Mechanical Synthesis of COF Nanosheet Cluster and its Mixed Matrix

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Mechanical Synthesis of COF Nanosheet Cluster and its Mixed Matrix Membrane for Efficient CO2 Removal Changchang Zou, Qianqian Li, Yinying Hua, Bihang Zhou, Jingui Duan, and Wanqin Jin ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b08032 • Publication Date (Web): 09 Aug 2017 Downloaded from http://pubs.acs.org on August 9, 2017

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ACS Applied Materials & Interfaces

Mechanical Synthesis of COF Nanosheet Cluster and its Mixed Matrix Membrane for Efficient CO2 Removal Changchang Zou‡, Qianqian Li‡, Yinying Hua, Bihang Zhou, Jingui Duan* and Wanqin Jin* State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Jiangsu National Synergetic Innovation Centre for Advanced Materials, Nanjing Tech University, Nanjing 210009, China Keywords: Solid reaction, Covalent organic framework, Morphology transformation, Mixed matrix membrane, CO2/N2 gas separation.

Abstract: Covalent organic framework (COF) membranes used to selective removal of CO2 was believed as an efficient and low-cost solution to energy and environmental sustainability. In this study, the amide modified COF nanosheet cluster with 2D structure was facilely prepared through solid reaction, exhibiting good adsorption-based CO2 selectivity (223 at 273K and 90 at 298K) towards N2. Remarkably, the mixed matrix membrane (MMM) that consist of less amount of COF filler (1wt%) shows promising CO2/N2 gas selectivity (~64). In addition, the competitive adsorption prompts the separation factor to ~72 under equimolar CO2/N2 mixture, which surpasses the values of all reported COF membranes. It is worth to note that the binary gas separation is stable during 120 h.

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Introduction As the primary anthropogenic greenhouse gas, CO2 is changing the global climate. The development of efficient selective carbon capture and storage (CCS), is therefore, a scientific challenge of the highest order1-2. Currently, a variety of methods, such as chemisorption with amide solvent, physical adsorption with porous adsorbents, and membrane technology, have been proposed to CO2 capture3-4. However, due to the group of benefits in lower energy consumption, ease of operation, environmental friendliness and mechanical simplicity, membrane based process was believed as one of the most promising technologies in CCS5-11. Due to its low cost, good mechanical simplicity, high scalability and water resistance, a organic polymer (cellulose acetate) membrane was first reported for gas separation in 200112. Since then, various organic membranes have begun to draw widespread attention for feasible usage in gas separation 13-16. However, polymeric membranes are often limited by a permeability and selectivity trade-off. In other words, inorganic membranes with good separation performance are expensive, brittle and difficult to upscale17. Due to the integrated advantages of size/shape selectivity of functional fillers and the processibility/mechanical stability of polymers, MMMs that consist of functional inorganic fillers, such as carbon tubes, mesoporous silicon, zeolites, metal organic frameworks and porous metal oxides, were developed as an alternative solution to overcome these limitations7, 14, 18-19. Despite those, the majority of MMMs usually suffer the poor compatibility between constituents, leading to decreased separation behavior, as the gas molecules bypass the particles18. Thus, the problems we now face are becoming practical, i.e., how to address the issue of filler agglomeration and precipitation during membrane preparation, and further boosting CO2 separation by MMMs14. The stability of matrix solution during the fabricating process is important. Thus, some


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technics, such as adding non-solvents into dope formulation, performing the spinning at high temperatures and optimizing the shear and elongational force, were developed to prepare homogenous dispersion of inorganic porous fillers within polymer solution19-21. Further, controlling the surface properties of fillers, according to the rule of similarity and intermiscibility, was believed as one of the most attractive way. For examples, the controlling of metal organic frameworks (MOFs)/polymer compatibility is a little easier than that of the zeolite/polymer, as the organic ligands in MOFs are more similar with polymer chains, but zeolites not22. In contrast with well-designed porous MOFs, COFs are another new kind of crystalline porous materials, which are assembled by the linkage of organic moieties only in periodic networks through strong covalent bonds with light elements23-24. Due to the diversity of organic building units and chemical reactions, more and more COF materials with tunable pore chemistry, robust stability, as well as good COF/polymer compatibility offer significant opportunity for advanced membrane preparation and application25-26. Whereas, unlike popular 3D MOF structures, most of the reported COFs show 2D lamellar structures that derived from the packing of organic planar by weak interactions. In other words, once the weak interaction was overcome, it is possible to prepare multilayered or even single layered COF nanosheets from bulk lamellar COFs. Therefore, the shorter transmission routes and functional pore properties will make 2D COF nanosheets extremely attractive for membrane-based separation purpose27-30. We are interested in porous material and membrane design for feasible applications31-37. In present study, the 2D COF structure with rich amide groups was selected as membrane filler, since its facile synthesis and also the preferred channel for CO2 transport (Scheme 1). Through solid reaction, the well prepared honeycomb-like COF nanosheet cluster (named as TpPa-1-nc)


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showed good adsorption-based CO2 selectivity (223 at 273K and 90 at 298K) towards N2. Remarkably, single gas permeation experiment showed that TpPa-1-nc incorporated MMM exhibited high CO2/N2 ideal separation factor (~64), which was further improved to ~72 under equimolar CO2/N2 mixture, as the preferred competitive adsorption. In addition, long term test showed that mixture gas separation is stable in 120h.

Scheme 1. COF structure with rich amide group: synthesized by schiff base aldehyde−amine condensation (a); Structure of PEBA (b); SEM image of cross-section of TpPa-1-nc/PEBA composite membrane (c). Experimental Materials All the reagents were commercially available and used as received. Dried phloroglucinol, trifluoroacetic acid, hexamethylenetetraamine and p-phenylenediamine were purchased from J&K Chemicals. Polyether-block-amide (PEBA) was purchased from Arkema, France. Methanol and dichloromethane were purchased from Sinopharm Chemical Reagent Co., Ltd. FTIR spectra were recorded in the range of 4000-400 cm-1 on a Nicolet ID5 ATR spectrometer. Powder X-ray


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diffraction (PXRD) patterns were collected using a Bruker AXS D8 Discover powder diffractometer equipped with a Cu Ka X-ray source at 40 kV, 40 mA. 1H and 13C NMR spectra were recorded on a Bruker 500 FT-NMR spectrometer. Solid

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C CP-MAS NMR spectra was

measured on a Bruker AVANCE III 400MHz spectrometer. The morphologies of COF materials during solid reaction were examined by field emission scanning electron microscope (SEM, S4800, Hitachi) and transmission electron microscopy (TEM, JEOL JEM-2010 UHR). Thermogravimetric analyzer (TGA, STA 209 F1, NETZSCH) was used to determine the thermal stability of the MMMs with a heating rate of 10 °C·min-1 in N2 atmosphere. Differential scanning calorimetry (DSC, Q2000, TA Instruments, USA) measurements were performed from -80 to -20℃ in N2 atmosphere to study the glass transition temperature (Tg) of the membranes. The gas adsorption isotherms of TpPa-1-nc were collected by BELSORP-mini II, Bel Inc., Japan. Synthesis of TpPa-1-nc. COF material was synthesized through solid reaction by schiff base aldehyde−amine condensation according to previous report24. 1,3,5-triformylphloroglucinol and p-phenylenediamine were placed in a mortar and ground using a pestle at room temperature. Following time’s passing, the color of materials changed from light yellow, yellow, orange, and then to dark red finally, indicating the formation of conjugated units (Figure S1). After 35 min, the reaction mixture was collected and washed for getting pure TpPa-1-nc. Preparation of MMMs. PEBA polymer was selected to disperse TpPa-1-nc. Poly(vinylidene fluoride) (PVDF) ultrafiltration membrane was used as support (average pore size: 450 nm). A certain amount of TpPa-1-nc was dispersed in ethanol and water with mass ration of (7:3), followed by stirring of 10 mins. Then PEBA were added and heated with stirring and refluxing under 80℃ for 2 h. The mass ratio of PEBA to solvent is 5:95 while the contents of TpPa-1-nc in


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polymer matrix varied from 0 to 2 wt%. The membrane was prepared by spin-coating the mixed solution on PVDF supports, which was prepared by being immersed in water for 24 h to infiltrate fully. The MMMs were then dried at room temperature for 24h, then curing in the oven at 70℃ for another 12h. A pristine PEBA membrane was also prepared using similar process for comparison. TpPa-1-nc loading in MMMs was calculated as following formula: WCOF=

୫ిోూ

×100%

୫ౌుాఽ

(1)

COF characterization. Solid reactions with number of advantages ripple throughout many industries. Generally, during the initial process of grinding, the particles of starting material assembled together and then reacted with each other. Then, the continuous grinding will break the formed product particle into smaller size. Taking this in consideration, the grinding of solid reaction can not only offer the energy for reaction, but also overcome the weak interaction of the layers during 2D COF formation. In order to confirm our idea, small amount samples were collected at different reaction time (5, 15, 25, 35, 45 and 55 min). IR and PXRD were used to monitor the reaction process during 55 mins (Figure 1). The new IR peaks around (1605, 1579 and 1286 cm-1) and their gradual increased intensity showed the formation of C-N, C=C and C=O bonds respectively (Figure 1a). Meanwhile, the crystallinity of obtained TpPa-1 at different time was evaluated by the powder X-ray diffraction (PXRD). As shown in Figure 1b, the newly emerged and gradually enhanced diffraction peaks at 8º (2θ) matched with the reported data, demonstrating the successful preparation of TpPa-124. It should be noted that, the PXRD peaks at high angle indicate the existence of partial unreacted starting materials. After washing by methanol and dichloromethane (for starting material removal), the structure and morphology of TpPa-1 particles were investigated by PXRD and scanning electron


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microscopy (SEM), respectively. As shown in Figure S2, the absent peaks around high angle

Figure 1. IR (a) and PXRD (b) of synthesized TpPa-1 during process of solid reaction. reveal the completely removal of starting materials and phase purity of TpPa-1. The similar IR spectra between as-synthesized and washed COF prove the maintenance of in-phase structure and bond connection. Additionally,

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C cross-polarization magic-angle-spinning (CP-MAS)

solid-state NMR spectra confirmed the successful COF synthesis (Figure S3). The morphology and size of TpPa-1 particles (after washing) were studied by SEM during solid reaction (Figure 2). At early stage (5 min), the products consist solely of amorphous solid with a relatively broad average size distribution (Figure 2a-2b). Then, some small species can be found on the surface of


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amorphous solid after 15 min grinding (Figure 2c-2d). As expected, plenty of nanosheet with

Figure 2. SEM image of TpPa-1 during solid reaction (after washing): 5 min (a and b), 15 min (c and d), 25 min (e and f), 35 min (g and h), 45 min (i and j) and 55 min (k and l).

Figure 3. TEM image of nanosheet from TpPa-1-nc (a and b); pore size analysis (c and d).


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about 13 nm average thickness, confirmed by atomic force microscope (AFM) study (Figure S6), were found after grinding the sample for another 20 min. The nanosheets assembled together and formed honeycomb-like cluster (TpPa-1-nc) (Figure 2g-2h). However, over time (55 mins), the honeycomb-like TpPa-1-nc gradual lost visible pore and became amorphous block with size of 5-10 µm (Figure 2k-2l). This first and direct observation of COF synthesis reveal a unique transformation: the amorphous solid could transform to honeycomb-like cluster with high aspect ratio nanosheet. Additionally, the flat nanosheet from TpPa-1-nc was also studied by TEM, shown in Figure 3. Further analysis showed that the average micorpore with 4.4-5.0 Å distributed evenly on those flat sheets (Figure 3c-d). Thus, as building block, the integrated features of light elements, regular microporosity and nanosheet morphology could greatly increase the compatibility and stability of TpPa-1-nc within polymeric matrix, leading to promising membrane structure and performance. CO2 and N2 gas isotherms were collected to evaluate the permanent porosity of TpPa-1-nc. As shown in Figure 4a. CO2 adsorption of TpPa-1-nc exhibits type-I adsorption isotherm, characteristic of microporous material. On the basis of CO2 adsorption isotherm, the Brunauer– Emmett–Teller (BET) and Langmuir surface area are around 255 and 436 m2·g−1, respectively. CO2 uptake of TpPa-1-nc reached to 100.6 cm3·g−1 at 195 K/1 bar, while, trace amount N2 (4.2 cm3·g−1) uptake was observed. Interestingly, similar adsorption trends were also found at 273 and 298K (Figure 4b). In light of these obvious adsorption gaps, gas selectivity of TpPa-1-nc was calculated by determining the Henrys law constants (Table S1). As expect, the CO2/N2 gas selectivity is as high as 223 at 273 (90 at 298K), and which should assign as the high CO2 adsorption heat toward TpPa-1-nc (35kJ·mol-1) (Figure 4c). In addition, the calculated pore size


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distribution from CO2 isotherm (273K) match well with the TEM result (Figure S10).

Figure 4. CO2 and N2 adsorption of TpPa-1-nc at 195 (a), 273 and 298K (b); Isosteric heats of adsorption for CO2 in TpPa-1-nc (c).

Membrane characterization. The thermogravimetric results showed that all MMMs started to decompose around 380℃, indicating high thermal stability (Figure S11). PXRD of series MMMs (peak around 11°) confirmed the integrity of TpPa-1 skeletal structure after membrane fabrication (Figure S12). To further unveil the uniform distribution of TpPa-1-nc within


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membranes, SEM images of surface and cross-section of MMMs were collected (Figure 5). The continuous membrane surfaces showed gradually increased granular protuberances without interfacial voids or pinholes, following increased ratio of TpPa-1-nc in PEBA matrix. The thicknesses of the MMMs are around 2.6-2.8 µm on support, while the TpPa-1-nc can be found clearly inside the membrane (Figure 5d inset).

Figure 5. SEM micrographs of surface (a, c, e and g) and cross-section (b, d, f and h) of MMMs with varied loading of TpPa-1-nc. Gas permeation tests. Before measurements, the as-prepared MMMs were activated to remove guest molecules at 60℃ under vacuum for 24 h. In addition, to guarantee the reliability of


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results, the measurements were repeated at least three times for each point. Unlike the defined ideal selectivity above (from single gas adsorption isotherms), the selectivity defined from membrane-based technology is the ratio of permeabilities, S(A/B)=PA/PB. Permeabilities (P) were determined using CO2/N2 gas pair at 25℃, 3 bar. As displayed in Figure 6, the MMMs exhibited gradually improved permeability of both CO2 and N2 companying the increase of TpPa-1-nc loading. This is because CO2 and N2 can diffuse freely through the TpPa-1-nc channel. In addition, differential scanning calorimetry measurements showed that the glass transition temperature (Tg) increased from -47.5℃ for pristine PEBA to -45.2 for 1wt% MMM (Figure S13). This means TpPa-1-nc could disrupt the inherent organization of the polymer chains, and enhance the accessible free volume in the matrix for gas molecule transmission38-40. Among these five MMMs, The ideal gas selectivity increases with TpPa-1-nc loading, and reaches to 64 at the loading of 1wt%, which is 56% improvement than that of pure PEBA membrane. This is because the increased permeability of CO2 is more rapid than that of N2 when the TpPa-1-nc loading is lower than 1wt%. Principally, the nature properties of high polarizability and quadrupole moment lead CO2 molecules themselves to aggregate and permeate into the membrane, then, the generated CO2 concentration gradient was manifested by amide modified TpPa-1-nc, and thus resulted in facilitated CO2 transport within MMM41. Whereas, with the loading above 1wt%, increased permeability of CO2 became slower than that of N2, and thus leads to decreased selectivity. This is because more non-selective interface defects (space between nanosheets in a cluster) were generated when larger amount of TpPa-1-nc was added into the matrix42. Despite the uniform distribution of TpPa-1-nc in polymer solution, such kind interface defects cannot be fully filled by polymer chains.


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Figure 6. Gas permeability and CO2/N2 separation factor of MMMs with varied TpPa-1-nc loadings at 298K. Generally, the permeation selectivity result from mixture gas test is higher than that of single gas test, as the competitive adsorption and diffusion will occur inside functional membrane. Thus, in light of high CO2/N2 separation factor from single gas test, we then performed CO2/N2 mixture (1:1) separation on the MMM with 1wt% COF filler at room temperature. As shown in Figure 7, the average separation factor increased to ~72, 12.5% higher than calculated ideal separation factor (~64). More importantly, such mixture gas separation is stable in 120h. To the best of our knowledge, the separation factor of CO2/N2 mixture by TpPa1-nc MMM (1wt%) surpasses the value of all COF based membranes27, 43-45. In contrast with other PEBA supported MMMs, TpPa-1-nc MMM (1wt%) has competitive advantage in CO2/N2 separation, even though it is hard to make a direct quantitative comparison due to different sample loading and operation conditions (Table 1).


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Figure 7. Long term test of equimolar CO2/N2 mixture separation on TpPa-1-nc MMM (1wt%) at room temperature. Table 1 Separation performance of CO2/N2 by PEBA supported MMMs with varied fillers.

a

Loading

PCO2 (GPU)

SCO2/N2

Refs

2

21.9 a

78.6

46

PEBA

15

9.6 a

30.3

47

4A Zeolite

PEBA

10

1.0 a

54

40

SWNT

PEBA

5

1.1 a

73

48

TpPa-1-nc

PEBA

1

7.5

72

This work

Fillers

Polymer

MWNT

PEBA

ZIF-8

(wt%)

The value was calculated according to the reported CO2 permeance and membrane thickness.


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Additionally, binary gas separation experiments by TpPa-1-nc MMM (1wt%) were also explored at different temperature (from 293 K to 333 K). As shown in Figure 8, high temperature leads to increased gas permeance. Because higher temperature promotes the motion of polymer and weakens the interaction between permeating molecule and polymer molecule, and then results in the reduced transfer resistance for faster diffusion. However, due to the higher ratio of increased N2 permeability, the reduced selectivity was observed at high temperature. Despite those, the gas selectivity remains as high as 45 at 313K, revealing the high possibility for selective CO2 removal under feasible condition.

Figure 8. Effect of temperature on separation performance of MMM-1.0. Conclusions In summary, the unique morphology change from amorphous COF particle to honeycomb-like COF nanosheet cluster was firstly observed during solid reaction. The functional amide group and uniform micropore make such COF cluster achieving good surface area and CO2/N2


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adsorption selectivity. More importantly, PEBA based MMM with 1wt% COF nanosheet cluster showed highest separation factor (~72) for equimolar CO2/N2 mixture in all COF-based membrane. gas separation is stable during 120 h. Thus, the excellent performance of energy saved MMMs along with easily prepared COF filler hold great promise for scale up selective CO2 removal from N2. Corresponding Author Email: [email protected]; [email protected] Author Contributions ‡

These authors contributed equally.

Supporting Information The Supporting Information is available free of charge on the ACS Publications website. Detailed experimental procedures and materials, COF synthesis, PXRD, Calculated Henrys constants, TG, SEM, TEM and Dual-site Langmuir-Freundlich fit of adsorption isotherms. Acknowledgements We thank the financial support of National Science Foundation of China (21671102), National Science Foundation of Jiangsu Province (BK20161538), and Innovative Research Team Program by the Ministry of Education of China (IRT13070), Six talent peaks project in Jiangsu Province (JY-030) and State Key Laboratory of Materials-Oriented Chemical Engineering (ZK201406). References 1. Nugent, P.; Belmabkhout, Y.; Burd, S. D.; Cairns, A. J.; Luebke, R.; Forrest, K.; Pham, T.; Ma, S. Q.; Space, B.; Wojtas, L.; Eddaoudi, M.; Zaworotko, M. J. Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation Nature 2013, 495, 80-84.


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Graphical Abstract Mechanical Synthesis of COF Nanosheet Cluster and its Mixed Matrix Membrane for Efficient CO2 Removal Changchang Zou‡, Qianqian Li‡, Yinying Hua, Bihang Zhou, Jingui Duan* and Wanqin Jin* State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Jiangsu National Synergetic Innovation Centre for Advanced Materials, Nanjing Tech University, Nanjing 210009, China Email:[email protected]; [email protected]


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Mechanical Synthesis of COF Nanosheet Cluster and its Mixed Matrix

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