scholarly journals Design and Gas Separation Performance of Imidazolium Poly(ILs) Containing Multivalent Imidazolium Fillers and Crosslinking Agents

Polymers ◽  
2021 ◽  
Vol 13 (9) ◽  
pp. 1388
Author(s):  
Kathryn E. O’Harra ◽  
Emily M. DeVriese ◽  
Erika M. Turflinger ◽  
Danielle M. Noll ◽  
Jason E. Bara

This work introduces a series of vinyl-imidazolium-based polyelectrolyte composites, which were structurally modified via impregnation with multivalent imidazolium-benzene ionic liquids (ILs) or crosslinked with novel cationic crosslinkers which possess internal imidazolium cations and vinylimidazolium cations at the periphery. A set of eight [C4vim][Tf2N]-based membranes were prepared via UV-initiated free radical polymerization, including four composites containing di-, tri-, tetra-, and hexa-imidazolium benzene ILs and four crosslinked derivatives which utilized tri- and tetra- vinylimidazolium benzene crosslinking agents. Structural and functional characterizations were performed, and pure gas permeation data were collected to better understand the effects of “free” ILs dispersed in the polymeric matrix versus integrated ionic crosslinks on the transport behaviors of these thin films. These imidazolium PIL:IL composites exhibited moderately high CO2 permeabilities (~20–40 Barrer), a 4–7× increase relative to corresponding neat PIL, with excellent selectivities against N2 or CH4. The addition of imidazolium-benzene fillers with increased imidazolium content were shown to correspondingly enhance CO2 solubility (di- < tri- < tetra- < hexa-), with the [C4vim][Tf2N]: [Hexa(Im+)Benz ][Tf2N] composite showing the highest CO2 permeability (PCO2 = 38.4 Barrer), while maintaining modest selectivities (αCO2/CH4 = 20.2, αCO2/N2 = 23.6). Additionally, these metrics were similarly improved with the integration of more ionic content bonded to the polymeric matrix; increased PCO2 with increased wt% of the tri- and tetra-vinylimidazolium benzene crosslinking agent was observed. This study demonstrates the intriguing interactions and effects of ionic additives or crosslinkers within a PIL matrix, revealing the potential for the tuning of the properties and transport behaviors of ionic polymers using ionic liquid-inspired small molecules.

Molecules ◽  
2022 ◽  
Vol 27 (2) ◽  
pp. 413
Author(s):  
Bruna F. Soares ◽  
Daniil R. Nosov ◽  
José M. Pires ◽  
Andrey A. Tyutyunov ◽  
Elena I. Lozinskaya ◽  
...  

This work aims to explore the gas permeation performance of two newly-designed ionic liquids, [C2mim][CF3BF3] and [C2mim][CF3SO2C(CN)2], in supported ionic liquid membranes (SILM) configuration, as another effort to provide an overall insight on the gas permeation performance of functionalized-ionic liquids with the [C2mim]+ cation. [C2mim][CF3BF3] and [C2mim][CF3SO2C(CN)2] single gas separation performance towards CO2, N2, and CH4 at T = 293 K and T = 308 K were measured using the time-lag method. Assessing the CO2 permeation results, [C2mim][CF3BF3] showed an undermined value of 710 Barrer at 293.15 K and 1 bar of feed pressure when compared to [C2mim][BF4], whereas for the [C2mim][CF3SO2C(CN)2] IL an unexpected CO2 permeability of 1095 Barrer was attained at the same experimental conditions, overcoming the results for the remaining ILs used for comparison. The prepared membranes exhibited diverse permselectivities, varying from 16.9 to 22.2 for CO2/CH4 and 37.0 to 44.4 for CO2/N2 gas pairs. The thermophysical properties of the [C2mim][CF3BF3] and [C2mim][CF3SO2C(CN)2] ILs were also determined in the range of T = 293.15 K up to T = 353.15 K at atmospheric pressure and compared with those for other ILs with the same cation and anion’s with similar chemical moieties.


Membranes ◽  
2021 ◽  
Vol 11 (9) ◽  
pp. 693
Author(s):  
Fei Guo ◽  
Bingzhang Li ◽  
Rui Ding ◽  
Dongsheng Li ◽  
Xiaobin Jiang ◽  
...  

Mixing a polymer matrix and nanofiller to prepare a mixed matrix membrane (MMM) is an effective method for enhancing gas separation performance. In this work, a unique UiO-66-decorated halloysite nanotubes composite material (UiO-66@HNT) was successfully synthesized via a solvothermal method and dispersed into the Pebax-1657 matrix to prepare MMMs for CO2/N2 separation. A remarkable characteristic of this MMM was that the HNT lumen provided the highway for CO2 diffusion due to the unique affinity of UiO-66 for CO2. Simultaneously, the close connection of the UiO-66 layer on the external surface of HNTs created relatively continuous pathways for gas permeation. A suite of microscopy, diffraction, and thermal techniques was used to characterize the morphology and structure of UiO-66@HNT and the membranes. As expected, the embedding UiO-66@HNT composite materials significantly improved the separation performances of the membranes. Impressively, the as-obtained membrane acquired a high CO2 permeability of 119.08 Barrer and CO2/N2 selectivity of 76.26. Additionally, the presence of UiO-66@HNT conferred good long-term stability and excellent interfacial compatibility on the MMMs. The results demonstrated that the composite filler with fast transport pathways designed in this study was an effective strategy to enhance gas separation performance of MMMs, verifying its application potential in the gas purification industry.


2014 ◽  
Vol 1025-1026 ◽  
pp. 770-775 ◽  
Author(s):  
W.N.W. Salleh ◽  
N.A.I.M. Isa ◽  
Norazlianie Sazali ◽  
Ahmad Fauzi Ismail

A series of research had been conducted to alter the performance of carbon membranes by manipulating the parameters during the fabrication process. In this study, the effects of carbonization temperature on the performance of carbon membrane were investigated. Matrimid-based carbon membrane supported on ceramic tube was fabricated through the dip-coating technique. The prepared membranes were characterized by using the scanning electron microscopy (SEM) and pure gas permeation test for the study on morphological structure and gas separation performance, respectively. The carbonization process was performed at different carbonization temperatures (600, 700, and 800 oC) for the same heating rate of 1 oC/min under Ar flow. The increment of carbonization temperature produced carbon membrane with small size of pores. The carbon membrane prepared at 800 oC showed the highest CO2/CH4 and CO2/N2 selectivity of 79.65 and 74.76, respectively.


2019 ◽  
Vol 15 (1) ◽  
pp. 50-53
Author(s):  
Kok Chung Chong ◽  
Yin Yin Chan ◽  
Woei Jye Lau ◽  
Soon Onn Lai ◽  
Ahmad Fauzi Ismail ◽  
...  

Oxygen enriched air (OEA) is widely applied in various areas such as chemical and medical applications. Currently, cryogenic distillation and pressure swing adsorption are the two common technologies that being commercially used for i the production of OEA. However, these two techniques are not economically favorable due to required intensive energy and large built-up area. With the advancement of membrane technology in separation process, it garners the interest from both industrial and academic to explore the feasibility of membrane in gas separation. In this study, polysulfone (PSF) hollow fiber membranes with poly(ether block amide) (PEBAX) coating were used for the separation of O2/N2 gas. The hollow fiber membranes used in this work were fabricated by phase inversion spinning process using PSF pellet, along with N,N-dimetyhlacetamide (DMAc) and ethanol (EtOH) as solvent and co-solvent, whereas tetrahydrofuran (THF) as additive. The fabricated membrane exhibited dense structure in the inner layer whereas finger like layer at the outer surface. The formation of this structure was attributed by rapid phase inversion of the solution arose from strong solvent used. The EDX surface mapping analysis confirmed the formation of PEBAX coating on the membrane surface. Gas permeation study in this work illustrated that the pristine PSF membrane exhibited better gas separation performance relative to the PEBAX coated membrane with 20% higher in terms of permeance. The results obtained from this work suggested that the PEBAX coating enhanced the membrane surface but not certain to improve the gas separation performance. Further study on the PEBAX materials for the membrane coating is essential to polish its potential in gas separation.


Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1269
Author(s):  
Vadim A. Dubskikh ◽  
Anna A. Lysova ◽  
Denis G. Samsonenko ◽  
Alexander N. Lavrov ◽  
Konstantin A. Kovalenko ◽  
...  

Three new 3D metal-organic porous frameworks based on Co(II) and 2,2′-bithiophen-5,5′-dicarboxylate (btdc2−) [Co3(btdc)3(bpy)2]·4DMF, 1; [Co3(btdc)3(pz)(dmf)2]·4DMF·1.5H2O, 2; [Co3(btdc)3(dmf)4]∙2DMF∙2H2O, 3 (bpy = 2,2′-bipyridyl, pz = pyrazine, dmf = N,N-dimethylformamide) were synthesized and structurally characterized. All compounds share the same trinuclear carboxylate building units {Co3(RCOO)6}, connected either by btdc2– ligands (1, 3) or by both btdc2– and pz bridging ligands (2). The permanent porosity of 1 was confirmed by N2, O2, CO, CO2, CH4 adsorption measurements at various temperatures (77 K, 273 K, 298 K), resulted in BET surface area 667 m2⋅g−1 and promising gas separation performance with selectivity factors up to 35.7 for CO2/N2, 45.4 for CO2/O2, 20.8 for CO2/CO, and 4.8 for CO2/CH4. The molar magnetic susceptibilities χp(T) were measured for 1 and 2 in the temperature range 1.77–330 K at magnetic fields up to 10 kOe. The room-temperature values of the effective magnetic moments for compounds 1 and 2 are μeff (300 K) ≈ 4.93 μB. The obtained results confirm the mainly paramagnetic nature of both compounds with some antiferromagnetic interactions at low-temperatures T < 20 K in 2 between the Co(II) cations separated by short pz linkers. Similar conclusions were also derived from the field-depending magnetization data of 1 and 2.


2021 ◽  
Author(s):  
Madhvi Garg ◽  
Navneet Bhullar ◽  
Bharat Bajaj ◽  
Dhiraj Sud

The present manuscript reports the ultrasound radiation induced synthesis of grafted chitosan hydrogels (CAAT and CAAG) using terephthalaldehyde/glutaraldehyde as crosslinking agents and its application for removal of synthetic dyes from...


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Nur’ Adilah Abdul Nasir ◽  
Ameen Gabr Ahmed Alshaghdari ◽  
Mohd Usman Mohd Junaidi ◽  
Nur Awanis Hashim ◽  
Mohamad Fairus Rabuni ◽  
...  

Abstract Efficient purification technology is crucial to fully utilize hydrogen (H2) as the next generation fuel source. Polyimide (PI) membranes have been intensively applied for H2 purification but its current separation performance of neat PI membranes is insufficient to fulfill industrial demand. This study employs blending and crosslinking modification simultaneously to enhance the separation efficiency of a membrane. Polyethersulfone (PES) and Co-PI (P84) blend asymmetric membranes have been prepared via dry–wet phase inversion with three different ratios. Pure H2 and carbon dioxide (CO2) gas permeation are conducted on the polymer blends to find the best formulation for membrane composition for effective H2 purification. Next, the membrane with the best blending ratio is chemically modified using 1,3-diaminopropane (PDA) with variable reaction time. Physical and chemical characterization of all membranes was evaluated using field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), and Fourier transform infrared (FTIR). Upon 15 min modification, the polymer membrane achieved an improvement on H2/CO2 selectivity by 88.9%. Moreover, similar membrane has demonstrated the best performance as it has surpassed Robeson’s upper bound curve for H2/CO2 gas pair performance. Therefore, this finding is significant towards the development of H2-selective membranes with improved performance.


Nanomaterials ◽  
2021 ◽  
Vol 11 (3) ◽  
pp. 582
Author(s):  
Fernando Pardo ◽  
Sergio V. Gutiérrez-Hernández ◽  
Carolina Hermida-Merino ◽  
João M. M. Araújo ◽  
Manuel M. Piñeiro ◽  
...  

Membrane technology can play a very influential role in the separation of the constituents of HFC refrigerant gas mixtures, which usually exhibit azeotropic or near-azeotropic behavior, with the goal of promoting the reuse of value-added compounds in the manufacture of new low-global warming potential (GWP) refrigerant mixtures that abide by the current F-gases regulations. In this context, the selective recovery of difluorometane (R32, GWP = 677) from the commercial blend R410A (GWP = 1924), an equimass mixture of R32 and pentafluoroethane (R125, GWP = 3170), is sought. To that end, this work explores for the first time the separation performance of novel mixed-matrix membranes (MMMs) functionalized with ioNanofluids (IoNFs) consisting in a stable suspension of exfoliated graphene nanoplatelets (xGnP) into a fluorinated ionic liquid (FIL), 1-ethyl-3-methylpyridinium perfluorobutanesulfonate ([C2C1py][C4F9SO3]). The results show that the presence of IoNF in the MMMs significantly enhances gas permeation, yet at the expense of slightly decreasing the selectivity of the base polymer. The best results were obtained with the MMM containing 40 wt% IoNF, which led to an improved permeability of the gas of interest (PR32 = 496 barrer) with respect to that of the neat polymer (PR32 = 279 barrer) with a mixed-gas separation factor of 3.0 at the highest feed R410A pressure tested. Overall, the newly fabricated IoNF-MMMs allowed the separation of the near-azeotropic R410A mixture to recover the low-GWP R32 gas, which is of great interest for the circular economy of the refrigeration sector.


RSC Advances ◽  
2021 ◽  
Vol 11 (9) ◽  
pp. 5086-5095
Author(s):  
Shuli Wang ◽  
Xiaohua Tong ◽  
Chunbo Wang ◽  
Xiaocui Han ◽  
Sizhuo Jin ◽  
...  

Effect of substituents on the dihedral angle and chain packing plays a critical role in the enhancement in the gas separation performance of polymer membranes.


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