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Energy, Environmental, and Catalysis Applications

Porous Aromatic Framework Modified Electrospun Fiber
Membrane as a Highly Efficient and Reusable Adsorbent
for Pharmaceuticals and Personal Care Products Removal
Rui Zhao, Tingting Ma, Shuying Li, Yuyang Tian, and Guangshan Zhu
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b04326 • Publication Date (Web): 22 Apr 2019
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Page 2 of 39 ACS Applied Materials & Interfaces
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Porous Aromatic Framework Modified Electrospun Fiber
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6 Membrane as a Highly Efficient and Reusable Adsorbent for
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9 Pharmaceuticals and Personal Care Products Removal
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14 Rui Zhao, Tingting Ma, Shuying Li, Yuyang Tian, Guangshan Zhu*
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19 Key Laboratory of Polyoxometalate Science of the Ministry of Education, Faculty of
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21 Chemistry, Northeast Normal University, Changchun 130024, PR China
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*Corresponding authors：
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29 Email address: zhugs@nenu.edu.cn.
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ACS Applied Materials & Interfaces Page 3 of 39
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Abstract
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6 Water contamination by emerging organic pollutants such as pharmaceuticals and
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8 personal care products (PPCPs) is becoming more and more serious. Porous aromatic
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11 frameworks (PAFs) are considered as promising adsorbents to remove the PPCPs. In
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13 order to overcome the limitation of PAFs in their powder forms for large-scale
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15 applications, herein we proposed a strategy to covalently anchor PAFs onto
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electrospun polymer fiber membranes. Polyaniline (PANI) played the role of aromatic
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20 seed layer, which was coated on the electrospun polyacrylonitrile (PAN) fiber
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22 membrane firstly. Then, PAF-45 modification was in-situ synthesized in the presence
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of the PANI coated electrospun PAN fiber membrane. This study could make the PAF
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27 based materials be handled more easily and improve the surface area of electrospun
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29 fiber membrane. The obtained composite adsorbent (PAF-45-PP FM) was applied for
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31 the adsorption of three PPCPs: ibuprofen (IBPF), chloroxylenol (CLXN) and N,N-
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34 diethyl-meta-toluamide (DEET), which exhibited high adsorption capacity and good
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36 recycling ability. According to the Langmuir model, the maximum adsorption
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38 capacities of PAF-45-PP FM toward IBPF, CLXN and DEET were 613.50, 429.18
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and 384.61 mg/g, respectively. In addition, after ten adsorption-desorption cycles, the
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43 adsorption capacities toward the three PPCPs decreased slightly. Through an
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45 adsorption comparison test, the adsorption capacity of PAF-45-PP FM almost
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attributed to the loading PAF-45. The adsorption mechanism analysis illustrated that
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50 there were pore capture, hydrophobic interaction and π-π interaction between PPCPs
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52 and PAF-45-PP FM. Therefore, the PAF-45-PP FM can be potential adsorbents to
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54 purify water contaminated with PPCPs.
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3 Keywords: electrospun fiber membranes; porous aromatic frameworks; adsorption;
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6 PPCPs
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11 Introduction
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13 Water pollution is an increasingly serious environmental problem around the world.
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As one group of emerging organic contaminants in water environment,
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18 pharmaceuticals and personal care products (PPCPs) have attracted much attention in
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20 recent years.1 PPCPs are widely used to increase living standards, especially in
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developed countries. It is reported that PPCPs could disturb hormonal actions and
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25 interfere with the endocrine system.2 Due to the extensive applications and poor
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27 elimination of PPCPs, they have been found in water resources (surface water and
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29 groundwater) and even in the tissues of fish and vegetables, which is a serious threat
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32 toward environment and human health.3 To treat this serious problem, many methods,
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34 including advanced oxidation,4 chlorination,5 photodegradation,6 biodegradation,7
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36 membrane separation8 and adsorption,9 have been applied. Among them, adsorption is
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considered as an effective way to remove PPCPs due to its easy operation, low cost
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41 and versatile property.
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43 As an important part of adsorption method, adsorbents determine the feasibility and
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efficiency of the adsorption processes. Up to now, several adsorbents such as
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48 activated carbon, graphene, carbon nanotube, zeolite, mesoporous silica, etc., have
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50 been developed to eliminate PPCPs from water.10 However, novel and non-
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52 conventional adsorbents with high adsorption performance still need to be explored
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55 and studied. Recently, new porous material adsorbents from metal-organic
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57 frameworks (MOFs) and covalent organic frameworks (COFs) have been used for
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59 PPCPs removal due to their appealing porous structural features and properties. For
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3 instance, Jhung’s group used porous metal-organic framework (MOF) MIL-101
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6 without and with –OH, –(OH)2, –NH2, and –NO2 groups for the adsorptive removal of
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8 PPCPs such as naproxen, ibuprofen, and oxybenzone from the aqueous solution.11
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10 MIL-101-OH and MIL-101-(OH)2 showed the highest PPCPs adsorption capacities,
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suggesting that H-bonding was an important mechanism. Moreover, Mellah and co-
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15 workers studied the capture of pharmaceutical pollutants from water by a novel
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17 fluorine-bearing covalent organic framework (COF) TpBD-(CF3)2.12 This COF
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showed ibuprofen adsorption capacity of 119 mg/g at neutral pH. Though much
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22 attention has been paid to MOFs and COFs, the exploitation of other new porous
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24 materials with intrinsic stability and good performance for PPCPs removal is still
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26 necessary.
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29 Porous aromatic frameworks (PAFs), one promising family of porous framework
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31 materials, have been successfully synthesized in our previous study,13 which attracts
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33 increasing interest.14 PAFs possess high stability, high surface area, tunable pore size
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and low framework density, making them a wide range of potential applications in gas
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38 adsorption, separation, catalysis, etc.15-17 Recently, PAF based materials have also
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40 been applied as adsorbents to remove pollutants from wastewater. Ma’s group
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prepared amidoxime-grafted PAF-1 for uranium extraction from water.18 The PAF
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45 adsorbent showed a uranium uptake capacity of over 300 mg/g and effectively
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47 reduced the uranyl concentration from 4.1 ppm to less than 1.0 ppb in aqueous
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49 solutions within 90 min. Recently, our group combined PAF material with molecular
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52 imprinting technology.19 Two functional groups (pyridine ring and carboxyl group)
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54 were incorporated together into the hierarchical porous aromatic framework material.
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56 Due to a synergistic effect, the PAFs exhibited a good adsorption capacity toward
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Pb2+ ions (90.36 mg/g) and high selectivity. However, PAFs are insoluble in most of
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3 the common solvent and thus face the problem of processability. PAFs in their
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6 powder form are difficult to recycle and can lead to the secondary pollution, which
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8 shows weak handleability and restricts their practical application. Usually, the
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10 blending of powdery PAF materials with flexible polymer membranes is an effective
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approach to overcome the mentioned shortcoming.20 However, these compact
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15 membranes could make PAF materials unable to fully contact with pollutants in
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17 wastewater treatment adsorption process.
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In the past decade, fiber membranes from electrospinning technique have received
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22 intensive interest from the researchers in diverse fields.21,22 Due to their easy
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24 preparation, high porosity and good membrane-forming properties, electrospun
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26 polymeric fiber membranes are often employed as flexible skeletons to load
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29 functional materials, which show great potential in catalysis, adsorption, biomedicine,
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31 sensor and energy fields.23-27 Single electrospun polymeric fiber membranes or their
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33 composition with functional materials have shown good adsorption capacities toward
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various pollutants from water, such as dyes, heavy metal ions, pesticides, radioactive
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38 element, inorganic phosphorus, etc.28-30 However, the adsorption toward PPCPs by
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40 electrospun fiber membranes is rarely reported. This is because that the adsorption
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capacities of electrospun fiber membranes toward common pollutants mainly attribute
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45 to the charged functional groups on the fibers via electrostatic or chelating
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47 interactions.31,32 Most of the PPCPs are lipophilic with a high octanol-water
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49 distribution coefficient (Kow) values.33 Adsorbents based on electrostatic or chelating
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52 interactions are usually not ideal for the adsorption of these PPCPs. Thus, for
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54 electrospun fiber adsorbents, the adsorption capacity should derive from the small
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56 porous structures of fibers. However, the specific surface area of electrospun fiber
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membrane is not high enough to obtain satisfying adsorption capacity toward PPCPs.
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3 Moreover, the macroporous structure among the electrospun fibers cannot capture the
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6 PPCPs effectively.
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8 In order to improve the adsorption efficiency of electrospun fiber membranes,
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10 coating their surface by PAFs is considered to be a promising strategy. Meanwhile the
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processability of PAFs could be significantly improved. Inspired by the synthesis of
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15 zeolite membrane,34 a seeding growth strategy has been proposed. In the present study,
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17 PAF material was modified onto electrospun fibers to obtain flexible composite
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adsorbent for PPCPs removal from wastewater. Electrospun polyacrylonitrile (PAN)
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22 fiber membrane acted as the skeleton. PAF-45, which shows easy preparation and
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24 low-cost properties, was used as the PAF model. PAF-45 was modified onto
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26 polyaniline (PANI, as the aromatic seed layer which is necessary for PAFs loading
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29 onto substrate’s surface) coated electropun PAN fiber membrane. The as-prepared
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31 composite adsorbent was applied for the adsorption of three typical PPCPs: ibuprofen
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33 (IBPF), chloroxylenol (CLXN) and N,N-diethyl-meta-toluamide (DEET). Their
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molecular structures and physical properties are shown in Table 1. Furthermore, the
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38 adsorption performance and adsorption mechanism toward the three PPCPs by
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40 prepared composite adsorbent were investigated in detail. Most importantly, this study
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may provide a universal method for PAFs loading onto different material’s surface,
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45 which can improve the PAFs’ practicability.
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5 Table 1 Properties of three selected PPCPs under study.
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7 PPCPs Molecular LogKow Dimension* Common usage Molecular Ref
weight (nm) structure .
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(g/mol)
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10 IBPF 206.3 3.97 1.06×0.47 Non-steroidal anti-inflammatory 35
11 drug
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13 CLXN 156.6 3.37 0.62×0.54 Antimildew and antibacterial
agent 36
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DEET 191.3 2.02 1.08×0.55 Insect repellent 36
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17 *Molecule size was measured by Materials Studio 8.0.
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21 Experimental
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24 Materials
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27 Polyacrylonitrile (PAN, Mw=150,000) was purchased from Shanghai Macklin
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30 Biochemical Co., Ltd. Aniline and ammonium persulfate ((NH4)2S2O8, APS) were
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33 purchased from Tiantai Chemical Corp. N,N-Dimethylformamide (DMF) was
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36 purchased from Beijing Chemical Factory. Biphenyl (99%) and anhydrous AlCl3 were
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39 received from Aladdin. Chloroform from Beijing Chemical Factory was dried over 4
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42 Å molecule sieves before being used. IBPF (C13H18O2, 99%), CLXN (C8H9ClO, 98%)
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45 and DEET (C12H17NO, 99%) were purchased from Energy Chemical. Granular
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48 activated carbon was purchased from Tianjin Guangfu Fine Chemical Research
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51 Institute. Other inorganic reagents were purchased from Beijing Chemical Factory.
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54 Except for chloroform, other reagents were used as received without further
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57 treatment.
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59 Preparation of PAF-45 modified electrospun fiber membrane
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3 Electrospun PAN fiber membrane preparation: 10 wt% PAN solution (dissolving
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6 PAN powder in DMF at 90 °C for 6 h) was loaded into a 10 mL syringe to conduct
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8 the electrospinning process using an electrospinning apparatus. 18 kV was provided
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10 between the cathode and anode at a distance of 20 cm with a flow rate of 0.5 mL/h.
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PAN fiber membrane was collected by a metallic rotating roller drum.
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15 PANI coating onto PAN fiber membrane: The PANI coating was synthesized via
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17 in-situ chemical oxidative polymerization technique. In detail, 0.9 g APS and 500 L
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20 aniline were dissolved in 10 mL and 40 mL 1 M HCl respectively. 300 mg PAN fiber
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22 membranes were added into the aniline HCl solution, and then the (NH4)2S2O8
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24 solution was added into to start the polymerization reaction. After stirring for 1.5 h at
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room temperature, the resultant fiber membrane was washed with 1M HCL, deionized
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29 water and ethanol three times, respectively; and then dried in a vacuum oven at 80 °C
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31 for 24 h.
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PAF-45 modification: 300 mg PANI coated electrospun PAN fiber membrane and
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36 500 mg anhydrous AlCl3 were added into a 100 ml round-shaped flask, and this flask
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38 was firstly evacuated and then inflated with N2 for 3 times. 40 ml dried CHCl3 was
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40 injected into the flask via a syringe and the mixture was heated to 60 °C for 3 h.
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43 Another solution containing 200 mg biphenyl in 20 ml dried CHCl3 was added into
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45 the above solution and the mixture was kept under stirring at 60 °C for 10 h. After
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47 reaction, the resultant fiber membrane was collected and washing with 1.0 M HCl,
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CH3OH, and acetone. The fiber membrane was further purified by Soxhlet extraction
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52 with methanol for 48 h. The final product was obtained after drying at 100 °C for 12 h
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54 in vacuum.
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Characterization
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3 The morphology and microstructure of obtained fiber membranes were observed
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6 with field emission scanning electron microscopy (SEM, Hitachi SU8010) and
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8 transmission electron microscopy (TEM, JEOL JEM-3010). The chemical
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10 compositions of the fiber membranes were investigated using an energy dispersive
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spectrometer (EDS) attached to the Hitachi SU8010 SEM. The mean diameter of the
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15 fibers was calculated from measuring the different parts of the fibers at 100 different
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17 fibers from the SEM images using the commercial software package Image-Pro Plus.
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The surface roughness of single fiber was measured by an atomic force microscope
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22 (AFM, Cypher ES, Asylum Research Oxford Instruments). The mechanical properties
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24 of the ﬁber membranes were performed by assembling the membranes (dimensions:
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26 length = 40 mm, width = 20 mm) between two stainless steel clamps with a tensile
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29 speed of 10 mm·min−1 on a mechanical strength microtest device (410R250, Test
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31 Resources, Shakopee, MN, USA). Fourier-Transform infrared (FT-IR) spectra were
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33 acquired using a Nicolet iS50 Fourier transform infrared spectrometer. Solid-state 13C
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cross polarization magic angle spinning nuclear magnetic resonance (CP/MAS NMR)
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38 measurement was performed on a Bruker Avance III model 400 MHz NMR
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40 spectrometer at a MAS rate of 5 kHz. The electrical conductivity of obtained fiber
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membranes was determined using a classical four-point probe (RTS-2, Guangzhou
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45 Four Probe Technology Co., Ltd.) with a SourceMeter (Keithley 2400, United States).
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47 The detailed process for electrical conductivity measurement was shown in the
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49 Supporting Information. Thermogravimetric analysis (TGA) data were obtained on a
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52 Mettler toledo thermal analyzer at heating rate of 10 °C/min under air atmosphere. N2
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54 adsorption-desorption isotherms were conducted on a Quantachrome Autosorb iQ SN
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56 analyzer at -196 °C. Analysis of the X-ray photoelectron spectra (XPS) was
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3 performed on Thermo ESCALAB 250 spectrometer with a Mg-K (1253.6 eV)
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6 achromatic X-ray source.
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8 Adsorption of PPCPs from water
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10 Stock solutions of the three PPCPs (500 mg/L) were prepared by dissolving them in
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water/methanol (9/1 v/v). The stock solutions were further diluted with deionized
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15 water to get the desired solution concentration. The pH of the PCPs solutions was
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17 adjusted to 7.0 ± 0.2 (considering the general pH of river and rain water37) by adding
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NaOH solution (0.1 M) or HCl solution (0.1 M). Kinetic experiments were performed
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22 by mixing 13 mg of adsorbent into 80 mL of PPCP solution with the initial
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24 concentration of 50 mg/L. The adsorption isotherms were investigated by initial
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26 concentrations ranging from 50 to 400 mg/L with the adsorbent dosage of 0.1 g/L. For
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29 the desorption-readsorption experiment, 3 mg adsorbent was added into 15 mL each
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31 PPCP solution (50 mg/L) for 6 h. The PPCP-adsorbed adsorbent was regenerated by
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33 immersing into ethanol at 60 °C for 6 h. After washing thoroughly with deionized
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water and ethanol, the adsorbent was reused in adsorption experiments and the
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38 process was repeated ten times. All the adsorption experiments were performed at
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40 20±2 °C. IBPF, CLXN and DEET concentrations were determined by measuring the
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absorbances of the solutions using a UV spectrometer at 220, 279 and 265 nm,
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45 respectively. The adsorption capacity (q) of PPCPs onto each adsorbent was
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47 calculated on the basis of the following equation:
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49 (C0 - Ce)V
50 q (mg g) = W
(1)
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52 where C0 and Ce (mg/L) are the initial and the equilibrium concentration of PPCP in
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55 the aqueous solution, respectively. V (L) is the volume of the solution, and W (g) is
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57 the mass of the dry adsorbent.
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3 Each adsorption experiment is conducted in triplicates to obtain reproductive
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6 results with standard deviation < 5%. In the case of deviation larger than 5%, more
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8 tests are carried out.
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13 Results and discussion
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36 Figure 1. Schematic representation of preparation of PAF-45-PP fiber membrane from electrospun PAN fiber
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membrane. The dashed box is the uncertain structures of PAF-45 (blue represents meta-substitution, while red and
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39 green stand for para-substitution and ortho-substitution, respectively).
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Composite fiber membrane preparation and characterization
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In this study, PAFs are used to modify electrospun fiber membranes. Since PAF-1
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49 was successfully synthesized by our group in 2009,13 various PAFs have been
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51 obtained through several coupling strategies to connect aromatic rings, such as Suzuki
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53 coupling reaction, Sonogashira-Hagihara coupling reaction, Yamamoto reaction,
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56 ethynyl trimerization reaction, carbazole-based coupling polymerization, etc.38
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58 However, most of these reactions are complicated, which need expensive catalysts
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3 and monomers. In consideration of practical industrial production, PAF-45 from
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6 Scholl reaction seems to be a good candidate due to its low-cost catalyst AlCl3 and
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8 monomer biphenyl.39 Polyacrylonitrile (PAN), a commonly used polymer, was
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10 electrospun into fiber membrane to act as the fibrous skeleton for PAF-45 loading.
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The schematic preparation process is displayed in Figure 1. To obtain stable and
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15 strong PAF-45 loading, electrospun PAN fibers were firstly coated with polyaniline
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17 (PANI) as the seed layer. PANI coated PAN (PANI-PAN) fiber membrane (FM) were
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placed into the liquid phase Scholl reaction for PAF material modification. During
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22 Scholl reaction, the coupling happened between the benzene rings from PANI and
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24 biphenyl; and then biphenyl further reacts with each other via C–C bonding to form
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26 PAF-45 (dashed box in Figure 1) which grows onto fibers to prepare PAF-45 coated
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29 PANI-PAN (PAF-45-PP) fiber membrane. The monomer and Scholl reaction for the
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31 construction of PAF-45 are shown in Figure S1.
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Figure 2. SEM images and diameter distributions of PAN FM (a, b, c), PANI-PAN FM (d, e, f) and PAF-45-PP
59 FM (g, h, i).
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5 The morphology of obtained fiber membranes was observed by SEM images
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7 (Figure 2). As shown in Figure 2a~2c, PAN fibers have smooth surfaces with an
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10 average diameter of 189 nm. PANI-PAN fibers show rough surface morphology due
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12 to the PANI coating and the average diameter increases to 268 nm (Figure 2d~2f).
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14 After PAF-45 modification, the fiber surface becomes rougher and obvious particles
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17 are observed, which load onto PAF-45-PP fibers uniformly (Figure 2g and 2h). For
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19 comparison, PAF-45 was grown onto PAN fibers without PANI seed layer. Its SEM
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21 image is shown in Figure S2. Few particles are coated onto PAN fiber surfaces,
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indicating that PANI seed layer is essential for PAF-45 loading. Moreover, the PAF-
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26 45-PP fibers still show long and continuous morphology. The average diameter has a
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28 large increase to 313 nm (Figure 2i). The microstructures of obtained fibers were also
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30 investigated by TEM images and are shown in Figure S3. The morphology observed
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33 from TEM images is consistent with the SEM results. In addition, the surface
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35 morphology and surface roughness of single fiber at each stage were evaluated by
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37 AFM (Figure 3). The surface morphology obtained from AFM images is similar with
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40 SEM and TEM observation. The surface topography of PAN FM and PANI-PAN FM
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42 show smooth hills with Ra values of about 20.59 and 57.21 nm, which reflect the
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44 surface roughness. After PAF-45 modification, the Ra value obviously increases to
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111.72 nm due to the larger PAF-45 particles loading onto the fiber surface. The
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49 morphology observation preliminarily confirms that PAF-45 is modified onto PANI-
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51 PAN fibers. Due to the coating property of PANI onto different materials, we predict
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53 that this method can make PAFs load onto various substrates’ surfaces, such as
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56 coating polymer film, steel mesh, ceramic disk, etc.
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13 Figure 3. AFM images of PAN FM (a), PANI-PAN FM (b) and PAF-45-PP FM (c).
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Figure 4. Stress-strain curves (a), FTIR spectra (b), EDS spectra (c) and TGA curves (d) of obtained fiber
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membranes.
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45 Though PAF-45 is coated onto fiber surfaces, PAF-45-PP fiber membrane still
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48 keeps its good flexibility (Figure S4). Stress-strain curves were conducted to study
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50 the mechanical properties of obtained fiber membranes (Figure 4a). Comparing with
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52 PAN fiber membrane, the tensile strength of PANI-PAN fiber membrane increases to
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8.11 MPa from 5.82 MPa and the elongation at break decreases to 10.85% from
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57 18.86%. This is because that the coating PANI makes the fibers connect with each
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59 other more tightly. PAF-45 consists of rigid framework with low flexibility. After
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3 PAF-45 modification, PAF-45-PP fiber membrane shows a decreased tensile strength
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6 of 6.67 MP and elongation at break of 8.14%. However, the mechanical property of
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8 PAF-45-PP fiber membrane can make PAF based adsorbents be separated from
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10 adsorption solution easily, which satisfies its usage in practical adsorption application.
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The chemical structures of obtained fiber membranes were characterized by FT-IR
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15 spectra (Figure 4b). In the spectrum of PAN FM, peaks at 2241 cm-1 and 1736 cm-1,
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17 are attributed to the stretching vibrations of the nitrile group and the carbonyl group of
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the ester of the methylacrylate comonomer, respectively.32 Moreover, the peaks at
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22 1455 cm-1 and 1378 cm-1 are assigned to C–H blending and CH3 symmetric blending,
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24 respectively.24 After PANI coating, a new peak at 1306 cm-1 is attributed to typical C–
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26 N stretching vibrations in aromatic amine.40 Other peaks at 1109, 795, and 504 cm-1
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29 assigning to C=N stretching, 1,4-substituted phenyl ring stretching and deformation of
30
31 benzenoid rings of PANI are also observed,41 indicating that PANI has been coated
32
33 onto PAN FM. The spectrum of PAF-45-PP FM shows the difference in low
34
35
36
wavenumber range (1000~500 cm-1). The peak of 795 cm-1 for 1,4-substituted phenyl
37
38 ring stretching shifts to 811 cm-1, suggesting that benzene rings from PANI are
39
40 reacted with biphenyl during Scholl reaction. The monomer biphenyl corresponds to
41
42
five adjacent hydrogens in benzene rings. The peaks in the range of 850~700 cm-1 are
43
44
45 ascribed to two, three and four adjacent hydrogen vibrations, respectively.39 In
46
47 addition, the new peak at 908 cm-1 is assigned to vibration of isolated hydrogen
48
49 atom.42 Solid-state 13C CP/MAS NMR spectrum of PAF-45-PP FM was conducted to
50
51
52 verify the structure of networks and their corresponding building blocks (Figure S5).
53
54 The peak at 29 ppm is attributed to the aliphatic carbons (–CH– or –CH2–) in the
55
56 PAN polymer.43 The several broad signals in the region 110–155 ppm are
57
58
59
corresponding to the aromatic carbon atoms in benzene rings. The peak at 125 ppm is
60
15

1
2
3 due to the non-substituted aromatic carbon from PANI and PAF-45.44,45 Moreover,
4
5
6 the signal belonging to nitrile groups (–CN) from PAN may overlap with this peak
7
8 (125 ppm).43 The peak at 147 ppm is assigned to the substituted aromatic carbon from
9
10 PAF-45.44 Additionally, a shoulder peak at 153 ppm is observed, which belongs to the
11
12
13
non-protonated carbon attached to the nitrogen in PANI.46 These results suggest that
14
15 biphenyl reacts with each other via C–C bonding to form PAF-45. According to
16
17 previous reports,39,42 PAF-45 is amorphous with uncertain structures. The main
18
19
substitution ours at para, ortho, and meta positions (Figure 1), which is consistent
20
21
22 with our FT-IR results. The surface element contents of obtained fiber membranes
23
24 were further analyzed by the qualitative SEM-EDS (Figure 4c). As the results listed
25
26 in Table 2, due to the introduction of aromatic amine, the C/N ratio increases to 3.10
27
28
29 from 2.93 after PANI coating. The C atomic fraction of PAF-45-PP FM has an
30
31 obvious increase to 77.85 at.% and the N atomic fraction decreases to 12.67 at.%. The
32
33 C/N ratio also increases to 6.14. This is because that the loaded PAF-45 is constructed
34
35
36
from biphenyl without nitrogen element. The element content results correspond to
37
38 the chemical reactions for fiber preparation and FT-IR results. The electrical
39
40 conductivity of obtained fiber membranes was also studied. Owning to the coating of
41
42
conducting polymer PANI, the electrical conductivity of PANI-PAN FM is 8.51×10-3
43
44
45 S/cm. However, PAF-45-PP FM shows almost no electrical conductivity property.
46
47 This is because that the fibers are covered with non-conducting PAF-45. Moreover,
48
49 the conjugated structure of PANI is also influenced by the bonding between aniline
50
51
52 ring and biphenyl from PAF-45, which blocks the electron transfer. The above
53
54 characterization results suggest that PAF-45 has been modified onto electrospun
55
56 fibers successfully.
57
58
59
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16

1
2
3
4
5
Table 2 Element content from EDS spectra and BET analysis results of obtained fiber membranes.
6
7 sample Element content (at.%) BET results
8 C N C/N SBET (m2/g) Pore size (nm) pore volume (cm3/g)
9 PAN FM 72.28 24.68 2.93 9.2 3.17 0.026
10 PANI-PAN FM 71.63 23.09 3.10 11.3 4.78 0.033
11 PAF-45-PP FM 77.85 12.67 6.14 262.4 0.62 0.151
12
13
14 The thermal stability of the obtained fiber membranes was investigated by TGA
15
16 analysis (Figure 4d). PAN FM shows a rapid and sharp weight loss of 24.6% in the
17
18 temperature range from 264 to 304 °C, which attributes to the cyclization of nitrile
19
20
21
groups on PAN.24 The following slow degradation is due to the decomposition of
22
23 PAN polymer chain and release of the oxidation of carbon. After coating PANI, the
24
25 rapid weight loss temperature becomes higher at 286 °C and the loss is 18.4%,
26
27
suggesting that PANI coating can improve the thermal stability of PAN FM.
28
29
30 Compared with PAN FM and PANI-PAN FM, PAF-45-PP FM shows higher initial
31
32 degradation temperature at 302 °C with a weight loss of 15.5% due to the good
33
34 thermal stability of PAF-45 (Figure S6, PAF-45 shows almost no weight loss before
35
36
37 325 °C). Moreover, the smaller weight loss 15.5% for PAF-45-PP FM can also
38
39 confirm the modification by PAF-45.
40
41
42
43
44
45
46
47
48
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30 Figure 5. N2 adsorption-desorption isotherms (a) and pore size distributions (b) of obtained fiber membranes.
31
32
33
The nitrogen sorption isotherms at 77 K (Figure 5a) were further conducted to
34
35
36 investigate the surface areas of the prepared membranes (Brunauer–Emmett–Teller
37
38 (BET) surface area here), which are important factors for PPCPs adsorption
39
40 applications. The BET surface area of PAN FM is only 9.2 m2/g due to its irregular
41
42
43 macroporous structure and the compactness of polymer fiber. PANI-PAN FM shows a
44
45 BET surface area of 11.3 m2/g, indicating that PANI has almost no influence on the
46
47 surface area. After PAF-45 modification, the BET surface area could reach 262.4
48
49
50
m2/g, which is attributed to the high surface area of PAF-45 (780.2 m2/g). PAF-45 and
51
52 PAF-45-PP FM exhibit sharp uptakes at low relative pressures, indicating the
53
54 existence of micropores in their structures. The pore sizes of PAF-45 and PAF-45-PP
55
56 FM distribute around at 0.60 nm and 0.62 nm (Figure 5b), respectively, suggesting
57
58
59 that loading PAF-45 onto electrospun fibers shows little impact on PAF-45’s pore
60
18

1
2
3 structure. The BET results confirm that PAF-45 loading can improve the surface area
4
5
6 of electrospun fiber membrane, which will be beneﬁcial to the adsorption process.
7
8
9 PPCPs adsorption performance
10
11
12
13
14
15
16
17
18
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20
21
22
23
24
25
26
27
Figure 6. PPCPs adsorption by different fiber membrane adsorbents (PPCP concentration: 50 mg/L and adsorbent
28
29 dosage: 0.2 g/L).
30
31
32
33
Three typical PPCPs ibuprofen (IBPF), chloroxylenol (CLXN) and N,N-diethyl-
34
35
36 meta-toluamide (DEET) were selected as the pollutant models for adsorption study. A
37
38 comparison of adsorption capacities for different fiber membranes was firstly studied
39
40 to explore the effect of PAF-45. As shown in Figure 6, PAN FM has almost no
41
42
43 adsorption capacities for the three PPCPs. After PANI coating, the adsorption
44
45 capacities show few improvements, which are less than 15 mg/g. However, for PAF-
46
47 45-PP FM, the adsorption capacities toward three PPCPs increase significantly
48
49
50
exceeding 110 mg/g. The results indicate that the adsorption capacities toward three
51
52 PPCPs by PAF-45-PP FM almost attribute to PAF-45 materials. Furthermore, the
53
54 adsorption performance of PAF-45-PP FM toward the three PPCPs was investigated
55
56
in detail.
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58
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7
8
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29
30 Figure 7. Adsorption kinetic curves of IBPF (a-c), CLXN (d-f) and DEET (g-i) onto PAF-45-PP FM:
31 experimental data (a, d and g), pseudo-first-order kinetic plots (b, e and h), and pseudo-second-order kinetic plots
(c, f and i).
32
33
34 To know the adsorption rate and saturation adsorption time which can give us
35
36
37 important information for wastewater treatment, the adsorption of PPCPs onto PAF-
38
39 45-PP FM in the initial concentration of 50 mg/L as functions of time is shown in
40
41 Figure 7a, 7d and 7g. Fast adsorption processes could be obtained in the first 60 min
42
43
44
for the three PPCPs due to the abundant available adsorption sites in initial stage.
45
46 Then, the adsorption rate becomes slow until the adsorption equilibrium of 360 min.
47
48 The kinetic data was further studied by two common kinetic models (the pseudo-first-
49
50
order kinetic model and the pseudo-second-order kinetic model). Their linear
51
52
53 equations are expressed as follows:31
54
55 k1t
log(qe - qt) = logqe - 2.303 (2)
56
57
58 t 1 t
qt = k q2 + qe (3)
59 2 e
60
20

1
2
3 where qt and qe (mg•g-1) are the adsorption capacity at time t and equilibrium time,
4
5
6 respectively. k1 (min-1) and k2 (g•min-1•mg-1) are the pseudo-first order model rate
7
8 constant and the pseudo-second order model rate constant, respectively. Their fitting
9
10 linear curves are displayed in Figure 7 (a, d and g) and Figure 7 (c, f and i). The
11
12
13
calculated kinetic parameters are summarized in Table 3. By comparing the fitting
14
15 curves and correlation coefficients (R2), pseudo-second-order model could better
16
17 describe the adsorption kinetics of IBPF, CLXN and DEET onto PAF-45-PP FM than
18
19
pseudo-first order model. In addition, the adsorption kinetics by commercial activated
20
21
22 carbon (AC) was also studied for comparison. As shown in Figure S7 and Table S1,
23
24 the adsorption capacities of AC are much lower than those of PAF-45-PP FM and the
25
26 adsorption rates are also slower.
27
28
29
30 Table 3 The fitting parameters of pseudo-first-order and pseudo-second-order model.
31
32 Pseudo-first-order model Pseudo-second-order model
33 PPCPs
qe k1 R2 qe k2 R2
34 (mg/g) (min-1) (mg/g) (g/mg•min)
35 IBPF 153.06±1.68 0.021±0.03 0.9037 166.67±2.71 (1.95±0.19)×10-4 0.9982
36 CLXN 116.27±1.56 0.026±0.02 0.9400 124.84±1.98 (3.80±0.27)×10-4 0.9984
37 DEET 117.49±1.45 0.033±0.02 0.9724 138.50±2.45 (4.12±0.17)×10-4 0.9977
38
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48
49
50 Figure 8. Adsorption isotherms of IBPF (a), CLXN (b) and DEET (c) onto PAF-45-PP FM.
51
52
53
54 Adsorption isotherms were applied to investigate the adsorption performance of
55
56 PAF-45-PP FM, which are useful for understanding the maximum adsorption capacity
57
58
and the interaction between an adsorbate and an adsorbent. The adsorption isotherms
59
60
22

1
2
3 for IBPF, CLXN and DEET onto PAF-45-PP FM are shown in Figure 8. The
4
5
6 isotherm data were analyzed by two widely-used isotherm models, namely Langmuir
7
8 and Freundlich. Their linear equations are as follows:47
9
10 Langmuir isotherm (homogeneous and monolayer adsorption):
11
12 Ce Ce 1
13 qe = qm + bqm (4)
14
15
16 Freundlich isotherm (heterogeneous and multilayer adsorption):
17
1
18 logqe = logKF + nlogCe (5)
19
20
21 where qe is the equilibrium adsorption capacity (mg/g), Ce is the equilibrium
22
23 concentration (mg/L), and qm and b are Langmuir constants related to maximum
24
25
adsorption capacity and binding energy, respectively; KF and n are empirical
26
27
28 constants that indicate the Freundlich constant and heterogeneity factor, respectively.
29
30 The linear fitting curves are shown in Figure S7. The obtained isotherm parameters
31
32 are listed in Table 4. According to R2 and fitted curves, the adsorption isotherms of
33
34
35 the three PPCPs by PAF-45-PP FM are all fitted better with Langmuir isotherm model,
36
37 suggesting a possible monolayer adsorption and specific homogenous sites within the
38
39 adsorbent. The maximum adsorption capacities for IBPF, CLXN and DEET from
40
41
42
Langmuir models are 613.50, 429.18 and 384.61 mg/g, respectively. To further
43
44 understand the adsorption performance of PAF-45-PP FM, maximum adsorption
45
46 capacities were compared with other PPCP adsorbents. As summarized in Table S2,
47
48
the adsorption capacity of PAF-45-PP FM is better than most of reported adsorbents.
49
50
51 It is also necessary to explore the removal efficiency of PAF-45-PP FM toward the
52
53 PPCPs in low concentration range. PAF-45-PP FM was used to remove the three
54
55
PPCPs (IBPF, CLXN and DEET) in the initial concentration of 500 g/L with the
56
57
58 adsorbent dosage of 0.1 g/L. The removal process was proven by the UV-Vis spectra
59
60
23

1
2
3 (Figure S9). The absorption peaks belonging to IBPF, CLXN and DEET almost
4
5
6 disappear after the adsorption process, confirming the good removal capability. The
7
8 removal efficiencies toward the three PPCPs are all above 99%, suggesting that PAF-
9
10 45-PP FM can remove traces of PPCPs from water.
11
12
13
14 Table 4 The fitting parameters of Langmuir and Freundlich equations.
15
16 Langmuir isotherm Freundlich isotherm
17 PPCPs qm b R2 KF n R2
18 (mg/g) (L/mg)
IBPF 613.50±21.73 0.0138±0.0017 0.9942 33.88±8.33 2.07±0.34 0.9403
19
CLXN 429.18±15.83 0.0128±0.0014 0.9946 23.01±7.63 2.05±0.02 0.9740
20 DEET 384.61±11.79 0.0171±0.0015 0.9964 34.49±8.46 3.46±0.56 0.9672
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37 Figure 9. Coexisting ions effect (a) and adsorption–desorption cycles (b) of PPCPs adsorption by PAF-45-PP FM
38 (PPCP concentration: 50 mg/L and adsorbent dosage: 0.2 g/L).
39
40
41 In real water environment, there are a variety of ionic species which may affect the
42
43 adsorption capacity of adsorbent to some extent. The effect of coexisting ions (Na+,
44
45 Mg2+, Ca2+, Cl-, NO3- and SO42-) on IBPF, CLXN and DEET adsorption by PAF-45-
46
47
48 PP FM was explored (Figure 9a). The concentration (10 mmol/L for each ion) of
49
50 coexisting ions is much higher than that of PPCPs (50 mg/L). In comparison with
51
52 control groups, the coexisting ions have no obvious influence on PPCPs adsorption,
53
54
suggesting that PAF-45-PP FM can remove PPCPs from complex saline waste-water.
55
56
57 Regeneration and reuse are of great significance in practical adsorption application.
58
59 For powdery adsorbents, the recycle has to go through a high consumption
60
24

1
2
3 centrifugation process. The loading of PAF-45 onto electrospun fibers could
4
5
6 transform PAF based materials from powder to membrane, which can be easily
7
8 separated from the adsorption solution by tweezers. In this study, ethanol is used as
9
10 the desorption eluent to regenerate PPCPs-adsorbed PAF-45-PP FM. Through
11
12
13
detecting the concentrations of PPCPs in the eluent, the desorption efficiencies are all
14
15 over 99%. As shown in Figure 9b, the adsorption capacities for the three PPCPs
16
17 decreased slightly after ten adsorption–desorption cycles. Moreover, the morphology
18
19
of PAF-45-PP FM could be well maintained after ten cycles (Figure S10). The results
20
21
22 indicate that PAF-45-PP FM has stability and reusability.
23
24
25 PPCPs adsorption mechanism
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 Figure 10. (a) Effect of pH on IBPF adsorption by PAF-45-PP FM. (b) Plot of logKow value and adsorption
54 capacity of PPCPs. (c) Adsorption comparison for PS FM and PAF-45-PP FM. (d) The proposed adsorption
55
56 mechanism toward PPCPs by PAF-45-PP FM.
57
58
59
60
25

1
2
3 It is important to understand the possible adsorption mechanism between PAF-45-
4
5
6 PP FM and PPCPs, which can give guidance for subsequent study. In general, several
7
8 adsorption mechanisms such as hydrophobic, π-π interactions, H-bond, electrostatic
9
10 and coordination have been used to explain the adsorption toward PPCPs.48-50 To have
11
12
13
an insight into the adsorption mechanism in this study, effect of solution pH on PPCP
14
15 adsorption (IBPF as the representative) was conducted and is shown in Figure 10a.
16
17 Solution pH can change the surface charges of adsorbent and adsorbate, and then
18
19
influence the adsorption process which is usually explained by electrostatic
20
21
22 interactions.51 In the selected pH range, pH values show little influence on the
23
24 adsorption toward IBPF. The result suggests that the adsorption by PAF-45-PP FM is
25
26 independent of electrostatic interactions. PAF-45 is a hydrophobic material, due to its
27
28
29 framework of benzene ring. IBPF, CLXN and DEET have high octanol-water
30
31 distribution coefficients (Kow), which are also hydrophobic (Table 1). Thus,
32
33 hydrophobic interaction may be considered as one possible adsorption mechanism.36
34
35
36
To account for hydrophobicity effects of PPCPs on adsorption process, log Kow was
37
38 plotted against their adsorption capacity (qm). As shown in Figure 10b, PPCP with
39
40 high logKow displays high adsorption capacity, suggesting that hydrophobic
41
42
interaction could be applied to explain the adsorption between PAF-45-PP FM and the
43
44
45 three PPCPs. To further explain the hydrophobic interaction, the solution pH effect on
46
47 DEET with low hydrophobicity was conducted. The result is shown in Figure S11
48
49 and pH values also have little influence on the adsorption toward DEET, indicating
50
51
52 that hydrophobic interaction is indeed one of the adsorption mechanisms.
53
54 Moreover, according to the chemical structures (Table 1 and Figure 1), PAF-45
55
56 and the three PPCPs all have the aromatic ring. Thus, the π-π interaction can be a
57
58
59
contribution to the adsorption mechanism.50 To further understand this adsorption
60
26

1
2
3 mechanism, XPS spectra of PAF-45-PP FM before and after IBPF adsorption were
4
5
6 investigated.52 As shown in Figure S12a, the intensity of the O 1s binding energy
7
8 peak at 532.7 eV increases obviously, confirming the IBPF adsorption. High
9
10 resolution XPS spectra of C1s before and after IBPF adsorption were studied (Figure
11
12
13
S12b). Before adsorption, the spectrum shows one peak at 284.9 eV assigning to C–C.
14
15 After adsorption, the spectrum shows two peaks at 284.4 eV and 288.8 eV, which are
16
17 assigned to C–C and C–O, respectively.53 In addition, the peak of C–C shifts to lower
18
19
binding energy after the adsorption, which is ascribed to the π-π interactions.54
20
21
22 PAF-45 is a porous organic framework material with abundant micropore structures.
23
24 The molecular size of three PPCPs at least one dimension (Figure S13) is less than or
25
26 similar to the pore diameter of PAF-45. Pore-filling mechanism may be considered as
27
28
29 a plausible mechanism. The pore-filling mechanism was studied by nitrogen
30
31 adsorption isotherms. As shown in Figure S14, the BET surface area of PAF-45-PP
32
33 FM decreases to 23.1 m2/g after adsorbing IBPF. This result indicates that the pore of
34
35
36
PAF-45 is occupied and pore-filling mechanism can be applied to explain the
37
38 adsorption of PPCPs. Moreover, the BET surface area of PAF-45-PP FM can recover
39
40 to 259.1 m2/g after the regeneration suggesting the good recyclable ability. To further
41
42
confirm this view, electrospun polystyrene (PS) fiber membrane was prepared. The
43
44
45 preparation process is displayed in the Supporting Information and its SEM images
46
47 are shown in Figure S15a. The structure of PS is similar to PAF-45 because they both
48
49 have aromatic rings (Figure S15b). In addition, PS fiber membrane is also
50
51
52 hydrophobic. The difference is that PS fiber membrane has no micropore structures.
53
54 Thus, PS fiber membrane is a good control group for exploring the pore-filling
55
56 mechanism of PAF-45-PP FM, which can eliminate the influence of hydrophobic
57
58
59
interaction and π-π interaction. Their adsorption toward PPCPs is illustrated in Figure
60
27

1
2
3 10c. The adsorption capacities of PAF-45-PP FM (115~132 mg/g) were much higher
4
5
6 than those of PS FM (39~43 mg/g). This can be seen that the micropore structures of
7
8 PAF-45 make a major contribution to the adsorption of the three PPCPs.
9
10 Therefore, on the basis of above investigation, it is proposed that PPCPS adsorption
11
12
13
by PAF-45-PP FM involves the following mechanism: firstly, PPCPs are adsorbed by
14
15 PAF-45-PP FM through hydrophobic interaction and π-π interaction. Subsequently,
16
17 PPCPs are captured into the micropore of PAF-45. The proposed adsorption
18
19
mechanism is schematically summarized in Figure 10d.
20
21
22
23
24
25
Conclusions
26
27 In conclusion, PAF-45 was successfully modified onto the surfaces of electrospun
28
29 PAN fibers with the assistance of seed layer PANI. The composition between PAF-45
30
31 and electrospun fiber membrane could increase the surface area of PAN fiber
32
33
34 membrane to 262.4 m2/g from 9.2 m2/g and make PAF based adsorbent be separated
35
36 from the adsorption solution easily. The prepared PAF-45 modified electrospun fiber
37
38 membrane (PAF-45-PP FM) showed good adsorption performance toward three
39
40
41
typical PPCPs: ibuprofen (IBPF), chloroxylenol (CLXN) and N,N-diethyl-meta-
42
43 toluamide (DEET). The adsorption comparison results indicated that the adsorption
44
45 capacity by PAF-45-PP FM almost attributed to PAF-45 materials. The adsorption
46
47
processes could all reach equilibrium at 360 min and the maximum adsorption
48
49
50 capacities toward IBPF, CLXN and DEET from Langmuir models were 613.50,
51
52 429.18 and 384.61 mg/g, respectively. In addition, PAF-45-PP FM also showed
53
54 excellent reusability. Through the mechanism analysis, hydrophobic interaction, π-π
55
56
57 interaction and pore capture mechanism contributed to the adsorption processes. The
58
59 present study provides the method for loading PAF materials onto electrospun fiber
60
28

1
2
3 membranes and demonstrates their potential applications for the purification of water
4
5
6 contaminated with PPCPs. Inspired by this work, further study will be conducted for
7
8 loading PAFs on other substrates’ surfaces which may show broad applications, such
9
10 as gas adsorption, gas separation, liquid separation, catalysis and so on.
11
12
13
14 ASSOCIATED CONTENT
15
16
17 Supporting Information
18
19 The supporting information is available free of charge on the ACS publications
20
21 website at DOI:
22
23
Details for electrical conductivity measurement, monomer and Scholl reaction for
24
25
26 PAF-45, SEM images of PAF-45 onto PAN fibers without PANI seed layer, TEM
27
28 images, optical image of PAF-45-PP FM, solid state 13C NMR spectrum, TGA curve
29
30 of PAF-45 powder, Adsorption kinetic curves and parameters for activated carbon,
31
32
33 Langmuir linear plots and Freundlich linear plots, comparison of the adsorption
34
35 capacity, SEM image of PAF-45-PP FM after ten adsorption–desorption cycles, effect
36
37 of solution pH on IBPF adsorption, XPS spectra of PAF-45-PP FM before and after
38
39
40 IBPF adsorption, molecule sizes of three PPCPs, N2 adsorption isotherms of PAF-45-
41
42 PP FM after IBPF adsorption and after regeneration, SEM image of PS fiber
43
44 membrane and chemical structure of PS.
45
46
47
48
49 AUTHOR INFORMATION
50
51 Corresponding Author
52
53 *E-mail: zhugs@nenu.edu.cn
54
55
56 Notes
57
58 The authors declare no competing financial interest.
59
60
29

1
2
3
4
5
6 Acknowledgements
7
8 This work was supported by the National Natural Science Foundation of China
9
10 (91622106, 21531003, 21601031 and 21802017) and the Fundamental Research
11
12
13
Funds for the Central Universities (2412019QD005).
14
15
16
17 References
18
19
(1) Rana, D.; Narbaitz, R. M.; Garand-Sheridan, A. M.; Westgate, A.; Matsuura, T.;
20
21
22 Tabe, S.; Jasim, S. Y. Development of Novel Charged Surface Modifying
23
24 Macromolecule Blended PES Membranes to Remove EDCs and PPCPs from
25
26 Drinking Water Sources. J. Mater. Chem. A 2014, 2, 10059-10072.
27
28
29 (2) Chen, C.; Chen, D.; Xie, S.; Quan, H.; Guo, L. Adsorption Behaviors of Organic
30
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