Three Dimensional Micro/Nano Structured Conjugated Polymer And Its Applications

Since the discovery of the electrical conductivity of polyacetylene in 1977,the upsurge of research and development of conducting polymers has been set up around the world.Conjugated conducting polymer is a conjugated Pi bond macromolecule materials,which change from insulator into conductor after chemical or electrochemical doped.Conjugated conducting polymers have attracted much attention due to their low density,high electrical conductivity,and solution prepare processing.Due to the poor environmental stability of polyacetylene,its application is limited.Other environmental stability polymer like Polyaniline,polypyrrole and polythiophene has become the three major varieties of structural conductive polymer.These conductive polymers have the advantages of both ionic and electronic carrier conductance mechanisms(with low interfacial impedance)and high electrochemical activity.Conductive polymers can easy change their properties.For example,by treating the chemical property,it can be made to capture simple anion material,or showing biological activity.The functional materials with different electrical conductivity and different oxidation/reduction properties can be obtained by properly treating their electrical properties.Even the polymers been synthesized,these attractive structural properties can be further treated by oxidation/reduction processes.However,most of the polymers obtained by chemical or electrochemical oxidation processes are typical amorphous solid.They are insoluble in organic solvents or water.These forms make it difficult to prepare on a large scale,which hinders the development of polymers' application.In the past few decades,a large amount of works have been carried out for the development of readily prepare electrically conductive polymers.There are two kinds of success ways:emulsion polymerization and gel polymerization.The conductive polymer hydrogel is a kind of latter,with water as the dispersion medium of the gel.The hydrophilic groups are introduced into the conducting polymers to cross-link water molecules with internal network.The hydrophobic groups become cross-linked polymer because swelling.It is a polymer network system,maintain a certain shape,can absorb a lot of water.As a new kind of polymer material,polymer hydrogel has the characteristics of organic conductor and hydrogel.This material has a lot of characteristics,such as high conductivity,high water content,pore structure,good biocompatibility,multi-connected micro/nano structure,high permeability of ions and molecules,which have great potential applications in energy storage devices,biosensors,and electrode materials etc.In this paper,we study on polyaniline hydrogel.We present a new type of superhydrophobic surface in which the key layer composed of a three-dimensional silica nanostructure is in situ replicated from a hydrogel template.The simple,efficient and scalable methodology use phytic acid as doping and crosslinking agent and TEOS as precursor solution.The resulting hybrid coating exhibit excellent superhydrophobic properties after salinization.The preparation process does not require any large-scale instruments and equipment and high-temperature.This hydrogel-based templating method offers a general yet versatile approach to achieve micro graphics combined with inkjet printing,spray coating techniques.Because the hydrogel precursors have good wettability,our hydrogel nanostructure-based coating are versatile and ready for coating onto virtually any substrates,including wood,cement,fabrics,glass and papers.Moreover,the superhydrophobic surfaces can be transparent and wear resistance after calculated or treated by nitric acid.Most importantly,the coating can sustain superhydrophobic property after mechanically stretching at 100%strain.According to the study of the inner morphology,the stretched coating was chapped to form mastoid domains with diameters of micro.The formation of the mastoid domains endows the coating stable and robust superhydrophobic properties against strains.In addition,we demonstrate the applications of these versatile surface as selective filters and sponges for the oil/water separation,which can continuously separate oils with the residue water contents less than 0.04%and selectively absorb oils up to 40 X their weight,respectively.It is necessary to point out that although PAni was proved to intrinsically favor its growth into fiber-like structure,PPy tends to grow into nanoparticles due preferred formation of branched and cross-linked chains.Moreover,there are a lot of methods,like seed method,interface synthesis method to prepare polyaniline nanowires without template.As for polypyrrole nanowires,we usually use hard or soft template method.In this letter,We propose for the first time a novel yet general supramolecular strategy to prepare morphology-controlled nanostructured conductive hydrogel using a dopant counterion of a disc-shaped liquid crystal phthalocyanine-3,4',4",4'''-tetrasulfonic acid tetrosodium salt(CuPcTs).The CuPcTs acts as both the dopant and gelator to self-assemble the PPy into nanostructured hydrogels.Through electrostatic interaction and hydrogen bonding between the tetra-functional CuPcTs and PPy chain,a self-sorting mechanism acts to align the PPy chains to form 1D nanostructured PPy.Our supramolecular self-assembly strategy exhibits several advantages,proving to be a facile approach to prepare nanostructured PPy hydrogels with tunable morphology by changing either the dopant used or its concentration.The diameter of the CuPcTs-PPy nanofibers can be tuned using different oxidative initiators from 40nm to 400nm.The conductivity of CuPcTs-PPy can enhance two order of magnitude compare to PPy.The nearly vertical shape of the obtained curve at lower frequencies indicates an ideal capacitive behavior of the CuPcTs-PPy hydrogel.The specific capacitance of the CuPcTs-doped PPy was calculated to be high as?400F g-1.The rate performance of CuPcTs-PPy is also shown to be higher than that of pristine PPy.This general supramolecular self-strategy with tunable morphology could be used to design and produce conducting polymer hydrogels with low-dimensional structures as material platforms for applications based on various structure-related properties,such as energy conversion and storage materials,sensors.The last part is about the study of the conjugated small molecule sodium rhodizonate dibasic(SR):A biomass-derived organic cathode material for rechargeable SIBs based on sodium rhodizonate dibasic with a high density of C=O groups was systematically investigated.SR samples with different sizes were synthesized using the anti-solvent method and used as model systems to investigate the size effect on sodium ion storage properties.Excellent cycle performance for SR nanorod electrodes was obtained over the potential range of 1.6-2.8 V,which corresponds to the insertion of less than 2 Na atoms.A stable discharge capacity of the SR nanorod reached?190 mA h g-1 at a current density of 0.1 C and retained over 90%of capacity after 100 charge/discharge cycles.The nanorod structure not only enhances the utilization of active materials but also improves the kinetics of the electrochemical reactions,thus limiting pulverization.This structure enables stable contact between SR and carbon black,which confers the high capacity,high rate capability,and long cycling stability of nanorod-based SIBs.We comprehensively investigated the sodiation mechanism of Na2C6O6 using cyclic voltammetry,DFT calculations,and XRD spectra.This combined approach allows for systematic investigation of the carbonyl-based organic SIB cathode materials,including their morphology,working potential,and electrochemical dynamics.With rational structure control,organic nanomaterials based electrodes may lead to the development of environmentally friendly,sustainable,yet high-performance SIBs.