Subscriber access provided by UNIV OF CAMBRIDGE

Materials and Interfaces

Two-step approach for fabrication of durable superamphiphobic fabrics
for self-cleaning, anti-fouling and on-demand oil/water separation
Jiahui Chen, Zihan Liu, Xiufang Wen, Shouping Xu, Feng Wang, and Pihui Pi
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.9b00049 • Publication Date (Web): 20 Mar 2019
Downloaded from http://pubs.acs.org on March 20, 2019

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 24 Industrial & Engineering Chemistry Research

1
2
3
4 Two-step approach for fabrication of durable superamphiphobic fabrics for self-cleaning, anti-fouling
5
6
7 and on-demand oil/water separation
8
9 Jiahui Chen, Zihan Liu, Xiufang Wen*, Shouping Xu, Feng Wang, Pihui Pi*
10
11
12 School of Chemistry and Chemical Engineering, Guangdong Provincial Key Lab of Green Chemical Product Technology, South China University of
13
14 Technology, Guangzhou 510640, China
15
16
17 *Corresponding author: Tel: +86-20-87112057-805;
18
19
Email address: xfwen@scut.edu.cn, phpi@scut.edu.cn.
20
21
22 Abstract
23
24 Superamphiphobic materials have attracted lots of attention due to its wide applications in many fields. However,
25
26 the preparation of most superamphiphobic materials was time-consuming and complicated. In this study, a durable
27
28 superamphiphobic fabric was prepared by vapor-liquid sol-gel method to deposit silica with thiol (SiO2-SH) and
29
30 thiol-ene click reaction to graft 1H,1H,2H,2H-heptadecafluorodecyl methacrylate (FMA). The superamphiphobic fabric
31
32 can repel liquids with surface tension as low as 27.5mN·m-1. Importantly, the fabric can maintain high amphiphobicity
33
34 after 15 laundry cycles, 40 tape-peeling cycles, 160 g sand abrasion, 24 h UV irradiation, as well as immersion in
35
acid/base solution for 12h, 95℃ water for 6h or 2℃ water for 24h. What’s more, the fabric shows excellent
36
37
self-cleaning and antifouling properties. After the superamphiphobic fabric was pre-wetted by ethanol, it shows
38
39
superhydrophilicity/underwater superoleophobicity and superoleophilicity/underoil superhydrophobicity, which can be
40
41 used for on-demand oil/water separation with high separation efficiency and outstanding reusability.
42
43 Keywords: superamphiphobic; thiol-ene click reaction; vapor-liquid sol-gel reaction; oil/water separation; self-cleaning;
44
45 antifouling
46
47 1.Introduction
48
49 Nowadays, superamphiphobic (superhydrophobic and superoleophobic) materials with a water and oil contact
50
51 angles > 150˚ and a sliding angles < 10˚, have attracted a great deal of attention for its wide applications including
52
53 anti-fouling1, water/oil separation2, self-cleaning3, anti-icing4 and guiding oil movement5. It is well known that
54
55 superhydrophobic materials generally have low surface energy combined with micro/nanoscale binary structures.
56
57 Inspired by nature plants and animals, such as lotus leaf6, rose petal7, butterfly wing8 and strider leg9, more and more
58
59 rough structures were built to gain superhydrophobic materials. However, superoleophobic materials are more difficult
60
1

ACS Paragon Plus Environment

 Industrial & Engineering Chemistry Research Page 2 of 24

1
2
3
4 to be fabricated than superhydrophobic materials due to the facts that the surface energy of oil is much lower than water
5
6 and that superhydrophobic surfaces do not always repel oils. Theoretically, the liquid-solid contact fraction and surface
7
8 energy of superoleophobic surfaces (in air) should be low enough to avoid liquids wetting the surfaces. Thus, special
9
rough surface structures, such as reentrant structure and doubly reentrant structure, and surface composites with very
10
11
low surface tension such as fluorinated materials with groups of -CF3 and -CF2- are usually demanded in fabricating
12
13
superamphiphobic materials10, which also increase the difficulties in preparation of superamphiphobic materials.
14
15 To date, lots of methods have been reported to fabricate superamphiphobic surfaces. These methods can be divided
16
17 into wet chemical method and dry physical method. Dip-coating11-12 , spray-coating13-14 and drop-coating method 15
18
19 which are performed by covering the surface with a layer of coating with superamphiphobic particles, especially
20
21 silica-containing coating, are most common and simple wet chemical techniques to fabricate superamphiphobic surfaces.
22
23 For example, Zhu et. al16 fabricated a superamphiphobic coating via 12 h traditional liquid sol-gel process to synthesize
24
25 carbon nanotubes-silica suspension, followed by spraying the suspension and chemical vapor deposition with
26
27 fluorosilane. Wu et al.17 fabricated a superamphiphobic fluorinated silica coating via a 16h traditional liquid sol-gel and
28
29 spraying process. Qu et al. 18fabricated a superamphiphobic kaolin-SiO2/PFOTS coating by a 11 h traditional sol-gel
30
31 reaction, followed by drop-coating on various substrates. Even typical superamphiphobic work reported by Lin and
32
33 co-workers11 still needed 4.5 h to fabricate a superamphiphobic coating by traditional sol-gel and dip-coating process.
34
35 Although traditional liquid sol-gel method whose entire reaction process was carried out in a solution can provide a
36
37 simple access to fabricate superamphiphobic silica-containing coating for dip-coating, spray-coating or drop-coating,
38
39 fabrication of most coating is time-consuming. Superamphiphobic materials can also be obtained by wet chemical
40
41 polymerization, such as atom transfer radical polymerization (ATRP)19-20, sequential anionic polymerization21 and
42
43 ring-opening anionic polymerization (ROAP)22, but these polymerization processes are tedious and complex. Other wet
44
45 chemical methods such as hydrothermal method23-24 and solvothermal method4, 25 can also be applied to create
46
47 superamphiphobic materials, however, the process might require rigorous operational condition (high temperature
48
or/and high pressure) and high cost. Dry physical method such as plasma etching26-28, 3D printing29 and
49
50
photolithography30 can provide a quick way to fabricated superamphiphobic surface, nevertheless, the expensive or/and
51
52
complex equipment is usually required. In summary, although preparation methods of superamphiphobic materials are
53
54 diverse, most of these methods have weaknesses of tedious fabrication process, long time preparation and expensive
55
56 equipment.
57
58 Besides, durability is also important for superamphiphobic materials, because superamphiphobic materials may lose
59
60
2

ACS Paragon Plus Environment

Page 3 of 24 Industrial & Engineering Chemistry Research

1
2
3
4 their superamphiphobicity after suffered from various damages. Until now, many superamphiphobic materials with
5
6 good durability, especially mechanical durability, have been reported11, 17-18, 31. For instance, Wang et al. 32 took 59 h to
7
8 prepare a HNTs-SiO2/PFDAE coating with mechanical and chemical durability by sol-gel and spray-coating process.
9
Jiang et al. 33 spent 8.5h to fabricated a superamphiphobic coating with mechanical durability through plasma etching
10
11
and dip-coating. Zhai et al.34 took 6 h to prepare a MWCNTs@fluoroPOS coating that could resist hot and cold liquids
12
13
and mechanical abrasion via sol-gel and spray-coating process. Deng et al. 35 spent 29 h to prepare a robust
14
15 superamphiphobic coating that could bear mechanical abrasion by using candle soot as a templet and a followed
16
17 fluorination process. Lots of efforts have been made to fabricate durable surfaces, however, these preparation process
18
19 usually require expensive equipment, long reaction time or complex operation. Therefore, it is still highly demanded to
20
21 develop more convenient, time-saving and low-cost methods to obtain superamphiphobic materials with good durability.
22
23 (The abbreviation was listed in the Table S2)
24
25 Recently, superwetting materials such as superhydrophobic/superoleophilic36-37 and superhydrophilic/underwater
26
27 sueperoleophobic38-39 materials, have been extensively utilized to solve the oil/water separation problems. However,
28
29 superhydrophobic/superoleophilic materials with water repellency and oil affinity are not appropriate for light oil (ρwater
30
31 > ρoil)/water separation by gravity. On the contrary, superhydrophilic/underwater superoleophobic materials with oil
32
33 repellency and water affinity are not suitable heavy oil (ρwater < ρoil)/water separation. Besides,
34
35 superhydrophobic/superoleophilic and superhydrophilic/underwater superoleophobic materials can be contaminated and
36
37 lose wettability easily due to the oleophilicity in air. Thus, superamphiphobic materials with good oil and water
38
39 repellency in air are highly desirable to create because it can not only effectively avoid contaminant in air compared to
40
41 other superwetting materials, but also solve on-demand oil/water separation by pre-wetting method2.
42
43 In this study, a superamphiphobic fabric was fabricated by a time-saving and simple two-step process including a
44
45 vapor-liquid sol-gel to deposit silica with thiol (SiO2-SH) within 20min and a followed thiol-ene click reaction to graft
46
47 1H,1H,2H,2H-heptadecafluorodecyl methacrylate (FMA) within 1 h. Vapor-liquid sol-gel reaction between tetraethyl
48
orthosilicate (TEOS) and 3-mercaptopropyltriethoxysilane (MPTES) in the present of NH3 catalyzation could avoid
49
50
time-consuming traditional liquid sol-gel process and construct rough structures within a short time. Photoinitiated
51
52
thiol-ene click reaction based on reaction between thiol-terminated surfaces and ene moieties of FMA could provide a
53
54 more time-saving and quick approach to decrease the surface energy compared to above-mentioned wet chemical
55
56 polymerization method. Besides, the whole preparation did not require any expensive or complex equipment. More
57
58 importantly, the fabric could keep high oil and water repellency after treated with various harsh conditions including
59
60
3

ACS Paragon Plus Environment

 Industrial & Engineering Chemistry Research Page 4 of 24

1
2
3
4 UV exposure, base(pH=12) or acid (pH=2) solution, 2℃ or 95℃ water, laundry and mechanical abrasion. After the
5
6 as-prepared superamphiphobic fabric was pre-wetted with ethanol, it exhibited both superhydrophilicity/underwater
7
8 superoleophobicity and superoleophilicity/underoil superhydrophobicity, which could be used for on-demand heavy
9
oil/water and light oil/water separation with high separation efficiency (>98%) and excellent reusability. What’s more
10
11
the fabric also shows self-cleaning and antifouling abilities for both water and oil whose surface energy are greater than
12
13
27.5 mN/m, which can effectively avoid contaminant in air.
14
15 2. Experimental
16
17 2.1 Materials: Tetraethyl orthosilicate (TEOS), anhydrous ethanol, hydrochloric acid (HCl), sodium hydroxide (NaOH),
18
19 n-hexane, petroleum ether, dichloromethane, 1,2-dichloroethane, chloroform, isooctane, glycerol, glycol, methylene
20
21 blue, and Sudan Ⅱ were purchased from Damao Chemical Reagent Co,. Ltd (Tianjin, China).
22
23 1H,1H,2H,2H-heptadecafluorodecyl methacrylate (FMA) was purchased from Shang Fluoro Inc (China).
24
25 2-hydroxy-2-methylpropiophenone (HMPF) was purchased from Bayer. 3-mercaptopropyltriethoxysilane (MPTES) and
26
27 hexadecane were obtained from Aladdin Industrial Corporation (Shanghai, China). All the regents were of analytical
28
29 grade and used without further purification. Cotton fabric, tape, detergent, and rapeseed oil were obtained commercially.
30
31 The commercial cotton fabrics were cleaned sequentially with distilled water and ethanol under ultrasonication for
32
33 20min before use.
34
35 2.2 Preparation of superamphiphobic SiO2-S-FMA@fabric.
36
37 The superamphiphobic fabric was fabricated by vapor-liquid sol-gel method and thiol-ene click reaction, as
38
39 illustrated in Figure 1. Firstly, a piece of clean fabric was dipped into an ethanol solution composed of TEOS and
40
41 MPTES (named TM solution) for 5 min at room temperature. The TEOS/MPTES mass ratio of TM solution were 1, 2,
42
43 3 or 4. The mass fraction of MPTES was fixed to 10%. Next, the TM solution pre-wetted fabric was transferred into a
44
45 closed reaction container which was full of NH3 and reacted at 45˚C for 5, 10, 15 or 20 min (The NH3 was produced by
46
47 evaporation of 28 wt% ammonia water at the bottom). After taken out from the reaction container, the fabric was dried
48
at 80˚C for 1h and a SiO2-SH@fabric was obtained. Then, the SiO2-SH@fabric was immersed in a quartz glass
49
50
container containing THF (6 ml), HMPF (0.02 g) and FMA (0.2872 g), and irradiated under 360 nm UV light (40 W)
51
52
for 1 h. After that, the fabric was washed with THF and a superamphiphobic fabric (SiO2-S-FMA@fabric) was
53
54 obtained.
55
56
57
58
59
60
4

ACS Paragon Plus Environment

Page 5 of 24 Industrial & Engineering Chemistry Research

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 Figure 1 Schematic illustration of fabrication of superamphiphobic SiO2-S-FMA@fabric.
24
25 2.3 Instruments and Characterization
26
27 The surface morphologies of the fabrics were characterized by a scanning electron microscopy (SEM, Merlin,
28
29 Zeiss). The surface composition of the fabric was measured by an energy dispersive spectrometer (EDS, X-MaxN20,
30
31 Oxford) attached to SEM, an X-ray photoelectron spectroscopy (XPS, Kratos Axis DLD,UK) equipped with Al Kα
32
33 X-ray source and operated at 300W and an attenuated total reflectance Fourier transform infrared spectrometer
34
35 (ATR-FTIR, VERTEX 70, Bruker).The water contact angles (WCAs), oil contact angles (OCAs), hexadecane contact
36
37 angles (HCAs), water sliding angles (WSAs), oil sliding angels(OSAs), hexadecane sliding angles(HSAs), were
38
39 measured by a contact angle measuring device (Model Powereach JC2000C1,Shanghai Zhongchen).The WCAs and
40
41 OCAs of each fabric were the average values of five different positions with 5μL liquid. Four organic liquids including
42
43 glycerol, glycol, rapeseed oil and hexadecane with different surface tension and density were used as oils. Their surface
44
45 tensions and densities are listed in Table 1.
46
47 Table 1. Liquids with different surfaces tension and density.
48
49 liquid Surface tension(mN/m) Density
50
51 20˚C (g/cm3)
52
53 water 72.8 1
54
55 glycerol 64 1.26
56
57 glycol 48.4 1.115
58
rapeseed oil 35.7 0.92
59
60
5

ACS Paragon Plus Environment

 Industrial & Engineering Chemistry Research Page 6 of 24

1
2
3
4 hexadecane 27.5 0.77
5
6
7
8 2.4 Stability evaluation
9
10 The mechanical stability of superamphiphobic fabric was tested by sand impact test38 and tape-peeling test40-41
11
12 (Figure 2). The sand impact test was conducted by using sand with different mass to impact the fabric from a height of
13
14 15 cm and the tilt angle is 45˚. After impacting test, WCAs, HCAs, WSAs and HSAs of the fabric were measured to
15
evaluate mechanical stability. The tape-peeling test was conducted as follows. An adhesive tape was applied uniformly
16
17
by rolling a 200g weight twice to make sure the fabric was stuck by the adhesive tape. Then the adhesive tape was
18
19
pulled off at full tilt transiently and quickly, and WCAs, HCAs, WSAs and HSAs were measured to evaluate the
20
21 mechanical stability, too. UV resistance was evaluated by irradiating the fabric under a UV lamp of 40 W for 24 h.
22
23 WCAs, HCAs, WSAs and HSAs were measured after every 6 h UV irradiation. Chemical resistance was tested by
24
25 immersing the fabric into acid solution (pH=2, adjusted by hydrochloric acid) for 12 h, base solution (pH=12, adjusted
26
27 by sodium hydroxide) for 12 h. The hot and cold water resistance was assessed by immersing the fabric in 95˚C water
28
29 for 6h and 2˚C water for 24h, respectively. WCAs, HCAs, WSAs and HSAs were also measured after immersing.
30
31 Washing durability was evaluated according to a modified ISO 105-C10:2006(C) method. In briefly, the
32
33 superamphiphobic fabric was washed with 0.5wt% detergent and other loading fabrics under a spinning rate of 40 rpm
34
35 at 45 ˚C for 30 min. And the washing was repeated for 15 cycles31, 42.
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 Figure 2 (a) Scheme of sand abrasion test. (b) Scheme of tape-peeling test.
59
60 3. Results and discussion
6

ACS Paragon Plus Environment

Page 7 of 24 Industrial & Engineering Chemistry Research

1
2
3
4 3.1 Fabrication of superamphiphobic SiO2-S-FMA@fabric.
5
6 The formation mechanism of SiO2-S-FMA@fabric is shown in Figure 3. Firstly, a SiO2-SH@fabric was fabricated
7
8 by vapor-liquid sol-gel method using TEOS and MPTES as reactants, NH3 as catalyst. Under the catalysis of NH3,
9
plenty of silica particles with thiol (named SiO2-SH) were formed on the fabric by hydrolysis and condensation reaction
10
11
between TEOS and MPTES. Simultaneously, the hydroxy of SiO2-SH could condensate with the hydroxy of fabric to
12
13
form chemical bond, which would be beneficial to increase durability of fabric. Secondly, the targeted
14
15 superamphiphobic fabric was prepared by thiol-ene click reaction between thiols of SiO2-SH@fabric and ene moieties
16
17 of FMA under the UV irradiation and photoinitiator. In the first step, hollow and hierarchical structures were built after
18
19 SiO2-SH deposited on the fabric. In the second step, grafted FMA with abundant fluorine atoms could decrease surface
20
21 energy of the fabric. Thus, the superamphiphobic fabric was obtained after two-step modification.
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43 Figure 3 Formation mechanism of the superamphiphobic SiO2-S-FMA@fabric.
44
45 Figure 4 shows the SEM images and photographs of the liquid droplets on the pristine fabric, SiO2-SH@fabric and
46
47 SiO2-S-FMA@fabric. The pristine cotton fabric owned a smooth surface and exhibited both hydrophilicity and
48
oleophilicity (Figure 4a-b). After the pristine fabric was wetted by TM solution with a TEOS/MPTES mass ratio of 3
49
50
and reacted for 20 min under the catalysis of NH3, lots of SiO2-SH deposited on the fabric and formed micro/nanoscale
51
52
hollow and hierarchical structures (Figure 4c). Due to the hydrophobicity of SiO2-SH and hollow and hierarchical
53
54 structures, the SiO2-SH@fabric could repel water and glycerol with WCA of 154˚ and a glycerol contact angel of 151˚,
55
56 but still exhibited oleophilicity for other three oils which have lower surface energy (Figure 4d). After the
57
58 SiO2-SH@fabric was modified with FMA, the SiO2-S-FMA@fabric displayed a fluorinated layer on the hollow and
59
60
7

ACS Paragon Plus Environment

 Industrial & Engineering Chemistry Research Page 8 of 24

1
2
3
4 hierarchical structures and all CAs (WCAs and OCAs) are greater than 150˚. Besides, the WSA and OSAs of the fabric
5
6 were all less than 10˚ (Figure 4f-g). Hence, the superamphiphobic behavior can be observed.
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 4. SEM images of (a) pristine fabric, (c) SiO2-SH@fabric, and (e)SiO2-S-FMA@fabric. Photographs of
36
37 different liquid droplets on (b) pristine fabric, (d) SiO2-SH@fabric, and (f)SiO2-S-FMA@fabric. (g) CAs and SAs of
38
39 pristine fabric, SiO2-SH@fabric, and SiO2-S-FMA@fabric.
40
41 Chemical compositions of fabrics were characterized by EDS, ATR-FTIR, and XPS. The EDS spectra of the
42
43 pristine cotton fabric, SiO2-SH@fabric and SiO2-S-FMA@fabric are shown in Figure S1. The SiO2-S-FMA@fabric
44
45 contained element C, O, S, Si and F (Figure S1c). The peaks of Si and S were attributed to MPTES and TEOS, and the
46
47 peaks of F was attributed to FMA. These suggested that the fabric was decorated by SiO2-SH and FMA. Besides,
48
chemical components of the fabric were further characterized by ATR-FTIR (Figure 5). As shown in spectrum of
49
50
SiO2-S-FMA@fabric, the peaks at 1072 and 1150 cm-1 were due to the stretching vibration of Si-O-Si. The peak at 950
51
52
cm-1 was assigned to bending vibration of Si-OH. The peak at 1443 cm-1 was assigned to stretching vibration of C-S.
53
54 These peaks were attributed to the hydrolysis and condensation reaction between TEOS and MPTES. The peaks at 1200
55
56 and 1723 cm-1 were ascribed to stretching vibrations of C-F and C=O of ester group, respectively, which belonged to
57
58 FMA. In addition, XPS measurement was also performed for further verifying the formation mechanism. The peaks of
59
60
8

ACS Paragon Plus Environment

Page 9 of 24 Industrial & Engineering Chemistry Research

1
2
3
4 C 1s and O 1s appeared in the pristine fabric while the peaks of Si 2s, Si 2p, and S 2p appeared in the SiO2-SH@fabric.
5
6 After the SiO2-SH@fabric was modified by FMA, new peaks of F1s and F KLL were observed (Figure 6a). These
7
8 results confirmed that the fabric was modified by SiO2-SH and FMA. The C 1s high-resolution spectra of pristine cotton
9
fabric displayed three peaks at 284.9, 286.2 and 287.0 eV, which are attributed to the -CHx (C-C, C=C, and C-H), C-O,
10
11
and C=O, respectively (Figure 6b)43. New peak of C-Si (284.3 eV) 44appeared in the C 1s high-resolution spectra of
12
13
SiO2-SH@fabric (Figure 6c). And three new peaks at 289.6, 292.25 and 294.39 eV are attributed to -COO45, C-F2 and
14
15 C-F346 bonds of FMA(Figure6d). These results again proved that MPTES reacted with TEOS and generated SiO2-SH,
16
17 and then SiO2-SH reacted with FMA.
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34 Figure 5. ATR-FTIR spectra of pristine cotton fabric, SiO2-SH@fabric and SiO2-S-FMA@fabric.
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
Figure 6. (a) XPS spectra of pristine cotton fabric, SiO2-SH@fabric and SiO2-S-FMA@fabric; The high-resolution
53
54 XPS spectra of C 1s region of (b) pristine cotton fabric, (c) SiO2-SH@fabric and (d) SiO2-S-FMA@fabric.
55
56 In order to investigate the factors affecting wettability and morphology, a series of experiments were conducted. It
57
58 is found that the mass ratio of TEOS/MPTES have influences on the wettability and morphology of the fabric. When
59
60
9

ACS Paragon Plus Environment

 Industrial & Engineering Chemistry Research Page 10 of 24

1
2
3
4 the NH3 treatment time was fixed at 20 min, SEM images, CAs and SAs of the SiO2-S-FMA@fabric at different
5
6 TEOS/MPTES mass ratio are shown in Figure 7. At the mass ratio of 1, the SiO2-SH on the fabric were relatively few,
7
8 and the fabric showed low CAs (a WCA of 152˚ and OCAs of <150˚) (Figure 7a). When the TEOS/MPTES mass ratio
9
increased to 2, the SiO2-SH on the fabric increased greatly and almost covered the surface of the fabric (Figure 7b). The
10
11
CAs also increased a little and SAs decreased, but the CAs and SAs for liquids with lower surface energy were still
12
13
lower than 150˚ and greater than 10˚, respectively. That is to say, increase of TEOS/MPTES mass ratio could provide
14
15 more hierarchical and hollower layer to enhance hydrophobity and oleophobicity of the fabric. As the TEOS/MPTES
16
17 mass ratio was 3, the SiO2-SH grew together to form hierarchical and hollow structures and covered the fabric
18
19 completely with a WCA of 158˚, an HCA of 152˚, a WSA of 2.0˚ and an HSAs of 8.3˚, which showed
20
21 superamphiphobicity (Figure 7c). However, when mass ratio increased to 4, the CAs decreased and SAs increased
22
23 (Fig.7e). It is mainly because oil or water droplets on the superamphiphobic surface exhibited a liquid-solid Wenzel
24
25 state. When the mass ratio was 4, numerous SiO2-SH grew together and formed a more compact structure, resulting in
26
27 decrease of amphiphobicity (Fig.7d and Fig.S2). Besides, the relative mass ratio of MPTES decreased, leading to a
28
29 decrease in the amount of -SH groups, which further decreased the fluorine content on the surface. Thus, the
30
31 superamphiphobic fabric could be obtained under the mass ratio of 3.
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
10

ACS Paragon Plus Environment

Page 11 of 24 Industrial & Engineering Chemistry Research

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
36
37
38
39
40 Figure 7. SEM images of SiO2-S-FMA@fabric with different TEOS/MPTES mass ratio: (a)1, (b) 2, (c) 3 and (d)4. (e)
41
42 CAs and SAs of different liquid on SiO2-S-FMA@fabric with different TEOS/MPTES mass ratio (the NH3 treatment
43
44 time was 20 min).
45
46 Except for the influence of mass ratio of TEOS/MPTES, the NH3 treatment time also had a great effect on the
47
48 wettability and morphology. The SEM images, CAs and SAs of the SiO2-S-FMA@fabric at different NH3 treatment
49
50 time with the TEOS/MPTES mass ratio of 3 are shown in Figure 8. With the reaction time was 5 min, only a little
51
52 SiO2-SH deposited on the fabric and the CAs of different liquids were quite low (WCA <150˚ and OCAs<150˚). As the
53
54 NH3 treatment time was extended to 10 min, SiO2-SH increased a little and distributed sparely with low CAs and high
55
56 SAs. When the reaction time increased to 15 min, numerous SiO2-SH were formed on the fabric, but it cannot
57
58 completely cover the fabric surface. The CAs and SAs for liquids with lower surface energy were still lower than 150˚
59
60 and greater than 10˚, respectively. When further increasing the treatment time to 20 min, a thicker SiO2-SH constructed
11

ACS Paragon Plus Environment

 Industrial & Engineering Chemistry Research Page 12 of 24

1
2
3
4 hierarchical and hollow structures and the fabric exhibited CAs of >150˚ and SAs of <10˚. So, we chose the fabric
5
6 sample at TEOS/MPTES mass ratio of 3 and NH3 treatment time of 20 min for following investigation.
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 Figure 8. SEM images of SiO2-S-FMA@fabric with different NH3 treatment time:(a) 5 min, (b)10 min, (c) 15 min,
45
46 (d)20 min. (e) CAs and SAs of different liquids on SiO2-S-FMA@fabric with different NH3 treatment time (The
47
48 TEOS/MPTES mass ratio is 3).
49
50 3.2 Stability of SiO2-S-FMA@fabric
51
52 The sand impact test and tape-peeling test were used to assess the mechanical stability of the fabric. After the
53
54 fabric suffered from 160g sand impact, the WCAs, HCAs, WSAs and HSAs of the fabric changed from 159˚ to 153˚,
55
56 152˚ to 146˚, 2.0˚ to 6.6˚ and 8.3˚ to 13.5˚, respectively (Figure9a). After forty tape-peeling cycles, the WCA and HCA
57
58 decreased from 158˚ to 150˚,152˚ to 146˚, respectively, and WSA and HSA increased from 2.0˚ to 6.0˚, 8.3˚to 11.6˚,
59
60 respectively (Figure 9b). Obviously, the SiO2-S-FMA@fabric still kept good water and oil repellency after mechanical
12

ACS Paragon Plus Environment

Page 13 of 24 Industrial & Engineering Chemistry Research

1
2
3
4 abrasion. The SEM images after 160g sand impact and 40 tape-peeling cycles showed that most of particles still
5
6 adhered to fabric, further indicating the good mechanical durability of the fabric (Figure S3b-c) The good mechanical
7
8 durability of the fabric may be due to the strong and stable covalent bonding among TEOS, MPTES, FMA and the
9
hydroxyl groups of fabric. The SEM images after 15 laundry cycles indicated that some of particles filled off (Figure
10
11
S3d), however, the fabric could still maintain a WCA of 156˚, a WSA of 3.4˚, an HCA of 149˚ and an HAS of 12.4 ˚
12
13
(Figure 9c), showing good washing durability. The decrease in CAs and increase in SAs are due to the damage of
14
15 superamphiphobic surface which result in the increase of adhesion force between liquids and fabric.41
16
17 UV irradiation from sunlight may affect the long-term use of the fabric. Figure 9d shows WCAs and HCAs of the
18
19 fabric after UV irradiation with different time. As irradiation time increased, the CAs and SAs displayed no obvious
20
21 change. Even after 24 h UV irradiation, the WCA, HCA, WSA and HSA still maintained 158˚, 151˚, 2.0˚ and 8.4˚,
22
23 respectively. The change in morphology after 24h UV irradiation was not obvious (Figure S3e). These results showed
24
25 that the fabric has remarkable UV resistance.
26
27 Figure 9e shows WCAs and HCAs of the SiO2-S-FMA@fabric after separately immersed in acid solution (pH=2)
28
29 for 12 h, base solution (pH=12) for 12 h, 2˚C water for 24 h, and 95 ˚C water for 6 h. After the fabric was immersed in
30
31 acid solution for 12 h, the WCA and HCA decreased a little but maintained 155.0˚ and 150.3˚, respectively, and the
32
33 WSA and HSA still kept 2.2˚ and 8.5˚, respectively. As for the fabric was immersed in base solution for 12h, the fabric
34
35 still maintained high amphiphobicity with a WCA, HCA, WSA and HSA of 152˚, 148˚, 4.5˚ and 13.6˚, respectively.
36
37 The morphology of the fabric was only damaged slightly after the fabric was immersed in acid or base solution for 12h
38
39 (Figure S3 f-g). These results indicated that the SiO2-S-FMA@fabric could well resist acid and base solution. This
40
41 resistance to acid and base solution may be due to the air layer trapped on the surface which can avoid the corrosion of
42
43 acid or alkali. Besides, when the fabric was dipped into 2˚C water for 24 h, the rough structure was still observed in
44
45 SEM images and the fabric kept superamphiphobicity (Figure S3h and Figure 9e). When the fabric was dipped into
46
47 95˚C water for 6 h, the CAs decreased slightly and still remained greater than 148˚, and the SAs increased a little but
48
kept lower than 15˚.The SEM image also indicated that the morphology of the fabric was damaged a little after treated
49
50
with hot water (Figure S3i). The fabric can remain high amphiphobicity after being treated in 2˚C water for 24 h or
51
52
95˚C water for 6 h, which is mainly ascribed to the stable covalent bonding between fabric and reactants and the
53
54 protection of an air layer trapped on the surface. However, the damages of morphology and fluorinated layer still result
55
56 in decrease in hydrophobicity and oleophobicity.
57
58
59
60
13

ACS Paragon Plus Environment

 Industrial & Engineering Chemistry Research Page 14 of 24

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23 Figure 9. (a)WCAs, HCAs, WSAs and HSAs of the fabric after sand impact with different mass sand. (b) WCAs and
24
25 HCAs of the fabric after tape-peel tests with different cycles. (c) WCAs, HCAs, WSAs and HSAs of the fabric after
26
27 different laundry cycles (d) WCAs, HCAs, WSAs and HSAs of the fabric after UV-light irradiation with different time.
28
29 (e) The WCAs, HCAs, WSAs and HSAs of the fabric after separately immersed in acid solution for 12 h, base solution
30
31 for 12 h, 3˚C water for 24 h, and 95 ˚C water for 6 h.
32
33 3.3 Self-cleaning and antifouling properties.
34
35 Since the SiO2-S-FMA@fabric showed both water and oil repellency, it could be used for self-cleaning and
36
37 anti-fouling. Here, sand was used as the dirt to be cleaned. As shown in Figure 10a-b and Video S1-S2, when water
38
39 droplets were placed on a slightly tilted (the tilted angle was 9 ° ) superhydrophobic SiO2-SH@fabric or
40
41 superamphiphobic SiO2-S-FMA@fabric, the water droplets could roll away and take the sand away at the same time,
42
43 and a clean fabric was regained. In addition to water self-cleaning which is common for superhydrophobic fabric, an oil
44
45 self-cleaning is also possible for the superamphiphobic fabric. Similarly, when glycol droplets were dropped on the
46
47 SiO2-SH@fabric, glycol droplets quickly spread out, and sand still remained on the surface (Figure 10c and Video S3).
48
49 However, as for SiO2-S-FMA@fabric, the glycol droplets rolled off easily and cleaned the fabric at the same time
50
51 (Figure 10d and Video S4), which indicated the superamphiphobic fabric had better self-cleaning property than
52
53 superhydrophobic fabric. To test antifouling properties, the SiO2-SH@fabric and SiO2-S-FMA@fabric were separately
54
55 dipped into rapeseed oil which has low surface tension and high viscosity for a moment and then taken out (Figure
56
57 10e-f and Video S5-6). Due to the lower surface tension of SiO2-S-FMA@fabric compared to SiO2-SH@fabric, the
58
59 SiO2-SH@fabric was contaminated, but the SiO2-S-FMA@fabric was clean without any residual oil. Dyed water which
60
14

ACS Paragon Plus Environment

Page 15 of 24 Industrial & Engineering Chemistry Research

1
2
3
4 could dye fabric easily was also used to evaluate antifouling property. After SiO2-SH@fabric and SiO2-S-FMA@fabric
5
6 were taken out from dyed water, both fabrics exhibited pure white (Figure 10g-h and Video S7-8). The primary reason
7
8 for water anti-fouling is that the air layer between water and fabrics can prevent dyed water from wetting and fouling
9
the surfaces, which also proved the high hydrophobicity of the rough structures. In conclusion, the superamphiphobic
10
11
fabric is not only a suitable candidate for self-cleaning, but also an ideal material for antifouling properties.
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 Figure 10 Water self-cleaning property of (a) SiO2-SH@fabric (b)SiO2-S-FMA@fabric. Oil self-cleaning property of (c)
43
44 SiO2-SH@fabric, (d)SiO2-S-FMA@fabric. (e)SiO2-SH@fabric and (f)SiO2-S-FMA@fabric were dipped into the
45
46 rapeseed oil and taken out, respectively. (g) SiO2-SH@fabric, (h) SiO2-S-FMA@fabric were dipped into dyed water
47
48 (dyed by methylene blue) the and taken out, respectively.
49
50 3.4 Oil/water separation.
51
52 Although the fabric exhibited good oil and water repellency, it could be wetted by ethanol which has a much lower
53
54 surface tension of 21.8 mN·m-1 than that of hexadecane (Figure S4). The schematic of wettability transition was shown
55
56 in Figure 11a. When the superamphiphobic fabric was pre-wetted by ethanol (named ethanol pre-wetted fabric), it
57
58 showed superamphiphilicity in air. Once the ethanol pre-wetted fabric was submerged in oil, the trapped oil and
59
60 fluorinated layer could prevent water from contacting with the surface due to the superhydrophobicity of the fabric,
15

ACS Paragon Plus Environment

 Industrial & Engineering Chemistry Research Page 16 of 24

1
2
3
4 resulting in underoil superhydrophobicity with an underoil water contact angles (UOWCA) of 161˚ (Figure S5a and
5
6 Figure 11a). Analogously, if the ethanol pre-wetted fabric was immersed in water, hollow and hierarchical
7
8 microstructures could form a stable water layer and the fluorinated layer could greatly increase the oleophobicity,
9
leading to underwater superoleophobicity with an underwater oil contact angle (UWOCA) of 161˚. (Figure S5b and
10
11
Figure 11a). Comparatively, we also tested the wettability of superhydrophobic SiO2-SH@fabric, and the results were
12
13
shown in Figure S5c-d. The SiO2-SH@fabric showed underoil superhydrophobicity with a UOWCA of 159˚, but it did
14
15 not show underwater superoleophobicity due to the superoleophilicity of the fabric, indicating that the fluorinated layer
16
17 is a vital factor for underwater superoleophobicity.
18
19 For better understanding oil/water separation, Figure 11b-e shows the schematic of oil/water separation. The
20
21 theoretical intrusion pressure (Δp) which means liquids do not penetrate the fabric below the pressure can be calculated
22
23 by following eq. (1)47-48
24
25 Δp=2γ/R=-lγ (cos θa)/A (1)
26
27 where γ is water/oil interfacial tension, R is the meniscus's radius, l is the pore’s size of perimeter, θa is the water or oil
28
29 contact angle on the fabric and A is the pore’s area. For example, when separating heavy oil/water mixture, because the
30
31 ethanol pre-wetted fabric is superoleophilic in air, θa is equal to 0˚, and the corresponding Δp<0, meaning that the
32
33 fabric cannot support any pressure and the heavy oil will permeate the fabric continuously (Figure 11b). However,
34
35 when water contact with the ethanol pre-wetted fabric under oil, the θa is greater than 90˚ due to the underoil
36
37 superhydrophobicity, and the corresponding Δp > 0, meaning that the fabric can support certain pressure and water
38
39 droplets can be suspended rather than penetrate fabric (Figure 11c). Thus, heavy oil/water mixtures will be separated.
40
41 When separating light oil/water mixtures, the fabric works oppositely (Figure 11d-e). Due to dual wettability, the
42
43 superamphiphobic fabric could be used for oil/water separation.
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
16

ACS Paragon Plus Environment

Page 17 of 24 Industrial & Engineering Chemistry Research

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
36
37
38
39
40
41
42
43 Figure 11 (a) Schematic of wettability transition. Schematic of (b-c) heavy oil/water and (d-e) light oil/water separation
44
45 mechanism.
46
47 Figure 12a-b shows the process of oil/water separation. The pre-wetted fabric was fixed between two glass tubes
48
49 by water pipe connector. When separating the light oil (isooctane, dyed with Sudan Ⅱ)/water (dyed with methylene
50
51 blue) mixture (with volume ratio of 1:1), the fabric sequentially pre-wetted by ethanol and water to obtain underwater
52
53 superoleophobicity. During the separation, water could pass through the pre-wetted fabric and be collected in beaker, in
54
55 which no dyed oil was visible, while the isooctane was hindered by the fabric and kept in the upper glass tube. More
56
57 interestingly, the dye (methylene blue) in the water was also kept in fabric and the water in baker showed transparency
58
59 because of the methylene blue adsorption property of silica (Figure 12a and Video S9)49. After light oil/water separation,
60
17

ACS Paragon Plus Environment

 Industrial & Engineering Chemistry Research Page 18 of 24

1
2
3
4 the fabric was cleaned with ethanal and dipped in oil for a moment, it switched from underwater superoleophobicity to
5
6 underoil superhydrophobicity. Similarly, when the heavy oil (chloroform, dyed with Sundan Ⅱ)/water mixture was
7
8 poured into the separator, the dyed oil would penetrate though the pre-wetted fabric and be collected in the beaker, and
9
the water was prevented by fabric and stayed in the upper glass tube (Figure 12b and VideoS10). Noticeably, the
10
11
collected water and oil were pure blue and red, respectively, indicating that the fabric could separate heavy oil/water
12
13
mixture successfully. The efficiency of oil/water separation was calculated using following eq.(2)
14
15 η (%) =ma/mb (2)
16
17 where ma and mb are the weight of water after and before separation. Isooctane/water, n-hexane/water, petroleum
18
19 ether/water, chloroform/water, dichloromethane/water and 1,2-dichloroethane/water mixtures were also separated
20
21 successfully by the fabric and the separation efficiencies were all above 98% (Figure12c). The fabric could maintain
22
23 separation efficiency of 98% after 40 separation cycles for dichloromethane/water or isooctane/water mixture,
24
25 indicating that the fabric owned outstanding reusability (Figure12d). Besides, the intrusion pressure (P) which means
26
27 water does not penetrate the fabric below the pressure was calculated by eq. (3):
28
29 P=ρghmax (3)
30
31 Where ρ is the density of water, g is acceleration gravity and hmax is the maximum height of the water that the fabric can
32
33 support. Figure 10e showed that the hmax is 47cm and the calculated P is 4.60 kPa, indicating that the fabric can support
34
35 high water pressure and is a suitable oil/water separation material.
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
18

ACS Paragon Plus Environment

Page 19 of 24 Industrial & Engineering Chemistry Research

1
2
3
4 Figure 12 Process of (a) Light oil/water separation and (b) Heavy oil/water separation. (c) Separation efficiency for
5
6 various oil/water mixtures. (d) Recycle efficiency of the fabric for dichloromethane/water and isooctane/water mixture.
7
8 (e) Image of the water column on the fabric with maximum height.
9
4. Conclusions
10
11
In this study, a durable and multifunctional superamphiphobic SiO2-S-FMA@fabric was fabricated by vapor-liquid
12
13
sol-gel method to deposit SiO2-SH first, followed by thiol-ene click reaction to graft FMA. Due to the hollow and
14
15 hierarchical structures and fluorinated layer on the fabric, it can repel liquids with surface tension as low as 27.5
16
17 mN·m-1. Importantly, the SiO2-S-FMA@fabric can resist harsh conditions, such as laundry, tape-peeling, sand abrasion,
18
19 UV irradiation, acid/base solution, and hot/cold water. More importantly, the superamphiphobic fabric owns multiple
20
21 functions, including self-cleaning, anti-fouling, heavy oil/water and light oil/water separation. The separation
22
23 efficiencies for various oil/water mixtures were all above 98%. What is more, the fabric could maintain separation
24
25 efficiencies of 98% after 40 separation cycles for various oil/water mixtures, showing remarkable reusability. With the
26
27 simple fabrication, good durability and multifunction, the superamphiphobic fabric may have an application prospect.
28
29 Supporting information
30
31 Other information on the pristine fabric, SiO2-SH@fabric and SiO2-S-FMA@fabric. (doc.)
32
33 Water self-cleaning property of SiO2-SH@fabric (Video S1) and SiO2-S-FMA @fabric (Video S2)
34
35 Oil self-cleaning property of SiO2-SH@fabric (Video S3) and SiO2-S-FMA @fabric (Video S4)
36
37 Rapeseed oil antifouling property of SiO2-SH@fabric (Video S5) and SiO2-S-FMA @fabric (Video S6)
38
39 Dye water antifouling property of SiO2-SH@fabric (Video S7) and SiO2-S-FMA @fabric(Video S8)
40
41 Light oil/separation process (Video S9).
42
43 Heavy oil/separation process(Video S10).
44
45 Acknowledgements
46
47
48 We are grateful for the financial support from the National Natural Science Foundation of China (Grant No.
49
50 21676102 and No. 21878110).
51
52
53 Reference
54
55 (1). Wu, Y.; Zhao, M.; Guo, Z., Multifunctional superamphiphobic SiO2 coating for crude oil transportation. Chem.
56
57 Eng. J. 2018, 334, 1584-1593.
58
59 (2). Ge, D.; Yang, L.; Wang, C.; Lee, E.; Zhang, Y.; Yang, S., A multi-functional oil–water separator from a
60
19

ACS Paragon Plus Environment

 Industrial & Engineering Chemistry Research Page 20 of 24

1
2
3
4 selectively pre-wetted superamphiphobic paper. Chem. Commun. 2015, 51 (28), 6149-6152.
5
6 (3). Qu, M.; Ma, X.; He, J.; Feng, J.; Liu, S.; Yao, Y.; Hou, L.; Liu, X., Facile Selective and Diverse Fabrication of
7
8 Superhydrophobic, Superoleophobic-Superhydrophilic and Superamphiphobic Materials from Kaolin. ACS Appl. Mater.
9
Interfaces 2017, 9 (1), 1011-1020.
10
11
(4). Chen, L.; Guo, Z.; Liu, W., Biomimetic Multi-Functional Superamphiphobic FOTS-TiO2 Particles beyond Lotus
12
13
Leaf. ACS Appl. Mater. Interfaces 2016, 8 (40), 27188-27198.
14
15 (5). Wong, W. S.; Liu, G.; Tricoli, A., Superamphiphobic Bionic Proboscis for Contamination-Free Manipulation of
16
17 Nano and Core-Shell Droplets. Small 2017, 13 (14).
18
19 (6). Sun, T.; Feng, L.; Gao, X.; Jiang, L., Bioinspired surfaces with special wettability. Acc. Chem. Res. 2005, 38 (8),
20
21 644-652.
22
23 (7). Bhushan, B.; Her, E. K., Fabrication of superhydrophobic surfaces with high and low adhesion inspired from rose
24
25 petal. Langmuir 2010, 26 (11), 8207-17.
26
27 (8). Zheng, Y.; Gao, X.; Jiang, L., Directional adhesion of superhydrophobic butterfly wings. Soft Matter. 2007, 3 (2),
28
29 178-182.
30
31 (9). Su, Y.; Ji, B.; Huang, Y.; Hwang, K. C., Nature's design of hierarchical superhydrophobic surfaces of a water
32
33 strider for low adhesion and low-energy dissipation. Langmuir 2010, 26 (24), 18926-37.
34
35 (10). Liu, T. L.; Kim, C. J., Repellent surfaces. Turning a surface superrepellent even to completely wetting liquids.
36
37 Science 2014, 346 (6213), 1096-1100.
38
39 (11). Zhou, H.; Wang, H.; Niu, H.; Gestos, A.; Lin, T., Robust, Self-Healing Superamphiphobic Fabrics Prepared by
40
41 Two-Step Coating of Fluoro-Containing Polymer, Fluoroalkyl Silane, and Modified Silica Nanoparticles. Adv. Funct.
42
43 Mater. 2013, 23 (13), 1664-1670.
44
45 (12). Xu, Z.; Zhao, Y.; Wang, H.; Wang, X.; Lin, T., A superamphiphobic coating with an ammonia-triggered transition
46
47 to superhydrophilic and superoleophobic for oil-water separation. Angew. Chem. Int. Ed. Engl. 2015, 54 (15), 4527-30.
48
(13). Wang, X.; Hu, H.; Ye, Q.; Gao, T.; Zhou, F.; Xue, Q., Superamphiphobic coatings with coralline-like structure
49
50
enabled by one-step spray of polyurethane/carbon nanotube composites. J. Mater. Chem. 2012, 22 (19), 9624.
51
52
(14). Li, B.; Zhang, J., Durable and self-healing superamphiphobic coatings repellent even to hot liquids. Chem.
53
54 Commun. 2016, 52 (13), 2744-7.
55
56 (15). Qu, M.; Yuan, M.; He, J.; Xue, M.; Ma, X.; Hou, L.; Zhang, T.; Liu, X.; He, J., Substrate-versatile approach to
57
58 multifunctional superamphiphobic coatings with mechanical durable property from quartz sand. Surf. Coat. Tech. 2018,
59
60
20

ACS Paragon Plus Environment

Page 21 of 24 Industrial & Engineering Chemistry Research

1
2
3
4 352, 191-200.
5
6 (16). Zhu, X.; Zhang, Z.; Ren, G.; Men, X.; Ge, B.; Zhou, X., Designing transparent superamphiphobic coatings
7
8 directed by carbon nanotubes. J. Colloid Interface Sci. 2014, 421, 141-5.
9
(17). Wu, X.; Fu, Q.; Kumar, D.; Ho, J. W. C.; Kanhere, P.; Zhou, H.; Chen, Z., Mechanically robust superhydrophobic
10
11
and superoleophobic coatings derived by sol–gel method. Mater. Design 2016, 89, 1302-1309.
12
13
(18). Qu, M.; Ma, X.; Hou, L.; Yuan, M.; He, J.; Xue, M.; Liu, X.; He, J., Fabrication of durable superamphiphobic
14
15 materials on various substrates with wear-resistance and self-cleaning performance from kaolin. Appl. Surf. Sci. 2018,
16
17 456, 737-750.
18
19 (19). Zhang, G.; Lin, S.; Wyman, I.; Zou, H.; Hu, J.; Liu, G.; Wang, J.; Li, F.; Liu, F.; Hu, M., Robust
20
21 superamphiphobic coatings based on silica particles bearing bifunctional random copolymers. ACS Appl. Mater.
22
23 Interfaces 2013, 5 (24), 13466-77.
24
25 (20). Zou, H.; Lin, S.; Tu, Y.; Li, F.; Hu, J.; Liu, G.; Hu, S.; Yang, G.; Yu, Z., An aqueous process for durable
26
27 superamphiphobic diblock copolymer coatings on fabrics. Adv. Mater. Interfaces 2016, 3 (8), 1500693.
28
29 (21). Xiong, D.; Liu, G.; Hong, L.; Duncan, E. J. S., Superamphiphobic Diblock Copolymer Coatings. Chem. Mater.
30
31 2011, 23 (19), 4357-4366.
32
33 (22). Schlaich, C.; Cuellar Camacho, L.; Yu, L.; Achazi, K.; Wei, Q.; Haag, R., Surface-Independent Hierarchical
34
35 Coatings with Superamphiphobic Properties. ACS Appl. Mater. Interfaces 2016, 8 (42), 29117-29127.
36
37 (23). Li, Z.; Hui, S.; Yang, J.; Hua, Y., A facile strategy for the fabrication of superamphiphobic MoS 2 film on steel
38
39 substrates with excellent anti-corrosion property. Mater. Lett. 2018, 229, 336-339.
40
41 (24). Wang, T.; Cui, J.; Ouyang, S.; Cui, W.; Wang, S., A new approach to understand the Cassie state of liquids on
42
43 superamphiphobic materials. Nanoscale 2016, 8 (5), 3031-9.
44
45 (25). Yu, J.; Wang, H.; Yin, N.; Xu, X., HF-assisted one-step synthesis of pompon-like/chip-like FeSe2 particles and
46
47 their superamphiphobic/antireflective property. RSC Adv. 2014, 4 (46), 24163-24169.
48
(26). Jiang, L.; Tang, Z.; Clinton, R. M.; Breedveld, V.; Hess, D. W., Two-Step Process to Create “Roll-Off”
49
50
Superamphiphobic Paper Surfaces. ACS Appl. Mater. Interfaces 2017, 9 (10), 9195-9203.
51
52
(27). Li, L.; Breedveld, V.; Hess, D. W., Design and fabrication of superamphiphobic paper surfaces. ACS Appl. Mater.
53
54 Interfaces 2013, 5 (11), 5381-6.
55
56 (28). Lee, S. E.; Kim, H. J.; Lee, S. H.; Choi, D. G., Superamphiphobic surface by nanotransfer molding and isotropic
57
58 etching. Langmuir 2013, 29 (25), 8070-5.
59
60
21

ACS Paragon Plus Environment

 Industrial & Engineering Chemistry Research Page 22 of 24

1
2
3
4 (29). Liu, X.; Gu, H.; Wang, M.; Du, X.; Gao, B.; Elbaz, A.; Sun, L.; Liao, J.; Xiao, P.; Gu, Z., 3D Printing of
5
6 Bioinspired Liquid Superrepellent Structures. Adv. Mater. 2018, 30, 1800103−1800110.
7
8 (30). Li, T.; Paliy, M.; Wang, X.; Kobe, B.; Lau, W. M.; Yang, J., Facile one-step photolithographic method for
9
engineering hierarchically nano/microstructured transparent superamphiphobic surfaces. ACS Appl. Mater. Interfaces
10
11
2015, 7 (20), 10988-92.
12
13
(31). Li, X.; Li, Y.; Guan, T.; Xu, F.; Sun, J., Durable, Highly Electrically Conductive Cotton Fabrics with Healable
14
15 Superamphiphobicity. ACS Appl. Mater. Interfaces 2018, 10 (14), 12042-12050.
16
17 (32). Wang, K.; Liu, X.; Tan, Y.; Zhang, W.; Zhang, S.; Li, J.; Huang, A., Highly Fluorinated and Hierarchical
18
19 HNTs/SiO2 Hybrid Particles for Substrate-Independent Superamphiphobic Coatings. Chem. Eng. J. 2018. 359,
20
21 626-640.
22
23 (33). Jiang, L.; Park-Lee, K. J.; Clinton, R. M.; Tang, Z.; Breedveld, V.; Hess, D. W., Mechanical durability of liquid
24
25 repellent coatings. Surf. Coat. Tech. 2017, 328, 182-191.
26
27 (34). Zhai, N.; Fan, L.; Li, L.; Zhang, J., Durable superamphiphobic coatings repelling both cool and hot liquids based
28
29 on carbon nanotubes. J. Colloid Interface Sci. 2017, 505, 622-630.
30
31 (35). Deng, X.; Mammen, L.; Butt, H.-J.; Vollmer, D., Candle soot as a template for a transparent robust
32
33 superamphiphobic coating. Science 2012, 335 (6064), 67-70.
34
35 (36). Chen, J.; Guo, D.; Huang, C.; Wen, X.; Xu, S.; Cheng, J.; Pi, P., Fabrication of superhydrophobic copper mesh by
36
37 depositing CuCl for oil/water separation. Mater. Lett. 2018, 233, 328-331.
38
39 (37). Kong, L. H.; Chen, X. H.; Yu, L. G.; Wu, Z. S.; Zhang, P. Y., Superhydrophobic cuprous oxide nanostructures on
40
41 phosphor-copper meshes and their oil-water separation and oil spill cleanup. ACS Appl. Mater. Interfaces 2015, 7 (4),
42
43 2616-25.
44
45 (38). Hou, K.; Zeng, Y.; Zhou, C.; Chen, J.; Wen, X.; Xu, S.; Cheng, J.; Lin, Y.; Pi, P., Durable underwater
46
47 superoleophobic PDDA/halloysite nanotubes decorated stainless steel mesh for efficient oil–water separation. Appl.
48
Surf. Sci. 2017, 416, 344-352.
49
50
(39). Li, H.; Liang, T.; Lai, X.; Su, X.; Zhang, L.; Zeng, X., Vapor-liquid interfacial reaction to fabricate
51
52
superhydrophilic and underwater superoleophobic thiol-ene/silica hybrid decorated fabric for oil/water separation. Appl.
53
54 Surf. Sci. 2018, 427, 92-101.
55
56 (40). Peng, C.; Chen, Z.; Tiwari, M. K., All-organic superhydrophobic coatings with mechanochemical robustness and
57
58 liquid impalement resistance. Nat. Mater. 2018, 17 (4), 355-360.
59
60
22

ACS Paragon Plus Environment

Page 23 of 24 Industrial & Engineering Chemistry Research

1
2
3
4 (41). Zhou, C.; Chen, Z.; Yang, H.; Hou, K.; Zeng, X.; Zheng, Y.; Cheng, J., Nature-Inspired Strategy toward
5
6 Superhydrophobic Fabrics for Versatile Oil/Water Separation. ACS Appl Mater Interfaces 2017, 9 (10), 9184-9194.
7
8 (42). Yazdanshenas, M. E.; Shateri-Khalilabad, M., One-Step Synthesis of Superhydrophobic Coating on Cotton Fabric
9
by Ultrasound Irradiation. Ind. Eng. Chem. Res. 2013, 52 (36), 12846-12854.
10
11
(43). Xiong, Z.; Luo, Y.; Zhao, Y.; Zhang, J.; Zheng, C.; Wu, J. C., Synthesis, characterization and enhanced
12
13
photocatalytic CO2 reduction activity of graphene supported TiO2 nanocrystals with coexposed {001} and {101} facets.
14
15 Phys. Chem. Chem. Phys. 2016, 18 (19), 13186-95.
16
17 (44). Hou, K.; Zeng, Y.; Zhou, C.; Chen, J.; Wen, X.; Xu, S.; Cheng, J.; Pi, P., Facile generation of robust POSS-based
18
19 superhydrophobic fabrics via thiol-ene click chemistry. Chem. Eng. J. 2018, 332, 150-159.
20
21 (45). Carbone, M. E.; Ciriello, R.; Moscarelli, P.; Boraldi, F.; Bianco, G.; Guerrieri, A.; Bochicchio, B.; Pepe, A.;
22
23 Quaglino, D.; Salvi, A. M., Interactions between elastin-like peptides and an insulating poly(ortho-aminophenol)
24
25 membrane investigated by AFM and XPS. Anal. Bioanal. Chem. 2018, 410 (20), 4925-4941.
26
27 (46). Praschak, D.; Bahners, T.; Schollmeyer, E., Excimer UV lamp irradiation induced grafting on synthetic polymers.
28
29 Appl. Phys. A 2000, 71 (5), 577-581.
30
31 (47). Zhang, E.; Cheng, Z.; Lv, T.; Qian, Y.; Liu, Y., Anti-corrosive hierarchical structured copper mesh film with
32
33 superhydrophilicity and underwater low adhesive superoleophobicity for highly efficient oil–water separation. J. Mater.
34
35 Chem. A 2015, 3 (25), 13411-13417.
36
37 (48). Youngblood, J. P.; Mccarthy, T. J., Ultrahydrophobic Polymer Surfaces Prepared by Simultaneous Ablation of
38
39 Polypropylene and Sputtering of Poly(tetrafluoroethylene) Using Radio Frequency Plasma. Macromolecules 1999, 32
40
41 (20), 6800.
42
43 (49). Li, J.; Guan, P.; Zhang, Y.; Xiang, B.; Tang, X.; She, H., A diatomite coated mesh with switchable wettability for
44
45 on-demand oil/water separation and organic pollutants adsorption. Sep. Purif. Tech. 2017, 174, 275-281.
46
47 Table of Contents (TOC)
48
49
50
51
52
53
54
55
56
57
58
59
60
23

ACS Paragon Plus Environment

 Industrial & Engineering Chemistry Research Page 24 of 24

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
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
24

ACS Paragon Plus Environment