Multicomponent transport of methanol and sodium acetate in poly(ethylene glycol) diacrylate membranes of varied fractional free volume

Dobyns, Breanna M.; Kim, Jung Min; Beckingham, Bryan S.

doi:10.1016/j.eurpolymj.2020.109809

Cited by 15 publications

(30 citation statements)

References 82 publications

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“…Here, the hydration number plays a role as the hydration number of HCO 3 − (7-8 [66]) is higher than that of Cl − (5.1-8.4 [67,68]) and, therefore, the films in HCO 3 − form are more likely to hold more water molecules compared to the films in Cl − form. The dry polymer density of A0 (1.22 g/mL) is consistent with previously reported values [35,41,48]. Generally, the densities of the PEGDA-based films are higher than those of PS-DVB-based AMVN, in part due to the difference in atomic compositions; see Supporting Information Table S5 for values.…”

Section: Water Uptake Density and Water Volume Fractionsupporting

confidence: 89%

“…Film density was measured by the buoyancy method with a density kit (ML-DNY-43, Mettler Toledo) coupled with a scale (ML204T, Mettler Toledo) [ 48 ]. The density, ρ p , was calculated as follows:

where ρ L is the density of water (997.8 kg/m 3 at 22 °C), ρ 0 is the density of air (1.225 kg/m 3 ), W 0 is the weight of the dried film in air, and W L is the weight of the film in water.…”

Section: Methodsmentioning

confidence: 99%

“…where W s is the mass of the swollen film and W d is the mass of the dried film. Film density was measured by the buoyancy method with a density kit (ML-DNY-43, Mettler Toledo) coupled with a scale (ML204T, Mettler Toledo) [48]. The density, ρ p , was calculated as follows:…”

Section: Water Content Density and Water Volume Fractionmentioning

confidence: 99%

“…Additionally, we measure carboxylate permeability (in co-diffusion) and solubility (from a mixture) with ethanol (EtOH). We then calculate diffusivities (D i ) to OFm − and OAc − in both K + and Na + forms (KOFm, KOAc, NaOFm and NaOAc) using the solution-diffusion model (Equation ( 1)) [39], which describes the overall solute permeation, which is dependent on solute sorption [22,[40][41][42][43] into the membrane and diffusion [18,42,44,45] through the fractional free volume [46][47][48][49] within the polymer matrix,…”

Section: Introductionmentioning

confidence: 99%

“…Additionally, we measure carboxylate permeability (in co-diffusion) and solubility (from a mixture) with ethanol (EtOH). We then calculate diffusivities ( D i ) to OFm − and OAc − in both K + and Na + forms (KOFm, KOAc, NaOFm and NaOAc) using the solution-diffusion model (Equation (1)) [ 39 ], which describes the overall solute permeation, which is dependent on solute sorption [ 22 , 40 , 41 , 42 , 43 ] into the membrane and diffusion [ 18 , 42 , 44 , 45 ] through the fractional free volume [ 46 , 47 , 48 , 49 ] within the polymer matrix, P i = D i K i , where

is the permeability to solute i ,

is the diffusivity to solute i , and

is the solubility to solute i , for EtOH [ 8 , 50 ] or a carboxylate anion (OFm − or OAc − [ 51 , 52 ]) in single and co-transport between EtOH and a carboxylate (EtOH-KOFm, EtOH-KOAc, EtOH-NaOFm and EtOH-NaOAc. The multi-solute permeability measurement was enabled by our in situ ATR–FTIR probe approach, which we recently devised [ 29 ].…”

Section: Introductionmentioning

confidence: 99%

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Transport and Co-Transport of Carboxylate Ions and Ethanol in Anion Exchange Membranes

et al. 2021

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Understanding multi-component transport behavior through hydrated dense membranes is of interest for numerous applications. For the particular case of photoelectrochemical CO2 reduction cells, it is important to understand the multi-component transport behavior of CO2 electrochemical reduction products including mobile formate, acetate and ethanol in the ion exchange membranes as one role of the membrane in these devices is to minimize the permeation of these products. Anion exchange membranes (AEM) have been employed in these and other electrochemical devices as they act to facilitate the transport of common electrolytes (i.e., bicarbonates). However, as they act to facilitate the transport of carboxylates as well, thereby reducing the overall performance, the design of new AEMs is necessary to improve device performance through the selective transport of the desired ion(s) or electrolyte(s). Here, we investigate the transport behavior of formate and acetate and their co-transport with ethanol in two types of AEMs: (1) a crosslinked AEM prepared by free-radical copolymerization of a monomer with a quaternary ammonium (QA) group and a crosslinker, and (2) Selemion® AMVN. We observe a decrease in diffusivities to carboxylates in co-diffusion. We attribute this behavior to charge screening by the co-diffusing alcohol, which reduces the electrostatic attraction between QAs and carboxylates.

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Section: Water Uptake Density and Water Volume Fractionsupporting

confidence: 89%

where ρ L is the density of water (997.8 kg/m 3 at 22 °C), ρ 0 is the density of air (1.225 kg/m 3 ), W 0 is the weight of the dried film in air, and W L is the weight of the film in water.…”

Section: Methodsmentioning

confidence: 99%

Section: Water Content Density and Water Volume Fractionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…Additionally, we measure carboxylate permeability (in co-diffusion) and solubility (from a mixture) with ethanol (EtOH). We then calculate diffusivities ( D i ) to OFm − and OAc − in both K + and Na + forms (KOFm, KOAc, NaOFm and NaOAc) using the solution-diffusion model (Equation (1)) [ 39 ], which describes the overall solute permeation, which is dependent on solute sorption [ 22 , 40 , 41 , 42 , 43 ] into the membrane and diffusion [ 18 , 42 , 44 , 45 ] through the fractional free volume [ 46 , 47 , 48 , 49 ] within the polymer matrix, P i = D i K i , where

is the permeability to solute i ,

is the diffusivity to solute i , and

Section: Introductionmentioning

confidence: 99%

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Transport and Co-Transport of Carboxylate Ions and Ethanol in Anion Exchange Membranes

et al. 2021

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Transport and co‐transport of carboxylate ions and alcohols in cation exchange membranes

Kim

Beckingham

2021

Journal of Polymer Science

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Understanding multi‐component transport behavior through hydrated dense membranes is of interest for numerous applications. For the particular case of photoelectrochemical CO2 reduction cells (PEC‐CRC), it is important to understand the multi‐component transport behavior of CO2 electrochemical reduction products including mobile carboxylates (formate and acetate) and alcohols (methanol and ethanol) in the ion exchange membranes as one role of the membrane in these devices is to minimize the permeation of these CO2 reduction products to the anolyte as they often oxidize back to CO2. Cation exchange membranes (CEM) are promising candidates for such devices as they act to minimize the permeation of mobile anions, such as carboxylates. However, the design of new CEMs is necessary as the permeation of carboxylates often increases in co‐permeation with alcohols. Here, we investigate the transport behavior of carboxylates and alcohols in two types of CEMs (1) a crosslinked CEM was prepared by free‐radical copolymerization of a sulfonated monomer (AMPS) with a crosslinker (PEGDA), and (2) Nafion® 117. We observe an increase in both PEGDA‐AMPS and Nafion® 117 diffusivities to carboxylates in co‐diffusion with alcohols. We attribute this behavior to charge screening by co‐diffusing alcohol that reduces the electrostatic repulsion between bound sulfonates and mobile carboxylates.

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Impact of hydrophobic pendant phenyl groups on transport and co-transport of methanol and acetate in PEGDA-SPMAK cation exchange membranes

Kim

Lin

Aravindhan

et al. 2022

Chemical Engineering Research and Design

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Multicomponent transport of methanol and sodium acetate in poly(ethylene glycol) diacrylate membranes of varied fractional free volume

Cited by 15 publications

References 82 publications

Transport and Co-Transport of Carboxylate Ions and Ethanol in Anion Exchange Membranes

Transport and Co-Transport of Carboxylate Ions and Ethanol in Anion Exchange Membranes

Transport and co‐transport of carboxylate ions and alcohols in cation exchange membranes

Impact of hydrophobic pendant phenyl groups on transport and co-transport of methanol and acetate in PEGDA-SPMAK cation exchange membranes

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