zeolite-coated anti-biofouling mesh film for efficient oil

物理化学学报

Acta Phys. -Chim. Sin. 2020, 36 (1), 1906044 (1 of 9)

Received: June 11, 2019; Revised: July 19, 2019; Accepted: July 19, 2019; Published online: July 26, 2019. *Corresponding authors. Emails: [email protected] (J.Y.); [email protected] (J.D.). Tel.: +86-431-85168608 (J.Y.).

The project was supported by the National Natural Science Foundation of China (21621001, 21835002), the 111 Project, China (B17020) and the Jilin

Province/Jilin University Co-construction Project-Funds for New Materials, China (SXGJSF2017-3).

国家自然科学基金(21621001, 21835002)，111 计划(B17020)和吉林省/吉林大学新材料合作建设项目资金(SXGJSF2017-3)资助

© Editorial office of Acta Physico-Chimica Sinica

[Article] doi: 10.3866/PKU.WHXB201906044 www.whxb.pku.edu.cn

Zeolite-Coated Anti-Biofouling Mesh Film for Efficient Oil-Water Separation

Baixian Wang 1, Qifei Wang 1, Jiancheng Di 1,*, Jihong Yu 1,2,*

1 State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012,

P. R. China. 2 International Center of Future Science, Jilin University, Changchun 130012, P. R. China.

Abstract: The development of the global economy has been accompanied by

frequent oil spills caused by accidental leaks and industrial manufacturing, which

have seriously threatened the aquatic environment and human health. Traditional

methods for the treatment of oily wastewater include centrifugation, skimming,

flotation, oil-absorbing technology, etc., which are limited by low separation

efficiency as well as secondary pollution during the post-processing of oil

absorption materials. Recently, separation technologies utilizing the special

wettabilities of filtration membranes have been developed to enrich and recycle

oils from wastewater. Among these, the fabrication of superhydrophilic/underwater

superhydrophobic membranes have attracted intensive research interest, which can selectively allow the passage of water

through the membrane while blocking the oils. However, microorganisms are more likely to breed on these hydrophilic

surfaces, eventually leading to the blockage of the membranes. In this study, ZSM-5 zeolite crystals (MFI topological

structure) were coated onto the stainless-steel meshes by means of seeding and secondary hydrothermal growth. Then,

70% of the total Na+ ions in the zeolite channels were substituted by Ag+ ions via an ion exchange process. The resultant

membranes (Ag@ZCMFs) were superamphiphilic in air, with both water contact angle and oil contact angle of

approximately 0°. However, they became superoleophobic when immersed in water, and the underwater oil contact angle

reached 151.27° ± 4.34°. In terms of special wettability, Ag@ZCMF achieved efficient separation for various oil-water

mixtures with separation efficiencies above 99%. The water flux and intrusion pressure of Ag@ZCMF depended on the

diameter of pinholes in the membrane, which could be modulated by altering the time of secondary hydrothermal growth.

For instance, the average diameter of pinholes in Ag@ZCMF with optimum secondary growth time of 14 h (Ag@ZCMF-

14) reached approximately 21 μm, giving rise to the water flux and intrusion pressure of 54720 L·m−2·h−1 and 4357 Pa,

respectively. The anti-corrosion test and rubbing test confirmed the high chemical and mechanical stability of Ag@ZCMF-

14, respectively. The separation efficiency of Ag@ZCMF-14 remained stable during ten purification−regeneration cycles,

and no obvious attenuation was observed, proving the high separation stability of Ag@ZCMF-14. Furthermore, the loaded

Ag+ ions afforded the membrane excellent anti-biofouling activity, which could effectively inhibit the growth of both alga and

bacteria in the operating environment, thus preventing membrane blockage during the oil-water separation process. In

particular, the bacteriostatic rate of Ag@ZCMF-14 to Escherichia coli reached to 99.6%. These results demonstrate that

Ag@ZCMFs with anti-biofouling activity has promising potential future applications in the removal of oil slicks from oily

wastewater.

Key Words: Zeolite; Wettability; Oil-water separation; Ion exchange; Anti-biofouling activity

物理化学学报 Acta Phys. -Chim. Sin. 2020, 36 (1), 1906044 (2 of 9)

具有抗生物污染活性的分子筛膜用于高效油水分离

王百先 1，王琪菲 1，邸建城 1,*，于吉红 1,2,* 1吉林大学化学学院，无机合成与制备化学国家重点实验室，长春 130012 2吉林大学未来科学国际合作联合实验室，长春 130012

摘要：随着经济全球化的发展，频发的石油泄露事故以及工业生产时排放的含油污水已经严重威胁到水体生态环境和人体

健康。传统上处理含油废水的方式主要包括离心法，撇沫法，浮选法和油吸附技术等等。然而较低的分离效率以及吸油材料

后处理过程中所产生的二次污染等缺点限制了这些方法在实际中的应用。最近，基于过滤膜材料表面特殊浸润性的分离技术

已被广泛用于含油废水中油污的富集和回收。其中，具有空气中超亲水/水下超疏油特性的分离膜的制备引起了人们广泛的

研究兴趣。在油水分离过程中，这种分离膜可以选择性地允许水通过，同时将油污阻隔在膜的上方。然而，水中的微生物易

于附着在此类亲水膜上，降低其分离性能，并最终导致膜的阻塞。在本工作中，我们利用晶种和二次水热生长技术，在不锈

钢网基底上包覆了具有MFI拓扑结构的ZSM-5分子筛涂层，并进一步通过离子交换过程将分子筛孔道中70%的Na+离子取代

为Ag+离子。所制备的分子筛膜(Ag@ZCMFs)在空气中表现出超双亲性(水和油的接触角均为0°)，而当被浸没在水中时，其

浸润性转变为水下超疏油性(水下油接触角为151.27° ± 4.34°)。基于这种特殊的浸润性，Ag@ZCMF可以实现对众多油水混

合物的有效分离，其分离效率均超过99%。在Ag@ZCMF的合成过程中，可通过改变二次水热生长时间来调变膜中所预留的

针孔的直径，从而调整分离膜的水通量和油侵入压。例如，二次水热生长时间为14 h的分子筛膜(Ag@ZCMF-14)中针孔的平

均直径约为21 μm，在分离过程中，该膜的水通量和油穿透压分别达到54720 L·m−2·h−1和4357 Pa。抗腐蚀试验和摩擦试验

证实Ag@ZCMF-14具有良好的化学稳定性和机械稳定性。经过10次分离-再生循环过程，Ag@ZCMF-14的分离能力没有明

显的衰减，说明Ag@ZCMF-14具有较高的分离稳定性。此外，负载的Ag+使得该分子筛膜具有优异的抗生物污染性能，可以

有效抑制操作环境中藻类和细菌的生长，由此避免油水分离过程中膜的阻塞。其中，Ag@ZCMF-14对大肠杆菌的抑菌率达

到99.6%。这些结果表明具有抗生物污染的Ag@ZCMF在处理含油废水方面有着广阔的实际应用前景。

关键词：分子筛；浸润性；油水分离；离子交换；抗生物污染

中图分类号：O647

1 Introduction Oil pollutions triggered by the industrial manufactures and oil

leaks not only are the waste of resources 1–3, but also cause

significant negative impact on the ecological environment 4–8.

Therefore, the enrichment and recovery of the oil slicks from

oily wastewater are of great importance in the field of

environmental protection 9,10. Traditional oil-water separation

methods, including centrifugation, skimming, flotation, and oil

absorbing technology, suffer from the limitation of low

separation efficiency, high cost, and secondary pollutants 11–16.

To overcome these drawbacks, the filtration technique by using

the separation membrane with special wettability has been

developed to separate the oil-water mixtures owing to its high

efficiency and low power consumption 17–24. Because of the

higher density of water than most oils, the fabrication of

membranes with superhydrophilicity/underwater superoleophobicity

has attracted intensive research interest, which are prone to

interact with water and form a barrier to repel the immiscible

oils 19,25–34. Moreover, the oil contaminations on the membrane

can be easily rinsed off by water. However, the aquatic organisms,

such as bacteria and algae, are more likely to adhere on these

hydrophilic surfaces, which will decrease the separation capacity

and eventually result in the blockage of the membranes 35,36. Till

now, several polymer membranes have been reported, which

are capable to simultaneously achieve the functions of oil-

water separation and anti-biofouling activity 5,37,38. However,

because of the inherent nature of polymers, the stability of these

membranes is poor in harsh conditions, which may limit the

practical applications in oil-water separation.

Zeolites are a kind of crystalline aluminosilicate materials

with regular molecule-sized pores, which have been widely used

in the fields of catalysis, adsorption, and ion exchange, etc. 39–46.

In our previous work, we successfully developed a pure-silica

zeolite-coated stainless-steel mesh film with superhydrophilicity

in air and underwater superoleophobicity, which could realize

the highly efficient separation for various oil-water mixtures 32.

But the framework of the pure-silica zeolite is constructed

entirely by silicon-oxygen tetrahedra, which is neutral and

restricts the further functionalization by ion exchange. To this

end, the trivalent Al element is introduced into the skeletons of

zeolites, which can result in the anionic frameworks of zeolites,

affording them excellent ion exchange ability 46–50. Taking

account of the broad-spectrum antibacterial performance of

silver 5,51,52, it is expected that the Ag+ loaded zeolite films can

integrate the abilities of oil-water separation and anti-biofouling

activity.


Herein, aluminosilicate ZSM-5 (MFI zeotype) zeolite crystals

are coated over the stainless-steel meshes through secondary

hydrothermal growth process, which are further functionalized

with Ag+ ions by means of ion exchange. The resultant

membranes (Ag@ZCMF) exhibit superamphiphilicity in

air/underwater superoleophobicity, which facilitate the gravity-

driven separation of various oil-water mixtures with high

separation efficiency and stability. Moreover, the loaded Ag+

ions in zeolite afford Ag@ZCMF superior inhibitory effect on

the growth of chlorella and Escherichia coli, exhibiting excellent

anti-biofouling performance.

2 Experimental 2.1 Materials

Tetrapropylammonium hydroxide (TPAOH, 25%),

tetraethylorthosilicate (TEOS), aqueous ammonia (28%),

aluminum isopropoxide, silver nitrate (AgNO3), cyclohexane,

methylbenzene, n-octane, petroleum ether, and n-hexane were of

analytical grade. Sodium hydroxide (NaOH) and sodium

chloride (NaCl) were of guarantee grade. Stainless-steel mesh

(360 mesh) was obtained from Xinxiang Kairui Co. Ultrapure

deionized water was generated by using a Millipore Milli-Q plus

system (US). Chlorella was purchased from Guangda Tech Co.

Escherichia coli (E. coli) (ATCC 25922) was from the

Guangdong culture collection center. All chemicals were used as

received without further purification.

2.2 Preparation of silicalite-1 crystal seeds

The nano-sized pure silica silicalite-1 (MFI) zeolite crystals

were used as the seeds for the preparation of ZSM-5 zeolite

coatings on stainless-steel meshes. The precursor solution was

composed of TPAOH, TEOS, water, and EtOH with the molar

ratio of 9 : 25 : 480 : 100. After the continuous stirring for 12 h,

the clear precursor solution was sealed in the polypropylene

bottle (50 mL), which was placed in an oven at 90 °C for 4 d.

The collected product was washed by repeating the

centrifugation/ultrasonic dispersion process to wash away the

residual alkalis. Finally, the product was dried in the oven

(60 °C) overnight.

2.3 Preparation of ZSM-5 zeolite coatings

The ZSM-5 zeolite coatings on the stainless-steel meshes

were prepared by seeding and secondary growth process. To

prepare the seed solution, the as-prepared silicalite-1

nanocrystals were evenly dispersed in diluted aqueous ammonia

(pH value was about 10 and the concentration was 20 g·L−1).

Then the stainless-steel mesh was cut into the size of 3.5 cm ×

3.5 cm and then immersed into the seed solution under ultrasonic

condition for 10 min. The seeded substrate was dried in the oven

at 120 °C for 2 h. The molar ratio of the reaction solution for the

secondary growth of zeolite coating was fixed at TPAOH :

Al2O3 : Na2O : TEOS : H2O : EtOH = 3: 0.1 : 0.4 : 25 : 1534 :

100. Then the vertically placed seeded mesh and 60 g reaction

solution were sealed in a 100 mL autoclave, and the reaction was

conducted at 170 °C for x h (x = 4, 8, 12, 14, 16, 18, 20, 22, and

24, respectively). The as-prepared ZSM-5 coated mesh films

(ZCMFs) and the ZSM-5 powders along with the ZCMFs were

calcined at 550 °C for 4 h in air with the heating rate of

1 °C·min−1.

2.4 Ag+ ion exchange process

The Ag+ ion exchange process was operated by immersing the

one piece of ZCMFs or 800 mg ZSM-5 powder into 100 mL

AgNO3 solution (0.05 mol·L−1) and stirring slowly at 50 °C for

24 h. Then the Ag+ ion exchanged ZCMFs (Ag@ZCMFs) or

ZSM-5 powder (Ag@ZSM-5) were washed with deionized

water for three times to remove the excessive Ag+ ions, and then

dried with nitrogen gas at room temperature.

2.5 Separation of oil–water mixtures

One piece of the as-prepared Ag@ZCMF was squeezed in the

stainless-steel flanges, on which two glass tubes were connected.

Water and oil were mixed with the volume ratio of 1 : 1, and the

filtrate through the water pre-wetted film was collected in a jar.

During the separation process, no external driving force was

applied on the system, which was only its own gravity. Water

flux was evaluated under the constant intrusion pressure of about

230.3 Pa, and then calculated according to the formula: F = V/St,

where V was the water volume (L) through the membrane in t

time (h), S was the effective area of the membrane (m2).

2.6 Anti-biofouling activity test of Ag@ZCMF

The anti-biofouling activity of Ag@ZCMF was tested by

evaluating the inhibitory performance of the membrane to the

growth assay of chlorella and E. coli, respectively. For instance,

one piece of Ag@ZCMF or ZCMF was placed in a 100 mL

chlorella suspension, which was incubated in a biochemical

incubator at 25 °C for different days, such as 7 and 14 d. The

optical density (OD) of the chlorella suspension at 540 nm was

measured to evaluate the inhibiting effect of the membrane to the

growth of chlorella.

The anti-bacterial property of membranes was measured by

the zone inhibition method and the bacterial dynamics curve. In

the zone inhibition method, the E. coli bacteria was inoculated

into the Luria-Bertani (LB) solid medium, on which the UV-

sterilized Ag@ZCMF-14 or ZCMF-14 membrane with diameter

of around 1.0 cm was placed. The width of the inhibition zone

was measured after culturing for 24 h at 37 °C. In the bacterial

dynamics curves, a volume of 100 μL E. coli bacteria

suspensions with the concentration of 3 × 108 colony forming

units per mL (CFU·mL−1) was added into LB liquid medium.

The UV-sterilized Ag@ZCMF-14 and ZCMF-14 membrane

were placed into LB liquid medium and incubated at 37 °C for

90 min, respectively. Then, the optical density was measured at

600 nm to evaluate the anti-bacterial efficacy of the membrane.

2.7 Release behavior of Ag+ ions

The release behavior of Ag+ ions was measured by adding 500

mg Ag@ZSM-5 powders into 100 mL water. The Ag+ ions

concentrations were measured after the release time for 2, 4, 6,

and 8 d, respectively. The average concentration of Ag+ ions at

each time point was obtained by three repeated measurements.


2.8 Characterizations

SEM images were performed using JEOL JSM-6510

microscopy (Japan). The energy dispersive spectrum (EDS)

mappings were recorded on JEOL FE-SEM 6700 F (Japan).

Powder X-ray diffraction analysis was conducted using a Rigaku

D-Max 2550 diffractometer with Cu Kα radiation (λ = 0.15418

nm, 50 kV) (Japan). Inductively coupled plasma (ICP) analysis

was carried out on an iCAP 7000 SERIES ICP spectrometer

(US). Contact angle measurement was recorded using the Data-

Physics OCA20 machine at ambient temperature, and five

different positions were measured for each sample. The residual

oil content in the collected water was examined on an OIL480

infrared spectrometer oil content analyzer. The optical density

value was measured using Shimadzu UV-visible

spectrophotometer UV-1700 (Japan). A digital differential

pressure gauge (AS510, Smart Sensor) was used to measure the

intrusion pressure.

3 Results and discussion 3.1 Preparation of Ag@ZCMFs

The ZSM-5 coated mesh films (ZCMFs) were prepared on the

stainless-steel meshes by means of a secondary hydrothermal

growth process for different time. Chemical composition

analysis by ICP measurement indicates that the ZCMFs contain

Si, Al, and Na elements. Fig. 1a presents the scanning electron

microscope (SEM) image of the ZCMF after the secondary

growth of 14 h (ZCMF-14), revealing that the stainless-steel

fibers have been uniformly coated by the zeolite crystals. The

pin-holes are intentionally kept to facilitate the passage of liquid

during the oil-water separation process. The enlarged SEM

image (Fig. 1b) exhibits the rough surface of ZCMF-14

containing micro- and nano-scale geometries. The X-ray

diffraction (XRD) pattern of ZCMF-14 (red line in Fig. 1c) fits

well with that of the simulated the MFI structure (blue line in

Fig. 1c). The ICP measurement reveals that the Si/Al molar ratio

of ZCMF-14 reaches to 120, which is closed to that in the

precursor solution. In addition, 70% of the dissociative Na+ ions

in the channels of ZCMF-14 have been substituted by Ag+ ions

after ion exchange process. Fig. 2 gives the energy dispersive

spectrum (EDS) mappings of the resultant membrane

(Ag@ZCMF-14). It can be seen that silver element (green) is

homogeneously dispersed in the zeolite coating.

3.2 Wettability of Ag@ZCMF-14

The wettability of the ZCMF-14 and Ag@ZCMF-14 were

measured on a contact angle meter and the cyclohexane was used

as the detecting oil. In Fig. 3, ZCMF-14 and Ag@ZCMF-14 are

all superamphiphilic in air, and the water contact angle (WCA)

and oil contact angle (OCA) of them are close to 0°. When

immersed in aqueous media, both of ZCMF-14 and Ag@ZCMF-

14 exhibit superior repellence to the oil droplet, and the

underwater oil contact angles (θo/w) reach to 149.77° ± 1.16° and

151.27° ± 4.34°, respectively (Fig. 3c, f). These results indicate

that the loaded Ag+ ions in the zeolite channels has no influence

on the wettability of the membrane. Moreover, the measured θo/w

values of Ag@ZCMF-14 for a selection of oils are all above

130°, proving the extraordinary underwater oleophobicity of the

Fig. 1 (a, b) SEM images of ZCMF-14. Scale bar: (a) 50 μm;

(b) 5 μm. (c) XRD patterns of ZCMF-14 (red line) and simulated

MFI structure (blue line).

Fig. 2 EDS mapping analysis of Ag@ZCMF-14. (a) Ag (blue color),

(b) Si (green), (c) Al (purple), and (d) O (red). Scale bar: 25 μm.

Fig. 3 The WCAs of (a) ZCMF-14 and (d) Ag@ZCMF-14 in air. The

OCAs of (b) ZCMF-14 and (e) Ag@ZCMF-14 in air. The θo/w of (c)

ZCMF-14 and (f) Ag@ZCMF-14, in which cyclohexane (3 μL) was used

as the detecting oil. (g) The θo/w of Ag@ZCMF-14 for a selection of oils.


membrane (Fig. 3g).

3.3 Separation of oil-water mixtures

As is well-known that the water flux and intrusion pressure

are the key factors that determine the separation capacity of the

membranes, which can be adjusted by turning the diameter of

the pin-holes in the membrane. Fig. 4a gives the linear relation

between the average diameter of the pin-holes in Ag@ZCMFs

and the crystallization time. As seen that the diameter of the pin-

holes decreases from 35 to 5 μm with the extension of

crystallization time from 4 to 24 h, leading to the increase of

intrusion pressure from around 376.9 to 9356.7 Pa (red line in

Fig. 4b). Meanwhile, the water flux sharply decreases from

127656 to 1411 L·m−2·h−1 (black line Fig. 4b). To achieve the

balance between water flux and intrusion pressure, the secondary

hydrothermal growth of 14 h was considered to be optimum

crystallization time, giving rise to the average diameter of the

pin-holes in the membrane (Ag@ZCMF-14) of about 21 μm.

Compared with the separation parameters of the lately reported

membranes with superhydrophilicity/underwater superoleophobicity

(Table 1), Ag@ZCMF-14 exhibits higher separation efficiency

(99.98%), water flux (54720 L·m−2·h−1), and intrusion pressure

(4356.7 Pa) than most reported membranes 12,25,32,33,53–58.

The cyclohexane/water mixture was employed to demonstrate

the oil-water separation process, which was conducted on the

equipment in Fig. 5a. The Ag@ZCMF-14 squeezed in the

flanges was pre-wetted by a small amount of water. Then, a

mixture of cyclohexane (red, dyed by Sudan III) and water with

volume ratio of 1 : 1 was poured onto the membrane. The filtrate

was collected in the jar, in which there was no visible oil (red),

suggesting the successful separation of oil-water mixture by

Ag@ZCMF-14 (Fig. 5b).

The separation efficiency of Ag@ZCMF-14 was evaluated by

measuring the residual oil content in the filtrate. Based on the

underwater oleophobicity, only a trace amount of oil was

Fig. 4 (a) The relationship between the average diameter of the pin-holes and the crystallization time of Ag@ZCMFs. (b) Influence of the diameter of

the pin-holes of Ag@ZCMFs on water flux and intrusion pressure. Black line: water flux; Red line: intrusion pressure of cyclohexane.

Table 1 The separation parameter of Ag@ZCMF-14 compared with other oil/water separation membranes.

Substrate Sample Performance

Ref. Separation efficiency/% Flux/(L·m−2·h−1) Intrusion pressure/Pa

Stainless-steel mesh UiO-66 99.99 12.7 × 104 6600 Zhang et al., 2018 12

Stainless-steel mesh TiO2 99.9 13554 Du et al., 2017 52

Stainless-steel mesh Silicalite-1 96 Zeng et al., 2014 32

Stainless-steel mesh PAM Hydrogel 99 1000 Xue et al., 2011 24

Stainless-steel mesh Silicalite-1 90000 729 Wen et al., 2013 31

Stainless-steel mesh Graphene Oxide 98 Dong et al., 2014 53

Stainless-steel mesh NiOOH 98 Li et al., 2015 54

Stainless-steel mesh Glass nanofiber 99 (0.11–7.0) × 104 Ma et al., 2017 55

NiO Ni mesh 99 5.4 × 104 2352 Yu et al., 2017 56

woven carbon microfiber ZnO 99 20933.4 Wang et al., 2017 57

Stainless-steel mesh ZSM-5 99.98 54720 4357 This work

Fig. 5 Separation process of cyclohexane/water mixture. (a) The oil-

water mixture was poured onto the water pre-wetted Ag@ZCMF-14.

(b) Water selectively permeated through the membrane and the

cyclohexane (red color dyed by Sudan III) was retained.


detected after the separation processes and the corresponding

separation efficiencies for various oil-water mixtures were all

above 99% (Fig. 6a), indicating the good separation capability

of Ag@ZCMF-14. The recyclability of Ag@ZCMF-14 was also

tested by repeating separation process for ten times. After each

separation cycle, the membrane was heated at 150 °C for 0.5 h

to remove the residual liquid. The separation efficiency kept

stable and no obvious attenuation was observed during the 10

cycles of testing (Fig. 6b), proving a stable performance of

Ag@ZCMF-14 on oil-water separation. The chemical stability

of Ag@ZCMF-14 was investigated by immersing the membrane

into corrosive medium of 1 mol·L−1 HCl and 1 mol·L−1 NaCl for

48 h, respectively. Compared with the pristine Ag@ZCMF-14,

the zeolite structure (Fig. 7a), surface morphology (Fig. 7b, c),

and underwater wettability (Fig. 7e, f) of the membrane were

almost unchanged after the corrosion test, ascertaining the high

chemical stability. The mechanical durability of the Ag@ZCMF-

14 was evaluated by rubbing the membrane using the sand paper

(grit No.800) under the pressure of 2800 Pa 59. After the rubbing

test, the Ag@ZCMF-14 was polished and the peak intensity in

the XRD pattern decreased (Fig. 7a). But the membrane

remained underwater superhydrophobic (Fig. 7g), and no defects

were observed on the membrane (Fig. 7d), indicating the high

mechanical durability.

3.4 Anti-biofouling activity of Ag@ZCMFs

As is known that the breeding of the biological contaminants,

such as alga and bacteria, in operating environments may lead to

the blockage of the oil-water separation membranes. To test the

anti-biofouling activity, the inhibition performance of

Ag@ZCMF-14 toward the growth of chlorella was first

evaluated. The OD value at 540 nm was measured to ascertain

the concentration of chlorella in the solution. After the

incubation for 7 d, the difference on the OD values of the

chlorella solution, the solution with ZCMF-14 or Ag@ZCMF-

14 was not significant (Fig. 8a). When prolonging the incubation

time to 14 d, the OD values of the chlorella solution and the

solution with ZCMF-14 sharply increased. In contrary, the

almost unchanged OD value of the solution with Ag@ZCMF-14

Fig. 7 (a) The XRD patterns of Ag@ZCMF-14 after the

corrosion test and the rubbing test. (b–d) SEM images and

(e–g) θo/w of Ag@ZCMF-14 after the corrosion test and the

rubbing test, respectively. Scale bar: 5 μm.

Fig. 8 (a) The OD values of chlorella solutions incubated after 7 and

14 d, respectively. (b) The release behavior of Ag+ ions.

Fig. 6 (a) The separation efficiencies of Ag@ZCMF-14 for a selection oils. (b) The separation efficiencies of Ag@ZCMF-14 for the

cyclohexane/water mixture during ten purification-regeneration cycles.


indicated the excellent inhibiting ability of the membrane to the

breeding of chlorella. To test the stability of Ag+ ions in zeolites,

we measured the time-dependent release behavior of Ag+ ions in

the solutions (Fig. 8b). The concentration of Ag+ ions in the

solution sharply increased in the first two days, and then kept

stable. The released quantity was about 5.0% of the total Ag+

ions in zeolites.

The agar diffusion method was employed to test the

bacteriostatic effect of the Ag@ZCMF-14, and the E. coli was

selected as the representative target bacteria. Compared with

ZCMF-14, a clear circular inhibition zone was observed around

Ag@ZCMF-14 with diameter of about 0.15 cm (Fig. 9a, b). Fig.

9c gives the bacterial dynamics curves of Ag@ZCMF-14 and

ZCMF-14, which obviously demonstrate the inhibition effect of

Ag@ZCMF-14 on the growth of bacteria, giving the

bacteriostatic rate of 99.6%. It is because that the Ag+ ions can

disrupt the cell membrane integrity, generate reactive oxygen

species (ROS), which will cause cell damage and eventually

limit the growth of bacteria 5,60–62. These results confirm the high

anti-biofouling activity of the Ag@ZCMF-14.

4 Conclusions In summary, the ZSM-5 zeolite coated mesh films have been

fabricated by a seeding and secondary hydrothermal growth

process, and then the Ag+ ions are loaded in the membranes by

means of ion exchange. The resultant membrane with secondary

growth time of 14 h (Ag@ZCMF-14) can achieve the efficient

separation of various oil-water mixtures in terms of their

superhydrophilicity/underwater superoleophobicity. The

Ag@ZCMF-14 exhibits excellent chemical and mechanical

stability. The separation efficiency remains stable during ten

purification-regeneration cycles, proving superior separation

stability of Ag@ZCMF-14. Furthermore, Ag@ZCMFs can

effectively inhibit the growth of alga and bacteria in the

operating environments, and prevent the membrane from being

blocked by the biological contaminants. These results

demonstrate that Ag@ZCMFs with anti-biofouling activity hold

promising potentials in future practical applications for the

removal of oil slicks from the oily wastewater.

References

(1) Kota, A. K.; Kwon, G.; Choi, W.; Mabry, J. M.; Tuteja, A. Nat.

Commun. 2012, 3, 1025. doi: 10.1038/ncomms2027

(2) Kota, A. K.; Li, Y.; Mabry, J. M.; Tuteja, A. Adv. Mater. 2012, 24

(43), 5838. doi: 10.1002/adma.201202554

(3) Kwon, G.; Kota, A. K.; Li, Y.; Sohani, A.; Mabry, J. M.; Tuteja, A.

Adv. Mater. 2012, 24 (27), 3666. doi: 10.1002/adma.201201364

(4) Wang, Y.; Di, J.; Wang, L.; Li, X.; Wang, N.; Wang, B.; Tian, Y.;

Jiang, L.; Yu, J. Nat. Commun. 2017, 8 (1), 575.

doi: 10.1038/s41467-017-00474-y

(5) Zhao, Y. H.; Zhang, M.; Wang, Z. K. Adv. Mater. Interfaces 2016, 3

(13), 1500664. doi: 10.1002/admi.201500664

(6) Field, R. W. Nature 2012, 489 (7414), 41. doi: 10.1038/489041a

(7) Ge, J.; Ye, Y. D.; Yao, H. B.; Zhu, X.; Wang, X.; Wu, L.; Wang, J. L.;

Ding, H.; Yong, N.; He, L. H.; et al. Angew. Chem. Int. Edit. 2014, 53

(14), 3612. doi: 10.1002/anie.201310151

(8) Li, J.; Zhao, Z. H.; Shen, Y. Q.; Feng, H.; Yang, Y. X.; Zha, F. Adv.

Mater. Interfaces 2017, 4 (16), 1700364.

doi: 10.1002/admi.201700364

(9) Ge, J.; Jin, Q.; Zong, D.; Yu, J.; Ding, B. ACS Appl. Mater. Inter.

2018, 10 (18), 16183. doi: 10.1021/acsami.8b01952

(10) Zhang, Z.; Zhang, Y.; Fan, H.; Wang, Y.; Zhou, C.; Ren, F.; Wu, S.;

Li, G.; Hu, Y.; Li, J.; Wu, D.; Chu, J. Nanoscale 2017, 9 (41), 15796.

doi: 10.1039/c7nr03829a

(11) Mousavi, S. H.; Ghadiri, M.; Buckley, M. Chem. Eng. Sci. 2014, 120,

130. doi: 10.1016/j.ces.2014.08.055

(12) Zhang, X.; Zhao, Y.; Mu, S.; Jiang, C.; Song, M.; Fang, Q.; Xue, M.;

Qiu, S.; Chen, B. ACS Appl. Mater. Inter. 2018, 10 (20), 17301.

doi: 10.1021/acsami.8b05137

(13) Zhou, W.; Li, S.; Liu, Y.; Xu, Z.; Wei, S.; Wang, G.; Lian, J.; Jiang, Q.

ACS Appl. Mater. Inter. 2018, 10 (11), 9841.

doi: 10.1021/acsami.7b19853

(14) Ge, J. L.; Zong, D. D.; Jin, Q.; Yu, J. Y.; Ding, B. Adv. Funct. Mater.

2018, 28 (10), 1705051. doi: 10.1002/adfm.201705051

(15) Lv, W. Y.; Mei, Q. Q.; Xiao, J. L.; Du, M.; Zheng, Q. Adv. Funct.

Mater. 2017, 27 (48), 1704293. doi: 10.1002/adfm.201704293

(16) Li, W.; Yong, J.; Yang, Q.; Chen, F.; Fang, Y.; Hou, X. Acta

Phys. -Chim. Sin. 2018, 34 (5), 456. [李文涛, 雍佳乐, 杨青, 陈烽,

方瑶, 侯洵. 物理化学学报, 2018, 34 (5), 456.]

doi: 10.3866/PKU.WHXB201709211

(17) Zhu, Q.; Chu, Y.; Wang, Z. K.; Chen, N.; Lin, L.; Liu, F. T.; Pan, Q.

Fig. 9 Digital images of inhibition zones of (a) ZCMF-14 and

(b) Ag@ZCMF-14. (c) The bacterial dynamics curve in liquid

medium of E. coli.


M. J. Mater. Chem. A 2013, 1 (17), 5386. doi: 10.1039/c3ta00125c

(18) Calcagnile, P.; Fragouli, D.; Bayer, I. S.; Anyfantis, G. C.;

Martiradonna, L.; Cozzoli, P. D.; Cingolani, R.; Athanassiou, A. ACS

Nano 2012, 6 (6), 5413. doi: 10.1021/nn3012948

(19) Zhang, W.; Zhu, Y.; Liu, X.; Wang, D.; Li, J.; Jiang, L.; Jin, J. Angew.

Chem. Int. Edit. 2014, 53 (3), 856. doi: 10.1002/anie.201308183

(20) Liu, J.; Wang, L.; Wang, N.; Guo, F.; Hou, L.; Chen, Y.; Liu, J.; Zhao,

Y.; Jiang, L. Small 2017, 13 (4), 1600499.

doi: 10.1002/smll.201600499

(21) Wen, L.; Tian, Y.; Jiang, L. Angew. Chem. Int. Edit. 2015, 54 (11),

3387. doi: 10.1002/anie.201409911

(22) Su, B.; Tian, Y.; Jiang, L. J. Am. Chem. Soc. 2016, 138 (6), 1727.

doi: 10.1021/jacs.5b12728

(23) Zheng, S.; Wang, D.; Tian, Y.; Jiang, L. Adv. Funct. Mater. 2016, 26

(48), 9018. doi: 10.1002/adfm.201602843

(24) Li, Y.; Wang, J. D.; Fan, L. N.; Chen, D. R. Acta Phys. -Chim. Sin.

2016, 32 (4), 990. [李杨, 汪家道, 樊丽宁, 陈大融. 物理化学学报,

2016, 32 (4), 990.] doi: 10.3866/PKU.WHXB201601131

(25) Xue, Z. X.; Wang, S. T.; Lin, L.; Chen, L.; Liu, M. J.; Feng, L.; Jiang,

L. Adv. Mater. 2011, 23 (37), 4270. doi: 10.1002/adma.201102616

(26) Zhang, F.; Zhang, W. B.; Shi, Z.; Wang, D.; Jin, J.; Jiang, L. Adv.

Mater. 2013, 25 (30), 4192. doi: 10.1002/adma.201301480

(27) Gao, X.; Xu, L. P.; Xue, Z.; Feng, L.; Peng, J.; Wen, Y.; Wang, S.;

Zhang, X. Adv. Mater. 2014, 26 (11), 1771.

doi: 10.1002/adma.201304487

(28) Tao, M.; Xue, L.; Liu, F.; Jiang, L. Adv. Mater. 2014, 26 (18), 2943.

doi: 10.1002/adma.201305112

(29) Liu, N.; Lin, X.; Zhang, W.; Cao, Y.; Chen, Y.; Feng, L.; Wei, Y. Sci.

Rep. 2015, 5, 9688. doi: 10.1038/srep09688

(30) Liu, X.; Leng, C.; Yu, L.; He, K.; Brown, L. J.; Chen, Z.; Cho, J.;

Wang, D. Angew. Chem. Int. Edit. 2015, 54 (16), 4851.

doi: 10.1002/anie.201411992

(31) Manna, U.; Lynn, D. M. Adv. Funct. Mater. 2015, 25 (11), 1672.

doi: 10.1002/adfm.201403735

(32) Wen, Q.; Di, J. C.; Jiang, L.; Yu, J. H.; Xu, R. R. Chem. Sci. 2013, 4

(2), 591. doi: 10.1039/c2sc21772d

(33) Zeng, J. W.; Guo, Z. G. Colloid Surface. A 2014, 444, 283.

doi: 10.1016/j.colsurfa.2013.12.071

(34) Zhang, X. K.; Li, H.; Miao, W. Z.; Shen, Q.; Wang, J.; Peng, D. L.;

Liu, J. D.; Zhang, Y. T. Aiche J. 2019, 65 (6), e16596.

doi: 10.1002/aic.16596

(35) He, K.; Duan, H.; Chen, G. Y.; Liu, X.; Yang, W.; Wang, D. ACS

Nano 2015, 9 (9), 9188. doi: 10.1021/acsnano.5b03791

(36) Chu, Z.; Feng, Y.; Seeger, S. Angew. Chem. Int. Edit. 2015, 54 (8),

2328. doi: 10.1002/anie.201405785

(37) Muthukumar, K.; Kaleekkal, N. J.; Lakshmi, D. S.; Srivastava, S.;

Bajaj, H. J. Appl. Polym. Sci. 2019, 136 (24), 47641.

doi: 10.1002/app.47641

(38) Lin, X.; Yang, M.; Jeong, H.; Chang, M.; Hong, J. J. Membrane. Sci.

2016, 506, 22. doi: 10.1016/j.memsci.2016.01.035

(39) Zhang, Q.; Chen, G. R.; Wang, Y. Y.; Chen, M. Y.; Guo, G. Q.; Shi, J.;

Luo, J.; Yu, J. H. Chem. Mater. 2018, 30 (8), 2750.

doi: 10.1021/acs.chemmater.8b00527

(40) Wang, N.; Sun, Q.; Bai, R.; Li, X.; Guo, G.; Yu, J. J. Am. Chem. Soc.

2016, 138 (24), 7484. doi: 10.1021/jacs.6b03518

(41) Zhang, Q.; Mayoral, A.; Terasaki, O.; Zhang, Q.; Ma, B.; Zhao, C.;

Yang, G.; Yu, J. J. Am. Chem. Soc. 2019, 141 (9), 3772.

doi: 10.1021/jacs.8b11734

(42) Wang, Z.; Yu, J.; Xu, R. Chem. Soc. Rev. 2012, 41 (5), 1729.

doi: 10.1039/c1cs15150a

(43) Li, Y.; Li, X.; Liu, J.; Duan, F.; Yu, J. Nat. Commun. 2015, 6, 8328.

doi: 10.1038/ncomms9328

(44) Feng, G.; Cheng, P.; Yan, W.; Boronat, M.; Li, X.; Su, J. H.; Wang, J.;

Li, Y.; Corma, A.; Xu, R.; et al. Science 2016, 351 (6278), 1188.

doi: 10.1126/science.aaf1559

(45) Li, Y.; Li, L.; Yu, J. H. Chem 2017, 3 (6), 928.

doi: 10.1016/j.chempr.2017.10.009

(46) Wang, S.; Li, R. Y.; Li, D. D.; Zhang, Z. Y.; Liu, G. C.; Liang, H. J.;

Qin, Y. G.; Yu, J. H.; Li, Y. Y. J. Mater. Chem. B 2018, 6 (20), 3254.

doi: 10.1039/c8tb00328a

(47) Singh, V. V.; Jurado-Sanchez, B.; Sattayasamitsathit, S.; Orozco, J.;

Li, J. X.; Galarnyk, M.; Fedorak, Y.; Wang, J. Adv. Funct. Mater.

2015, 25 (14), 2147. doi: 10.1002/adfm.201500033

(48) Wang, J. C.; Wang, Z. P.; Guo, S.; Zhang, J. Y.; Song, Y.; Dong, X.

M.; Wang, X. N.; Yu, J. H. Micropor. Mesopor. Mat. 2011, 146 (1–3),

216. doi: 10.1016/j.micromeso.2011.04.005

(49) Tekin, R.; Bac, N. Micropor. Mesopor. Mat. 2016, 234, 55.

doi: 10.1016/j.micromeso.2016.07.006

(50) Yuan, Z.; Zhu, X.; Li, M.; Lu, W.; Li, X.; Zhang, H. Angew. Chem.

Int. Edit. 2016, 55 (9), 3058. doi: 10.1002/anie.201510849

(51) Wang, C. Y.; Wu, S. Y.; Jian, M. Q.; Xie, J. R.; Xu, L. P.; Yang, X. D.;

Zheng, Q. S.; Zhang, Y. Y. Nano Res. 2016, 9 (9), 2597.

doi: 10.1007/s12274-016-1145-3

(52) Xiong, Z. -C.; Yang, R. -L.; Zhu, Y. -J.; Chen, F. -F.; Dong, L. -Y.

J. Mater. Chem. A 2017, 5 (33), 17482. doi: 10.1039/c7ta03870d

(53) Du, X.; You, S.; Wang, X.; Wang, Q.; Lu, J. Chem. Eng. J. 2017, 313,

398. doi: 10.1016/j.cej.2016.12.092

(54) Dong, Y.; Li, J.; Shi, L.; Wang, X.; Guo, Z.; Liu, W. Chem. Commun.

2014, 50 (42), 5586. doi: 10.1039/c4cc01408a

(55) Li, J.; Cheng, H. M.; Chan, C. Y.; Ng, P. F.; Chen, L.; Fei, B.; Xin, J.

H. RSC Adv. 2015, 5 (64), 51537. doi: 10.1039/c5ra06118k

(56) Ma, Q.; Cheng, H.; Yu, Y.; Huang, Y.; Lu, Q.; Han, S.; Chen, J.;


Wang, R.; Fane, A. G.; Zhang, H. Small 2017, 13 (19), 1700391.

doi: 10.1002/smll.201700391

(57) Yu, Z.; Yun, F. F.; Gong, Z.; Yao, Q.; Dou, S.; Liu, K.; Jiang, L.;

Wang, X. J. Mater. Chem. A 2017, 5 (22), 10821.

doi: 10.1039/c7ta01987d

(58) Wang, K.; Han, D. S.; Yiming, W.; Ahzi, S.; Abdel-Wahab, A.; Liu, Z.

Sci. Rep. 2017, 7, 16081. doi: 10.1038/s41598-017-16402-5

(59) Xu, Z.; Zhu, Z.; Li, N.; Tian, Y.; Jiang, L. ACS Nano 2018, 12 (10),

10000. doi: 10.1021/acsnano.8b04328

(60) Liu, J.; Sonshine, D. A.; Shervani, S.; Hurt, R. H. ACS Nano 2010, 4

(11), 6903. doi: 10.1021/nn102272n

(61) AshaRani, P. V.; Mun, G. L. K.; Hande, M. P.; Valiyaveettil, S. ACS

Nano 2009, 3 (2), 279. doi: 10.1021/nn800596w

(62) Carlson, C.; Hussain, S. M.; Schrand, A. M.; Braydich-Stolle, L. K.;

Hess, K. L.; Jones, R. L.; Schlager, J. J. J. Phys. Chem. B 2008, 112

(43), 13608. doi: 10.1021/jp712087m

zeolite-coated anti-biofouling mesh film for efficient oil

Documents