Mesoscopic Simulations of the Hydrated Morphology of the Short-Side-Chain Perfluorosulfonic Acid Ionomer

Wang, Dongsheng; Paddison, Stephen J.

doi:10.1021/bk-2010-1040.ch006

Cited by 3 publications

(7 citation statements)

References 61 publications

(80 reference statements)

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“…Chlorosulfonation of Phenylphosphonic acid was carried out using Chlorosulfonic acid. This was confirmed by 1 H (Figure 129), 31 P and 13 C NMR. The product is highly prone to hydrolysis as observed by NMR.…”

Section: Chlorosulfonation Of Phenylphosphonic Acidsupporting

confidence: 53%

“…The resulting polymer was then reacted with lacunary heteropolyacid K 8 SiW 11 O 39 , and the resulting product was analyzed by NMR (see Figure 156). 31 P-NMR of the product after HPA attachment reaction shows three new peaks at 25.56, 10.93 and 8.31ppm, while the 31 P NMR of the starting polymer shows a peak at 12.80ppm which disappeared/shifts during the course of the reaction.…”

Section: Figure 155 Further Reactions Of Phosphonated/brominated 3m mentioning

confidence: 95%

“…This hydrolysis reaction was confirmed by NMR. -OCH 2 CH 3 of phosphonate ester peaks at 4.0ppm and 1.3ppm disappeared in 1 H-NMR spectrum (see Figure 153) and new phosphonic acid peak appeared at 13.7ppm in 31 P NMR spectrum (Figure 154). …”

Section: Phosphonation Of 3m Ionomer Containing Aryl-bromide Pendant mentioning

confidence: 99%

“…We resorted to 31 Phosphorus NMR to solve this puzzle because any loss of structure of Zirconium phosphonate, V should lead to formation of free phosphonic acid I, which should be detected by solution 31 P NMR, however, the 31 P NMR did not show any signal indicating that no free phosphorus was present in the solution (Figure 147). We also looked at the solid via 31 P NMR and indeed we see phosphorus signal around -8ppm corresponding to Zirconium phosphonate (Figure 148). This confirms that all the phosphorus is still bound in the solid to zirconium thereby indicating the stability of the Zr-O-P linkage.…”

Section: %mentioning

confidence: 99%

“…The polymer was reacted with Zirconyl chloride hydrate in a fluoride medium. The resulting material was analyzed by 31 P NMR in solid state (Figure 158). The peaks at -5.38 and 3.7 ppm clearly indicate that phosphonate groups are linked to Zirconium atoms.…”

Section: Figure 155 Further Reactions Of Phosphonated/brominated 3m mentioning

confidence: 99%

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Final Report - Membranes and MEA's for Dry, Hot Operating Conditions

Hamrock¹

2011

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Section: Chlorosulfonation Of Phenylphosphonic Acidsupporting

confidence: 53%

Section: Figure 155 Further Reactions Of Phosphonated/brominated 3m mentioning

confidence: 95%

Section: Phosphonation Of 3m Ionomer Containing Aryl-bromide Pendant mentioning

confidence: 99%

Section: %mentioning

confidence: 99%

Section: Figure 155 Further Reactions Of Phosphonated/brominated 3m mentioning

confidence: 99%

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Final Report - Membranes and MEA's for Dry, Hot Operating Conditions

Hamrock¹

2011

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Understanding short-side-chain perfluorinated sulfonic acid and its application for high temperature polymer electrolyte membrane fuel cells

Pan

Tang

2014

RSC Adv.

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The great demand for high-temperature operation of polymer electrolyte membrane fuel cells (PEMFCs) has been well answered by short-side-chain perfluorinated sulfonic acid (SSC-PFSA) membranes through a good balance between transport properties and stability. It has been evidenced that fuel cells assembled with SSC-PFSA possess higher and more stable performance at elevated temperature up to 130 C compared to that of fuel cells based on conventional long-side-chain (LSC) PFSA (Nafion®) membranes. Moreover, the shorter side-pendent chains and the absence of the ether group and of the tertiary carbon also endow SSC-PFSAs with better durability, making them more suitable for working at harsh conditions in fuel cell systems. This critical review is dedicated to summarizing the properties of SSC-PFSA and providing insight into an understanding of their micro-morphologies, mass diffusion, enhanced proton transportation and their mutual correlation. Diversified measurement techniques applied to investigate the evolution of micro-morphologies, unique diffusion and transportation properties of SSC-PFSAs are reviewed. Despite the higher crystalline and higher water absorption of SSC-PFSAs than those of LSC-PFSAs, the notably less developed and less interconnected ionic clusters in SSC-PFSAs lead to lower mass permeability, and hence the high water uptake is not as well translated into transportation performance as expected. The factors and reasons for the enhanced electrochemical performance of SSC-PFSAs such as higher proton conductivity at elevated temperatures and low humidity conditions are also discussed and understood. Highlights of recent advances in SSC-PFSAbased membranes for fuel cell applications at wider temperature ranges are summarized as general references for researchers to further prompt the development of SSC-PFSAs. The SSC-PFSAs based membranes give a bright future for the next generation of high-temperature PEMFCs.

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Coarse-grained model of water diffusion and proton conductivity in hydrated polyelectrolyte membrane

Lee

Vishnyakov

Neimark

2016

The Journal of Chemical Physics

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Using dissipative particle dynamics (DPD), we simulate nanoscale segregation, water diffusion, and proton conductivity in hydrated sulfonated polystyrene (sPS). We employ a novel model [Lee et al. J. Chem. Theory Comput. 11(9), 4395-4403 (2015)] that incorporates protonation/deprotonation equilibria into DPD simulations. The polymer and water are modeled by coarse-grained beads interacting via short-range soft repulsion and smeared charge electrostatic potentials. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with the base beads representing water and sulfonate anions. Morse bond formation and breakup artificially mimics the Grotthuss mechanism of proton hopping between the bases. The DPD model is parameterized by matching the proton mobility in bulk water, dissociation constant of benzenesulfonic acid, and liquid-liquid equilibrium of water-ethylbenzene solutions. The DPD simulations semi-quantitatively predict nanoscale segregation in the hydrated sPS into hydrophobic and hydrophilic subphases, water self-diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from isolated water clusters to a 3D network. The analysis of hydrophilic subphase connectivity and water diffusion demonstrates the importance of the dynamic percolation effect of formation and breakup of temporary junctions between water clusters. The proposed DPD model qualitatively predicts the ratio of proton to water self-diffusion and its dependence on the hydration level that is in reasonable agreement with experiments.

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Mesoscopic Simulations of the Hydrated Morphology of the Short-Side-Chain Perfluorosulfonic Acid Ionomer

Cited by 3 publications

References 61 publications

Final Report - Membranes and MEA's for Dry, Hot Operating Conditions

Final Report - Membranes and MEA's for Dry, Hot Operating Conditions

Understanding short-side-chain perfluorinated sulfonic acid and its application for high temperature polymer electrolyte membrane fuel cells

Coarse-grained model of water diffusion and proton conductivity in hydrated polyelectrolyte membrane

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