Impact of PEGMA on transport and co-transport of methanol and acetate in PEGDA-AMPS cation exchange membranes

Kim, Jung Min; Mazumder, Antara; Li, Jing; Jiang, Zhihua; Beckingham, Bryan S.

doi:10.1016/j.memsci.2021.119950

Cited by 6 publications

(11 citation statements)

References 55 publications

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“…While diffusion of H 2(aq) is slower across thicker membranes, ion flux will also be proportionally depressed. The free volume model works reasonably well for neutral solutes with relatively high molecule weights and high swelling degree IEMs, suggesting that the permeants indeed transport through the solvated fraction of the membranes (Yasuda et al, 1969;Kato et al, 1992;Dischinger et al, 2020;Kim and Beckingham, 2021;Kim et al, 2021a;Kim et al, 2022a). However, for smaller solutes, such as H 2(aq) , and low swelling degree membranes, the permeant can plausibly be transported through the unsolvated free volumes within the polymer chains, akin to gas permeation across dense films (Baker, 2012).…”

Section: Ion/uncharged Solute Selectivitymentioning

confidence: 99%

Advancing ion-exchange membranes to ion-selective membranes: principles, status, and opportunities

Fan

Huang

Yip

2022

Front. Environ. Sci. Eng.

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Ion-exchange membranes (IEMs) are utilized in numerous established, emergent, and emerging applications for water, energy, and the environment. This article reviews the five different types of IEM selectivity, namely charge, valence, specific ion, ion/solvent, and ion/uncharged solute selectivities. Technological pathways to advance the selectivities through the sorption and migration mechanisms of transport in IEM are critically analyzed. Because of the underlying principles governing transport, efforts to enhance selectivity by tuning the membrane structural and chemical properties are almost always accompanied by a concomitant decline in permeability of the desired ion. Suppressing the undesired crossover of solvent and neutral species is crucial to realize the practical implementation of several technologies, including bioelectrochemical systems, hypersaline electrodialysis desalination, fuel cells, and redox flow batteries, but the ion/solvent and ion/uncharged solute selectivities are relatively understudied, compared to the ion/ion selectivities. Deepening fundamental understanding of the transport phenomena, specifically the factors underpinning structure-property-performance relationships, will be vital to guide the informed development of more selective IEMs. Innovations in material and membrane design offer opportunities to utilize ion discrimination mechanisms that are radically different from conventional IEMs and potentially depart from the putative permeability-selectivity tradeoff. Advancements in IEM selectivity can contribute to meeting the aqueous separation needs of water, energy, and environmental challenges.

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Section: Ion/uncharged Solute Selectivitymentioning

confidence: 99%

Advancing ion-exchange membranes to ion-selective membranes: principles, status, and opportunities

Fan

Huang

Yip

2022

Front. Environ. Sci. Eng.

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“…For all diffusion cell experiments containing one of the alcohols (methanol & ethanol), an in situ ATR-FTIR spectroscopy probe (Mettler-Toledo ReactIR™ 15 with shallow tip 9.5 mm DSub AgX DiComp probe, Columbus, OH, USA) was inserted into the sample port of the receiver cell in lieu of the conductivity meter as these solutes do not result in a large enough change in conductivity for accurate measurement. For the ATR FTIR spectroscopy analysis, the molar absorptivity coefficient is obtained following a calibration procedure which has been elaborately described in our previous work [ 15 , 16 , 17 , 18 ]; see Supporting Materials Table S2 for molar absorptivity values for all the solutes in all the wavelengths. The concentration versus time data extracted from either the conductivity or absorbance was analyzed by best fitting with the Yasuda model, Equation (1), to extract the permeability values of each solute in single, and multi-solute solutions.…”

Section: Methodsmentioning

confidence: 99%

“…To understand how membrane chemistry and structure impact solute transport and co-transport in an electrochemical cell, a tunable membrane platform is required to investigate structure-property relationships systematically. Crosslinked polyether-acrylate-based materials are one such platform that provides the leverage to synthesize membranes of various physiochemical properties by tuning the chemistry and structure [ 15 , 16 , 17 , 18 , 19 ].…”

Section: Introductionmentioning

confidence: 99%

“…Kim et al (2021) [ 17 ] investigated UV-crosslinked PEGDA membranes with three different uncharged comonomers acrylic acid (AA, n = 0), hydroxyethyl methacrylate (HEMA, n = 1), and poly(ethylene glycol) methacrylate (PEGMA, n = 5), where the permeability to carboxylates (including sodium acetate) was suppressed in PEGMA-containing cation exchange membranes in co-transport compared to the other comonomer membranes. To expand understanding of the role of the long-chain pendant group PEGMA in solute transport and co-transport in the PEGDA-based cation exchange membranes, Kim et al (2022) [ 18 ] prepared a series of PEGMA ( n = 5) containing films with varied PEGMA and AMPS content where permeability to NaOAc decreased in PEGMA containing membranes while co-transporting with MeOH compared to PEGMA-free membranes.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Controlling Fractional Free Volume, Transport, and Co-Transport of Alcohols and Carboxylate Salts in PEGDA Membranes

et al. 2022

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Understanding multi-component transport through polymer membranes is critical for separation applications such as water purification, energy devices, etc. Specifically for CO2 reduction cells, where the CO2 reduction products (alcohols and carboxylate salts), crossover of these species is undesirable and improving the design of ion exchange membranes to prevent this behavior is needed. Previously, it was observed that acetate transport increased in copermeation with alcohols for cation exchange membranes consisting of poly(ethylene glycol) diacrylate (PEGDA) and 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and that the inclusion of poly(ethylene glycol) methacrylate (PEGMA) (n = 5, n represents the number of ethylene oxide repeat units) could suppress this behavior. Here, we further investigate the role of PEGMA in modulating fractional free volume and transport behavior of alcohols and carboxylates. PEGDA-PEGMA membranes of varied membranes are fabricated with both varied pre −polymerization water content at constant PEGMA (n = 9) content and varied PEGMA content at two pre −polymerization water contents (20 and 60 wt.% water). Permeability to sodium acetate also decreases in these charge-neutral PEGDA-PEGMA membranes compared to PEGMA-free films. Therefore, incorporation of comonomers such as PEGMA with long side chains may provide a useful membrane chemistry structural motif for preventing undesirable carboxylate crossover in polymer membranes.

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“…Using in situ ATR FTIR spectroscopy for permeability and sorption-desorption experiment for solubility is an attractive approach for investigating relationships between membrane chemistry, solute mixtures, and transport behavior [ 12 , 23 , 24 , 25 , 66 , 67 ]. Dobyns et al [ 12 ] investigated transport of methanol and sodium acetate in crosslinked PEGDA membranes, where differences in permeabilities to methanol and sodium acetate in co-transport relative to single solute transport were observed depending on the amount of fractional free volume in the membrane.…”

Section: Experimental Approaches To Investigating Multicomponent Diff...mentioning

confidence: 99%

Theoretical and Experimental Considerations for Investigating Multicomponent Diffusion in Hydrated, Dense Polymer Membranes

et al. 2022

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In many applications of hydrated, dense polymer membranes—including fuel cells, desalination, molecular separations, electrolyzers, and solar fuels devices—the membrane is challenged with aqueous streams that contain multiple solutes. The presence of multiple solutes presents a complex process because each solute can have different interactions with the polymer membrane and with other solutes, which collectively determine the transport behavior and separation performance that is observed. It is critical to understand the theoretical framework behind and experimental considerations for understanding how the presence of multiple solutes impacts diffusion, and thereby, the design of membranes. Here, we review models for multicomponent diffusion in the context of the solution-diffusion framework and the associated experiments for characterizing multicomponent transport using diffusion cells. Notably, multicomponent effects are typically not considered when discussing or investigating transport in dense, hydrated polymer membranes, however recent research has shown that these effects can be large and important for understanding the transport behavior.

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Impact of PEGMA on transport and co-transport of methanol and acetate in PEGDA-AMPS cation exchange membranes

Cited by 6 publications

References 55 publications

Advancing ion-exchange membranes to ion-selective membranes: principles, status, and opportunities

Advancing ion-exchange membranes to ion-selective membranes: principles, status, and opportunities

Controlling Fractional Free Volume, Transport, and Co-Transport of Alcohols and Carboxylate Salts in PEGDA Membranes

Theoretical and Experimental Considerations for Investigating Multicomponent Diffusion in Hydrated, Dense Polymer Membranes

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