Understanding the Degradation Mechanisms of Conducting Polymer Supercapacitors.

Conducting polymers like polyaniline (PANI) are promising pseudocapacitive electrode materials, yet experience instability in cycling performance. Since polymers often degrade into oligomers, short chain length anilines have been developed to improve the cycling stability of PANI-based supercapacitors. However, the capacitance degradation mechanisms of aniline oligomer-based materials have not been systematically investigated and are little understood. Herein, two composite electrodes based on aniline trimers (AT) and carbon nanotubes (CNTs) are studied as model systems and evaluated at both pre-cycling and post-cycling states through physicochemical and electrochemical characterizations. The favorable effect of covalent bonding between AT and CNTs is confirmed to enhance cycling stability by preventing the detachment of aniline trimer and preserving the electrode microstructure throughout the charge/discharge cycling process. In addition, higher porosity has a positive effect on electron/ion transfer and the adaptation to volumetric changes, resulting in higher conductivity and extended cycle life. This work provides insights into the mechanism of enhanced cycling stability of aniline oligomers, indicating design features for aniline oligomer electrode materials to improve their electrochemical performance.

Conducting Polyaniline for Antifouling Ultrafiltration Membranes: Solutions and Challenges.

Conjugated polyaniline can impact the field of water filtration membranes due to its hydrophilic and antibacterial nature, facile and inexpensive synthesis procedure, heat and acid tolerance, and unique doping/dedoping chemistry. However, the gelation effect, its rigid backbone, and the limited hydrophilicity of polyaniline severely restrict the adaptability to membranes and their antifouling performance. This Mini Review summarizes important works of polyaniline-related ultrafiltration membranes, highlighting solutions to conquer engineering obstacles in processing and challenges in enhancing surface hydrophilicity with an emphasis on chemistry. As a pH-responsive polymer convertible to a conductive salt, this classic material should continue to bring unconventional advances into the realm of water filtration membranes.

Polyaniline-Lignin Interpenetrating Network for Supercapacitive Energy Storage.

Because of increasing interest in environmentally benign supercapacitors, earth-abundant biopolymers have found their way into value-added applications. Herein, a promising nanocomposite based on an interpenetrating network of polyaniline and sulfonated lignin (lignosulfonate, LS) is presented. On the basis of an appropriate regulation of the nucleation kinetics and growth behavior via applying a series of rationally designed potential pulse patterns, a uniform PANI-LS film is achieved. On the basis of the fast rate of H+ insertion-deinsertion kinetics, rather than the slow SO42- doping-dedoping process, the PANI-LS nanocomposite delivers specific capacitance of 1200 F g-1 at 1 A g-1 surpassing the best conducting polymer-lignin supercapacitors known. A symmetric PANI-LS||PANI-LS device delivers a high specific energy of 21.2 W h kg-1, an outstanding specific power of 26.0 kW kg-1, along with superb flexibility and excellent cycling stability. Thus, combining charge storage attributes of polyaniline and lignosulfonate enables a waste-to-wealth approach to improve the supercapacitive performance of polyaniline.

Scalable antifouling reverse osmosis membranes utilizing perfluorophenyl azide photochemistry.

We present a method to produce anti-fouling reverse osmosis (RO) membranes that maintains the process and scalability of current RO membrane manufacturing. Utilizing perfluorophenyl azide (PFPA) photochemistry, commercial reverse osmosis membranes were dipped into an aqueous solution containing PFPA-terminated poly(ethyleneglycol) species and then exposed to ultraviolet light under ambient conditions, a process that can easily be adapted to a roll-to-roll process. Successful covalent modification of commercial reverse osmosis membranes was confirmed with attenuated total reflectance infrared spectroscopy and contact angle measurements. By employing X-ray photoelectron spectroscopy, it was determined that PFPAs undergo UV-generated nitrene addition and bind to the membrane through an aziridine linkage. After modification with the PFPA-PEG derivatives, the reverse osmosis membranes exhibit high fouling-resistance.

Versatile solution for growing thin films of conducting polymers.

The method employed for depositing nanostructures of conducting polymers dictates potential uses in a variety of applications such as organic solar cells, light-emitting diodes, electrochromics, and sensors. A simple and scalable film fabrication technique that allows reproducible control of thickness, and morphological homogeneity at the nanoscale, is an attractive option for industrial applications. Here we demonstrate that under the proper conditions of volume, doping, and polymer concentration, films consisting of monolayers of conducting polymer nanofibers such as polyaniline, polythiophene, and poly(3-hexylthiophene) can be produced in a matter of seconds. A thermodynamically driven solution-based process leads to the growth of transparent thin films of interfacially adsorbed nanofibers. High quality transparent thin films are deposited at ambient conditions on virtually any substrate. This inexpensive process uses solutions that are recyclable and affords a new technique in the field of conducting polymers for coating large substrate areas.

A Readily Scalable, Clinically Demonstrated, Antibiofouling Zwitterionic Surface Treatment for Implantable Medical Devices.

Unlike growth on tissue, microbes can grow freely on implantable devices with minimal immune system intervention and often form resilient biofilms that continuously pump out pathogenic cells. The efficacy of antibiotics used to treat infection is declining due to increased rates of pathogenic resistance. A simple, one-step zwitterionic surface modification is developed to significantly reduce protein and microbial adhesion to synthetic materials and demonstrate the successful modification of several clinically relevant materials, including recalcitrant materials such as elastomeric polydimethylsiloxane. The treated surfaces exhibit robust adhesion resistance against proteins and microorganisms in both static and flow conditions. Furthermore, the surface treatment prevents the adhesion of mammalian fibroblast cells while displaying no cytotoxicity. To demonstrate the clinical efficacy of the novel technology in the real-world, a surface-treated, commercial silicone foley catheter is developed that is cleared for use by the U.S. Food and Drug Administration (K192034). 16 long-term catheterized patients received surface-treated catheters and completed a Patient Global Impression of Improvement (PGI-I) questionnaire. 10 out of 16 patients described their urinary tract condition post implantation as "much better" or "very much better" and 72% (n = 13) of patients desire to continue using the surface-treated catheter over conventional latex or silicone catheters.

Applications of oligomers for nanostructured conducting polymers.

This Feature Article provides an overview of the distinctive nanostructures that aniline oligomers form and the applications of these oligomers for shaping the nanoscale morphologies and chirality of conducting polymers. We focus on the synthetic methods for achieving such goals and highlight the underlying mechanisms. The clear advantages of each method and their possible drawbacks are discussed. Assembly and applications of these novel organic (semi)conducting nanomaterials are also outlined. We conclude this article with our perspective on the main challenges, new opportunities, and future directions for this nascent yet vibrant field of research.

Low-Fouling Antibacterial Reverse Osmosis Membranes via Surface Grafting of Graphene Oxide.

Azide-functionalized graphene oxide (AGO) was covalently anchored onto commercial reverse osmosis (RO) membrane surfaces via azide photochemistry. Surface modification was carried out by coating the RO membrane with an aqueous dispersion of AGO followed by UV exposure under ambient conditions. This simple process produces a hydrophilic, smooth, antibacterial membrane with limited reduction in water permeability or salt selectivity. The GO-RO membrane exhibited a 17-fold reduction in biofouling after 24 h of Escherichia coli contact and almost 2 times reduced BSA fouling after a 1 week cross-flow test compared to its unmodified counterpart.

Vapor-phase polymerization of nanofibrillar poly(3,4-ethylenedioxythiophene) for supercapacitors.

Nanostructures of the conducting polymer poly(3,4-ethylenedioxythiophene) with large surface areas enhance the performance of energy storage devices such as electrochemical supercapacitors. However, until now, high aspect ratio nanofibers of this polymer could only be deposited from the vapor-phase, utilizing extrinsic hard templates such as electrospun nanofibers and anodized aluminum oxide. These routes result in low conductivity and require postsynthetic template removal, conditions that stifle the development of conducting polymer electronics. Here we introduce a simple process that overcomes these drawbacks and results in vertically directed high aspect ratio poly(3,4-ethylenedioxythiophene) nanofibers possessing a high conductivity of 130 S/cm. Nanofibers deposit as a freestanding mechanically robust film that is easily processable into a supercapacitor without using organic binders or conductive additives and is characterized by excellent cycling stability, retaining more than 92% of its initial capacitance after 10,000 charge/discharge cycles. Deposition of nanofibers on a hard carbon fiber paper current collector affords a highly efficient and stable electrode for a supercapacitor exhibiting gravimetric capacitance of 175 F/g and 94% capacitance retention after 1000 cycles.

Facile synthesis of water-dispersible conducting polymer nanospheres.

Water-dispersible polypyrrole nanospheres with diameters of less than 100 nm were synthesized in high yield without any templates, surfactants, or functional dopants by the introduction of 2,4-diaminodiphenylamine as an initiator into a reaction mixture of pyrrole monomer, oxidant, and acid. The initiator plays a critical role in tailoring the nanostructures of polypyrrole. 2,4-Diaminodiphenylamine interacts with acid to form cations, which combine with various anions to self-assemble resulting in different size nanomicelles. These nanomicelles, stabilized by initiator molecules, act as templates to encapsulate pyrrole and oxidant leading to the formation of nanospheres during polymerization. When smaller acids are used, smaller diameter sphere-like polypyrrole nanostructures are obtained. The as-synthesized polypyrrole nanospheres can then be used to fabricate highly conducting nitrogen-doped carbon nanospheres with controllable sizes of 50-220 nm with monodispersities up to 95% after pyrolysis. The size of the carbon nanospheres decreases by 20-30 nm due to carbonization when compared to the original polymer nanospheres. The molecular structures, morphologies, and electrical properties along with the formation mechanism of the polypyrrole and carbon nanospheres are discussed.

Processable aqueous dispersions of graphene nanosheets.

Graphene sheets offer extraordinary electronic, thermal and mechanical properties and are expected to find a variety of applications. A prerequisite for exploiting most proposed applications for graphene is the availability of processable graphene sheets in large quantities. The direct dispersion of hydrophobic graphite or graphene sheets in water without the assistance of dispersing agents has generally been considered to be an insurmountable challenge. Here we report that chemically converted graphene sheets obtained from graphite can readily form stable aqueous colloids through electrostatic stabilization. This discovery has enabled us to develop a facile approach to large-scale production of aqueous graphene dispersions without the need for polymeric or surfactant stabilizers. Our findings make it possible to process graphene materials using low-cost solution processing techniques, opening up enormous opportunities to use this unique carbon nanostructure for many technological applications.

Toward an understanding of the formation of conducting polymer nanofibers.

Introducing small amounts of additives into polymerization reactions to produce conducting polymers can have a profound impact on the resulting polymer morphology. When an oligomer such as aniline dimer is added to the polymerization of aniline, the nanofibers produced are longer and less entangled than those typically observed. The addition of aniline dimer can even induce nanofiber formation under synthetic conditions that generally do not favor a nanofibrillar morphology. This finding can be extended to both the synthesis of polythiophene and polypyrrole nanofibers. The traditional oxidative polymerization of thiophene or pyrrole only produces agglomerated particles. However, when minute amounts of thiophene or pyrrole oligomers are added to the reaction, the resulting polymers possess a nanofibrillar morphology. These results reveal important insights into a semirigid rod nucleation phenomenon that has hitherto been little explored. When polyaniline nucleates homogeneously, surface energy requirements necessitate the formation of ordered nuclei which leads to the directional polymerization of aniline. This ultimately leads to the one-dimensional nanofibrillar morphology observed in the final product. The synthetic procedures developed here are simple, scalable, and do not require any templates or other additives that are not inherent to the polymer.

Polyaniline nanofiber/gold nanoparticle nonvolatile memory.

A nonvolatile plastic digital memory device based on nanofibers of the conjugated polymer polyaniline decorated with gold nanoparticles is reported. The device has a simple structure consisting of the plastic composite film sandwiched between two electrodes. An external bias is used to program the ON and OFF states of the device that are separated by a 3-orders-of-magnitude difference in conductivity. ON-OFF switching times of less than 25 ns are observed by electrical pulse measurements. The devices possess prolonged retention times of several days after they have been programmed. Write-read-erase cycles are also demonstrated. The switching mechanism is attributed to an electric-field-induced charge transfer from the polyaniline nanofibers to the gold nanoparticles. The active polymer layer is created by growing nanometer size gold particles within 30-nm-diameter polyaniline nanofibers using a redox reaction with chloroauric acid. This device combines two exciting research areas--nanoparticles and conducting polymers--to form a novel materials system with unique functionality.

Flash welding of conducting polymer nanofibres.

The absorption of light by a material generates heat through non-radiative energy dissipation and exothermic photochemical reactions. In nanostructured materials, the heat generated through photothermal processes will be confined within the individual nanostructures when heat transfer to neighbouring nanostructures and the environment is slow. This leads to unprecedented photothermal effects that cannot be observed in bulk materials, especially when a strong, pulsed light source is used. Here we demonstrate an enhanced photothermal phenomenon with conducting polymer nanofibres in which a camera flash causes instantaneous welding. Under flash irradiation, polyaniline nanofibres 'melt' to form a smooth and continuous film from an originally random network of nanofibres. This photothermal effect can be used to form asymmetric nanofibre films, to melt-blend polymer-polymer nanocomposites rapidly and to photo-pattern polymer nanofibre films.