Evaluation of carboxylic, phosphonic, and sulfonic acid protogenic moieties on tunable poly(<i>meta</i>‐phenylene oxide) ionomer scaffolds

Hudson, Reuben; Adhikari, Ramesh; Tuominen, Mark; Hanzu, Ilie; Wilkening, Martin; Thayumanavan, S.; Katz, Jeffrey L.

doi:10.1002/pola.29503

Cited by 10 publications

(6 citation statements)

References 30 publications

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“…Notably, in FSP6 , the lower value of σ = 2.80 × 10 –5 S cm –1 ( R = 6857.80 Ω) at pH = 8.0 confirmed the prevalence of proton conductivity by −C(O)N H , −C(N)O H , and – SO 3 H , and −CH 2 O H (Table ). , Indeed, the presence of good proton acceptor −C(O)N in HMMIDPSA, semicrystallinity of PVA, AMMPSA-encapsulated water proton-bridges along with the hydrophilic channel generated by hydrogen-bonded dipolar functional groups of HMAMD, AMMPSA, HMMIDPSA, and PVA facilitated Grotthuss proton jump in the supramolecular network of FSP6 . − In addition to proton conductivity, highly facilitated through-space π – π * transitions in FSP6 / FSP6 -amide-aggregate were expected to endow electrical conductivity, as evident from the CV study of FSP6 . In this regard, band gaps of FSP6 -amide, FSP6 -amide canonical, and FSP6 -imidol, i.e., 3.76, 3.01, and 2.38 eV, calculated from the Tauc plots, were in the range of semiconducting materials (Figure S40).…”

Section: Results and Discussionmentioning

confidence: 99%

Excited-State Intramolecular Proton- and Inter-Polymer Charge-Transfer of Semiconducting Redox Polymers for Fe(III), Cd(II), and Hg(II) Sensing

Deb,

Roy,

Mitra

et al. 2024

ACS Appl. Polym. Mater.

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Herein, IPCT-ESIPT exhibiting nonconventional fluorescent semiconducting polymers (FSPs) are synthesized using poly(vinyl alcohol) (PVA), 2-acrylamido-2-methylpropanesulfonic acid, N-hydroxymethyl acrylamide, and in situ-generated 2-(3-(N-(hydroxymethyl)acrylamido)propanamido)-2-methylpropane-1-sulfonic acid. The IPCT- and ESIPT-mediated triple-light emission at different excitation wavelengths (λex); coexistence of FSP6-amide, FSP6-imidol, and FSP6-amide canonical; and ICT-/PET-assisted sensing capabilities of FSP6 are explored via spectroscopic analyses, computational calculations, electrochemical measurements, and impedance analyses. The π–π* transitions, IPCT–ESIPT, N-branching- and −CH3 group (side chain)-associated rigidity, alongside hydrophilic/hydrophobic balance are facilitated by −C(O)NH/–C(O)N, −C(N)OH, −C(O–)N+, and −SO3H heteroatomic subluminophores. The enhancement in hydrogen bonds and stabilization of −C(O–)N+/–C(N)OH in a polar-protic environment by the hydroxyl functionalities of semicrystalline PVA facilitate IPCT/ESIPT emission and electron/proton transport through the channels generated in the polymer matrix. The ICT-mediated reduction and oxidation of Fe(III) and Cd(II), respectively, and PET-mediated reduction of Hg(II) are explored via quenching/enhancement of photoluminescence in the presence of Fe(III) and Hg(II)/Cd(II), spectroscopic analyses, cyclic voltammetry, and impedance data. The detections of Fe(III), Cd(II), and Hg(II) by FSP6-amide, FSP6-amide canonical, and FSP6-imidol, respectively, are confirmed by low limits of detection of 1.225 (λex1), 5.241 (λex2), and 2.249 (λex3) ppb. The ac impedance spectroscopy and I–V data of semiconducting FSP6 indicate proton/electron conductivity = 3.37 × 10–5/2.80 × 10–5 S cm–1 (pH = 7.0/8.0).

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Section: Results and Discussionmentioning

confidence: 99%

Excited-State Intramolecular Proton- and Inter-Polymer Charge-Transfer of Semiconducting Redox Polymers for Fe(III), Cd(II), and Hg(II) Sensing

Deb,

Roy,

Mitra

et al. 2024

ACS Appl. Polym. Mater.

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“…Particularly, the nitrogen sites in imidazole-based IL form hydrogen bonds with the sulfonic group of Nafion, allowing for facile proton hopping in systems with low water content [ 108 , 109 ]. Additionally, because of its negligible low vapor pressure, IL does not readily evaporate and thus has shown promise as an alternative strategy for the creation of low humidity and high-temperature PEM materials [ 110 ].…”

Section: Modification Strategiesmentioning

confidence: 99%

A State-of-Art on the Development of Nafion-Based Membrane for Performance Improvement in Direct Methanol Fuel Cells

Thiam

Pang

et al. 2022

Membranes

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Nafion, a perfluorosulfonic acid proton exchange membrane (PEM), has been widely used in direct methanol fuel cells (DMFCs) to serve as a proton carrier, methanol barrier, and separator for the anode and cathode. A significant drawback of Nafion in DMFC applications is the high anode-to-cathode methanol fuel permeability that results in over 40% fuel waste. Therefore, the development of a new membrane with lower permeability while retaining the high proton conductivity and other inherent properties of Nafion is greatly desired. In light of these considerations, this paper discusses the research findings on developing Nafion-based membranes for DMFC. Several aspects of the DMFC membrane are also presented, including functional requirements, transport mechanisms, and preparation strategies. More importantly, the effect of the various modification approaches on the performance of the Nafion membrane is highlighted. These include the incorporation of inorganic fillers, carbon nanomaterials, ionic liquids, polymers, or other techniques. The feasibility of these membranes for DMFC applications is discussed critically in terms of transport phenomena-related characteristics such as proton conductivity and methanol permeability. Moreover, the current challenges and future prospects of Nafion-based membranes for DMFC are presented. This paper will serve as a resource for the DMFC research community, with the goal of improving the cost-effectiveness and performance of DMFC membranes.

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“…The higher the density of sulfonic acid groups in the membrane, the higher the density of hydronium ions composed of ionized protons and water molecules, resulting in a PEM exhibiting high proton conductivities. To develop better performance PEMs, hydrocarbon-based proton-conducting PEMs without fluorinated chemical structures, such as sulfonated polysulfone, − polyphenylene, − poly(ether ether ketone) (PEEK), − polyimide, − polybenzimidazole, − cross-linked polystyrene, , and vinyl monomer-based block polymers, − etc., − have also been widely studied.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of a Cross-Linked Polymer Electrolyte Membrane with an Ultra-High Density of Sulfonic Acid Groups

Sato

Kajita

Noro

2023

ACS Appl. Polym. Mater.

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Sulfonated cross-linked polystyrene membranes, one of the hydrocarbon-based polymer electrolytes membranes (PEMs), are typically synthesized via sulfonation of cross-linked polystyrene. However, it is difficult to prepare a sulfonated cross-linked polystyrene with a high sulfonation level, i.e., a high mole fraction of styrenesulfonic acid unit (f sSA), by using conventional synthetic methods. In this study, to synthesize a relatively homogeneous cross-linked poly(styrenesulfonic acid) (CL-sSA) membrane with an f sSA of 90 mol % or higher, sulfonic acid groups in a styrenesulfonate monomer were protected by esterification, and then a cross-linked polymer was synthesized using the monomer and divinylbenzene. Finally, the cross-linked polymer was converted to CL-sSA by deprotecting the alkyl groups with a base. The conductivity of the CL-sSA membrane at 80 °C and 90% RH was 0.93 S cm–1, which is extremely high and much higher than those of commercially available Nafion 212 and Selemion HSFN membranes with a low f sSA. The synthetic scheme of the CL-sSA membrane used in this study is a very effective route for preparing highly conductive cross-linked PEMs with a high f sSA.

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Evaluation of carboxylic, phosphonic, and sulfonic acid protogenic moieties on tunable poly(meta‐phenylene oxide) ionomer scaffolds

Cited by 10 publications

References 30 publications

Excited-State Intramolecular Proton- and Inter-Polymer Charge-Transfer of Semiconducting Redox Polymers for Fe(III), Cd(II), and Hg(II) Sensing

Excited-State Intramolecular Proton- and Inter-Polymer Charge-Transfer of Semiconducting Redox Polymers for Fe(III), Cd(II), and Hg(II) Sensing

A State-of-Art on the Development of Nafion-Based Membrane for Performance Improvement in Direct Methanol Fuel Cells

Synthesis of a Cross-Linked Polymer Electrolyte Membrane with an Ultra-High Density of Sulfonic Acid Groups

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