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Superhydrophobic/Superoleophilic Polycarbonate/Carbon Nanotubes Porous Monolith for Selective Oil Adsorption from Water Zhenzhen Li, Bo Wang, Xiuming Qin, Yingke Wang, Chuntai Liu, Qian Shao, Ning Wang, Jiaoxia Zhang, Changyu Shen, and Zhanhu Guo ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b01637 • Publication Date (Web): 11 Sep 2018 Downloaded from http://pubs.acs.org on September 12, 2018

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ACS Sustainable Chemistry & Engineering

Superhydrophobic/Superoleophilic Polycarbonate/Carbon Nanotubes Porous Monolith for Selective Oil Adsorption from Water

†

Zhenzhen Li, Bo Wang,*,† Xiuming Qin,† Yingke Wang,† Chuntai Liu,*,† Qian Shao,∆ Ning Wang,¥ Jiaoxia Zhang,‡,& Zikang Wang,€ Changyu Shen,† and Zhanhu Guo*,‡

†

College of Materials Science and Engineering, National Engineering Research Center for

Advanced Polymer Processing Technology, Zhengzhou University, Zhengzhou, Henan 450001, China ‡

Integrated Composites Laboratory (ICL), Department of Chemical & Biomolecular Engineering, University of Tennessee, Knoxville, Tennessee 37996, USA ∆

College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao, Shandong 266590, China

¥

State Key Laboratory of Marine Resource Utilization in South China Sea, Hainan University, Haikou, Hainan 570228, China

&

School of Material Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang, Jiangsu 212003, China

€

College of Eco-environmental Engineering, Guizhou Minzu University, Guiyang, Guizhou 550025, China

*

Corresponding Authors E-mail: [email protected] (B.W.); [email protected] (C.L.); [email protected] (Z.G.). 1 ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering 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

ABSTRACT:

A

superhydrophobic/superoleophilic

porous

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polycarbonate/carboxyl-

functionalized multiwalled carbon nanotubes (PC/cMWCNTs) monolith with novel hierarchical micro-nanostructure was facilely fabricated via thermally impacted nonsolvent induced phase separation method. Novel porous microstructure endowed PC/cMWCNTs monolith with a high porosity of 90.1%. Based on excellent superhydrophobicity (water contact angle of 159°) and superoleophilicity (oil contact angle of 0°), this porous monolith could selectively adsorb various types of oils/organic solvents from oil-water mixture. Additionally, the monolith exhibited outstanding oil/water separation performance including fast adsorption speed, high saturation capacity and superior recycling ability. The equilibrium adsorption time and saturated adsorption capacity of soybean oil were 20 s and 12.62 g g-1, respectively. By simple centrifugation or evaporation, the recovered PC/cMWCNTs monolith could be reused for at least 10 cycles. Thus, porous PC/cMWCNTs monolith is a promising candidate for oil-polluted water treatment. KEYWORDS: porous monolith, phase separation, polycarbonate, multiwalled carbon nanotube, superhydrophobicity, oil/water separation.

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INTRODUCTION Nowadays, the environmental and ecological damages resulted from oil spill and chemical (such as heavy metal or organic dyes) leakage/disposal have been an area of great concern on a global scale.1-20 To conquer the worldwide challenge, multifarious approaches including chemical dispersant, oil skimmer, adsorbent, in-situ burning, and hydrocarbon-degrading microorganism are used to deal with water pollution.21-26 Among all these methods, adsorption is considered as the most economical and efficient choice due to low cost, simple operation and prevention of secondary pollution. However, most of conventional adsorption materials cannot meet the demand of oil/water separation application, such as low separation efficiency, poor recyclability, and so on.27-30 Thus, the development of new adsorption materials for oil-polluted water treatment is of great significance.31-35 Porous polymer-based monoliths with outstanding hydrophobicity, a new type of adsorption material, are attracting increasing attention in academic field because they are a promising candidate for the removal of oil and organic solvent from water.36 For example, Liu et al. prepared biodegradable polylactic acid porous monoliths as effective sorbents for collecting oil on water surface.37 Fang et al. fabricated porous polymeric composite monoliths with superior performances in oil-water separation.38 Our previous study also reported a porous polycarbonate (PC, a typical engineering plastics39,40) monolith with good hydrophobicity, oil adsorbability and self-cleaning ability, which could be used for oil/water separation.41 In order to endow PC monolith with superhydrophobicity and superoleophilicity so as to further improve its separation efficiency, tailoring pore structure using multiwalled carbon nanotubes (MWCNTs, with unique 3 ACS Paragon Plus Environment


structure and remarkable mechanical property) during the preparation of monolith is expected to be an effective pathway,42-44 and has not been reported yet. In this work, carboxyl-functionalized multiwalled carbon nanotubes (cMWCNTs) were chosen on account of their good dispersion in organic solvents and strong interaction with PC.45-47 A three-dimensional porous PC/cMWCNTs monolith with novel hierarchical micro-nanostructure was facilely fabricated by thermally impacted nonsolvent induced phase separation (TINIPS) method.48-50 The effect of cMWCNTs on the microstructure of porous monolith was comparatively investigated. The wetting characteristics of PC/cMWCNTs monolith was measured to confirm its superhydrophobicity and superoleophilicity. The oil/water separation properties of monolith were systematically characterized.

EXPERIMENTAL SECTION Materials PC granules (Wonderlite PC-110 with a density of 1.20 g/cm3) were purchased from Chi Mei Corporation, Taiwan. cMWCNTs with a length of 10-30 µm, outer diameter of 10-20 nm and carboxyl content of 2.00 wt % were supplied by Chengdu Organic Chemicals Co., Ltd., China. Tetrahydrofuran (THF), tetrachloromethane, n-hexane, octane and cyclohexane were obtained from Tianjin Fuyu Fine Chemical Co., Ltd., China. Deionized water, oils, colouring agents, hydrochloric acid (HCl) and sodium hydroxide (NaOH) were used as received. Preparation of Porous PC/cMWCNTs Monolith Figure 1 schematically shows the preparation procedure of PC/cMWCNTs monolith. A weighed amount of cMWCNTs (28 mg) was firstly mixed into tetrahydrofuran (40 mL) and 4 ACS Paragon Plus Environment

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subjected to ultrasonication for 30 min. PC granules (2.8 g) were dissolved in the mixture by magnetic stirring at 40 oC to form homogeneous solution. When the solution was cooled down to room temperature, deionized water as nonsolvent (2.7 mL) was added dropwise using an injection syringe under vigorous stirring. Subsequently, the resulting liquid was poured into glass tube and kept at 4 oC in a refrigerator. After 24 h, a black porous monolith was formed by phase separation process. Deionized water was used to replace the residual solvent in porous monolith by immersion method for 72 h (deionized water was changed at least 3 times every 24 h). Eventually, PC/cMWCNTs monolith was obtained by vacuum freeze-drying at -90 oC for 48 h. On the basis of the same procedure, porous monoliths with four kinds of cMWCNTs loadings (1, 2, 3 and 4 wt % relative to PC weight) were fabricated. Due to lower cost and superior performance of the 1 wt % monolith, the following is focused on this sample.

Figure 1. Preparation procedure of porous PC/cMWCNTs monolith. 5 ACS Paragon Plus Environment


Characterization Fourier transform infrared spectroscopy (FTIR) was carried out by a Nicolet iS50 device in the wavenumber range of 650-4000 cm-1. The scan times and spectral resolution were 32 and 4 cm-1, respectively. Thermogravimetric analysis (TGA) was implemented on a TA Instruments Q50 analyzer with a heating rate of 20 oC/min under nitrogen protection. The morphology of porous PC/cMWCNTs monolith was observed by a field emission scanning electron microscope (FE-SEM, JEOL JSM-7500F) at an acceleration voltage of 5 kV. Before observation, the sample cut from the center of monolith with a blade was sputter-coated with a layer of gold. Nitrogen adsorption/desorption isotherms were obtained using a Micromeritics ASAP 2460 surface area and porosity analyzer at 77 K. Sample was degassed under vacuum at 100 oC for 10 h prior to measurement. Specific surface area and pore size distribution were determined by the Brunauer-Emmett-Teller (BET) method and Barret-Joyner-Halenda (BJH) method, respectively. Porosity measurement (mercury porosimetry) was performed on a Quantachrome PoreMaster-60 instrument with the test pressure range from 0.1 to 60000 psia. Contact angles (CA) of water and oil were measured using a Powereach JC2000C instrument at ambient temperature. At least five points of monolith cross section were tested to guarantee data accuracy. Adsorption kinetics was investigated by placing a monolith onto the surface of soybean oil in a beaker and then measuring the weight of monolith at different time intervals until equilibrium 6 ACS Paragon Plus Environment

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point was reached. The saturation adsorption capacities of porous monolith were determined at ambient temperature. Firstly, 50 mL oil or organic solvent was poured into a 100 mL beaker, and a weighed amount of porous monolith was put into the beaker for 3 min. After that, the porous monolith was taken out. When the residual surface liquid dripped off (holding for 15 s), the saturated monolith was weighed. Saturation adsorption capacity can be calculated by eq 1: Qm = (M1 – M0)/M0

(1)

where Qm is the saturated adsorption capacity, M0 and M1 are the initial weight and the final weight after saturation, respectively. The recyclability of porous PC/cMWCNTs monolith was tested via evaporation for organic solvent or centrifugation for oil. The process parameters of centrifugation and evaporation were 1000 rpm for 2 min and 40 °C for 30 min, respectively. 10 cycles were performed in the experiments.

RESULTS AND DISCUSSION Structure Analysis: Figure 2 shows the FTIR spectra of PC, cMWCNTs and porous PC/cMWCNTs monolith. For PC, some typical characteristic peaks are observed. The absorption peaks at 2968, 1772 and 1507 cm-1 are attributed to the stretching vibrations of C–H (methyl), C=O, and C–C (phenyl) groups, respectively. The absorption peaks at 1235, 1190 and 1161 cm-1 are all ascribed to C–O stretching vibration. Compared to PC, two characteristic peaks belonging to cMWCNT, including O–H stretching vibration at 3440 cm-1 and C=C stretching vibration at 1630 cm-1,51 are found in the spectrum of PC/cMWCNTs monolith. The FTIR results 7 ACS Paragon Plus Environment


demonstrate the presence of cMWCNTs in the monolith. In addition, no other new characteristic peak in PC/cMWCNTs monolith indicates that there is no chemical reaction between cMWCNTs and PC during the phase separation. TGA was performed to further confirm the cMWCNTs composition in the composite monolith. Figure S1 shows the TGA curves of pure PC monolith (studied in our previous work41) and PC/cMWCNTs monolith. Compared to pure PC monolith, the onset degradation temperature and the residue weight at 700 oC of PC/cMWCNTs monolith increase by 19.4 oC and 18.2%, respectively. This is ascribed to the incorporation of cMWCNTs.

Figure 2. The FTIR results of PC, cMWCNTs and porous PC/cMWCNTs monolith. Morphology Observation: The SEM images of porous PC/cMWCNTs monolith are shown in Figure 3. Interestingly, a novel hierarchical micro-nanostructure is observed. At low magnification (micron scale), the PC/cMWCNTs monolith possesses coral-like morphology composed of plentiful stacked granules with diameter of 3-12 µm (Figure 3a1). At high magnification (nanometer scale), the micron-scaled granules are constituted of interconnected 8 ACS Paragon Plus Environment

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nest-like pore structure (Figure 3a2). The average pore size measured by Nano Measurer software is 218 nm. Furthermore, no exposed cMWCNTs are found on the surface of porous skeleton, indicating that cMWCNTs are entirely encapsulated into PC fiber-like skeleton. In order to understand the effects of cMWCNTs on the microstructure and properties of porous monolith, pure PC monolith studied in our previous work41 was comparatively investigated (Table S1). As shown in Figure 3b1&b2, the morphology of pure PC monolith exhibits a homogeneous nest-like porous structure constituted of nanofiber network. Obviously, there is a significant morphology difference between both monoliths. This indicates that adding a small number of cMWCNTs (1 wt % relative to the weight of PC) can not only tailor pore and skeleton sizes due to their supporting effect,43,44 but also generate hierarchical structures owing to complicated interactions among cMWCNTs, PC and solvent system (such as π-π stacking and hydrogen bond interactions between PC and cMWCNTs) during the phase separation process.



Figure 3. SEM images of PC/cMWCNTs monolith (a) and pure PC monolith (b) at different magnifications. Evaluation of Porous Feature: Nitrogen adsorption/desorption analysis was carried out to further evaluate the porous feature of PC/cMWCNTs monolith. In Figure 4, the type of isothermal curve is type IV, manifesting the presence of mesopores.52,53 The hysteresis loop is attributed to capillary condensation occurring in the mesopores.54 The pore size distribution (see inset) is mainly in the range of 2-110 nm, and a peak position appears at about 23 nm. Based on the pore size information obtained from both nitrogen adsorption-desorption analysis and SEM observation, the PC/cMWCNTs monolith owns a broad pore size distribution (abundant mesopores and macropores). The specific surface area derived from BET method is 82.26 m2/g. 10 ACS Paragon Plus Environment

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Moreover, due to well-formed porous structure, the PC/cMWCNTs monolith possesses a high porosity of 90.1%.

Figure 4. N2 adsorption/desorption isothermal curve and pore size distribution curve (inset) of porous PC/cMWCNTs monolith. Wetting Characteristics: Wettability is a key characteristic of adsorption materials used for oil/water separation. Thus, the water and oil contact angles of porous PC/cMWCNTs monolith were measured to evaluate its hydrophobic and oleophilic properties. As shown in Figure 5a,b, the water droplets (coloured with potassium permanganate) remain completely spherical on monolith cross section, and the water contact angle of cross section is 159°. The excellent superhydrophobicity of PC/cMWCNTs monolith is attributed to its novel hierarchical micro-nanostructure. The unique microstructure can increase surface roughness and provide numerous microscopic pores serving as contact barrier between water and monolith.55 The wettability of monolith for soybean oil is presented in Figure 5c,d. The oil contact angle of 11 ACS Paragon Plus Environment


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monolith cross section is 0° and the monolith fully and rapidly adsorbs oil droplets due to capillary

force,56

showing

outstanding

superoleophilicity.

Additionally,

the

side

of

PC/cMWCNTs monolith also possesses prominent water repellency. When the PC/cMWCNTs monolith is tilted, water droplets quickly roll off monolith side (Figure 5e). In Figure 5f,g, the porous monolith is partly or totally immersed in water. Mirror-like phenomenon is clearly seen on the surface of monolith, suggesting superior hydrophobicity.57 It can be explained by the light refraction occurring at the interface between air and water encompassing monolith surface. Furthermore, the water contact angles of PC/cMWCNTs monoliths with different cMWCNTs loadings were comparatively studied. As shown in Figure S2, all of the water contact angles are more than 158°, showing excellent superhydrophobic property. With the increase of cMWCNTs loading, the maximum value of water contact angle appears at 3 wt %.


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Figure 5. (a) Digital photograph of the water droplets (coloured with potassium permanganate) on monolith cross section; (b) water CA; (c) wettability of porous monolith for soybean oil; (d) oil CA; (e) digital photograph of the water droplets rolling off monolith side; (f-g) digital photographs of porous monolith partly or totally immersed in water. From the point of practical applications, the superhydrophobic stability of porous PC/cMWCNTs monolith was investigated under different pH conditions. The contact angles of water droplets with different pH values (1-14) are displayed in Figure 6. All the water contact angles are observed to be greater than 157°, indicating very stable superhydrophobicity of the PC/cMWCNTs monolith.58 Hence, the PC/cMWCNTs monolith can be used for oil-polluted 13 ACS Paragon Plus Environment


water treatment in corrosive environments.

Figure 6. Water contact angles of porous PC/cMWCNTs monolith under different pH conditions. Selective Oil/Water Separation: The ability of porous PC/cMWCNTs monolith to selectively adsorb oil or organic solvent from water was evaluated by oil/water separation experiments, as shown in Figure 7. After being placed on the surface of oil/water mixture, the porous monolith rapidly adsorbs the soybean oil (dyed with Sudan III) on water surface under capillary force. The soybean oil spontaneously penetrates into the pores of monolith and disappears completely in 12 s (Figure 7a1-a3 and Movie S1). Due to lower density and superior hydrophobicity, the oil-filled PC/cMWCNTs monolith remains floated on water surface, which is in favor of oil-polluted water treatment. In addition, the monolith has the ability to selectively adsorb underwater organic solvent or oil. In Figure 7b1-b3, underwater tetrachloromethane (dyed with Sudan III) is quickly adsorbed by porous monolith, during which water is completely excluded by superhydrophobic surface of monolith. These results indicate that the PC/cMWCNTs monolith possesses 14 ACS Paragon Plus Environment

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tremendous potential in oil/water separation application.

Figure 7. Selective separation processes of soybean oil on water surface (a1-a3) and tetrachloromethane under water (b1-b3) (soybean oil and tetrachloromethane are dyed with Sudan III). Oil Adsorption Performance: Adsorption kinetics was measured to estimate the adsorption rate of porous PC/cMWCNTs monolith. The adsorption capacity (Qt) for soybean oil is plotted as a function of adsorption time (t) in Figure 8. With the increase of adsorption time, the adsorption capacity increases rapidly until a saturated state is reached within 20 s, implying a very fast adsorption process. To explicitly describe the adsorption kinetic process, a pseudo-first-order kinetics model is selected following eq 2:59 ln(Qm – Qt) = lnQm – Kt 15 ACS Paragon Plus Environment

(2)


where K is the adsorption constant, t is the adsorption time, Qm is the saturated adsorption capacity, and Qt is the adsorption capacity at time t. The linear regression plot of ln(Qm – Qt) versus t is shown in the inset. The fitting result (R2 = 0.994) demonstrates that the adsorption kinetic process follows eq 2. The K value obtained from the slope of regression line is 0.343, which is comparable to that of reported porous polylactic acid/reduced graphene oxide monolith.37 The fast adsorption rate of PC/cMWCNTs monolith is mainly ascribed to its superoleophilicity, broad pore size distribution and large specific surface area.

Figure 8. Adsorption capacity as a function of adsorption time and adsorption kinetics model (inset) for soybean oil. The saturation adsorption capacities of PC/cMWCNTs monolith for various organic solvents and oils are shown in Figure 9. The Qm values of pump oil, soybean oil, gasoline, n-hexane, octane and cyclohexane are 10.48, 12.62, 9.09, 8.06, 8.61 and 9.21 g g-1, respectively. The saturation adsorption capacity depends on the density and viscosity of these liquids.60-62 During 16 ACS Paragon Plus Environment

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adsorption process, the oils and organic solvents diffuse gradually into the three-dimensional interconnected pores in monolith and occupy the pore volume. Therefore, the high saturated adsorption capability of PC/cMWCNTs monolith is mainly attributed to its large porosity. The comparison of Qm values between PC/cMWCNTs monolith and multifarious oil sorbents reported before is listed in Table S2. It is obvious that the PC/cMWCNTs monolith owns superior saturated adsorption capacity.

Figure 9. Saturation adsorption capacities of PC/cMWCNTs monolith for various organic solvents and oils. Recyclability: The recyclability of porous PC/cMWCNTs monolith is of great significance because it not only determines service life but also saves resources. As shown in Figure S3, the PC/cMWCNTs monolith can endure 400 times of its bulk weight without any deformation, indicating that it has good mechanical property for recycling. The recycling performance for different oils by adsorption/centrifugation is shown in Figure 10a. On the whole, the PC/cMWCNTs monolith exhibits analogous recyclable adsorption behavior. With increasing the 17 ACS Paragon Plus Environment


cycle, the saturated adsorption capacity decreases and achieves a relatively stable state. It should be noted that the biggest reductions in saturation adsorption capacity all occur in the second cycle. This is ascribed to the fact that the high viscosity of these oils results in a strong adhesion between oil and monolith, thus impeding the complete removal of the oils inside the porous monolith by centrifugation.63 The saturation adsorption capacity still maintains 4.58-6.24 g g-1 after 10 cycles. The recyclable use for different organic solvents by adsorption/evaporation is depicted in Figure 10b. During 10 cycles, no obvious change in saturation adsorption capacity is found. Based on the above results, the porous PC/cMWCNTs monolith possesses good recyclability.

Figure 10. Recyclability of porous PC/cMWCNTs monolith for various oils by centrifugation (a) and organic solvents by evaporation (b).

CONCLUSION A porous PC/cMWCNTs monolith with novel hierarchical micro-nanostructure was facilely prepared by TINIPS method without any template or complicated equipment. Owing to unique porous structure, the monolith owns superhydrophobicity and superoleophilicity so that it can 18 ACS Paragon Plus Environment

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selectively adsorb various oils and organic solvents from water. In addition, the porous monolith as adsorption materials exhibits fast adsorption speed, high saturation capacity, and superior recycling ability. Predictably, porous PC/cMWCNTs monolith will play an important role in oil-polluted water treatment. This method can be used for other polymer systems such as poly(p-phenylene benzobisoxazole),64 polyimide,65 poly(p-phenylene-2,6-benzobisoxazole),66 cationic fluorinated polymer67 and polynorbornene anion polymers68,69 to include some functional fillers such as graphene70,71 and barium titanate72 for other applications such as sensors and electromagnetic interference shielding.73-78

ASSOCIATED CONTENT Supporting Information：： TGA curves of pure PC monolith and PC/cMWCNTs monolith, Figure S1; water contact angles of PC/cMWCNTs monoliths with various cMWCNTs loadings, Figure S2; digital photograph of PC/cMWCNTs monolith (250 mg) after loading with 100 g weight, Figure S3; comparison of microstructure and properties between pure PC monolith and PC/cMWCNTs monolith, Table S1; comparison of saturated adsorption capacities of various adsorption materials, Table S2 Selective separation process of soybean oil (dyed with Sudan III) on water surface, Movie S1

AUTHOR INFORMATION Corresponding Authors: *E-mail: [email protected] (B.W.). *E-mail: [email protected] (C.L.). *E-mail: [email protected] (Z.G.). 19 ACS Paragon Plus Environment


Notes The authors declare no competing financial interest.

ACKNOWLEDGEMENTS The authors gratefully acknowledge the financial support of this work by National Natural Science Foundation of China (Contract Number: 51603190, 11572290, 11432003), National Natural Science Foundation of China-Henan Province Joint Funds (Contract Number: U1604253). Zhanhu Guo appreciates the start-up funds from University of Tennessee.

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Table of Contents Entry

Porous hierarchical micro-nanostructure demonstrated superhydrophobicity and efficient oil-polluted water treatment.


Carbon Nanotubes

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