Chen, T. Janus Polymer/Carbon
54 Nanotube Hybrid Membranes for Oil/Water Separation. ACS Appl. Mater. Interfaces
55
2014, 6 (18), 16204.
56
57 (49) Mimi, T.; Lixin, X.; Fu, L.; Lei, J. An Intelligent Superwetting PVDF Membrane
58 Showing Switchable Transport Performance for Oil/Water Separation. Adv. Mater. 2014,
59 26 (18), 2943-2948.
60
29

ACS Paragon Plus Environment

 ACS Applied Materials & Interfaces Page 30 of 31

1
2
3
(50) Zhang, W.; Liu, N.; Cao, Y.; Chen, Y.; Xu, L.; Lin, X.; Feng, L. A Solvothermal
4
5 Route Decorated on Different Substrates: Controllable Separation of an Oil/Water
6 Mixture to a Stabilized Nanoscale Emulsion. Adv. Mater. 2015, 27 (45), 7349-7355.
7 (51) Liao, Y.; Tian, M.; Wang, R. A High-Performance and Robust Membrane with
8
9 Switchable Super-wettability for Oil/Water Separation Under Ultralow Pressure. J.
10 Membr. Sci. 2017, 543, 123-132.
11 (52) Liu, M.; Wang, S.; Wei, Z.; Song, Y.; Jiang, L. Superoleophobic Surfaces:
12
13
Bioinspired Design of a Superoleophobic and Low Adhesive Water/Solid Interface. Adv.
14 Mater. 2009, 21 (6), 665-669.
15 (53) Youngblood, J. P.; Mccarthy, T. J. Ultrahydrophobic Polymer Surfaces Prepared
16
by Simultaneous Ablation of Polypropylene and Sputtering of Poly(tetrafluoroethylene)
17
18 Using Radio Frequency Plasma. Macromolecules 1999, 32 (20), 6800-6806.
19 (54) Liang, S.; Zhang, D.; Yao, X.; Han, R.; Zhang, Q.; Jin, C.; Pu, X.; Geng, Y.
20 Deposition-precipitation synthesis of Yb3+/Er3+ Co-doped BiOBr/AgBr Heterojunction
21
22 Photocatalysts with Enhanced Photocatalytic Activity Under Vis/NIR Light Irradiation.
23 Sep. Purif. Technol. 2020, 238, 116450.
24 (55) Zhan, Y.; Guan, X.; Ren, E.; Lin, S.; Lan, J. Fabrication of Zeolitic Imidazolate
25
26
Framework-8 Functional Polyacrylonitrile Nanofibrous Mats for Dye Removal. J.
27 Polym. Res. 2019, 26 (6), 145.
28 (56) Jie, X.; Sha, H.; Zhang, H.; Huang, J.; Lin, H.; Wang, X.; Long, J. Layered Metal–
29
Organic Framework/Graphene Nanoarchitectures for Organic Photosynthesis Under
30
31 Visible Light. J. Mater. Chem. 2015, 3 (48), 24261-24271.
32 (57) Shaban, M.; Ahmed, A. M.; Shehata, N.; Betiha, M. A.; Rabie, A. M. Ni-doped
33 and Ni/Cr Co-doped TiO2 Nanotubes for Enhancement of Photocatalytic Degradation
34
35 of Methylene Blue. J. Colloid Interface Sci. 2019, 555, 31-41.
36 (58) Gao, W.; Liang, H.; Ma, J.; Han, M.; Chen, Z.-l.; Han, Z.-s.; Li, G.-b. Membrane
37 Fouling Control in Ultrafiltration Technology for Drinking Water Production: A Review.
38
39
Desalination 2011, 272 (1-3), 1-8.
40 (59) Sabaa, M. W.; Mohamed, N. A.; Mohamed, R. R.; Khalil, N. M.; El Latif, S. M. A.
41 Synthesis, Characterization and Antimicrobial Activity of Poly (N-vinyl imidazole)
42
Grafted Carboxymethyl Chitosan. Carbohydr. Polym. 2010, 79 (4), 998-1005.
43
44 (60) Cui, S.-F.; Peng, L.-P.; Zhang, H.-Z.; Rasheed, S.; Kumar, K. V.; Zhou, C.-H.
45 Novel Hybrids of Metronidazole and Quinolones: Synthesis, Bioactive Evaluation,
46 Cytotoxicity, Preliminary Antimicrobial Mechanism and Effect of Metal Ions on Their
47
48 Transportation by Human Serum Albumin. Eur. J. Med. Chem. 2014, 86, 318-334.
49 (61) Sud, I. J.; Feingold, D. S. Mechanisms of Action of the Antimycotic Imidazoles. J.
50 Invest. Dermatol. 1981, 76 (6), 438-441.
51
52
(62) Brayner, R.; Ferrari-Iliou, R.; Brivois, N.; Djediat, S.; Benedetti, M. F.; Fiévet, F.
53 Toxicological Impact Studies Based on Escherichia Coli Bacteria in Ultrafine ZnO
54 Nanoparticles Colloidal Medium. Nano Lett. 2006, 6 (4), 866-870.
55
(63) Wyszogrodzka, G.; Marszałek, B.; Gil, B.; Dorożyński, P. Metal-Organic
56
57 Frameworks: Mechanisms of Antibacterial Action and Potential Applications. Drug
58 Discov. Today 2016, 21 (6), 1009-1018.
59
60
30

ACS Paragon Plus Environment

Page 31 of 31 ACS Applied Materials & Interfaces

1
2
3
4
5 For Table of Contents Only
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
31

ACS Paragon Plus Environment