Tailoring molecular interactions between microporous polymers in high performance mixed matrix membranes for gas separations

Lau, Cher Hon; Konstas, Kristina; Doherty, Cara M.; Smith, Stefan J. D.; Hou, Rujing; Wang, Huanting; Carta, Mariolino; Yoon, Hyunwoo; Park, Jaesung; Freeman, Benny D.; Malpass‐Evans, Richard; Lasseuguette, Elsa; Ferrari, Maria-Chiara; McKeown, Neil B.; Hill, Matthew

doi:10.1039/d0nr04801a

Cited by 22 publications

(12 citation statements)

References 46 publications

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“…In fact, they typically exhibit pore sizes between 3.5 and 8.5 Å so that CO 2 , which has a kinetic diameter of 3.3 Å, can interact with both sidewalls of the pores . However, the main advantage of PIMs probably lies in the ease of their synthesis and functionalization, which consents to introduce polar groups that improve the affinity for CO 2 .…”

Section: Introductionmentioning

confidence: 99%

Adjustable Functionalization of Hyper-Cross-Linked Polymers of Intrinsic Microporosity for Enhanced CO₂ Adsorption and Selectivity over N₂ and CH₄

Zhou

Rayer

Antonangelo

et al. 2022

ACS Appl. Mater. Interfaces

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In this paper, we report the design, synthesis, and characterization of a series of hyper-cross-linked polymers of intrinsic microporosity (PIMs), with high CO 2 uptake and good CO 2 /N 2 and CO 2 /CH 4 selectivity, which makes them competitive for carbon capture and biogas upgrading. The starting hydrocarbon polymers' backbones were functionalized with groups such as −NO 2 , −NH 2 , and −HSO 3 , with the aim of tuning their adsorption selectivity toward CO 2 over nitrogen and methane. This led to a significant improvement in the performance in the potential separation of these gases. All polymers were characterized via Fourier transform infrared (FTIR) spectroscopy and 13 C solid-state NMR to confirm their molecular structures and isothermal gas adsorption to assess their porosity, pore size distribution, and selectivity. The insertion of the functional groups resulted in an overall decrease in the porosity of the starting polymers, which was compensated with an improvement in the final CO 2 uptake and selectivity over the chosen gases. The best uptakes were achieved with the sulfonated polymers, which reached up to 298 mg g −1 (6.77 mmol g −1 ), whereas the best CO 2 /N 2 selectivities were recorded by the aminated polymers, which reached 26.5. Regarding CH 4 , the most interesting selectivities over CO 2 were also obtained with the aminated PIMs, with values up to 8.6. The reason for the improvements was ascribed to a synergetic contribution of porosity, choice of the functional group, and optimal isosteric heat of adsorption of the materials.

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Section: Introductionmentioning

confidence: 99%

Adjustable Functionalization of Hyper-Cross-Linked Polymers of Intrinsic Microporosity for Enhanced CO₂ Adsorption and Selectivity over N₂ and CH₄

Zhou

Rayer

Antonangelo

et al. 2022

ACS Appl. Mater. Interfaces

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“…The addition of porous fillers in the continuous phase plays an important role in the transport properties of MMMs, providing new pathways for gas transport, hence increasing gas permeability [ 16 , 17 , 18 , 19 , 20 , 21 ]. Furthermore, the incorporation of fillers might be a solution to tackle the physical aging of glassy polymers [ 22 , 23 , 24 , 25 , 26 , 27 ].…”

Section: Introductionmentioning

confidence: 99%

Hyper Cross-Linked Polymers as Additives for Preventing Aging of PIM-1 Membranes

et al. 2021

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Mixed-matrix membranes (MMMs) are membranes that are composed of polymers embedded with inorganic particles. By combining the polymers with the inorganic fillers, improvements can be made to the permeability compared to the pure polymer membranes due to new pathways for gas transport. However, the fillers, such as hyper cross-linked polymers (HCP), can also help to reduce the physical aging of the MMMs composed of a glassy polymer matrix. Here we report the synthesis of two novel HCP fillers, based on the Friedel–Crafts reaction between a tetraphenyl methane monomer and a bromomethyl benzene monomer. According to the temperature and the solvent used during the reaction (dichloromethane (DCM) or dichloroethane (DCE)), two different particle sizes have been obtained, 498 nm with DCM and 120 nm with DCE. The change in the reaction process also induces a change in the surface area and pore volumes. Several MMMs have been developed with PIM-1 as matrix and HCPs as fillers at 3% and 10wt % loading. Their permeation performances have been studied over the course of two years in order to explore physical aging effects over time. Without filler, PIM-1 exhibits the classical aging behavior of polymers of intrinsic microporosity, namely, a progressive decline in gas permeation, up to 90% for CO2 permeability. On the contrary, with HCPs, the physical aging at longer terms in PIM-1 is moderated with a decrease of 60% for CO2 permeability. 13C spin-lattice relaxation times (T1) indicates that this slowdown is related to the interactions between HCPs and PIM-1.

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“…CO 2 , with a slightly larger kinetic diameter than H 2 (3.30 vs 2.89 Å), was affected more by the UV irradiation, that showed permeability lower than the control membrane ( P (CO 2 ) MUV5 = 16700 Barrer vs P (CO 2 ) PUV0 = 25520 Barrer) but still higher than most of the recently published advanced materials including PIMs, thermally rearrangeable (TR) membranes, and cross-linked PTMSP, XPIM-BM/TB, and TOXPIM-1 membranes (Figure and Table S3). ,,,,,,,− On the other hand, compared with methods of thermal cross-linking (∼300–400 °C, several hours) and photochemically cross-linking by adding an extra cross-linking agent as compared in Figure , photo-oxidation is a more simple and rapid way to improve membrane selectivity (5 min UV irradiation at ambient atmosphere needed for PTMSP based membranes in this study). As a result, desirable membrane performance with both high permeability and selectivity achieved by the coupling effect of PAF-1 incorporation and UV exposure presents more opportunities for the commercially available PTMSP membrane applied to gas separation.…”

Section: Resultsmentioning

confidence: 88%

Enhanced Membrane Performance for Gas Separation by Coupling Effect of the Porous Aromatic Framework (PAF) Incorporation and Photo-Oxidation

Hou

Eden

Fong

et al. 2021

Ind. Eng. Chem. Res.

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Membrane separation is a promising technology for hydrogen purification or carbon capture due to its high energy efficiency. However, the trade-off between permeability versus selectivity and the gradual reduction of membrane permeability caused by physical aging restrict further development of glassy membranes. Poly(1-trimethylsilyl-1-propyne) (PTMSP), a highly permeable polymer, is limited by its low selectivity and fast physical aging properties. Mixed matrix membranes (MMMs) have been considered as an effective approach to improve membrane performance by embedding nanoparticles into a polymer matrix. By expanding our previous studies on PTMSP MMMs, which illustrated the effects of the incorporated nanoparticle size, their dispersion behavior, and interaction at the polymer−nanoparticle interface on the overall membrane performance, this study further investigated the coupling effects of porous aromatic framework (PAF-1) incorporation and the subsequent post-UV treatment on PTMSP/PAF-1 MMMs. The resulting membrane had enhanced gas permeability (up to 76% increase) contributed by highly porous PAF-1 incorporation and simultaneously improved gas selectivity (up to 260% increase) granted by the densified/selective thin layer formed on the membrane surface upon UV irradiation. This optimum membrane performance surpassed the 2008 upper bound [Robeson, L. M. The upper bound revisited. Journal of Membrane Science 2008, 320 (1), 390−400] for CO 2 gas pairs (CO 2 /CH 4 and CO 2 /N 2 ) and reached the 2015 upper bound [

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Tailoring molecular interactions between microporous polymers in high performance mixed matrix membranes for gas separations

Abstract: Membranes are crucial to lowering the huge energy costs of chemical separations. Whilst some promising polymers demonstrate excellent transport properties, problems of plasticisation and physical aging due to mobile polymer...

Cited by 22 publications

References 46 publications

Adjustable Functionalization of Hyper-Cross-Linked Polymers of Intrinsic Microporosity for Enhanced CO₂ Adsorption and Selectivity over N₂ and CH₄

Adjustable Functionalization of Hyper-Cross-Linked Polymers of Intrinsic Microporosity for Enhanced CO₂ Adsorption and Selectivity over N₂ and CH₄

Hyper Cross-Linked Polymers as Additives for Preventing Aging of PIM-1 Membranes

Enhanced Membrane Performance for Gas Separation by Coupling Effect of the Porous Aromatic Framework (PAF) Incorporation and Photo-Oxidation

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Tailoring molecular interactions between microporous polymers in high performance mixed matrix membranes for gas separations

Abstract: Membranes are crucial to lowering the huge energy costs of chemical separations. Whilst some promising polymers demonstrate excellent transport properties, problems of plasticisation and physical aging due to mobile polymer...

Cited by 22 publications

References 46 publications

Adjustable Functionalization of Hyper-Cross-Linked Polymers of Intrinsic Microporosity for Enhanced CO2 Adsorption and Selectivity over N2 and CH4

Adjustable Functionalization of Hyper-Cross-Linked Polymers of Intrinsic Microporosity for Enhanced CO2 Adsorption and Selectivity over N2 and CH4

Hyper Cross-Linked Polymers as Additives for Preventing Aging of PIM-1 Membranes

Enhanced Membrane Performance for Gas Separation by Coupling Effect of the Porous Aromatic Framework (PAF) Incorporation and Photo-Oxidation

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Adjustable Functionalization of Hyper-Cross-Linked Polymers of Intrinsic Microporosity for Enhanced CO₂ Adsorption and Selectivity over N₂ and CH₄

Adjustable Functionalization of Hyper-Cross-Linked Polymers of Intrinsic Microporosity for Enhanced CO₂ Adsorption and Selectivity over N₂ and CH₄