EFFECT OF ULTRASONIC WAVE ON THE ELECTROPOLYMERIZATION OF PYRROLE

Electropolymerization of pyrrole under ultrasonic field at 20kHz was performed in a series of aqueous and propylene carbonate (PC) solutions. The ultrasonic wave with moderate intensity at the power of 44W, which is the power threshold of the ultrasonic generator used in this work to produce cavitation effect, enhance the conductivity and tensile strength of the polypyrrole films as prepared. However, too high intensity of the ultrasonic wave is harmful to the polymerization.

ELECTROPOLYMERIZATION OF ANILINE ON ZINC-ELECTROPLATED STEEL FROM NEUTRAL AQUEOUS MEDIUM BY SINGLE-STEP PROCESS

Polyaniline films were successfully synthesized on zinc-electroplated steel sheets in sodium salicylate (1mol·dm-3) aqueous medium. This one-step aniline electropolymerization process has been studied in this paper using different electrochemical techniques. And scanning electron microscopy (SEM) showed that the polymer coatings rapidly formed by either galvanostatic or potentiostatic mode performed compact and uniform in morphology. Potentiodynamic polarization was used to test the anticorrosion properties of this polymer.

Electropolymerization of cobalt porphyrins and corroles for the oxygen evolution reaction

Developing large-scale electrocatalysts using molecular complexes for the oxygen evolution reaction(OER)is of great importance. Herein, four cobalt porphyrins and corroles are deposited on electrode substrates using a simple and fast electropolymerization method. Our results showed that Co-1-P@CC, formed by electropolymerizing Co tetrakis(p-N-pyrrolylphenyl)porphyrin(Co-1-P) on carbon cloth(CC), is the most active OER catalyst in the examined Co porphyrins and corroles in alkaline aqueous solutions by displaying an onset overpotential of 380 m V. Long-term electrolysis tests confirmed the stability of these electropolymerized films by functioning as OER electrocatalysts.

Formation of Nanotubular Structures with Petal Effect by Soft-Template Electropolymerization of Benzotrithiophene with Hydrophilic Carboxyl Group

The bioinspiration is one of the best ways to make a breakthrough in a field,and particularly in the wetting properties.Bioinspired by natural species,such as rose petals and gecko foot,and previous researches,nanotubular structures are prepared here by soft-template electropolymerization in organic solvent and using an original benzotrithiophene with a hydrophilic carboxyl group,as the monomer.The best results are obtained by cyclic voltammetry because of a much higher amount of gas bubbles released with this deposition method.Both nanoparticles and nanotubes are observed while the water content has an influence on the number of nanotubes.Even if the monomer has hydrophilic carboxyl group,the best films have both high hydrophobicity(apparent water contact angle up to 130.7°)and strong water adhesion(petal effect).These surfaces could be used in future in applications such as water harvesting systems.

in-situ ESR AND RAMAN SPECTROSCOPIC STUDIES ON ELECTROPOLYMERIZATION OF PYRROLE

The in-situ transient ESR measurements reveal that the oxidized structure (PP++) of polypyrrole (PP) films has an electrocatalytic activity to the oxidation of pyrrole during the electropolymerization process. Surface-enhanced resonance Raman scattering (SERRS) effect was used to probe the structure of PP films in very early stages of the polymerization on gold electrodes. It is of special interest that the electropolymerization can take place at much less positive potentials (about 300 mV) under the irradiation of light. This photocatalytic effect may be applied to the pattern deposition of polymers.

Effect of Electrolyte Nature on Micellar Soft-Template Electropolymerization in Organic Solvent to Form Nanoporous Polymer Films with a Bioinspired Strategy

Here,using a bioinspired approach,the soft-template electropolymerization of naphtho[2,3-b]thieno[3,4-e][1,4]dioxine(NaphDOT)was conducted in dichloromethane with different water content,and using different supporting electrolytes.The role of the electrolytes in the formation of reverse micelles that constitutes the soft template is investigated.The reverse micelles stabilized by the electrolyte and the monomer were observed by TEM and related to the various porous nanostructures of the obtained polymer films.We show that the nature of the electrolyte is not only fundamental for the formation of reverse micelles and thus porous nanostructures,but also plays a huge role in the good deposition of the oligomers upon the soft template.Surfaces with nanostructures such as nanotubes,nanorings or nanomembranes were realized.

SYNTHESIS, PROPERTIES AND ELECTROPOLYMERIZATION OF STAR-SHAPED OLIGOTHIOPHENES WITH HEXAKIS(FLUOREN-2-YL)BENZENE AS CORE

Star-shaped oligothiophenes with hexakis（fluoren-2-yl）benzene （HFB） as cores were designed and synthesized. Grafting thiophene units to HFB results in a bond flattening of the core, and makes the molecules a flipping-twist shape. Their thermal, photophysical and electrochemical properties were studied. Highly cross-linked conjugated polymers can be produced by electropolymerization of T1-T3.

Polyaniline Formed in Alkaline Solution─A New Luminous Material

Electropolymerization of aniline in KOH solution and properties of the polymer are studied by using in situ reflex ellipsometry, cyclic voltammetry and fluorescence spectroscopic method. The change patterns of ellipsometric parameters and the thickness of film in the process of electropolymerization are investigated. The complex refractive indices and the fluorescence spectra of PAN indicate that the PAN is a new kind of luminous material.

A selective voltammetric detection for dopamine using poly(gallic acid) film modified electrode

The electrochemistry behavior of dopamine was investigated by cyclic voltammetry and differential pulse voltammetry at a poly (gallic acid) film modified glassy carbon electrode.Two electrons and two protons participated in the diffusion-controlled electrocatalytic oxidation of dopamine with a diffusion coefficient of 2.186×10^(-5) cm^2/s.The interference of ascorbic acid with the determination of dopamine could be efficiently eliminated.This work provided a simple approach to selectively and sensitively de...

HIGHLY SENSITIVE CATALASE ELECTRODE BASED ON POLYPYRROLE FILMS WITH MICROCONTAINERS

Highly sensitive catalase electrodes for sensing hydrogen peroxide have been fabricated based on polypyrrole films with microcontainers. The microcontainers have a cup-like morphology and are arranged in a density of 4000 units cm^-2. Catalase was immobilized into the polypyrrole films with microcontainers （Ppy-mc）, which were coated on a Pt substrate electrode. The catalase/Ppy-mc/Pt electrode showed linear response to hydrogen peroxide in the range of 0-18 mmol/L at a potential of-0.3 V （versus SCE）. Its sensitivity was measured to be approximately 3.64 μA （mmol/L） ^-1 cm^- 2, which is about two times that of the electrode fabricated from a flat Ppy film （catalase/Ppy-flat/Pt electrode）. The electrode is highly selective for hydrogen peroxide and its sensitivity is interfered by potential interferents such as ascorbic acid, urea and fructose. Furthermore, such catalase electrodes showed long-term storage stability of 15 days under dry conditions at 4℃.

Synthesis of Novel Covalent-linked Linear Porphyrin-Thiophene Copolymers

Linear porphyrin-thiophene copolymers were synthesized by linking 5, 15-positions of porphyrin with tetrathiophene or bithiophene moieties for preparing conducting polymer. 2,8,12,18-tetraethyl-3,7,13,17-tetramethyl-5, 15-dithienylporphyrin4a (45.1%), 5, 15-di-bithienyl- 2,8,12,18-tetraethyl-3, 7, 13, 17-tetramethylporphyrin4b (61. 2%) and their metal complexes were also reported in high yields (>90%) as the monomers. 5, 15-di-bithienylporphyrin and its metal complexes could be polymerized by oxidation using FeCl3 as oxidant. However, 5,15-dithienylporphyrin and its metal complexes can not be polymerized by same reaction. Their polymers were synthesized by electrochemical oxidation on the gold-plate electrode. The structures of copolymers were identified by elemental analysis and IR spectra. And the conductivity of poly 5,15-di-bithienylporphyrin was measured to reach over 1.0× 10?6S/cm. Key words organic conductor - thienylporphyrin - porphyrin-thiophene copolymer - electropolymerization CLC number O 62 Foundation item: Supported by the National Natural Science Foundation of China (29872033, 20272046)Biography: CHEN Zhang-ping (1946-), male, Professor, research direction: porphyrin chemistry.

Electrocatalytic Determination of Dopamine in the Presence of Ascorbic Acid by Poly-L-proline and Ferricyanide Compound Film Modified Electrode

A novel biosensor was fabricated by the electrochemical polymerization of poly-L-proline（P-LP） and ferricyanide（FC） to form a compound film on a glassy carbon electrode（GCE）. The compound film modified electrode（P-LP/FC/GCE） shows electrocatalytic activity toward dopamine（DA） in a phosphate buffer solution（PBS, pH = 4.0） with a diminution of the overpotential and an increase in peak current. P-LP/FC/GCE was used to study the electrocatalytic oxidation of DA and ascorbic acid（AA） by means of cyclic voltammetry（CV）, differential pulse voltammetry（DPV） and amperometric i-t curve techniques. The overlapping anodic peaks of DA and AA were resolved into two well-defined voltammetric peaks in CV and DPV with the potential differences of about 200 and 225 mV, respectively. The peak current of DA is linearly change with the concentration of DA in a range of 1 × 10^-7 to 1.14 × 10^-4 mol/L with the correlation coefficient of 0.9997. The detection limit is 4.4~10-8 mol/L（S/N=3）. P-LP/FC/GCE exhibited an excellent selectivity, sensibility and stability for the determination of DA, and can be applied to the determination of dopamine injections with satisfied results.

Conjugated microporous polymer membranes for chemical separations

Conjugated microporous polymers(CMPs) are a unique class of porous organic materials, which are constructed with π-conjugation structures leading to intrinsic micropores. The CMPs properties such as high surface area, intrinsic and rich micropores, interlocking and rigid structure, extensive π-conjugation and tunable band-gap, chemical and thermal stability, together with tailored functionalities, contribute to its abundant potential for application in fields such as photocatalysis, optoelectronics, energy storage, and chemical sensors. Recently, CMPs have gained importance in the field of membranes for chemical separation. In this review, we briefly discuss the historical development of CMPs, followed by a detailed description of the progress in state-of-the-art design, preparation, and application of CMPs in membranes. Additionally, we provide inference on the future prospects of CMPs as membranes.

Polymer Film Supported Bimetallic Au–Ag Catalysts for Electrocatalytic Oxidation of Ammonia Borane in Alkaline Media

Ammonia borane is widely used in most areas including fuel cell applications.The present paper describes electrochemical behavior of ammonia borane in alkaline media on the poly(p-aminophenol) film modified with Au and Ag bimetallic nanoparticles.The glassy carbon electrode was firstly covered with polymeric film electrochemically and then,Au,Ag,and Au–Ag nanoparticles were deposited on the polymeric film,respectively.The surface morphology and chemical composition of these electrodes were examined by scanning electron microscopy,transmission electron microscopy,electrochemical impedance spectroscopy,X-ray diffraction,and X-ray photoelectron spectroscopy.It was found that alloyed Au–Ag bimetallic nanoparticles are formed.Electrochemical measurements indicate that the developed electrode modified by Au–Ag bimetallic nanoparticles exhibit the highest electrocatalytic activity for ammonia borane oxidation in alkaline media.The rotating disk electrode voltammetry demonstrates that the developed electrode can catalyze almost six-electron oxidation pathway of ammonia borane.Our results may be attractive for anode materials of ammonia borane fuel cells under alkaline conditions.

The Electrochemical Behaviour of PEDOT Film Electrosynthesized in Presence of Some Dopants

Electropolymerization and characterization of poly(3,4-ethylene dioxythiophene) (PEDOT) doped with functionalized single-walled carbon nanotubes (SWANTs) polyaminobenzene sulfonic acid (PABS) and different dopants were studied. It was fabricated by a simple oxidative electropolymerization method. The nanocomposite coatings have been prepared by using electrochemical methods from aqueous solutions, such that the components were deposited onto platinum electrode substrate. The morphology of composite films was analyzed by scanning electron microscopy (SEM). The electrochemical and physical properties of the resulting composites were evaluated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and Fourier transform infrared spectroscopy (FT-IR) techniques in 0.1 M LiClO4 aqueous solutions. The value of specific electrochemical capacitance of the composite films is considerably higher than that of the pure polymers films. The improved properties of the electrodes were obtained by using these composite films. The dopant substances used were sodium dodecyl sulfate (SDS) and 1,2-Dihydroxy- benzene-3,5-disulfonic acid disodium salt hydrate (tiron).

CONDUCTIVE COMPOSITES FROM POLYPYRROLE ELECTROPOLYMERIZED IN A POLYURETHANE MATRIX

In order to improve the mechanical properties of polypyrrole, composites were made by electropolymerizing polypyrrole in a polyurethane matrix. Polypyrrole/polyurethane (PPY/PU) composite films containing CLO_4^-, BF_4^- or CH_3-C_6H_4-SO_3^- counter ions were made in a variety of solvent systems and characterized by SEM, electronic conductivity, FTIR, and mechanical properties. Composite films showing much greater fiexibility than pure polypyrrole were obtained, but their electronic conductivities were substantially lower. Measured eonductivities ranged from 0.001 to 8 S/cm, tensile strengths from 44 to 592 psi, and elongation to failure from 3 to 70%.

Towards Ultrahigh Capacity and High Cycling Stability Lithium-Conducting Polymer Batteries by In Situ Construction of Nanostructured Porous Cathodes

Conducting polymers(CPs)have long been studied as cathode materials for lithium-ion batteries,but the low doping level(maximum:30–50%or even lower)and poor cycling stability limit their applications.Herein,we have developed a method of nanoporeconfined in situ electropolymerization to prepare nanostructured polythiophene-type porous cathodes,achieving significantly improved doping availability and long cycle life.It was verified that the nanosized polymer formed in situ and loose porous structure are conducive to the doping reaction and maintain high electrochemical stability.The constructed thieno[3,2-b]thiophene(TtTP)/active carbon cathode delivers an ultrahigh reversible capacity of 309.2 mAh g^(−1)(doping level up to 80.9%)along with an ultrahigh energy density of 1252.3 Wh Kg^(−1),and an ultrahigh rate capability(172.4 mAh g^(−1) at 30 A g^(−1)),which far exceed all the CPs and even all the p-type organic cathode materials reported.Moreover,an excellent long cycle life of 2000 cycles at 5 A g^(−1) is also revealed,which is a new record for CPs-based cathode materials in nonaqueous lithium-ion batteries.Our method provides an effective strategy to improve the doping level and cycling stability of CP-based cathode materials.

Constructing a lithiophilic polyaniline coating via in situ polymerization for dendrite-free lithium metal anode

Metallic lithium is regarded as one of the most promising electrode materials to break through the energy density bottleneck of current commercial lithium-ion batteries.However,the practical implementation of lithium metal anode is limited by the unstable electrode interface significantly,which directly induces a low Coulombic efficiency,short cycling lifespan,and dendritic lithium growth behavior.In this study,via in situ electropolymerization,lithiophilic and conformal polyaniline layer is developed to improve the initial lithium nucleation and plating process,reducing the interface charge transfer resistance and promoting uniform lithium plating/stripping behavior.Meanwhile,the polyaniline layer exhibits good adhesion to the substrate.As a result,the Li/Cu half cell delivers a high Coulombic efficiency of 99.1%for 400 cycles at 1.0 mA·cm^(−2)with polyaniline layer.In addition,long-term stable cycling at a current density of 1.0 mA·cm^(−2)for 1300 h has been achieved for lithium metal anode.This strategy provides a new perspective for the practical lithium metal batteries.

A Brief Introduction to Organic Electrodeposition and a Review of the Fabrication of OLEDs based on Electrodeposition Technology

Electrodeposition is an old and effective method for the fabrication of organic films.Though electrodeposited organic films have been widely used in various applications,highly luminescent films have been a great challenge because the electrochemically doped state may strongly quench the fluorescence.In the first part of this review,the organic electrodeposition techniques,along with general electropolymerization and other special electrodepositions are introduced.In the second part of the review,we describe how to electrochemically fabricate luminescent films for organic light-emitting diodes(OLEDs).With the rational molecular design and well-controlled electrodeposition process,we have not only demonstrated high-performance OLEDs,but also paved a promising way to practice active-matrix OLEDs(AMOLEDs)and super-resolution OLEDs.In particular,RGB 3×3 array OLEDs based on active-matrix substrates,RGB passive-matrix OLEDs(PMOLEDs)with a resolution of 210 ppi,and monochromatic OLEDs with a super-resolution of 2822 ppi have been successfully fabricated.It is highly anticipated that the organic electrodeposition technology is of comparable or perhaps even higher contenders in manufacturing and downscaling OLEDs and AMOLEDs with low-cost and high-resolution for the human-computer interaction fields such as augmented reality(AR),virtual reality(VR),etc.

Electropolymerized films of redox-active ruthenium complexes for multistate near-infrared electrochromism,ion sensing,and information storage

This paper summarizes our recent progress on the preparations and applications of electropolymerized thin films of redox-active ruthenium complexes.Thin films of vinyl-functionalized diruthenium or ruthenium-amine conjugated complexes are prepared by reductive electropolymerization.The resulting films are useful for multistate near-infrared electrochromism,ion sensing,and mimicking flip-flop and flip-flap-flop logic gates.The oxidative electropolymerization of diruthenium complexes with two distal triarylamine units affords electropolymers with an alternating diruthenium and tetraphenylbenzidine structural unit.The applications of the resulting films in multistate near-infrared electrochromism and resistive memory are discussed.