Recent advances in synthesis, physical properties and applications of conducting polymer nanotubes and nanofibers

This article summarizes and reviews the various preparation methods, physical properties, and potential applications of one-dimensional nanostructures of conjugated polyaniline (PANI), polypyrrole (PPY) and poly(3,4-ethylenedioxythiophene) (PEDOT). The synthesis approaches include hard physical template method, soft chemical template method, electrospinning, and lithography techniques. Particularly, the electronic transport (e.g., electrical conductivity, current-voltage (I-V) characteristics, magnetoresistance, and nanocontact resistance) and mechanical properties of individual nanowires/tubes, and specific heat capacity, magnetic susceptibility, and optical properties of the polymer nanostructures are presented with emphasis on size-dependent behaviors. Several potential applications and corresponding challenges of these nanofibers and nanotubes in chemical, optical and bio-sensors, nano-diodes, field effect transistors, field emission and electrochromic displays, super-capacitors and energy storage, actuators, drug delivery, neural interfaces, and protein purification are also discussed.     

导电高分子纳米材料的制备方法研究现状

导电高分子纳米材料不仅具有一定的导电性能,而且兼具纳米材料的特殊性能,因而在很多领域具有广泛的应用前景。本文将导电高分子纳米材料的制备方法分为模板法和无模板法两大类进行探讨,模板法又分为硬模板和软模板法,主要以聚苯胺的制备进行举例,对每种方法的优缺点进行了分析,并对导电高分子纳米材料的未来发展进行了展望。     

Conducting Polymer Nanostructures and their Derivatives for Flexible Supercapacitors

This review provides a brief summary of the recent research developments in the fabrication and application of conducting polymer nanostructures and their derivatives as electrodes for flexible supercapacitors (SCs). By controlling the nucleation and growth process of polymerization, conducting polymers (CPs) with different nanostructures can be prepared by employing chemical polymerization, electrochemical polymerization and photo-induced polymerization. These CPs (such as polyaniline and polypyrrole) with special nanostructures possess high capacitance, superior rate capability ascribed to large electrochemical surface, and optimal ion diffusion path in the ordered nanostructures. The composites of nano-structured conducting polymer and some conductive flexible substrates (such as carbon nanotube film and graphene film) are proved to be ideal electrode materials for high performance flexible SCs. Furthermore, high N-containing CPs are very prospective for preparing N-doped carbon materials used as flexible electrodes for flexible SCs. With respect to the extra pseudo-capacitance induced by N atoms and superior stability derived from the conjugated graphitic structure of carbon materials, the obtained flexible SCs based on N-doped carbon materials could achieve high capacitance, high rate performance, and superior cycling stability.     

Trends in Conducting Polymer and Hybrids of Conducting Polymer/Carbon Nanotube: A Review

Several conducting polymers, including polyaniline, polypyrrole, polythiophene, polyvinylpyrrolidone, poly(3,4-ethylenedioxythiophene), poly(m-phenylenediamine), polynaphthylamine, poly(p-phenylene sulfide), and their carbon nanotube reinforced nanocomposites are discussed in this review. The physical, electrical, structural and thermal properties of polymers along with synthesis methods are discussed. A concise note on carbon nanotubes regarding their purification, functionalization, properties and production are reported. Moreover, the article focuses upon synthesis methods, properties and applications of conducting polymer/carbon nanotube nanocomposites are focused. Nanotube dispersion, loading concentration and alignment within conducting polymer/carbon nanotube nanocomposite affect their performance and morphology. The conducting polymer/carbon nanotube nanocomposites are substantially used in sensors, energy storage devices, supercapacitors, solar cells, EMI materials, diodes, and coatings.     

聚合物相变储能材料的合成及应用研究进展

相变储能技术在节能、环保方面有着巨大的市场潜力和广阔的应用前景,因此越来越受到人们的重视。本文着重介绍了聚合物相变储能材料的合成方法,并综述了聚合物相变储能材料在建筑、电力、太阳能利用等方面的应用研究进展。     

多级孔金属有机骨架材料的合成及其在生物医药中的应用研究进展

金属有机骨架（metal-organic frameworks,MOFs）是多孔材料领域的研究热点之一。MOFs具有高比表面积和孔道均一等特点,但微孔MOFs在大分子应用领域受到限制。本文介绍了延长配体法、模板剂法和聚合物法等多种制备多级孔MOFs的方法,合成后的多级孔MOFs兼具微孔、介孔和大孔,能够参与大分子反应,同时具有水热稳定性和化学稳定性,在催化、气体吸附分离、储能材料等诸多领域表现出优异性能。本文重点介绍了多级孔MOFs在生物医药领域的研究进展,结果表明多级孔MOFs是一种孔道可调节、可在特定条件下分解的生物相容性材料,用于固定化酶和负载医药分子均表现出良好性能。最后讨论了多级孔MOFs材料制备和应用目前存在的问题与挑战,展望了多级孔MOFs材料作为一类新型功能化多孔材料的应用前景。     

纳米纤维素复合相变储能气凝胶制备进展

超轻质材料气凝胶具有超低密度、高比表面积等性能,是高分子材料领域的研究热点之一.综述了纤维素气凝胶的制备、纤维素复合相变储能材料的制备等.纳米纤维素特殊的物性及其模板效应,以纳米纤维素为软模板,自组装制备纳米纤维素复合相变储能气凝胶.探讨了纳米纤维素复合相变储能气凝胶的应用趋势.     

锂离子电池聚合物正极材料研究进展

高储能的锂电池聚合物正极材料是近年来新型电化学能源研究发展的热点。本文综述了自由基聚合物、导电聚合物、有机多硫聚合物以及多骨架碳硫交联聚合物正极材料的结构、制备、导电机理和电化学性能。重点介绍了自由基聚合物氮氧结构的特点和快速充放电性能,导电聚合物的合成方法和掺杂机理,以及有机多硫聚合物和多骨架碳硫交联聚合物中—(S—S)n—键的高效储能特性和超高比容量性质。最后提出了解决聚合物材料容量的衰减和易降解性以保证稳定的循环性能以及完善合成及制备工艺是未来的研究重点。     

Polyaniline–vanadium oxide hybrid hierarchical architectures assembled from nanoscale building blocks by homogeneous polymerization

BACKGROUND: Polyaniline–vanadium oxide hybrid materials have been much researched due to their potential applications in lithium batteries. Although many methods have been reported for the fabrication of conventional polyaniline–vanadium oxide hybrid materials by in situ oxidative polymerization/intercalation of aniline in V₂O₅ and by layer‐by‐layer approaches, studies on polyaniline–vanadium oxide hybrid nanostructures have been rare. RESULTS: Polyaniline–vanadium oxide hybrid hierarchical architectures assembled from nanoscale building blocks, such as nanoplates and nanobelts, have been synthesized by a one‐step hydrothermal homogeneous reaction between aniline and peroxovanadic acid without the aid of any surfactant or template. The influences of synthesis parameters, i.e. reaction time, temperature and medium, on the morphologies of the polyaniline–vanadium oxide hybrid nanostructures have been investigated. With increasing reaction time/temperature, the alignment of nanoplates in the hierarchical architectures becomes gradually dense. CONCLUSION: The formation mechanism of the polyaniline–vanadium oxide hybrid hierarchical architectures involves a one‐step precipitation–polymerization–assembly process. The method may be applicable for the synthesis of other conducting polymer–vanadium oxide hybrid nanostructures. Copyright © 2009 Society of Chemical Industry     

A review on porous polymer composite materials for multifunctional electronic applications

ABSTRACT

This review is focused on the rapidly expanding field of porous materials for the sensor, actuator, energy storage and energy generation application. The synthesis methods to produce excellent porous composites and designs required for the domestic applications are also discussed. The properties of the porous composite materials are characterized and compared with non-porous polymer composite materials. In addition, porous materials based on polymer blends and their controllable synthesis methods for adjusting anticipated properties are highlighted. The properties, processing methods, applications, limitations, challenges and promising directions of porous composite materials for imminent advancement in this field are discussed.     

Green Carbon Nanostructures for Functional Composite Materials

Carbon nanostructures are widely used as fillers to tailor the mechanical, thermal, barrier, and electrical properties of polymeric matrices employed for a wide range of applications. Reduced graphene oxide (rGO), a carbon nanostructure from the graphene derivatives family, has been incorporated in composite materials due to its remarkable electrical conductivity, mechanical strength capacity, and low cost. Graphene oxide (GO) is typically synthesized by the improved Hummers’ method and then chemically reduced to obtain rGO. However, the chemical reduction commonly uses toxic reducing agents, such as hydrazine, being environmentally unfriendly and limiting the final application of composites. Therefore, green chemical reducing agents and synthesis methods of carbon nanostructures should be employed. This paper reviews the state of the art regarding the green chemical reduction of graphene oxide reported in the last 3 years. Moreover, alternative graphitic nanostructures, such as carbons derived from biomass and carbon nanostructures supported on clays, are pointed as eco-friendly and sustainable carbonaceous additives to engineering polymer properties in composites. Finally, the application of these carbon nanostructures in polymer composites is briefly overviewed.     

三维金属氧化物纳米材料的研究进展

三维金属氧化物纳米材料（3D-MONs）具有独特的连续多孔网络结构特点,不仅使其保留了金属氧化物特有的化学性质,而且表现出低密度、高比表面积、高孔隙率、低热导率等优异的物理性能,是近年来纳米材料领域一个新的研究热点。综述了3D-MONs制备方法的研究进展,重点介绍了水热合成法、溶胶-凝胶法、模板法、溶液喷射法、直接发泡法,并对其共性与差异进行了讨论;探讨了3D-MONs在污水治理、空气净化、储能、隔热领域应用的研究进展;在此基础上,提出了合成3D-MONs需要解决的问题及其应用展望。     

Innovative polyelectrolytes/poly(ionic liquid)s for energy and the environment

This paper presents the work carried out within the European project RENAISSANCE‐ITN, which was dedicated to the development of innovative polyelectrolytes for energy and environmental applications. Within the project different types of innovative polyelectrolytes were synthesized such as poly(ionic liquid)s coming from renewable or natural ions, thiazolium cations, catechol functionalities or from a new generation of cheap deep eutectic monomers. Further, macromolecular architectures such as new poly(ionic liquid) block copolymers and new (semi)conducting polymer/polyelectrolyte complexes were also developed. As the final goal, the application of these innovative polymers in energy and the environment was investigated. Important advances in energy storage technologies included the development of new carbonaceous materials, new lignin/conducting polymer biopolymer electrodes, new iongels and single‐ion conducting polymer electrolytes for supercapacitors and batteries and new poly(ionic liquid) binders for batteries. On the other hand, the use of innovative polyelectrolytes in sustainable environmental technologies led to the development of new liquid and dry water, new materials for water cleaning technologies such as flocculants, oil absorbers, new recyclable organocatalyst platforms and new multifunctional polymer coatings with antifouling and antimicrobial properties. All in all this paper demonstrates the potential of poly(ionic liquid)s for high‐value applications in energy and enviromental areas. © 2017 Society of Chemical Industry     

Formation of polymer nanowires through electropolymerization of polybithiophene from mixed electrolyte solutions of tetrabutylammonium hexafluorophosphate and tetrabutylammonium chloride

Preparation of one-dimensional conducting polymer structures such as nanowires and nanotubes require anisotropic growth conditions. Usually, such conditions are achieved by applying a certain template or by patterning the substrate. In this work, we employ a new approach to facilitate the anisotropic growth of electrochemically deposited polybithiophene through variations of the conductivity of the growing material. If the deposited material varies in conductivity, the areas with less conducting material will sustain little or no electrochemical current and only the areas with sufficient conductivity will experience further growth. In this work, the conductivity variations and the resulting anisotropic growth are achieved by performing electropolymerization in mixed electrolyte solutions of tetrabutylammonium hexafluorophosphate and tetrabutylammonium chloride. No growth can be observed in pure tetrabutylammonium chloride because the resulting films are insulating. However, addition of small amounts of tetrabutylammonium hexafluorophosphate was found to selectively activate local nanometer-sized areas of the polymer surface where polymer nanowire growth was observed. The latter was confirmed by atomic-force microscopy (AFM). The local properties of the polymer nanostructures obtained with varying contents of tetrabutylammonium hexafluorophosphate were characterized.     

Polyelectrolyte templated polyaniline—film morphology and conductivity

A simple synthesis protocol for stable aqueous colloidal solutions of poly(4-styrenesulfonate) templated polyaniline is developed. The electrical conductivity and submicro/nano features observed in their spin-coated films are shown to be correlated to the polyelectrolyte template molecular weight. This demonstrates the utility of the latter as a new design element for conducting polymer films.     

Controlled accommodation of metal nanostructures within the matrices of polymer architectures through solution-based synthetic strategies

Controlled accommodation of metal nanostructures (MNSs) into the matrix of a well-defined polymer architecture offers an effective approach to achieve hierarchically structured nanocomposites with tunable synergistic properties to broaden application potentials in the emerging fields of energy, environmental science, and medicine. This review focuses on the recently developed zero-dimensional and one-dimensional MNSs@polymer hybrid nanostructures obtained by solution-based synthetic strategies. Progress in the controlled synthesis of those hybrid nanostructures in terms of the number (e.g., monomer, dimer and trimer), organization manner (e.g., linear alignment or confined assembly in certain domains), and spatial arrangement (e.g., in the core and shell) of the MNSs within the distinct polymer matrices are detailed. The synergistic properties and potential applications of those MNSs@polymer hybrids associated with their compositions and morphologies are also reviewed.     

Applications of Terminal Deoxynucleotidyl Transferase Enzyme in Biotechnology

The use of polymerase enzymes in biotechnology has allowed us to gain unprecedented control over the manipulation of DNA, opening up new and exciting applications in areas such as biosensing, polynucleotide synthesis, and DNA storage, aptamer development and DNA-nanotechnology. One of the most intriguing enzymes which has gained prominence in the last decade is terminal deoxynucleotidyl transferase (TdT), which is one of the only polymerase enzymes capable of catalysing the template independent stepwise addition of nucleotides onto an oligonucleotide chain. This unique enzyme has seen a significant increase in a variety of different applications. In this review, we give a comprehensive discussion of the unique properties and applications of TdT as a biotechnology tool, and the application in the enzymatic synthesis of poly/oligonucleotides. Finally, we look at the increasing role of TdT enzyme in biosensing, DNA storage, synthesis of DNA nanostructures and aptamer development, and give a future outlook for this technology.     

Electrochemical activity and microscopy of electrosynthesised poly(o-phenylenediamine) nanotubes

Poly(o-phenylenediamine) (PoPD) nanotube electrodes were obtained by templated electropolymerization employing anodic porous alumina membrane. Infrared Spectroscopy measurements confirmed the polymerization of oPD into the alumina templates. The electrochemical activity of the PoPD nanotube electrodes were assessed by cyclic voltammetry (CV) as a function of monomer concentration. The morphology of the obtained nanostructures was assessed by scanning electron microscopy measurements. The results showed that poly(o-phenylenediamine) nanotube arrays have uniform diameter and they match the aspect ratio of the anodic porous membrane used for the synthesis. A high filling factor of the polymer within the alumina template was also revealed. The CV studies showed that the electrochemical properties of the PoPD nanotubes are greatly influenced by the monomer concentration in the synthesis electrolyte.     

Novel actuators based on polypyrrole/carbide-derived carbon hybrid materials

Polypyrrole (PPy) hybrid films incorporated with porous carbide-derived carbon (CDC) particles are synthesized through a novel one-step electrochemical synthesis process that provides a simple and efficient alternative for current tape-casting and inkjet printing technologies to make conducting polymer–CDC-based electroactive composites. The resulting porous, robust and electrically conductive hybrid layer was used to fabricate electroactive polymer actuators both as perpendicularly expanding actuators and as bending trilayer actuators. Raman and FTIR spectroscopy confirm successful incorporation of CDC in the PPy matrix. Cyclic voltammograms confirm slightly higher charging/discharging currents of the PPyCDC hybrid. This indicates the successful coupling of CDC in order to increase electric double-layer capacitance in the hybrid films. The maximum steady state electromechanical diametrical strain is 13% for hybrid material which is in the same order of magnitude as for PPy and 10× more than previously reported CDC films made with non-conducting polymer binders. Furthermore, the expanding actuators made from hybrid material are more efficient than non-modified PPy actuators, having doubled the amount of swelling per injected charge. This improvement is very important since the low energy efficiency is a major shortcoming for ionic electroactive polymers. The high pseudocapacitance makes these new hybrid materials also interesting for energy storage applications.