Impact of the synthesis method on the solid-state charge transport of radical polymers

Zhang, Yiren; Park, Albert; Cintora, Alicia; McMillan, Stephen R.; Harmon, Nicholas J.; Moehle, Austin; Flatté, Michael E.; Fuchs, Gregory D.; Ober, Christopher K.

doi:10.1039/c7tc04645f

Cited by 54 publications

(79 citation statements)

References 45 publications

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“…Similarly with PVF‐CNT, PTMA‐CNT exhibited homogeneous and nanoporous morphology (Figure S2.3, Supporting Information), with a specific capacitance of 75.6 mAh g −1 estimated from galvanostatic measurements (Figure S1.6, Supporting Information). Electron paramagnetic resonance (EPR) measurements indicated a radical yield of 72.5% for the PTMA polymer (Figure S1.5, Supporting Information), which is in the comparable range to literature values …”

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confidence: 83%

Asymmetric Redox‐Polymer Interfaces for Electrochemical Reactive Separations: Synergistic Capture and Conversion of Arsenic

et al. 2019

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in water as anionic arsenate (As(V)) or arsenite (As(III)), with the latter being acutely toxic and difficult to remove. [3] Commonly employed techniques to remove arsenic are coagulation-flocculation or chemical adsorption, both which require significant chemical input, and extensive pretreatment steps for As(III) to As(V) conversion. [3c] Thus, novel removal technologies that integrate removal and conversion of arsenic are critical for sustainable environmental management.The development of advanced materials for water purification, selective contaminant removal, and improved energy efficiency is critical to tackling water-energy nexus challenges, including through the design of more effective membranes and field-assisted adsorbents. [4] Electrochemical methods for water treatment such as capacitive deionization (CDI) have garnered increased attention as a desalination technology, and also as a heavy metal removal platform, due to their efficiency and low environmental footprint compared to typical methods. [5] Electrosorption systems benefit from inherent modularity and scalability, which opens the door to point of source remediation systems. Electrochemical conversion of As(III) to As(V) on carbon electrode has been investigated previously for CDI-based arsenic remediation. [5l,6] However, low arsenic selectivity in the presence of competing ions has limited the total uptake capacity of carbon-based CDI, [5c,h-l] as most arsenic contaminated water sources are composed of 10 to 1000-fold excess salts. [7] Thus, the design of molecularly selective functional adsorbents is necessary to address these materials chemistry limitations.Recent work has shown redox-active/Faradaic materials as an attractive platform for selective water contaminant removal. [8] Redox-active metallopolymers have demonstrated remarkable uptake of anions with significant selectivity, both of organic anions and heavy metal oxyanions. [8b,9] At the same time, asymmetric electrochemical systems have traditionally been proposed in energy-storage applications to enhance capacitance and electrochemical properties. [10] Here, we leverage this electrochemical design for the first time to integrate both the separation and the reactions step electrochemically at functionalized electrodes. We seek to combine two redox-active polymer Advanced redox-polymer materials offer a powerful platform for integrating electroseparations and electrocatalysis, especially for water purification and environmental remediation applications. The selective capture and remediation of trivalent arsenic (As(III)) is a central challenge for water purification due to its high toxicity and difficulty to remove at ultra-dilute concentrations. Current methods present low ion selectivity, and require multistep processes to transform arsenic to the less harmful As(V) state. The tandem selective capture and conversion of As(III) to As(V) is achieved using an asymmetric design of two redox-active polymers, poly(vinyl)ferrocene (PVF) and poly-TEMPO-methacrylate (PTMA). D...

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confidence: 83%

Asymmetric Redox‐Polymer Interfaces for Electrochemical Reactive Separations: Synergistic Capture and Conversion of Arsenic

et al. 2019

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“…2,[6][7] Zhang et al compared the conductivities of poly(2,2,6,6tetramethylpiperidinyloxy methacrylate) (PTMA) prepared by various synthetic routes and showed that varying the preparation conditions did not affect the radical yield or conductivities. 8 Recently, Joo et al reported an organic radical polymer exhibiting a remarkably high conductivity (20 S m -1 ) when prepared as a thin film, which is comparable to values reported for semiconducting conjugated polymers. 6 This enhanced conductivity was postulated to be the result of a self-organized percolating structure.…”

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confidence: 69%

Aqueous one-pot synthesis of epoxy-functional diblock copolymer worms from a single monomer: new anisotropic scaffolds for potential charge storage applications

et al. 2019

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“…A high dispersity is undesirable because low‐molecular‐weight polymer chains dispersed within the electrode gradually dissolve into the electrolyte . In contrast, controlled‐radical polymerization usually yields PTMA with a low dispersity ( Ð <1.2), but it is exceedingly difficult to achieve high molecular weights (>24 000 g mol −1 ) because of reversible chain transfer . Single‐electron‐transfer living radical polymerization can yield even higher PTMA molecular weights of 169 000 g mol −1 , but capacity fade is still an issue.…”

Section: Introductionmentioning

confidence: 99%

Solution‐Processable Thermally Crosslinked Organic Radical Polymer Battery Cathodes

et al. 2020

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Organic radical polymers are promising cathode materials for next‐generation batteries because of their rapid charge transfer and high cycling stability. However, these organic polymer electrodes gradually dissolve in the electrolyte, resulting in capacity fade. Several crosslinking methods have been developed to improve the performance of these electrodes, but they are either not compatible with carbon additives or compromise the solution processability of the electrodes. A one‐step post‐synthetic, carbon‐compatible crosslinking method was developed to effectively crosslink an organic polymer electrode and allow for easy solution processing. The highest electrode capacity of 104 mAh g−1 (vs. a theoretical capacity of 111 mAh g−1) is achieved by introducing 1 mol % of the crosslinker, whereas the highest capacity retention (99.6 %) is obtained with 3 mol % crosslinker. In addition, mass transfer was observed in situ by using electrochemical quartz crystal microbalance with dissipation monitoring. These results may guide future electrode design toward fast‐charging and high‐capacity organic electrodes.

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Impact of the synthesis method on the solid-state charge transport of radical polymers

Cited by 54 publications

References 45 publications

Asymmetric Redox‐Polymer Interfaces for Electrochemical Reactive Separations: Synergistic Capture and Conversion of Arsenic

Asymmetric Redox‐Polymer Interfaces for Electrochemical Reactive Separations: Synergistic Capture and Conversion of Arsenic

Aqueous one-pot synthesis of epoxy-functional diblock copolymer worms from a single monomer: new anisotropic scaffolds for potential charge storage applications

Solution‐Processable Thermally Crosslinked Organic Radical Polymer Battery Cathodes

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