Conducting polyaniline/nano-zinc phosphate composite as a pigment for corrosion protection of low-carbon steel

Zinc phosphate (Zn₃(PO₄)₂) nanocrystals were synthesized and used for making conducting polyaniline/nano-zinc phosphate composite by chemical oxidative method. The product was characterized by UV–visible absorption spectroscopy. The crystal structure, morphology and thermal stability of the product were studied by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and thermo gravimetric analysis, respectively. The epoxy-based paint containing conducting polyaniline/nano-zinc phosphate composite pigment was applied on low-carbon steel samples. Corrosion protection performance of the painted low-carbon steel samples in 3.5 mass % sodium chloride solution was evaluated using electrochemical technique. Transmission electron microscopic image revealed the formation of core shell structure of the composite. Composite was found to be more thermally stable than the conducting polyaniline. The corrosion rate of conducting polyaniline/nano-zinc phosphate-painted low-carbon steel was found to be 5.1 × 10^?4 mm per year, about 34 times lower than that of unpainted low-carbon steel and 10 times lower than that of epoxy nano-zinc phosphate paint-coated steel. The study reveals the possibility of using conducting polyaniline/nano-zinc phosphate as a pigment for corrosion protection.     

Fibriform polyaniline/nano-TiO2 composite as an electrode material for aqueous redox supercapacitors

Fibriform polyaniline/nano-TiO₂ composite is prepared by one-step in situ oxidation polymerization of aniline in the presence of nano-TiO₂ particles, which contains 80% conducting polyaniline by mass, with a conductivity of 2.45 S/cm at 25 °C. Its maximum specific capacitance is 330 F g^?1 at a constant current density of 1.5 A g^?1, and can be subjected to charge/discharge over 10,000 cycles in the voltage range of 0.05–0.55 V.     

Electrodeposition of Three‐Dimensional Porous Platinum Film on Removable Polyaniline Template for High‐Performance Electroanalysis

Three‐dimensional porous platinum (Pt_por) films are prepared based on Pt electrodeposition on polyaniline (PANI) modified electrodes followed by selective dissolution of PANI with HNO₃. Electrochemical quartz crystal microbalance data suggest that the PANI‐H₂PtCl₆ interaction involves redox and coordination reactions, depending on the working potential. The Pt_por shows better electrocatalytic performance than the Pt/PANI and conventionally electrodeposited Pt. The Pt_por modified glassy carbon electrode (GCE) can electrocatalyze the oxidation of H₂O₂ with a sensitivity of 414 µA cm^?2 mM^?1 and a detection limit of 9 nM, and the chitosan‐glucose oxidase/Pt_por/GCE can sense glucose with a sensitivity of 93.4 µA cm^?2 mM^?1.     

Synthesis and characterization of epoxidized polybutadiene/polyaniline graft conducting copolymer

In this article the synthesis and characterization of an elastomeric conducting material, obtained by grafting polyaniline (EB) on commercial cis‐1,4‐polybutadiene (PB), are described. PB was first partially epoxidized in chloroform solution using meta‐chloroperbenzoic acid (MCPBA). The conducting polymer was then grafted to the activated polybutadiene (EPB) via the aminolysis reaction between the polyaniline NH₂ terminal groups and the oxirane rings. The material so obtained (EPBPAN) and the epoxidized intermediate product were characterized by ¹H NMR, ¹³C NMR, Fourier transform infrared, and ultraviolet–visible spectroscopy, thermal and mechanical analysis, and electrical conductivity measurements. The effect of the sample deformation on conductivity also was analyzed. The HCl doping of the EPBPAN film induced crosslinking reactions, generated by the acid cleavage of unreacted oxirane groups. The electrical conductivity of the doped material reached values of about 10^?5 Ω^?1 cm^?1. The key characteristics of our elastomeric conducting material are its simple synthesis, its starting as a commercial product, and the solubility of its undoped form in a common low‐boiling organic solvent like chloroform. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3082–3090, 2004     

Conducting film-forming composites based on polyaniline-polyimide blends

A procedure is developed for preparing conducting films by their casting from polymer solutions containing polyaniline in the form of a protonated emeraldin base and polyimides in two cosolvents, N-methylpyrrolidone or m-cresol. Self-supporting films cast from composites based on polyimides and camphorsulfonic acid-protonated polyaniline combine a conductivity of 10^?1?10^?2S/cm with good mechanical properties: elastic modulus E = 2.0?2.4 GPa, breaking strength σ_b = 55?60 MPa, and elongation at break ?_b = 8?10%. It has been shown that, when m-cresol and N-methylpyrrolidone are used as cosolvents, the maximum film conductivity is achieved at polyaniline amounts in the composites of 20 and 3%, respectively. In the latter case, films with good strength parameters are formed.     

pH‐Dependent Proton Conducting Behavior in a Metal–Organic Framework Material

A porous metal–organic framework (MOF), [Ni₂(dobdc)(H₂O)₂]?6 H₂O (Ni₂(dobdc) or Ni‐MOF‐74; dobdc^4?=2,5‐dioxido‐1,4‐benzenedicarboxylate) with hexagonal channels was synthesized using a microwave‐assisted solvothermal reaction. Soaking Ni₂(dobdc) in sulfuric acid solutions at different pH values afforded new proton‐conducting frameworks, H⁺@Ni₂(dobdc). At pH 1.8, the acidified MOF shows proton conductivity of 2.2×10^?2 S cm^?1 at 80 °C and 95 % relative humidity (RH), approaching the highest values reported for MOFs. Proton conduction occurs via the Grotthuss mechanism with a significantly low activation energy as compared to other proton‐conducting MOFs. Protonated water clusters within the pores of H⁺@Ni₂(dobdc) play an important role in the conduction process.     

Methyl triphenylphosphonium permanganate as a novel oxidant for aniline to polyaniline-manganese(II,IV) oxide: material for high performance pseudocapacitor

In this work, organic-inorganic composite materials of polyaniline and manganese oxide were synthesized and investigated their electrochemical performance. This composite material was prepared by oxidizing aniline with methyl triphenylphosphonium permanganate as a novel organic oxidant via aqueous, emulsion, and interfacial polymerization pathways. This process led to the formation of polyaniline-sulfate salt (PANI-SA-Mn₅O₈). Formation of polyaniline-sulfate salt was confirmed from FT-IR, EDAX, and XRD results. Formation of Mn₅O₈ was supported by XRD spectrum. PANI-SA-Mn₅O₈ prepared via emulsion polymerization pathway was obtained in porous nanorod morphology with high conductivity (9.4 S cm^?1) compared to that of the other sample prepared via interfacial pathway (1.7 S cm^?1). Whereas, aqueous polymerization pathway resulted in sheet-like morphology with a conductivity of 0.8 S cm^?1. These composites were used as pseudocapacitive electrode materials. Electrochemical characterization (cyclic voltammetry, charge-discharge, and electrochemical impedance measurement) showed that composite prepared via emulsion polymerization pathway gave better electrochemical performance, and showed good cycling behavior.     

Nanostructured ferrite/graphene/polyaniline using for supercapacitor to enhance the capacitive behavior

Graphene nanosheets, polyaniline (PANI), and nanocrystallites of transition metal ferrite {Fe₃O₄ (Mag), NiFe₂O₄ (NiF), and CoFe₂O₄ (CoF)} have been prepared and characterized via XRD, FTIR, SEM, TEM, UV–vis spectroscopy, cyclic voltammetry, galvanostatic charge discharges, and impedance spectroscopy. Electrochemical measurements showed that supercapacitances of hybrid electrodes made of the ternary materials are higher than that of hybrid electrode made of binary or single material. The ternary hybrid CoF/graphene (G)/PANI electrode exhibits a highest specific capacitance reaching 1123 Fg^?1, an energy density of 240 Wh kg^?1 at 1 A g^?1, and a power density of 2680 Wkg^?1 at 1 A g^?1 and outstanding cycling performance, with 98.2% capacitance retained over 2000 cycles. The extraordinary electrochemical performance of the ternary CoF/G/PANI hybrid can be attributed to the synergistic effects of the individual components. The PANI conducting polymer enhances an electron transport. The Ferrite nanoparticles prevent the restocking of the carbon sheets and provide Faradaic processes to increase the total capacitance.     

Post-synthetic Modification of Covalent Organic Frameworks through in situ Polymerization of Aniline for Enhanced Capacitive Energy Storage

Covalent organic frameworks (COFs) having layered architecture with open nanochannels and high specific surface area are promising candidates for energy storage. However, the low electrical conductivity of two-dimensional COFs often limits their scope in energy storage applications. The conductivity of COFs can be enhanced through post-synthetic modification with conducting polymers. Herein, we developed polyaniline (PANI) modified triazine-based COFs via in situ polymerization of aniline within the porous frameworks. The composite materials showed high conductivity of 1.4–1.9×10⁻² S cm⁻¹ at room temperature with a 20-fold enhancement of the specific capacitance than the pristine frameworks. The fabricated supercapacitor exhibited a high energy density of 24.4 W h kg⁻¹ and a power density of 200 W kg⁻¹ at 0.5 A g⁻¹ current density. Moreover, the device fabricated using the conducting polymer-triazine COF composite could light up a green light-emitting diode for 1 min after being charged for 10 s.     

Interfacial growth of free-standing PANI films: toward high-performance all-polymer supercapacitors

Along with high power capability and energy density, long cycle life is regarded an essential performance requirement for energy storage devices. The rapid capacitance decline of conducting polymer-based electrodes remains a major technical challenge and precludes their practical applications in supercapacitors. In this work, a polyaniline (PANI) network is synthesized via interfacial Buchwald–Hartwig polymerization for the first time, facilitating the construction of covalently connected PANI networks by ligand-promoted C–N bond formation. Particularly, the interfacial synthesis and subsequent gas release from pre-anchored protecting groups allow bottom-up and efficient access to porous cross-linked PANI (PCL-PANI) films that are free-standing and solvent-resistant. Upon assembling into supercapacitors, the PCL-PANI material enables an unprecedent long-term charge–discharge cycling performance (>18 000 times) without clear capacitance loss for an additive-free pseudocapacitive system. In addition, this synthesis affords electrodes entirely consisting of conducting polymers, yielding highly reversible gravimetric capacitance at 435 F g_electrode⁻¹ in a two-electrode system, and a high gravimetric energy of 12.5 W h kg_electrode⁻¹ while delivering an outstanding power density of 16 000 W kg_electrode⁻¹, which is 10-fold higher than those of conventional linear PANI composite supercapacitors. This synthetic approach represents a novel and versatile strategy to generate additive/binder-free and high-performance conducting thin-films for energy storage.

A covalently cross-linked polyaniline network is synthesized via interfacial Buchwald-Hartwig polymerization/deprotection, enabling the generation of additive/binder-free and high-performance conducting thin-films for energy storage.      

The electrochemical properties of Li/TEGDME/MoS2 cells using multi-wall carbon nanotubes as a conducting agent

We investigated the first charge–discharge behavior and cycling property of Li batteries using MoS₂ electrodes with multi-wall carbon nanotubes (MWNT) as a conducting agent. The MoS₂ electrode was prepared using MWNT as the conducting agent. The battery gave a high first discharge capacity of 440 mAhg^?1 with a plateau potential region at 1.1 V. The Li/MoS₂ battery using MWNT showed a higher discharge capacity compared to acetylene black. After ten cycles of the battery using MWNT, the discharge capacity decreased to 120 mAhg^?1, which corresponded to 30% of the first discharge capacity. Adding a carbon nanotube into the MoS₂ electrode improved the first discharge behavior, but did not affect the cycling property of the Li/MoS₂ cell.     

Hydrogen‐Bonded Organic Frameworks (HOFs): A New Class of Porous Crystalline Proton‐Conducting Materials

Two porous hydrogen‐bonded organic frameworks (HOFs) based on arene sulfonates and guanidinium ions are reported. As a result of the presence of ionic backbones appended with protonic source, the compounds exhibit ultra‐high proton conduction values (σ) 0.75× 10^?2 S cm^?1 and 1.8×10^?2 S cm^?1 under humidified conditions. Also, they have very low activation energy values and the highest proton conductivity at ambient conditions (low humidity and at moderate temperature) among porous crystalline materials, such as metal–organic frameworks (MOFs) and covalent organic frameworks (COFs). These values are not only comparable to the conventionally used proton exchange membranes, such as Nafion used in fuel cell technologies, but is also the highest value reported in organic‐based porous architectures. Notably, this report inaugurates the usage of crystalline hydrogen‐bonded porous organic frameworks as solid‐state proton conducting materials.     

Fabrication of vesicular polyaniline using hard templates and composites with graphene for supercapacitor

Vesicular polyaniline (VPANI) has been fabricated for the first time via a facile two-step method, which uses high-quality multilamellar vesicular SiO₂ as hard templates. The graphene-wrapped VPANI (VPANI@RGO) composites were prepared by self-assembling graphene oxide onto VPANI and subsequently conducting the hydrothermal reduction process. The morphological characterization of the composites confirms the uniform wrapping of the graphene sheets on the VPANI. The structural characterization of the composites reveals a strong π–π electron and hydrogen bond interaction in the composites. The VPANI@RGO composites exhibit an excellent supercapacitor performance with an enhanced specific capacitance (573 F g^?1) and a good cycling stability, which maintains its capacity of up to 85.7 % over 1000 cycles at 1 A g^?1.     

Development of a Sustainable Resource Based Conducting Composite of Polyaniline‐Poly(esteramideurethane)

Polymers synthesized from coconut oil as a precursor find scarce applications. Polyesteramide urethane synthesized from coconut oil, a natural resource, is a dough‐like material, unusable in our study. Upon loading with polyaniline it becomes tough and flexible. Composites of ClO₄ ^? doped polyaniline with coconut oil based poly(esteramide urethane) (CPEAU) were prepared by a solution blending technique, using different ratios of polyaniline(2 wt%, 4 wt% and 8 wt%). The composites were further characterized by FT‐IR, DSC, TGA, XRD, and SEM. Conductivity was found to be in the range 2.5×10^?5?5.7×10^?4 S cm^?1. The composite was found to show weak hydrogen bonding interactions between PANI and CPEAU at 8 wt% loading.     

One‐Pot Fabrication of Hierarchical Nanosheet‐Based TiO2–Carbon Hollow Microspheres for Anode Materials of High‐Rate Lithium‐Ion Batteries

Hierarchical and hollow nanostructures have recently attracted considerable attention because of their fantastic architectures and tunable property for facile lithium ion insertion and good cycling stability. In this study, a one‐pot and unusual carving protocol is demonstrated for engineering hollow structures with a porous shell. Hierarchical TiO₂ hollow spheres with nanosheet‐assembled shells (TiO₂ NHS) were synthesized by the sequestration between the titanium source and 2,2′‐bipyridine‐5,5′‐dicarboxylic acid, and kinetically controlled etching in trifluoroacetic acid medium. In addition, annealing such porous nanostructures presents the advantage of imparting carbon‐doped functional performance to its counterpart under different atmospheres. Such highly porous structures endow very large specifics surface area of 404 m² g^?1 and 336 m² g^?1 for the as‐prepared and calcination under nitrogen gas. C/TiO₂ NHS has high capacity of 204 mA h g^?1 at 1 C and a reversible capacity of 105 mA h g^?1 at a high rate of 20 C, and exhibits good cycling stability and superior rate capability as an anode material for lithium‐ion batteries.     

Synthesis of a Rigid C3v‐Symmetric Tris‐salicylaldehyde as a Precursor for a Highly Porous Molecular Cube

The development of a synthetic approach to a C_3v‐symmetric tris‐salicylaldehyde based on triptycene is presented. The tris‐salicylaldehyde is a versatile precursor for porous molecular materials, as demonstrated in the [4+4] condensation reaction with a triptycene triamine to form a molecular shape‐persistent porous cube. The amorphous material of the molecular porous cube shows a very high surface area of 1014 m² g^?1 (BET model) and a high uptake of CO₂ (18.2 wt % at 273 K and 1 bar). Furthermore, during the multistep synthesis of the tris‐salicylaldehyde precursor, a relatively rare (twofold) addition of the aryne to the anthracene in the 1,4‐ and 1,4,5,8‐positions have been found during a Diels–Alder reaction, as proven by X‐ray structure analysis.     

Hierarchically Porous Carbons Derived from Metal–Organic Framework/Chitosan Composites for High‐Performance Supercapacitors

Hierarchically porous carbon materials with high surface areas are promising candidates for energy storage and conversion. Herein, the facile synthesis of hierarchically porous carbons through the calcination of metal–organic framework (MOF)/chitosan composites is reported. The effects of the chitosan (CS) additive on the pore structure of the resultant carbons are discussed. The corresponding MOF/chitosan precursors could be readily converted into hierarchically porous carbons (NPC‐V, V=1, 2, 4, and 6) with much higher ratios of meso‐/macropore volume to micropore volume (V_meso‐macro/V_micro). The derived carbon NPC‐2 with the high ratio of V_meso‐macro/V_micro=1.47 demonstrates a high specific surface area of 2375 m² g^?1, and a high pore volume of 2.49 cm³ g^?1, as well as a high graphitization degree, in comparison to its counterpart (NPC) without chitosan addition. These excellent features are favorable for rapid ion diffusion/transport, endowing NPC‐2 with enhanced electrochemical behavior as supercapacitor electrodes in a symmetric electrode system, corresponding to a high specific capacitance of 199.9 F g^?1 in the aqueous electrolyte and good rate capability. Good cycling stability is also observed after 10 000 cycles.     

Electrochemical storage properties of polyaniline-, poly(N-methylaniline)-, and poly(N-ethylaniline)-coated pencil graphite electrodes

Three types of conducting polymers, polyaniline (PANI), poly(N-methylaniline) (PNMA), poly(N-ethylaniline) (PNEA) were electrochemically deposited on pencil graphite electrode (PGE) surfaces characterized as electrode active materials for supercapacitor applications. The obtained films were electrochemically characterized using different electrochemical methods. Redox parameters, electro-active characteristics, and electrostability of the polymer films were investigated via cyclic voltammetry (CV). Doping types of the polymer films were determined by the Mott-Schottky method. Electrochemical capacitance properties of the polymer film coating PGE (PGE/PANI, PGE/PNMA, and PGE/PNEA) were investigated by the CV and potentiostatic electrochemical impedance spectroscopy (EIS) methods in a 0.1 M H₂SO₄ aqueous solution. Thus, capacitance values of the electrodes were calculated. Results show that PGE/PANI, PGE/PNMA, and PGE/PNEA exhibit maximum specific capacitances of 131.78 F g^?1 (≈ 436.50 mF cm^?2), 38.00 F g^?1 (≈ 130.70 mF cm^?2), and 16.50 F g^?1 (≈ 57.83 mF cm^?2), respectively. Moreover, charge-discharge capacities of the electrodes are reported and the specific power (SP) and specific energy (SE) values of the electrodes as supercapacitor materials were calculated using repeating chronopotentiometry.     

Two‐Dimensional Mesoscale‐Ordered Conducting Polymers

Despite the availability of numerous two‐dimensional (2D) materials with structural ordering at the atomic or molecular level, direct construction of mesoscale‐ordered superstructures within a 2D monolayer remains an enormous challenge. Here, we report the synergic manipulation of two types of assemblies in different dimensions to achieve 2D conducting polymer nanosheets with structural ordering at the mesoscale. The supramolecular assemblies of amphipathic perfluorinated carboxylic acids and block co‐polymers serve as 2D interfaces and meso‐inducing moieties, respectively, which guide the polymerization of aniline into 2D, free‐standing mesoporous conducting polymer nanosheets. Grazing‐incidence small‐angle X‐ray scattering combined with various microscopy demonstrates that the resulting mesoscale‐ordered nanosheets have hexagonal lattice with d‐spacing of about 30 nm, customizable pore sizes of 7–18 nm and thicknesses of 13–45 nm, and high surface area. Such template‐directed assembly produces polyaniline nanosheets with enhanced π–π stacking interactions, thereby resulting in anisotropic and record‐high electrical conductivity of approximately 41 S cm^?1 for the pristine polyaniline nanosheet based film and approximately 188 S cm^?1 for the hydrochloric acid‐doped counterpart. Our moldable approach creates a new family of mesoscale‐ordered structures as well as opens avenues to the programmed assembly of multifunctional materials.     

Excellent Capacitive Performance of a Three‐Dimensional Hierarchical Porous Graphene/Carbon Composite with a Superhigh Surface Area

Three‐dimensional hierarchical porous graphene/carbon composite was successfully synthesized from a solution of graphene oxide and a phenolic resin by using a facile and efficient method. The morphology, structure, and surface property of the composite were investigated intensively by a variety of means such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption, Raman spectroscopy, and Fourier transform infrared spectroscopy (FTIR). It is found that graphene serves as a scaffold to form a hierarchical pore texture in the composite, resulting in its superhigh surface area of 2034 m²g^?1, thin macropore wall, and high conductivity (152 S m^?1). As evidenced by electrochemical measurements in both EMImBF₄ ionic liquid and KOH electrolyte, the composite exhibits ideal capacitive behavior, high capacitance, and excellent rate performance due to its unique structure. In EMImBF₄, the composite has a high energy density of up to 50.1 Wh kg^?1 and also possesses quite stable cycling stability at 100 °C, suggesting its promising application in high‐temperature supercapacitors. In KOH electrolyte, the specific capacitance of this composite can reach up to an unprecedented value of 186.5 F g^?1, even at a very high current density of 50 A g^?1, suggesting its prosperous application in high‐power applications.