Polyphenylene Sulfide Ultrafine Fibrous Membrane Modified by

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Polyphenylene sulfide ultra-fine fibrous membrane modified by nanoscale ZIF-8 for highly effective adsorption, interception and recycling of iodine vapor Yan Yu, Lipei Ren, Man Liu, Shiqi Huang, Xingfang Xiao, Ruina Liu, Luoxin Wang, and Weilin Xu ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b09345 • Publication Date (Web): 05 Aug 2019 Downloaded from pubs.acs.org on August 6, 2019

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ACS Applied Materials & Interfaces

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Polyphenylene sulfide ultra-fine fibrous membrane modified by

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nanoscale ZIF-8 for highly effective adsorption, interception and

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recycling of iodine vapor

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Yan Yu, Lipei Ren, Man Liu, shiqi Huang, Xingfang Xiao, Ruina Liu*, Luoxin

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Wang*, Weilin Xu*

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College of Materials Science and Engineering, Key Laboratory of Textile Fiber and

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Products (Ministry of Education), State Key Laboratory of New Textile Materials and

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Advanced Processing Technologies, Wuhan Textile University, Wuhan 430073, P. R.

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China.

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* Corresponding author: E-mail address: [email protected]; [email protected];

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[email protected]

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Abstract: In this study, two novel composite membranes containing nanoscale ZIF-8

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and polyphenylene sulfide (PPS) non-woven fabric were prepared via hydrothermal

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(PPS-ZIF-8) and biomimetic mineralization (PPS-ZIF-8-BSA) approaches. The

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biomimetic mineralization approach in particular was extremely rapid and mild, and

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crystalline ZIF-8 was coated on the PPS substrate in only several seconds at room

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temperature. The maximum iodine adsorption capacities of the PPS-ZIF-8 and

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PPS-ZIF-8-BSA membranes were 2.51 and 2.07 g/g, respectively. The composite

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fibrous membranes were able to capture trace iodine vapor under differential

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pressures ranging from 0 to 1000 Pa without almost any iodine vapor leakage. The

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composite membranes can be applied in harsh environments because of the excellent

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ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 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

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stability of ZIF-8 and the PPS high-performance fibers. This study provides a

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promising strategy to fabricate novel adsorption materials for the collection of

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radioactive iodine during nuclear waste disposal.

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Keywords: ZIF-8; PPS; biomimetic mineralization; iodine adsorption; interception of

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trace iodine

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1. Introduction

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Metal organic frameworks (MOFs) are a novel class of porous and crystalline

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materials fabricated by individual or multiple metal ions with organic linkages.

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Because of their excellent properties, MOFs have been applied in many fields.1-3 The

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applications of MOFs materials in adsorption have increased rapidly on account of

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their promising structures and varieties.4-8 The large specific surface areas and

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nanocage structures of MOFs are suitable for capturing gaseous contaminants.9,10

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ZIF-8 is a MOF comprised of zinc ions coordinated by four 2-MeIM rings. ZIF-8 has

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stable nanopores, a large specific surface area, open metal sites, and excellent

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stability. Furthermore, because of its ease of preparation, ZIF-8 is extensively

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applied.11-13 However, as a result of the light and breakable crystal form of ZIF-8, it

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cannot be easily recycled during the adsorption process. To improve its recyclability

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and applicability in adsorption applications, coating ZIF-8 on suitable substrates is

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an effective strategy.14,15

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Macroscopic-scale fibrous membranes can be used as flexible substrates for

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adsorption and are conducive to the collection of pollutants and recycling.16

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Polyphenylene sulfide (PPS) fiber is a high-performance material that is obtained via

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melt-blowing and exhibits excellent heat resistance, fire resistance, corrosion

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resistance, and dimensional stabilization.17 PPS can be used in harsh environments

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(e.g., high-temperatures, damp, acidic, and alkaline environments) without changes to

5

its physical and chemical properties.18 Various methods have been reported for

6

compounding ZIF-8 and membranes substrates, including hydrothermal growth,19

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layer-by-layer

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hydrothermal methods are the most commonly used and efficient methods for coating

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MOF crystals on substrates. Composites can be easily obtained during the MOF

10

growth process by placing fiber-based substrates in the MOF precursor in advance.

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Biomimetic mineralization was first applied to MOF preparation in 2015.23 ZIF-8 can

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be obtained only within several seconds at room temperature induced by bovine

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serum albumin (BSA). However, when ZIF-8 is grown on PPS fiber substrates, the

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effects of biomimetic mineralization are unknown. The ability to produce composites

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of ZIF-8 and PPS fibrous membranes quickly and under mild conditions would

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provide a novel strategy for the preparation of MOF composite materials for

17

adsorption applications.

assembly,20

spray-coating,21

and

hot-pressing.22

Currently,

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Radioactive iodine isotopes pose great harm to the human body and the

19

environment.24-26 Some porous materials have been developed to remove I2 vapor,

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including inorganic and organic porous materials along with hybrid materials.27-30

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However, I2 vapor is typically only present in trace amounts in the environment. The

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interception of iodine vapor is an effective strategy for cleaning air.25 In 2014,

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129I

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atmospheric pollutants were intercepted by sea ice using

as a representative

2

pollutant.31 Since then, no related studies on I2 vapor interception by membranes or

3

other materials have been reported. Therefore, further efforts are needed to develop

4

materials for I2 vapor interception.

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In this study, composite PPS and ZIF-8 membranes for the adsorption and

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interception of I2 vapor were designed and fabricated via hydrothermal and

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biomimetic mineralization approaches (termed PPS-ZIF-8 and PPS-ZIF-8-BSA,

8

respectively). The PPS fibers are suitable for application in harsh environments such

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as nuclear power stations. In real environments, I2 vapor and particularly trace I2

10

diffusion must be effectively intercepted without leakage. The PPS-ZIF-8 (BSA)

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fibrous composite membrane exhibited high adsorption capacity for I2 vapor and

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effectively intercepted trace I2 molecules under differential pressures ranging from 0

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to 1000 Pa between the two sides of the membrane. Thus, PPS-ZIF-8 (BSA) shows

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promise for practical applications. The results of this study provide a novel strategy

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for preparing MOFs/fiber composite materials for adsorption applications in harsh

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environments.

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2. Experimental

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2.1. Materials

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Superfine PPS fibers were prepared via melt-blowing in our laboratory. Zinc

20

nitrate hexahydrate [Zn(NO3)2·6H2O], 2-methylimidazole (2-MeIM), bovine serum

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albumin (BSA), methanol, and ethanol were purchased from Sinopharm Chemical

22

Reagent Co., Ltd. (Shanghai, China). Chitosan (CS) was provided by Zhejiang

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Golden-Shell Pharmaceutical Co. (Zhejiang, China). Deionized water was produced

2

by a Milli-Q system (Flom, China). All reagents were of analytical grade and used

3

without further purification.

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2.2. Preparation of superfine PPS fibers via melt-blowing

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First, the PPS masterbatch was dried at 120 °C for 48 h. Subsequently, the PPS

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masterbatch was melted by screw stem shearing and heating. The melt was then

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ejected from the orifice by extrusion of screw. Simultaneously, high-pressure hot gas

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was flowed on both sides of the spinneret orifice at a certain angle with the direction

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in which the melt is ejected. The melt was refined into ultrafine fibers via the emitting

10

and stretching action of the high-pressure stream of hot gas. The fibers were formed at

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a high rate, resulting in the formation of a fine fibrous web.

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2.3 Preparation of PPS-ZIF-8 membranes

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Non-woven PPS fabric (1 g) was refined by a beater, and the obtained PPS pulp

14

was modified by CS solution (0.5 g/L). Next, 2-MeIM (3.244 g, 39.6 mmol) and

15

Zn(NO3)2·6H2O (1.466 g, 5 mmol) were dissolved in 100 mL deionized water. The

16

modified PPS pulp was added into the Zn2+ solution under stirring for 10 min. The

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content of ZIF-8 loaded on the PPS depended on the amount of MOF precursor.

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Subsequently, the Zn2+ solution containing PPS pulp was rapidly stirred with the

19

2-MeIM solution for 10 min and then transferred into a 100-mL hydrothermal reactor.

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The mixture was heated to 80 °C at 2 °C/min in an autoclave and then held at this

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temperature for 24 h. Finally, the PPS-ZIF-8 pulp was filtered by ethanol and

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deionized water and dried under vacuum at 80 °C for 12 h to the obtain PPS-ZIF-8

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1

membrane.

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2.4. Preparation of PPS-ZIF-8-BSA membrane

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Typically, 2-MeIM (1.312 g, 16 mmol) and 0.05 g BSA were dissolved in 100

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mL deionized water to obtain a homogeneous solution. Meanwhile, Zn(NO3)2·6H2O

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(1.19 g, 4 mmol) was dissolved in 100 mL deionized water. The PPS pulp, coated

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with CS, was dipped into Zn2+ solution under stirring for 10 min. Subsequently, the

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Zn2+ solution containing PPS pulp was added into 2-MeIM solution and stirred for 5 s

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to obtain a milky ZIF-8-BSA suspension. Finally, the PPS-ZIF-8 pulp was filtered

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twice by water and ethanol and then dried under vacuum at 80 °C for 12 h. The

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fabrication processes of PPS-ZIF-8 and PPS-ZIF-8-BSA are shown in Scheme 1.

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Scheme

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PPS-ZIF-8-BSA membrane.

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2.5. I2 Vapor capture, release and interception

15

1.

The

fabrication

schematically

illustrated

of

PPS-ZIF-8

and

All I2 used in the experiments was nonradioactive. The PPS-ZIF-8 and

6


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PPS-ZIF-8-BSA membranes were used to capture I2 vapor in closed hydrothermal

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reactors under a dry and humid environment. Excess crystalline iodine was placed on

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the bottom of the hydrothermal reactor, and the PPS-ZIF-8 or PPS-ZIF-8-BSA

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membrane was supported by triangular steel sheet at the top of the hydrothermal

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reactor and adjusted the ambient humidity. The reactor was maintained at 100 °C in

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an oven during the experiment. After 2 h, the reactor was cooled to room temperature,

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and the iodine vapor capture capacity was estimated from the changes in the color and

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weight of the membrane after adsorption. The weights of the PPS-ZIF-8 and

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PPS-ZIF-8-BSA membranes were directly calculated during the adsorption process

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until no further changes in mass were observed. The I2 uptake of each membrane was

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calculated by Equation (1):

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W = (m2 − m1)/m1, 13

where W (g/g) is the adsorption capacity of the membrane for iodine vapor, and m1 (g)

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and m2 (g) are the masses of the membrane before and after I2 adsorption,

15

respectively.

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An I2 gas interception experiment was conducted using a self-assembled

17

experimental device. Trace iodine was placed in a 250-mL conical flask on a heater,

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and the PPS, PPS-ZIF-8 or PPS-ZIF-8-BSA membrane was fixed in the middle of a

19

separator arranged on the mouth of the conical flask. A tube was connected to the

20

separator with a rubber stopper, while the other end of the tube was placed in ethanol.

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The reactor was maintained at 100 °C under a pressure differential of 1000 Pa during

22

the experiment. The I2 gas that was not intercepted entered the ethanol solution

7



1

through the tube. The I2 interception coefficient R was determined from the I2

2

concentrations in the ethanol solution before (C0) and after (Cp) interception

3

according to Equation (2):

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R = (C0 − Cp)/C0 × 100%.

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Iodine release occurred when the iodine-adsorbed PPS-ZIF-8 sample was placed

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in a sealed container at 150 °C for 1 h. The release rate of iodine vapor was estimated

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from the weight change of the membrane before and after release.

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2.6. Material characterization

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The Fourier transform infrared (FTIR) spectra of PPS, PPS-ZIF-8, and

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PPS-ZIF-8-BSA were obtained using an FTIR spectrophotometer (Nicolet 5700,

11

USA). X-ray photoelectron spectroscopy (XPS) was performed using a Thermo

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Scientific ESCALAB 250 Xi spectrometer equipped with a monochromatic Al Kα

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X-ray source (1486.6 eV) and operated at 300 W. Scanning electron microscopy

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(SEM) was conducted using a field-emission scanning electron microscope (JEOL

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JSM-5400) at an accelerating voltage of 15 kV. The mechanical properties of PPS

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were evaluated using an electronic universal testing machine (UTM 2502, China).

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The crystal structure of ZIF-8 was determined using powder X-ray diffraction (XRD;

18

D8 Advance, Germany). Thermogravimetry (TG) was conducted using a thermal

19

instrument (Shimadzu Corp. Japan) at a heating rate of 10 °C/min.

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3. Results and discussion

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3.1. Morphologies and structures of PPS, PPS-ZIF-8, and PPS-ZIF-8-BSA

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The surface morphologies of PPS, PPS-ZIF-8, and PPS-ZIF-8-BSA are shown in

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Figure 1a–i. The pristine PPS fibers were round with diameters of 2–6 μm (Figure

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1a). The fiber surfaces appeared smooth at high magnification; in theory, this

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smoothness makes the PPS fibers unsuitable for coating with ZIF-8 nanocrystals,

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which have low roughness. However, after modification by CS, the surfaces of the

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PPS fibers became rough, as shown in Figure S1. Furthermore, the surfaces of the

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CS-coated PPS fibers were rich in functional groups that can coordinate with metal

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ions. Figure 1b–e show the microscopic surface topographies of the PPS-ZIF-8

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membranes containing different contents of ZIF-8 (6.5%, 11.1%, 21.5%, and 30.5%).

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The crystals are very sparse with the content of ZIF-8 6.5% coated on the PPS fibers,

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and its morphology of ZIF-8 is not obvious. When the ZIF-8 content was 11.1%,

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ZIF-8 crystals uniformly covered the entire surfaces of the PPS fibers. As the ZIF-8

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content increased, the amount of ZIF-8 nanocrystals increased. When the ZIF-8

13

content was 30.5%, a dense ZIF-8 crystalline layer formed, and agglomeration was

14

observed (Figure 1e).32 The SEM images of the PPS-ZIF-8-BSA membranes

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containing different contents of ZIF-8-BSA (5%, 12.2%, 23.1%, and 30.3%) are

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shown in Figure 1f–i. The ZIF-8-BSA nanocrystals on the surfaces of the PSS fibers

17

exhibited elliptical shapes. For the same ZIF-8 content, the amount of ZIF-8-BSA

18

crystals observed on the PSS fibers was obviously more than the amount of ZIF-8

19

crystals. This difference may be attributed to BSA-induced effects, which allowed the

20

ZIF-8-BSA nanocrystals to form quickly (within several seconds). When the

21

ZIF-8-BSA content was 30.3%, a dense ZIF-8-BSA crystalline layer formed, and

22

agglomeration occurred, as for PPS-ZIF-8. Therefore, the ZIF-8 (BSA) content of

9



1

about 20% was chosen for further structural and compositional characterization.

2 3

Figure 1 SEM images of (a) pure PPS; PPS-ZIF-8 with (b) 6.5% ZIF-8, (c) 11.1%

4

ZIF-8, (d) 21.5% ZIF-8, and (e) 30.5% ZIF-8; and ZIF-8-BSA with (f) 5% ZIF-8, (g)

5

12.2% ZIF-8, (h) 23.1% ZIF-8, and (i) 30.3% ZIF-8.

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Figure 2 shows the XRD patterns of PPS, ZIF-8, PPS-ZIF-8, and

7

PPS-ZIF-8-BSA. The XRD pattern of the ZIF-8 nanocrystals was identical to that of

8

the simulated ZIF-8 pattern. The characteristic peaks of ZIF-8 nanocrystals were

9

observed at 7.2°, 10.3°, 12.6°, 14.6°, 16.3°, and 17.9°, consistent with the standard

10

XRD pattern of ZIF-8.33 In the spectra of PPS-ZIF-8 and PPS-ZIF-8-BSA, the

11

characteristic peaks of ZIF-8 nanocrystals were observed at 7.2°, 10.3°, 12.6°, and

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17.9°. The peak intensity was lower for PPS-ZIF-8-BSA than for pure PPS,

13

confirming that ZIF-8 (BSA) existed on the surface of PPS. The characteristic peaks

10


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1

at 18.9° and 27° can be assigned to PPS fibers. The intensities of the peaks at 18.9°

2

and 27° were higher for PPS-ZIF-8 and PPS-ZIF-8-BSA than for the ZIF-8

3

nanocrystals, which might be attributed to the superposition of PPS and ZIF-8 peaks.

4

Compared to PPS-ZIF-8, PPS-ZIF-8-BSA generated an additional peak at 22°, which

5

can be assigned to BSA.34 As shown in the XRD patterns, the ZIF-8 peaks of

6

PPS-ZIF-8 and PPS-ZIF-8-BSA were shifted to slightly lower 2θ values compared to

7

the spectrum of ZIF-8. This phenomenon was attributed to increased lattice strain and

8

lattice distortion during nanostructure formation.35

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Figure 2 XRD patterns of PPS, pure ZIF-8 nanocrystals, PPS-ZIF-8, and

11

PPS-ZIF-8-BSA.

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Figure 3 shows the FTIR spectra of PPS, PPS-ZIF-8, and PPS-ZIF-8-BSA. In

13

the spectrum of pure PPS, vibration peaks were observed at 1560, 806, 1466, and

14

1382 cm−1, corresponding to the in-plane stretching vibration of C–C in the benzene

15

ring and out-of-plane deformation of C–H in the benzene ring. Vibration peaks at

16

3124–2912 cm−1 were detected in the spectra of PPS-ZIF-8 and PPS-ZIF-8-BSA;

17

these can be assigned to the aromatic and aliphatic C–H stretching vibrations of

11



1

imidazole. The convoluted vibration peaks at 1645 and 1500–1000 cm−1 correspond

2

to C=N and C–N and result from the effects of the imidazole ring or BSA stretching

3

and/or bending. Compared to PPS-ZIF-8, PPS-ZIF-8-BSA did not show clear

4

differences when trace amounts of BSA were added.22 The intensities of the

5

characteristic peaks were higher for pure PPS than for PPS-ZIF-8 and

6

PPS-ZIF-8-BSA, confirming that ZIF-8 nanocrystals were loaded on the membrane

7

surfaces. Consistent with the SEM and XRD results, the FTIR spectra confirmed the

8

presence of the ZIF-8 nanocrystals on the surfaces of the PPS-ZIF-8 and

9

PPS-ZIF-8-BSA membranes.

10 11

Figure 3 FTIR spectra of PPS, PPS-ZIF-8, and PPS-ZIF-8-BSA.

12

XPS was performed to further confirm the presence of ZIF-8 on PPS-ZIF-8 and

13

PPS-ZIF-8-BSA. Figure 4 shows the full XPS survey spectra of PPS, PPS-ZIF-8, and

14

PPS-ZIF-8-BSA. The three peaks observed in the spectrum of PPS at 284.84, 532.13,

15

and 165.24 eV can be assigned to C 1s, O 1s, and S 2s/2p, respectively. The spectrum

16

of PPS-ZIF-8 (BSA) exhibited two additional peaks at 399.24 and 1045.20 eV,

17

corresponding to N 1s and Zn 2p, respectively. The percentages of C 1s, N 1s, O 1s, S

12


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1

2s/2p, and Zn 2p were 72.22%, 8.03%, 12.14%, 4.02%, and 3.59%, respectively,

2

verifying the presence of ZIF-8 on the surface of PPS. The high-resolution XPS

3

spectra of PPS-ZIF-8 and PPS-ZIF-8-BSA are shown in Figure 5a–c and Figure

4

S2a–c, respectively. The C 1s, N 1s, and O 1s spectra indicated the presence of

5

numerous bonds involving C, O, and N. The C 1s XPS spectrum could be further

6

deconvoluted into three carbon states at 284.81, 285.70, and 286.75 eV, which can be

7

assigned to C–C/C–H, C–N/C–O, and imidazole groups, respectively. The N 1s

8

spectrum displayed two peaks at 399.77 and 400.98 eV, corresponding to the

9

–NH2/C–N and imidazole groups, respectively. Figure S3 shown the C 1s and N 1s

10

spectra of PPS-ZIF-8 and PPS-ZIF-8-BSA. The addition of BSA increased the

11

intensities of the C–C/C–H and –NH2/C–N peaks and slightly weakened the intensity

12

of the peak of the imidazole ring, indicating that some imidazole sites were occupied

13

by BSA. The O 1s spectrum showed two peaks at 531.74 and 532.65 eV,

14

corresponding to C=O and C–O, respectively. As shown in the Zn 2p XPS spectra

15

(Figure 5d) of PPS-ZIF-8 and I2 loaded on PPS-ZIF-8, I2 adsorption caused the Zn 2p

16

peak to move slightly towards lower binding energy, which may be attributed to the

17

coordination interactions between Zn and I2 after adsorption.36

18

13



1 2

Figure 4 XPS survey spectra of PPS, PPS-ZIF-8, and PPS-ZIF-8-BSA.

3 4

Figure 5 (a) C1s, (b) N1s, (c) O1s, and (d) Zn 2P spectra of PPS-ZIF-8.

5

The thermal stabilities of PPS, ZIF-8 nanocrystals, PPS-ZIF-8, and

6

PPS-ZIF-8-BSA were examined by TG (Figure 6). Pure PPS exhibited excellent

7

thermal stability with nearly no mass loss up to 450 °C. A sudden drop in weight was 14


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1

observed between 500 °C and 600 °C, and the residual mass percentage at 800 °C was

2

approximately 45%. The TG curve of ZIF-8 nanocrystals in nitrogen was similar to

3

that reported previously.19 The curve of ZIF-8 exhibited a gradual weight-loss step of

4

approximately 7% at temperatures up to 500 °C. This weight loss can be primarily

5

attributed to the loss of water and an extremely small amount of organic ligands

6

adhered to the nanocrystals. The most significant weight loss occurred from 550 °C to

7

800 °C, when the linkers decomposed and the structure of ZIF-8 collapsed. Both

8

PPS-ZIF-8 and PPS-ZIF-8-BSA exhibited excellent stability below 200 °C.

9

Subsequently, PPS-ZIF-8-BSA exhibited a sudden weight loss compared to

10

PPS-ZIF-8, this difference primarily attributed to the occupation of some active sites

11

by BSA. The non-coordinating imidazole ring and combined water of BSA were the

12

first to be degraded in PPS-ZIF-8-BSA. At 450 °C, the percentages of mass loss for

13

PPS-ZIF-8 and PPS-ZIF-8-BSA were 7% and 12%, respectively. Both composite

14

membranes maintained the framework structure of ZIF-8 until the structure collapsed

15

at 550 °C. Therefore, the composites can be applied in high-temperature adsorption.

16 17

Figure 6 TG curves of PPS, PPS-ZIF-8, and PPS-ZIF-8-BSA.

15



1

3.2. Capture of iodine vapor

2

The iodine vapor adsorption properties of the PPS, PPS-ZIF-8 and

3

PPS-ZIF-8-BSA membranes were evaluated. The process of iodine vapor capture by

4

the PPS-ZIF-8 (BSA) is shown in Figure 7a. Large amounts of iodine molecules were

5

captured by PPS-ZIF-8 (BSA), primarily due to the following effects. First, the iodine

6

molecules were captured by the ZIF-8 nanocages and surface sites because of the

7

strong binding of iodine by ZIF-8. The interactions between iodine and ZIF-8 exist

8

both within the nanocages and on the surface.24,37 Second, iodine was captured by the

9

phenyl groups of PPS via π···I bonding. Materials rich in π electrons have been

10

reported to show gas adsorption capability.38 Abundant π electrons from the phenyl

11

groups of PPS interacted with iodine, resulting in I2 adsorption. Third, nanoscale

12

ZIF-8 and the micro/nano fibers of PPS have large specific surface areas for iodine

13

adsorption. The color of the PPS-ZIF-8 sample changed from light yellow to black

14

during the adsorption experiment (Figure 7b). As shown in Figure 7c, 0.62 g of

15

iodine was captured by 1 g of pure PPS, indicating a maximum iodine capture

16

capacity of 0.62 g/g. This capacity may be ascribed to the high specific surface area of

17

PPS and the phenyl groups, which served as adsorption sites through π···I interactions.

18

When the mass contents of ZIF-8 (BSA) were 6.5%, 11.1%, 21.5%, and 30.5%, the I2

19

capture capacities of PPS-ZIF-8 were 1.31, 1.59, 2.51, and 1.53 g/g, while those of

20

PPS-ZIF-8-BSA were 1.11, 1.37, 2.07, and 1.44 g/g, respectively. The maximum

21

adsorption capacities of were 2.51 g/g for the PPS-ZIF-8 membrane and 2.07 g/g for

22

the PPS-ZIF-8-BSA membrane. This may be explained to the occupation of some

16


Page 16 of 32

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1

adsorption sites by BSA. During the biomimetic mineralization process between

2

ZIF-8 and BSA, a small amount of BSA was bioconjugated or encapsulated in the

3

MOF, and the number of adsorption sites along with the I2 adsorption capacity

4

decreased. However, the I2 adsorption capacity of PPS-ZIF-8-BSA was still higher

5

than those of the pure ZIF-8 crystals (1.25 g/g)24 and pure PPS membrane (0.62 g/g).

6

Moreover, the PPS-ZIF-8-BSA membrane could be prepared in only several seconds

7

via biomimetic mineralization induced by BSA. This synthetic method is very rapid,

8

simple, and efficient.

9 17



1

Figure 7 (a) The process of iodine vapor capture by the PPS-ZIF-8 (BSA) membrane.

2

(b) Digital photos of the PPS-ZIF-8 membranes containing different ZIF-8 contents

3

before and after iodine absorption. (c) Iodine adsorption capacities of PPS-ZIF-8 and

4

PPS-ZIF-8-BSA containing different contents of ZIF-8.

5

Table 1 compares the I2 adsorption capacities of some reported adsorbents with

6

those of PPS-ZIF-8 and PPS-ZIF-8-BSA in this study. The maximum loading

7

capacities of the PPS-ZIF-8 and PPS-ZIF-8-BSA membranes were 2.51 and 2.07 g/g,

8

respectively, much higher than those of Ag@Mon-POF,39 ZIF-8,33 Sn2S3 chalcogel

9

granue or powder (SnSg/SnSp),40 Pt−Ge−S chalcogen aerogels (CG-5C),41

10

(BYA)2[PbBr4]m,42 and layered double hydroxide intercalated with polysulfides

11

(Sx-LDH).27 Although the adsorption capacity of PSIF-1a43 can reach 4.85 g/g,

12

PSIF-1a cannot intercept iodine vapor under driving force. In view of the adsorption

13

and interception capacities, the PPS-ZIF-8 and PPS-ZIF-8-BSA composite

14

membranes are clearly superior to reported adsorbents for the practical removal of

15

iodine vapor. Furthermore, PPS is a high-performance fiber that can be applied in

16

harsh environments. The ZIF-8 nanocrystals are very stable, even at temperatures

17

exceeding 300 °C. The PPS-ZIF-8 (BSA) composite membrane has excellent stability

18

and shows promise for applications in nuclear fuel reprocessing.

19 20 21 22

18


Page 18 of 32

Page 19 of 32 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


1

Table 1. Comparison of the Iodine Adsorption Capacities of Various Absorbents in

2

Previous Studies and the Composite Membranes in this Work T (°C)

Iodine uptake capacity (g/g)

reference

Ag@Mon-POF

70

0.25

39

ZIF-8

77

1.25

33

SnSg/SnSp

125

0.67–0.68

40

SnS33

125

0.33

40

SnS50

125

0.53

40

Cg-5Ck

140

2.39

41

(BYA)2[PbBr4]m

--

0.75

42

Sx-LDH

70

1.32–1.55

28

PSIF-1a

60

4.85

43

PPS-ZIF-8

100

2.51±0.13

This work

PPS-ZIF-8-BSA

100

2.07±0.08

This work

3 4

The FTIR spectra of PPS, PPS-ZIF-8, and PPS-ZIF-8-BSA before and after

5

iodine vapor adsorption are shown in Figure 8a–c. For pristine PPS, the vibration

6

peaks did not shift after I2 loading (Figure 8a), likely because of weak π···I

7

interactions. In contrast, some vibration of PPS-ZIF-8 and PPS-ZIF-8-BSA shifted

8

slightly after I2 adsorption (Figure 8b and c). Specifically, the vibration peaks at 3042

9

and 1289 cm−1, which correspond to the aromatic rings of imidazole stretching or

10

bending, shifted to 3001 and 1328 cm−1, respectively. This verifies that I2 molecules

11

were captured by the surface sites of ZIF-8 via chemical forces. The results

12

demonstrate that the PPS-ZIF-8 and PPS-ZIF-8-BSA membranes adsorbed iodine via

13

both physisorption and chemisorption, which exhibited higher adsorption capacity.10 19



1

Therefore, the PPS-ZIF-8 (BSA) composite membrane can be employed as an

2

efficient adsorbent for iodine vapor.

3 4

Figure 8 FTIR spectra of (a) PPS, (b) PPS-ZIF-8, and (c) PPS-ZIF-8-BSA before and

5

after iodine absorption.

6

3.3. Iodine uptake and interception under a simulated real environment

7

To simulate real nuclear fuel reprocessing, competitive I2/H2O gas adsorption

8

experiments were conducted. The process of iodine vapor capture by PPS-ZIF-8

9

(BSA) under a humid environment (Figure 9a). PPS-ZIF-8 (21.5%) and

10

PPS-ZIF-8-BSA (23.1%) were sealed with excess I2 in a hydrothermal reactor under

11

ambient pressure at 100 °C and 4.0% relative humidity to form I2@PPS-ZIF-8

12

(BSA).44 Digital photos of the PPS-ZIF-8 membrane under dry and humid

13

environments as shown in Figure 9b. The adsorption capacity of the PPS-ZIF-8 and 20


Page 20 of 32

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1

PPS-ZIF-8 (BSA) was 2.41 g/g, 1.91 g/g, respectively, slightly lower than in a dry

2

environment. This may be attributed to the removal of extra iodine vapor on the

3

surface of the sample under humid conditions. The results demonstrate that the

4

adsorption capacity of the PPS-ZIF-8 membrane is maintained under humid

5

conditions, indicating that the composite materials are suitable for the real adsorption

6

environments.

7 8

Figure 9 (a) The process of iodine vapor capture by PPS-ZIF-8 (BSA) under a humid

9

environment. (b) Digital photos of the PPS-ZIF-8 membrane under dry and humid

10

environments.

11

To evaluate the iodine vapor interception capacity of PPS, PPS-ZIF-8 and

12

PPS-ZIF-8-BSA, I2 gas filtration and sorption experiments were conducted. Figure

13

10a shows the adsorption process. Briefly, 4 mg of iodine was placed in a 250-mL 21



1

conical flask, and 0.01 g PPS, PPS-ZIF-8 (21.5%) or PPS-ZIF-8-BSA (23.1%) were

2

fixed at the interface of the tube, while the other end of the tube was placed in ethanol.

3

The ethanol in the beaker was detected whether the iodine vapor pass through the

4

PPS-ZIF-8 (BSA). During the experiment, the reactor was kept at 100 °C and under

5

the pressure drop of 1000 Pa. Ultraviolet–visible (UV–Vis) spectrometry was used to

6

analyze the concentration of iodine in solution. As shown in Figure 10b, the change

7

in absorbance at 230 nm, corresponding to the characteristic peak, was evaluated after

8

filtration. The rejection coefficient of the PPS membrane for iodine was determined to

9

be approximately 35.6%, while those of the PPS-ZIF-8 and PPS-ZIF-8-BSA reached

10

99.0%. The differential pressure of the PPS-ZIF-8 (BSA) membrane reached 1000 Pa

11

with hardly any iodine vapor leakage. These results indicate that PPS-ZIF-8 (BSA)

12

was able to capture trace iodine vapor under a driving force. The trace iodine residues

13

in nuclear fuel for reprocessing are known to cause great harm to human health. The

14

fast and efficient method presented herein for intercepting trace iodine is applicable to

15

nuclear power plants.

16 17

Figure 10 (a) The process of iodine vapor capture by PPS, PPS-ZIF-8 and

18

PPS-ZIF-8-BSA under a driving force. (b) UV-Vis spectra of PPS, PPS-ZIF-8, and 22


Page 22 of 32

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1

PPS-ZIF-8-BSA before and after I2 filtration.

2

3.4. Release of iodine vapor

3

Iodine release occurred when the iodine-adsorbed PPS-ZIF-8 sample was placed

4

in a sealed container at 150 °C for 1 h. Figure 11a show the digital photos of the

5

PPS-ZIF-8 sample during an iodine adsorption and desorption experiment. After

6

iodine capture, the PPS-ZIF-8 membrane appeared black. When some of the iodine

7

was released, the membrane became yellowish brown, indicating the release of a large

8

amount of iodine, with a small amount of iodine retained in the membrane. The mass

9

of the PPS-ZIF-8 membrane in this experiment was 0.2 g, and the ZIF-8 content was

10

17.8%. The mass of I2 adsorbed on the PPS-ZIF-8 membrane was 0.5 g. As shown in

11

Figure 11b, the iodine release efficiency was 93.3%, indicating that only 0.0305 g of

12

I2 was retained on the PPS-ZIF-8 sample at 150 °C. According to a previous report,

13

the I2 absorption capacity of a ZIF-8 cage is 1 g/g;24 thus, theoretically, 0.0365 g I2

14

should remain confined within the cage of the PPS-ZIF-8 sample and would not be

15

released until framework disintegration at 300 °C, consistent with our results. The

16

iodine release capability encouraged us to study the recyclability of the PPS-ZIF-8

17

sample as follows. Iodine-loaded PPS-ZIF-8 samples were heated at 150 °C for 60

18

min to release iodine and then reused for iodine uptake (100 °C). After the first cycle,

19

the iodine uptake capacity (CI) and release rate (RI) were 2.51 g/g and 93.3%,

20

respectively (Figure 11c). After another two cycles, the PPS-ZIF-8 sample retained

21

high CI and RI values of 2.31 g/g and 91.1%, respectively. The recycling experiment

22

results confirmed that PPS-ZIF-8 can be used as a reversible adsorbent for iodine

23



1

uptake.

2 3

Figure 11 (a) Digital photos of PPS-ZIF-8 during an iodine adsorption and desorption

4

experiment. (b) Iodine release rate vs. release time. (c) Iodine uptake and release rate

5

of PPS-ZIF-8 after recycling.

6

4. Conclusion

7

In summary, two novel composites, PPS-ZIF-8 and PPS-ZIF-8-BSA, were

8

successfully prepared and employed for I2 adsorption. The PPS-ZIF-8-BSA composite

9

could be synthesized in only 5 s using a biomimetic mineralization approach. The

10

PPS-ZIF-8-BSA exhibited a high I2 adsorption capacity and excellent stability. The

11

PPS membrane acted as a supporting substrate, providing the ZIF-8 nanocrystals with

12

a protective and accessible space for capturing iodine vapor. The PPS-ZIF-8 (21.5%)

13

and PPS-ZIF-8-BSA (23.1%) membranes demonstrated maximum uptake capacities

14

of 2.51 and 2.07 g/g, respectively. The as-prepared membranes were also able to

15

intercept trace iodine vapor under differential pressures ranging from 0 to 1000 Pa

16

with hardly any iodine vapor leakage. The PPS-ZIF-8 (BSA) adsorbent could also be 24


Page 24 of 32

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1

recycled three times while retaining an iodine release and uptake efficiency greater

2

than 90%. The composite membranes prepared in this study provides a fast and

3

efficient strategy for capturing trace iodine in nuclear power plants and other

4

applications.

5

Acknowledgments

6

This work was financially supported by the National Natural Science Foundation

7

of China (Nos. 51502208 and 51325306), the National Science and Technology

8

Support Plan of China (2015BAE01B04), Sichuan province Science and Technology

9

Planning Project (2018GZ0522), and the China Scholarship Council (No.

10

201608420039).

11

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Graphical Abstract


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Polyphenylene Sulfide Ultrafine Fibrous Membrane Modified by

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