Embedding Molecular Amine Functionalized Polydopamine

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Embedding molecular amine functionalized polydopamine nanoparticles into polymeric membrane for carbon capture SILU CHEN, Tiantian Zhou, Hong Wu, Yingzhen Wu, and Zhongyi Jiang Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.7b01546 • Publication Date (Web): 26 Jun 2017 Downloaded from http://pubs.acs.org on June 27, 2017

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Industrial & Engineering Chemistry Research

Embedding molecular amine functionalized polydopamine submicro-particles into polymeric membrane for carbon capture Silu Chen a,b,d, Tiantian Zhou a,b, Hong Wu a,b,c,*, Yingzhen Wu a,b, Zhongyi Jiang a,b

a

Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

b

Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin, 300072, China

c

Tianjin Key Laboratory of Membrane Science and Desalination Technology, Tianjin University, Tianjin 300072, China

d

Department of Chemical Engineering, Faculty of Engineering, University of Waterloo, Waterloo, ON N2L 3G1, Canada

*

Corresponding author: School of Chemical Engineering and Technology, Tianjin

University, Tianjin 300072, P R China. Tel: 86-22-23500086. Fax: 86-22-23500086. Email: [email protected] (H. Wu) 1 ACS Paragon Plus Environment


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Abstract

In this study, a facile and novel facilitated transport mixed matrix membrane (FT-MMM) was fabricated by incorporating molecular amine functionalized polydopamine (PDA) into Pebax® MH 1657. Polydopamine submicro-particles were chemically modified by tetraethylenepentamine (TEPA). The catechol groups on PDA can react with amino groups through the Michael addition reaction and Schiff base reaction. Grafting molecular amines onto PDA submicro-particles can not only improve interfacial compatibility between the fillers and a polymeric matrix, but also enhance the facilitated transport of CO2 in the membrane because of the abundant CO2-philic groups. The effects of modified PDA submicro-particle content on the membrane permselectivity were investigated, and it was found that FT-MMM with a loading of 5% PDA submicro-particles exhibited the optimum CO2/CH4 separation property under humid conditions. The selectivity of PebaxPDA/TEPA (5) membrane was 27.5, about 1.5-fold higher than that of the pristine Pebax membrane under identical operating conditions, while the membrane permeability remained comparable. Furthermore, the effects of operating pressure and temperature on the membrane separation performance were evaluated as well.

Keywords: Pebax; Functionalized polydopamine; Mixed matrix membranes; Facilitated transport; Carbon capture

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1. Introduction Comparing with traditional carbon capture methods, membrane separation is an environmentally friendly technology and has the merits of high separation efficiency, low energy consumption, and no phase change1–4. However, the permeability-selectivity tradeoff in membranes restricts further enhancement in membrane gas separation performance for large-scale industrial applications. Mixed matrix membranes take the synergistic effect of the dispersed fillers and the polymer matrix, and have the potential to transcend the Robeson’s upper-bound line2,5–8. In many cases, the dispersed fillers (e.g. zeolite9–11, silica12,13, graphene oxide8,14, carbon nanotubes15–17, zeolitic imidazolate framework (ZIF)18,19, and metal organic frameworks (MOF)20–22) are embedded into a continuous phase of polymer matrix in order to promote the diffusivity and diffusion selectivity of membranes. Nevertheless, the addition of the fillers in the membrane may cause non-selective interface defects between the polymer and the fillers2. Modifying the fillers with CO2-philic groups can not only enhance interface compatibility but also facilitate CO2 transport23–25. Certain CO2 transport carriers, including amino groups (-NH2), carboxylate group (-COOH), and sulfonic acid groups (SO3H), can react with CO2 specifically and reversibly12,26–28. Therefore, along with the solution-diffusion mechanism, facilitated transport is also used to explain the mass transport in facilitated transport mixed matrix membranes (FT-MMMs)17,20,26,29,30. 3 ACS Paragon Plus Environment


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The studies on amine groups for facilitating CO2 transport have attracted considerable attention recently31–34. Both primary and secondary amine groups can react with CO2 reversibly and enhance the rate of CO2 transportation in the membranes in humidified conditions35–37: 2 CO2 + 2 RNH2 + H2O ⇋ RHNCOOH + RNH3+ + HCO3– 2 CO2 + 2 RR′NH + H2O ⇋ RR′NCOOH + RR′NH2+ + HCO3Amine groups can be classified into sterically hindered amines and non-sterically hindered amines38. Branched polyethyleneimine (PEI) is a representative sterically hindered amine, and it has been widely used as a CO2 transport carrier32,39. Meanwhile, tetraethylenepentamine (TEPA) is a small molecule with amine groups and sterically unhindered amine as well, which is rich in primary and secondary amine groups (Figure 1)40. TEPA, a low cost chemical, has low toxicity and excellent CO2 absorption capacity. Since small molecules with amine groups have abundant reactive sites, a number of materials can be modified by TEPA for uses in carbon capture29,41,42.

Figure 1. Chemical structure of TEPA


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Figure 2. The preparation procedures of TEPA-functionalized polydopamine (PDA/TEPA) submicro-particles Polydopamine (PDA) can be obtained by the oxidization polymerization of dopamine (DA) in aqueous weak alkaline solutions43–45. The catechol groups on PDA remain reactive and can react small molecules terminated with amino groups (-NH2) by the Michael addition reaction46 and Schiff base reaction (Figure 2)47. Therefore, TEPA can be modified and fixed on the PDA submicro-particles to act as fixed CO2 carriers in membranes. The bio-adhesion property of PDA can ameliorate the polymer/filler interface compatibility and reduce the defects in membranes48–50. Moreover, the PDA/TEPA submicro-particles render CO2 facilitated transport carriers to adapt the gas separation performance because of abundant –OH and –NH2 groups. Pebax® MH 1657 is a commercial block copolymer that 5 ACS Paragon Plus Environment


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holds great promise for gas separation. It consists of around 40 wt% Nylon 6 (PA6) segment and 60 wt% polyethylene oxide (PEO) segment (Figure 3)33,51. The PA6 blocks favors the mechanical property of the membranes, while the PEO blocks dominates the separation property due to dipole-quadrupole interactions52–54.

Figure 3. Chemical structure of Pebax 1657 In this study, Pebax 1657 was used as the continuous polymer matrix phase, while TEPA modified PDA was used as the dispersed fillers. A series of FT-MMMs with different filler contents were fabricated for CO2/CH4 separation. Transmission electron microscopy (TEM), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), elemental analysis (EA) and differential scanning calorimeter (DSC) were utilized to study the chemical structure, morphology, thermal properties of fillers and the membranes. Their gas separation performance for CO2/CH4 mixture under a humidified condition was measured. Moreover, the effects of filler content, feed gas pressure and temperature on the gas permselectivity of the membranes were investigated as well.


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2. Experimental 2.1 Materials

Pebax® MH 1657 (Pebax) was purchased from Shanghai Rongtian Chemical Co., Ltd. 3-2-(3,4-dihydroxyphenyl) ethylamine (Dopamine) was purchased from Yuancheng Technology Development Co., Ltd. (Wuhan, China). Tris (hydroxymethyl) aminomethane (Tris) and tetraethylenepentamine (TEPA) were purchased from Sigma-Aldrich. Hydrochloric acid was purchased from Tianjin Guangfu Fine Chemical Research Institute (Tianjin, China). All agents were of analytical degree and used without additional purification. Purified water was used during the entire study.

2.2 Synthesis of PDA/TEPA submicro-particles

At first, a certain amount of Tris was dissolved in 500 mL of deionized water. After stirring evenly, hydrochloric acid (HCl) was used to adjust the pH to 8.5. Tris-HCl was transferred to a flask placed in a 50 °C water bath. Then, 1 g of dopamine (DA) was added slowly into the flask under stirring. After continuously and vigorously stirring for 5 h, the polydopamine (PDA) nanospheres were collected by centrifugation and washed with deionized water. After purification, the obtained PDA nanospheres were dispersed into 500 mL of deionized water. 6 g of TEPA was added gradually as a modification agent and the solution was stirred vigorously for 6 h. TEPA reacted with PDA via the Michael addition 7 ACS Paragon Plus Environment


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and Schiff base reactions. PDA/TEPA submicro-particles were collected by centrifugation, purified with deionized water, and dried in a vacuum oven at 60 °C for 24 h.

2.3 Preparation of membranes

FT-MMMs and pristine Pebax membranes were prepared by a solution-casting method. Pebax pellets were dissolved in a mixed solvent of ethanol/water (70/30 wt%) and the Pebax content was 4 wt%. The mixture was refluxed for 3 h at 80 °C to form a homogenous Pebax solution. A certain amount of the PDA/TEPA submicro-particles was dispersed into the prepared Pebax solution under ultrasonic treatment for 30 min. Afterward, the suspension was stirred vigorously for 5 h, cast on a flat glass plate, and dried at ambient temperature for 24 h and then in a vacuum oven at 50 °C for 24 h so that the remaining solvent were completely removed. The obtained FT-MMMs were designed as PebaxPDA/TEPA (X), where X (X=0, 1, 2.5, 5, 10) represents the weight percentage of fillers (PDA/TEPA) in the membranes. The thicknesses of membranes were in the range of 7595 µm.

2.4 Characterization of the PDA/TEPA and membranes

The morphologies of the synthesized PDA and PDA/TEPA submicro-particles were observed under a JEOL Tecnai G2 F20 transmission electron microscope. The infrared spectrograms of the PDA/TEPA and the prepared membranes were obtained using 8 ACS Paragon Plus Environment

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BRUKER Vertex 70 Fourier transform infrared spectrometer in the scan range of 4000400 cm-1 with an accuracy of 1.93 cm-1. The FT-MMMs were measured directly, and the PDA/TEPA submicro-particles were prepared by mixing with KBr in advance. The crosssectional morphology and the dispersion of PDA/TEPA in the FT-MMMs were observed under a Nanosem 430 field emission scanning electron microscope. All membranes were freeze-fractured in liquid nitrogen and then sputter-coated with gold for the SEM analysis. The element composition of PDA/TEPA was determined by an Elementar vario EL CUBE elemental analysis. The glass transition temperatures (Tg) of the pristine Pebax membranes and the FT-MMMs were determined with a 204 F1 NETZSCH differential scanning calorimeter in the range of -100 to 250 °C with a heating rate of 10 °C/min in the nitrogen atmosphere.

2.5 Gas permeation tests

The gas separation performance of membranes was measured using an apparatus which was described previously23. The conventional constant pressure/variable volume method was used to test mixed gas (CO2/CH4 (30 vol%: 70 vol%)) permeation performance under humidified conditions. In a typical experiment, a flat-sheet membrane was mounted in a circular stainless steel membrane permeation cell with an effective area of 12.56 cm2. The feed gas was saturated with water vapor by bubbling through a humidifier (35 °C), followed by passing through an empty tank for separating fine water droplets. Then, the humid gas 9 ACS Paragon Plus Environment


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was introduced into the membrane cell. A sweep gas (N2) also humidified in a similar way at room temperature was allowed to flow to the membrane cell at the permeate side. The flow rates of both streams were measured by mass flowmeters. The downstream side was maintained at atmospheric pressure. The composition of the gas from the permeate side was measured using a gas chromatography (Agilent 6820 gas chromatograph) equipped with a thermal conductivity detector (TCD)). The gas permeability (𝑃 , Barrer, 1 Barrer = 1× 10−10 cm3 (STP) cm/(cm2s cmHg)) of the membranes was measured in triplicate, and the permeability data presented was the average of the triplicate measured. Membrane samples from the same batch showed a difference of within 5% of relative standard deviation in permeability. The gas permeability was determined by using the following equation: 𝑃=

𝑄𝑙 𝐴∆𝑝

where 𝑄 is the gas volumetric flow rate (cm3/s (STP)), 𝑙 is membrane thickness (cm), ∆𝑝 is the pressure difference (cmHg), and 𝐴 was the effective membrane area. The CO2/CH4 selectivity (𝛼𝑖𝑗 ) was calculated by this equation: 𝛼𝑖𝑗 =

𝑃𝑖 𝑃𝑗

where 𝑖 and 𝑗 represent a certain kind of gasses. All gas permeation test results were achieved under steady conditions.


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3. Results and discussion 3.1 Characterization of PDA/TEPA

3.1.1 Transmission electron microscopy (TEM)

The morphology of PDA/TEPA was observed under TEM. Figure 4 shows the TEM images of PDA and PDA/TEPA. After modified by TEPA, the PDA/TEPA submicroparticles maintained the spherical shape as PDA. The PDA/TEPA submicro-particles had rather uniform sizes, with a diameter in the rage of 180-220 nm.

Figure 4. The TEM image of PDA/TEPA submicro-particles (a) and a single PDA/TEPA submicro-particle (b) 3.1.2 Fourier transform infrared (FT-IR) spectroscopy The functional groups and chemical composition of PDA/TEPA were characterized by FT-IR, and the FT-IR spectra were shown in Figure 5. The peak at around 1026 cm-1 represents the C-N stretching vibration, and the peak at around 1286.4 cm-1 may be assigned to C-O-H stretching vibrations in PDA and –NH2 stretching vibration in TEPA. 11 ACS Paragon Plus Environment


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The C=C stretching vibration in benzene is shown at 1508.2 cm-1, while the N-H scissoring bending stretching is observed at 1645.2 cm-1. The peak at 2914.3 cm-1 is assigned to C-H stretching vibration, and the wide peak at 3396.4 cm-1 can be attributed to N-H and O-H stretching vibrations. These results show that PDA submicro-particles have been chemically modified with TEPA.

Figure 5. FT-IR spectrum of PDA/TEPA submicro-particles

3.1.3 Elemental analysis (EA)

The loading amount of TEPA on PDA was measured by elemental analysis. Three groups of PDA/TEPA submicro-particles were prepared by the same method, three samples from each group were tested, and then averages were calculated and recorded in the Table 1. TEPA loading amount was calculated by using the C/N atom ratios of PDA and PDA/TEPA. Therefore, the loading amount of TEPA reached 11.9 wt%, which indicated


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that high amino groups loading amount provided a lot of fixed carriers for CO2 transport in the membrane. Table 1. Elemental analysis of PDA and PDA/TEPA submicro-particles Particle

PDA

PDA/TEPA

C (wt %)

38.8

56.1

C (atom %)

3.23

4.67

N (wt %)

7.17

15.3

N (atom %)

0.510

1.09

C/N (mass ratio)

5.41

3.67

C/N (atom ratio)

6.33

4.28

3.2 Characterization of FT-MMMs

3.2.1 Field emission scanning electron microscope (FESEM)

In order to study the effects of PDA/TEPA submicro-particles on the morphologies of the FT-MMMs, the cross-sections of the membranes were investigated by FESEM. As illustrated in Figure 6 (a) and (b), compared with the unfilled Pebax membrane, there was little change in the microstructure of the Pebax-PDA/TEPA (5) membrane. In the Pebax matrix, the PDA/TEPA submicro-particles dispersed homogenously and not considerable agglomeration phenomena was observed. As observed in Figure 6 (c), the fillers



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maintained the shape of a sphere, and there was no obvious defect between the Pebax matrix and the fillers.

Figure 6. The cross-section morphologies of pure Pebax membrane (a), Pebax-PDA/TEPA (5) membrane under various scales ((b) and (c)) 3.2.2 Fourier transform infrared (FT-IR) spectroscopy The influence of the PDA/TEPA submicro-particles on the chemical structure of the membranes was investigated using FT-TR, as shown in Figure 7(a). It obviously showed that the peak intensities of the FT-MMMs increases with an increase in the filler contents. The main vibration peaks of the pristine Pebax membrane at 1537.2 cm-1 and 1639.4 cm-1 were observed in all the FT-MMMs, which were related to the bending vibration of –NHand the stretching vibration of C=O, respectively. As for PDA/TEPA, the peak at 1095.5 cm-1 was assigned to the C=C vibration of the benzene in PDA; the peak at 1257.5 cm-1 was due to C-O-H stretching vibration in the benzene of PDA and –NH2 bending vibration in TEPA. Moreover, the N-H stretching vibration and the C-H bending vibration in the FT14 ACS Paragon Plus Environment

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MMMs were observed at around 2860.3 cm-1 and 2939.4 cm-1, respectively. Also, the stretching vibrations of amino and phenolic hydroxyl groups were overlapped at around 3294.2 cm-1. In the Figure 7(b), both the stretching vibration of NH2 around 3294.2 cm-1 and the stretching vibration of C=O around 1639.4 cm-1 redshifted which indicated there might be hydrogen bonds between amino groups of TEPA and carbonyls of PA blocks55,56. Although the FT-IR spectra indicated that there was no chemical bond between the Pebax matrix and the PDA/TEPA submicro-particles, the interaction between polymer chains and PDA/TEPA might reduce the existence of non-selective region and guaranteed the favorable membrane selectivity15,23,45.



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Figure 7. FT-IR spectra of Pebax-PDA/TEPA FT-MMMs (a) wavenumber from 4000800 cm-1 and (b) the amplification of wavenumber from 3400-3200 cm-1 and 1700-1550 cm-1 3.2.3 Differential scanning calorimeter (DSC) measurements The glass transition temperatures (Tg) of the membranes were determined using DSC, and the results were presented in Table 2. The Tg of the unfilled Pebax membrane was 50.5 °C, indicating a rubbery property of Pebax. As the contents of PDA/TEPA submicroparticles increased, the Tgs of FT-MMMs were increased gradually, which implied that the chain flexibility was influenced by the addition of PDA/TEPA submicro-particles. The strong interfacial interaction between the polymer chains and the submicro-particles resulted in the formation of polymer chain rigidification zone with the increase of the filler content, which had effect on the selectivity of the FT-MMMs48,57.


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Table 2. DSC results of Pebax-PDA/TEPA membranes Membrane

Tg (°C)

Pebax

-50.5

Pebax-PDA/TEPA(1)

-49.3

Pebax-PDA/TEPA(2.5)

-48.5

Pebax-PDA/TEPA(5)

-47.8

Pebax-PDA/TEPA(10)

-44.4

3.3 Gas separation performance

3.3.1 Effect of filler content

The effect of filler content on gas separation performance of the membranes for binary mixed gasses was plotted in Figure 8. To simulate the real gas components, 30 vol % of CO2 and 70 vol % of CH4 was used as feed gas mixture. The gas separation performance tests were conducted at 35 °C and 0.2 MPa. It can be observed that the unfilled Pebax membrane had a CO2 permeability of 463.87 Barrers and CO2/CH4 selectivity of 18.54. As the filler content increased from 0 wt% to 10 wt%, the CO2 permeability of the membranes decreased initially and then increased slightly. On the contrary, the CO2/CH4 selectivity of the membranes increased at first and then fell sharply. The optimum gas separation performance of the membranes was the FT-MMMs with a filler content of 5 wt%, of which the CO2 permeability was 463.87 Barrers and the CO2/CH4 selectivity was 18.54. 17 ACS Paragon Plus Environment


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In humidified condition, the decrease in the CO2 permeability of the membranes resulted from the increase in the mass transfer resistance in membranes. When the content of fillers in membranes were increased gradually, the interface between PDA/TEPA submicroparticles and Pebax membranes caused polymer chain rigidification, which agreed with the variation of Tg. Furthermore, the increase in the CO2/CH4 selectivity of the membranes could be attributed to two reasons. On the one hand, the polymer chain rigidification region resulted in the molecule sieve effect. The kinetic diameter of CO2 molecules (0.33 nm) is smaller than that of CH4 molecules (0.38 nm)58,59, and thus the diffusion rate of CO2 was faster than that of CH4 in membranes. On the other hand, since PDA submicro-particles were modified by a large amount of TEPA, both -NH2 and -NH- groups can be used as the facilitated transport carriers of CO2 in membranes, which have the reversible reactions with CO2 in humidified state. Although the CO2 permeability decreased due to the polymer chain rigidification effect, the facilitated transport in the membranes compensated the decrease in the CO2 permeability16,60,61, and thus FT- MMMs maintained the intrinsic high permeability of Pebax polymers. As the contents of fillers increased, PDA/TEPA submicro-particles agglomerated together and the zone between polymer and submicro-particles became a non-selective region, which led to the deterioration of membrane permselectivity.


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Figure 8. Effect of PDA/TEPA submicro-particle content on FT-MMMs gas separation performance

3.3.2 Effect of feed gas pressure

Apart from the filler content in the membranes, the feed gas pressure affects the gas separation performance as well. Due to optimum gas separation performance, the PebaxPDA/TEPA (5) membrane was examined in the following experiments. Figure 9 (a) and (b) show the tendency of CO2 permeability and the CO2/CH4 selectivity of the pristine Pebax membrane and the Pebax-PDA/TEPA (5) membrane at different feed gas pressures. As the gas feed pressure increased from 0.2 to 0.8 MPa, the CO2 permeability of the pristine Pebax membrane fluctuated slightly and remained at approximately 470 Barrers, while the CO2 permeability of the Pebax- PDA/TEPA (5) membrane declined from 451 Barrers to 413 Barrers.



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The variation in gas separation performance with the pressure was in accordance with common facilitated transport membranes. One of the reasons was that the swollen polymers was compacted and the polymer chains behaved inflexibly under high pressure. The other reason might be the carrier saturation in the membranes when the pressure is sufficiently high, which is the unique characteristic of facilitated transport membranes. When the carriers reached saturated, the reversible reaction between CO2 and amine groups became balanced, which resulted in the decrease of the CO2 permeability. Different from the transport mechanism of CO2 molecules, CH4 molecules permeate the membrane only by the solution-diffusion mechanism which is usually not related to the feed gas pressure62. Hence, the diminishment of CH4 permeability resulted from the decrease of free volume and the increase of mass transport resistance. As demonstrated in the Figure 9 (b), the CO2/CH4 selectivity of pristine Pebax membrane decreased to a small extent, while that of Pebax-PDA/TEPA (5) membrane reduced as well with an increase in feed gas pressure. Due to different behaviors of CO2 and CH4 during the transport process, the CO2/CH4 selectivity of Pebax-PDA/TEPA (5) membrane declined from 27.10 to 21.71 when the total gas pressure increased.


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Figure 9. Effect of feed gas pressure on the gas separation performance of pristine Pebax and Pebax-PDA/TEPA (5) membranes

3.3.3 Effect of operating temperature

Operating temperature influences gas separation performance. In this study, the gas separation performances at different temperatures was investigated. As described in Figure 10 (a), when the operating temperature increased from 25 to 75 °C, both the CO2 permeability of the pristine Pebax membrane and the Pebax-PDA/TEPA (5) membrane 21 ACS Paragon Plus Environment


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increased. Since both the mobility of gas molecules and the flexibility of polymer chains can be enhanced at elevated temperatures, polymer fractional free volume increased and mass transfer resistance decreased as well, so the CO2 molecules can permeate through the membranes more quickly and easily. However, as shown in Figure 10 (b), the CO2/CH4 selectivity of pristine Pebax membrane and Pebax-PDA/TEPA (5) membrane diminished with increasing temperatures because polyether-based membranes suffer from the decrease of CO2 selectivity over the light gas (CH4)48. Besides, it was reported that the decreased selectivity of polyether-based membranes resulted from the decrease in the solubility selectivity at elevated temperatures63.


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Figure 10. Effect of operating temperature on the gas separation performance of pristine Pebax and Pebax-PDA/TEPA (5) membranes

4. Conclusions FT-MMMs were fabricated by embedding PDA/TEPA submicro-particles into the Pebax polymeric matrix and their gas separation performance under humid condition was exploited. The Michael addition reaction and Schiff base reaction between catechol and amino groups can be manipulated to modify PDA with molecular amines. As a result, the loading of TEPA on PDA submicro-particles achieved 11.9%. The addition of PDA-TEPA submicro-particles can change the chemical and physical properties of the membranes. They not only decrease the interfacial defects but also affect the permeability and selectivity of membranes. To be specific, the optimum gas separation performance of the FT-MMMs was obtained with the permeability of 450.36 Barrers and the CO2/CH4 selectivity of 27.53 at 0.2 MPa and 25 °C. Considering the CO2/CH4 selectivity of pristine 23 ACS Paragon Plus Environment


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Pebax membranes, the increasing selectivity of Pebax-PDA/TEPA (5) was attributed to the existence of amino groups by doping PDA-TEPA submicro-particles. Fixed CO2 carriers provided more transfer sites and facilitated transport of CO2. Moreover, the permeability of Pebax-PDA/TEPA (5) membranes decreased with the increase of feed pressure which showed the typical characteristics of facilitated transportation mechanism.

Acknowledgments The author appreciates the financial support from the National Natural Science Foundation of China (21576189, 21490583, 213906131 and 21621004), Natural Science Foundation of Tianjin (16JCZDJC36500), National Science Fund for Distinguished Young Scholars (21125627), State Key Laboratory of Separation Membranes and Membrane Processes (Tianjin Polytechnic University) (M2-201504, M1-201501), Programme of Introducing Talents of Discipline to Universities (No. B06006).


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Graphical Abstract


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Embedding Molecular Amine Functionalized Polydopamine

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