Polypyrrole Films Research Articles

A Facile Electrochemical Strategy for Achieving a High-Conductivity Polypyrrole Derivative with Intrinsic Metallic Transport as a High-Performance Electrochromic Conducting Polymer Film.

Conjugated polymer electrochromic materials (PECMs) with tailored optical and electrical properties are applied in smart windows, electronic displays, and adaptive camouflage. The limitation in the electrical conductivity results in slow and monotonous color switching. We present a polypyrrole film incorporated with a toluene-p-sulfonic group (PPy-TSO-F), via a one-step electrodeposition technique. The PPy-TSO-F thin film (110 nm) achieves an impressive electrical conductivity of 1011 S cm-1, a high carrier mobility of 82 cm2 V-1 s-1, and intrinsic metallic electronic behavior. It demonstrates exceptionally reversible multicolor switching, transitioning from emerald green (-1.5 V), to bluish green (-1.4 V), bright yellow (-1.2 V), greenish yellow (-0.6 V), reddish brown (0.1 V), dark brown (0.3 V), and atrovirens (0.6 V). The fast charge transport and high carrier mobility render the film with an ultrafast electrochromic switching speed of 0.01 s/0.02 s. This research provides a new route to designing ultrafast multicolor switching PECMs with metallic charge transport.

A disposable, portable electrochemical immunosensor for rapid in situ detection of bovine tuberculosis

This contribution describes the development of a simple, fast, cost-effective, and sensitive impedimetric immunosensor for quantifying bovine tuberculosis (TB) in bovine serum samples. The construction of the immunosensor involved immobilizing the purified protein derivative (PPD) of M. bovis onto a screen-printed electrode that was modified with gold nanoparticles (AuNPs) and a polypyrrole (pPy) film synthesized electrochemically. The immunosensor exhibited a linear range from 0.5 μg mL−1 to 100 μg mL−1 and achieved a limit of detection (LD) of 100 ng mL−1 for the detection of anti-M. bovis antibody. The recovery percentages obtained in bovine serum samples were excellent, ranging between 98 % and 103 %.This device presents several advantages over alternative methods for determining TB in bovine serum samples. These include direct, in situ measurement without the need for pre-treatment, utilization of small volumes, thus avoiding harmful solvents and expensive reagents, and portability. In addition, the immunosensor exhibits both physical and chemical stability, retaining effectiveness even after 30 days of modification. This allows simultaneous incubations and facilitates large-scale detection.Hence, this immunosensor presents itself as a promising diagnostic tool for detecting anti-M. bovis antibodies in bovine serum. It serves as a viable alternative to tuberculin and ELISA tests.

Investigation of the effect of electrodeposited Cu from graphite wrapped in polypyrrole film formed by chemical oxidation

The metallization of graphite substrates is currently confronted by negative issues including insufficient adhesion and inherent instability. In an effort to surmount these challenges, a layer of conductive polypyrrole (PPy) film on a graphite surface is formed through simple polymerization, followed by an electroplating copper layer. The graphite enveloped by the PPy film, subjected to cyclic voltammetry (CV) and linear sweep voltammetry (LSV) analyses, demonstrates enhanced electrochemical activity and thus renders the more efficient electrodeposition of copper. Further investigation was conducted through orthogonal experiments to explore the optimal formulation of electroplating solutions containing popular additives including 3, 3′-dithiobis-1-propanesulfonic acid disodium salt (SPS), Janus Green B (JGB), and polyethylene glycol 8000 (PEG8000)., According to the optimal additive formulation, a dense copper layer with superior adhesion was electroplated on the graphite substrate employing PPy as an intermediate layer.

Enhanced enzymatic electrochemical detection of an organophosphate Pesticide: Achieving Wide linearity and femtomolar detection via gold nanoparticles growth within polypyrrole films

The indiscriminate use of pesticides in agriculture demands the development of devices capable of monitoring contaminations in food supplies, in the environment and biological fluids. Simplicity, easy handling, high sensitivities, and low limits-of-detection (LOD) and quantification are some of the required properties for these devices. In this work, we evaluated the effect of incorporating gold nanoparticles into indigo carmine-doped polypyrrole during the electropolymerization of films for use as an acetylcholinesterase (AChE) enzyme-based biosensor. As proof of concept, the pesticide methyl parathion was tested towards the inhibition of AChE. The enzyme was immobilized simply by drop-casting a solution, eliminating the need for any prior surface modification. The biosensors were characterized with cyclic voltammetry, scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The assays for the detection of methyl parathion with films containing polypyrrole, indigo carmine and AChE (PPy–IC–AChE) presented a sensitivity of 5.7 μA cm−2 g−1 mL and a LOD of 12 nmol L−1 (3.0 ng L−1) with a linear range from 1.3 x 10−7 mol L−1 to 1.0 x 10−5 mol L−1. The introduction of gold nanoparticles (AuNP) into the film (PPy–IC–AuNP-AChE) led to remarkable improvements on the overall performance, such as a lower redox potential for the enzymatic reaction, a 145 % increase in sensitivity (14 μA cm−2 g−1 mL), a wider detection dynamic range (from 1.3x10−7 to 1.0x10−3 mol L−1), and a very low LOD of 24 fmol L−1 (64 ag mL−1). These findings underscore the potential of using AuNPs to improve the enzymatic performance of biosensor devices.

Electropolymerization of Pyrrole Using a Single-Electrode Electrochemical System

Bipolar electrochemistry emerges as an appealing technique for gradient surface fabrication thanks to the controllable potential distribution on bipolar electrodes (BPEs) in a wireless manner [1]. Here we report a BPE array named the single-electrode electrochemical system (SEES) [2] for the high-throughput electrosynthesis of gradient polypyrrole (PPy) films via electropolymerization. The SEES consists of a plastic board with holes attached to an indium-tin oxide (ITO) electrode to create multiple microelectrochemical cell arrays. Benefiting from this technique, the effects of various electrolysis conditions on film growth, such as applied voltage, electrodeposition time and electrolyte, etc., were systematically investigated. The length, thickness, surface morphology, and wettability, of the obtained PPy films were investigated [3]. The SEES provides a straightforward comparison of experimental results and hence facilitates the condition screening process.

Síntese e caracterização de filmes de Polipirrol dopados com Tetraquis(4-carboxifenil) porfirina para aplicações fotoelectroquímicas

Photoelectrochemistry is emerging as a promising technology for harvesting and utilizing solar energy in a wide range of applications. However, electrode materials still need to be improved to achieve optimal performance. Conductive polymers emerge as particularly promising organic compounds for this purpose due to their highly versatile properties. In this study, the galvanostatic synthesis of polypyrrole films co-doped with tetrakis(4-carboxyphenyl) porphyrin (PPy/TCPP) on fluorine doped tin oxide (FTO)-coated glass substrates was performed for the first time. In addition, an evaluation of these films as photoelectrodes was performed, focusing on key properties. The incorporation of porphyrin into the polymer matrix was confirmed by UV-Vis and IR characterization. SEM micrographs showed the morphological changes induced by the codopant. Cyclovoltammetry was used to evaluate the conductivity of the film, its electroactivity, electroactive area and HOMO energy level. The chopped chronoamperometry confirmed the photoactivity of the material and its stability for 3000 s. The electrical and optical properties of the polymer were characterized by EIS and light absorption measurements to propose its energy level diagram. The PPy/TCPP coatings were obtained with high homogeneity on FTO, good conductivity, quasi-reversible electrochemical activity to ferrocene probe and stable photoactivity. Electrical characterization indicates high charge flow under illumination. An indirect bandgap of 2.51 eV and a HOMO level value of -4.59 eV were obtained for PPy/TCPP.

Double-side super-hydrophilic/superspreading fabric for ultrafast asymmetric sweat transport and in-situ power generation

Asymmetric (viz. Janus or one-way transport) fabrics that can promote directional sweat transport from the next-to-the-skin surface to the outer surface by the hydrophobic-hydrophilic difference across the fabric thickness have been developed. However, the hydrophobic next-to-the-skin surface inevitably increases the inherent resistance to sweat transportation into the fabric, fundamentally hampering its moisture management property. In this work, by selectively coating a poly-pyrrole (ppy) film with Turing patterns on one side of the fabric to achieve superspreading property, we demonstrated an all-hydrophilic asymmetric fabric with outstanding one-way liquid sweat transport property. Benefiting from the low resistance of sweat absorption, the all-hydrophilic fabric exhibited a dramatically increased directional sweat transport rate of 13.6 mm/s, which is 5.9 times that of the untreated fabric, and significantly enhanced sweat evaporation rate (1.56 times of the untreated fabric) and cooling performance. Furthermore, the conductive ppy-fabric, during the process of ultra-fast sweat transport, generated a potential of 150 mV over an area of 2×2 cm2 or scalable electrical energy output of 2.5 mW/m2 under continuous sweat transportation. The finding in this work not only provided new insight into the design and development of asymmetric fabric for ultrafast sweat transport but also proposed a novel method for the in-situ energy harvesting during the sweat transportation process, which has potential applications in self-powered smart wearables and functional clothing.

One-pot synthesis of a network of Mn2O3–MnO2–poly(m-methylaniline) composite nanorods on a polypyrrole film presents a promising and efficient optoelectronic and solar cell device

Abstract A one-pot synthesis approach was employed to create a composite nanorod structure (Mn2O3–MnO2–poly(m-methylaniline) or Mn2O3–MnO2–PmMA) on a polypyrrole (Ppy) film. Optoelectronic and solar cell thin film devices were constructed using n- and p-type layers of Mn2O3–MnO2–PmMA and Ppy, respectively. The optical characteristics of the n-layer, coupled with the morphological behavior of its nanorods, enhance optical absorbance efficiency, reducing the bandgap value to 2.48 eV. The behavior of the optoelectronic device is chiefly determined by the significantly higher current density (J ph) value of 0.017 mA/cm2 compared to the dark current density (J o) value of 0.002 mA/cm2. Additionally, the linear dynamic range is 85 dB, and the noise ratio is 12%. The optimized values for the photosensitivity (R) and detectivity (D) at 340 nm are 0.22 mA W−1 and 0.47 × 10⁸ Jones, respectively. Even at 540 nm, these values decrease to 0.08 and 0.2 × 10⁸ Jones, respectively. For solar cell behavior, the short-circuit current (J SC) and open-circuit voltage (V OC) at 540 nm are determined, yielding values of 0.001 mA/cm2 and 0.98 V, respectively. The outstanding performance of this optoelectronic device, coupled with its solar cell behavior, positions the thin film material for a dual role in various industrial applications.

Polypyrrole film formation using DC biasing of substrate in in-solution plasma process

Beyond the existing in-solution plasma (iSP) process used for nanoparticle synthesis, polymer film synthesis has recently been demonstrated via iSP, which occurs at a specific cycle in a substrate with electrical potential. Herein, we propose an iSP reactor designed to tune the characteristics of polypyrrole (PPy) films by applying varied DC biases to the substrate during the solution plasma process. Applying DC bias to the substrate notably enhances the iSP during the negative cycle, thereby generating ionic precursors from pyrrole monomers for PPy film formation. These films demonstrated morphological variances as a function of the applied VDC. At a low voltage (VDC = 0.5 kV), a uniform film was formed via a layer-by-layer growth mechanism, and as the voltage was increased, the film exhibited a structured morphology. Specifically, at VDC = 0.5 kV, the PPy film was successfully coated onto a finely patterned electrode. The proposed iSP process, under specific DC biasing conditions, enables polymer coating without necessitating additional chemicals, catalysts, or masks. This method holds potential for a wide range of applications.

Properties and corrosion protection of polypyrrole prepared by electrochemical polymerization on aluminum

AbstractIn a one‐step procedure that did not require any surface preparation, polypyrrole (PPy) films doped with 3‐nitrosalicylic acid (3Nisa) became effectively electropolymerized on the aluminum substrate in aqueous solutions. Fourier transform infrared, scanning electron microscopy, and thermal gravimetric analysis were used to analyze the properties of PPy‐based films. Open circuit potential (OCP), electrochemical impedance spectroscopy, Tafel polarization, and salt spray tests were used to study the corrosion‐resistant efficiency of the coatings. The as‐prepared PPy films performed corrosion resistance on aluminum in the 3% NaCl solution. However, the PPy films prepared in the 0.01 m solution of 3Nisa showed the best protection ability on aluminum. The self‐healing characteristic of the PPy films was recorded by varying the potential in the OCP measurement. The findings indicate the potential of using 3‐nitrosalicylic acid‐doped PPy films for applications as anti‐corrosion coatings for aluminum.

A Universal Biomineralization‐Like Interfacial‐Confined Strategy Enables Practicable, Meter‐Scale, Transmittance‐Adjustable, Highly‐Ordered, Photothermal‐Capable, 2D Conducting Polymers

AbstractConducting polymers (CPs) encompass various cutting‐edge fields owing to their combination of polymer and conducting properties. However, the mismatch between the polymer growth process and the carrier mobility design leads to poor material and device consistency, and insufficient long‐term device stability, thus hindering the practical application of CPs. Although 2D construction has been explored to address these challenges, it typically leads to materials instability and lacks methods for large‐scale synthesis, making it unsuitable for many application scenarios. Here a universal biomineralization‐like strategy relying on the joint impaction of hydrogen‐bond and gravity for large‐scale fabrication of 2D CPs is developed. As‐fabricated meter‐scale Polypyrrole films exhibit high orderliness and can be assembled into multilayers, allowing for adjustable thickness and transparency. Notably, these films demonstrate exceptional photothermal properties and remarkable long‐term stability, as their surface temperature can reach 140 °C when irradiated with an 808 nm laser at 0.7 W cm−2, with almost no attenuation after 170 days. Furthermore, under sunlight, the temperature can reach nearly 100 °C, showcasing significant potential in smart building and energy management applications. Importantly, this strategy can be extended to the 2D design of numerous light organic compounds, thus opening up possibilities for their practical applications.

Biphasic nanocomposite films of polypyrrole and poly(3,4-ethylene dioxythiophene) using a surface-tethered dopant strategy

Using a newly invented surface-tethered dopant approach for the electrochemical polymerization growth of conductive polymer films, nanocomposites are created consisting of two distinct phases of polypyrrole (PPy) and Poly(3,4-ethylene dioxythiophene) (PEDOT). The growth of the conductive nanocomposite films takes advantage of the unique way in which a conductive polymer film forms when grown using a surface-tethered dopant, starting out as a highly nanoporous film that gradually becomes more and more solid as additional polymer deposition occurs preferentially within the nanopores rather than at the films outer surface. Nanocomposite films can thus be fabricated simply and controllably by first growing one nanoporous conductive polymer film followed by the deposition of a second conductive polymer within the nanopores of the first. This study investigates the morphological and electrochemical properties of nanocomposite films grown using a surface-tethered dopant and how these properties are affected by simple changes in electrochemical polymerization parameters.

FLEXIBLE COMPOSITE AgNPs-PPy/CELLULOSIC PAPER ELECTRODE FOR ELECTROCHEMICAL DETECTION OF NITRATE

In this work, we describe a simple strategy for the preparation of a low-cost electrode material based on polypyrrole (PPy) film grown on an insulating cellulosic paper (CP) substrate via in-situ oxidative polymerization technique and functionalized by silver nanoparticles (AgNPs) uniformly dispersed on its surface. The properties of the obtained AgNPs-PPy composites were characterized using X-ray diffraction, scanning electron microscopy and energy dispersive X-ray analysis. The electrocatalytic activity of the prepared electrode was investigated for the electroreduction of nitrate using cyclic voltammetry in 0.1 M KOH solution. Results demonstrated that the incorporation of AgNPs into the PPy matrix significantly improves the catalytic behaviour of this film. The effect of the amount of incorporated AgNPs on the electrode response was also investigated.

Role of Surface Chemistry in Pyrrole Autoxidation.

Chemical compounds in liquid hydrocarbon fuels that contain five-membered pyrrole (Py) rings readily react with oxygen from air and polymerize through a process known as autoxidation. Autoxidation degrades the quality of fuel and leads to the formation of unwanted gum deposits in fuel storage vessels and engine components. Recent work has found that the rate of formation of these gum deposits is affected by material surfaces exposed to the fuel, but the origins of these effects are not yet understood. In this work, atomic layer deposition (ALD) is employed to grow aluminum oxide, zinc oxide, titanium dioxide, and manganese oxide films on silicon substrates to control material surface chemistry and study Py adsorption and gum nucleation on these surfaces. Quartz crystal microbalance (QCM) studies of gas-phase Py adsorption indicate 1.5-2.8 kcal/mol exergonic adsorption of Lewis basic Py onto Lewis acidic surface sites. More favorable Py adsorption onto Lewis acidic surfaces correlates with faster polypyrrole (PPy) film nucleation in vapor phase oxidative molecular deposition (oMLD) polymerization studies. Liquid-phase studies of Py autoxidation reveal primarily particulate formation, indicating a homogeneous PPy propagation step rather than a completely surface-based polymerization mechanism. The amount of PPy particulate formation is positively correlated with more acidic surfaces (lower pH-PZC values), indicating that the rate-limiting step for Py autoxidation involves Lewis acidic surface sites. These studies help to establish new mechanistic insights into the role of surface chemistry in the autoxidation of pyrrolic species. We apply this knowledge to demonstrate a polymer coating formed by vapor phase polymer deposition that slows autoxidation by 2 orders of magnitude.

Structure and electrochromic properties of polypyrrole films synthesized by AC electrochemical impedance spectroscopy under different amplitude

Alternating current (AC) electrochemical impedance spectroscopy (EIS) was employed to synthesize polypyrrole (PPy) electrochromic films on fluorine-doped tin oxide (FTO) transparent conductive glasses. When depositing the PPy films, a fixed initial voltage was 700 mV and AC of different amplitudes was applied. The influence of AC voltage amplitude on the structure and electrochromic performance of PPy films was investigated. Scanning electron microscope (SEM) observation reveals that the PPy films prepared under AC are composed of uniform-distributed nanospheres when the AC amplitude is below 400 mV, which is different from the submicron structure displayed by PPy films prepared under direct current (DC). This kind of nanospherical structure is helpful to ion transport, resulting in improved electrochromic properties of the PPy films prepared under AC compared with the PPy film prepared under DC. In particular, the PPy film prepared under 100 mV amplitude AC shows ideal electrochromic properties, with an ion diffusion coefficient of 8.13 × 10−10 cm2·s−1, a coloring efficiency of 137.4 cm2·C−1, quick coloration and bleaching switching times of 5.0 s and 6.5 s, respectively, and retains 65.7% of its optical modulation after 100 cycles.

Tailoring polypyrrole film characteristics with multi-step oxygen plasma treatment for high-performance strain sensors: Impact on bonding, microstructure, and electrical responsivity

We investigate the impact of oxygen plasma treatment (O2 PT) on the performance of polypyrrole (PPy)/polydimethylsiloxane strain sensors. Utilizing a three-step chemical oxidative polymerization method for PPy growth, we explore various durations of O2 PT (0, 30, 60, and 90 s) during intermediate growth stages. Through analyses using X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy, we elucidate the relationship between O2 PT, structural changes, and strain sensor performance. Sensor devices plasma-treated for 30 s exhibit exceptional characteristics: a gauge factor of 432 at 50% strain and a response time of 50 ms under quasi-step function strain variation from 0% to 1% in 40 ms. These results underscore the pivotal role of O2 PT in enhancing the performance of PPy-based strain sensors, providing insights for advanced sensor design and fabrication techniques.

Improvement of Electrical Conductivity of In Situ Iodine-Doped Polypyrrole Film Using Atmospheric Pressure Plasma Reactor with Capillary Electrodes.

To improve the electrical conductivity of polypyrrole (PPy) nanostructure film through in situ iodine (I2) doping, this study proposes an atmospheric pressure plasma reactor (APPR) where heated I2 dopant vapor is fed through capillary electrodes that serve as electrodes for discharge ignition. A large amount of the heated I2 vapor introduced into the reactor separately from a monomer gas can be effectively activated by an intense plasma via capillary electrodes. In particular, intensive plasma is obtained by properly adjusting the bluff body position in the APPR. Based on the ICCD and OES results, the I2 vapor injected through the capillary nozzle electrode is observed to form I2 charge species. The formed I2 species could directly participate in growing in situ I2-doped PPy films. Thus, in situ I2-doped PPy nanostructure films grown using the proposed APPR exhibit higher thicknesses of 15.3 μm and good electrical conductivities, compared to the corresponding non-doped films.

MODIFICATION OF POLYPYRROLE FILM WITH GOLD MICROPARTICLES FOR GLUCOSE OXIDATION

This work presents the preparation of a gold-polypyrrole (Au-PPy) composite film on a silicon (Si) semiconductor supported by electrodeposition, and the study of its electrocatalytic activity as an anode catalyst for the glucose oxidation reaction in alkaline media. The microstructure of the as-prepared Au-PPy film is characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results show that the presence of the polymer film on the Si support improves the conductivity of the latter and enables better distribution of the Au microparticles on the electrode surface, thus helping to increase their catalytic activity for glucose oxidation.

Development of a novel fluorimetric sensor based on polypyrrole doped with 4-(methylsulfonyl)-2-nitrobenzoic acid (MSNBA) for sensitive detection of copper (Cu2+)

In this study, we successfully electrochemically synthesized a polypyrrole film doped with 4-methylsulfonyl-2-nitrobenzoic acid (MSNBA) within an aqueous medium containing 0.01 M MSNBA, 0.003 M NaOH, and 0.01 M pyrrole. Our investigation encompassed a thorough exploration of both electrochemical and spectroscopic properties, confirming the effective incorporation of MSNBA as a dopant within the electroactive PPy chain. The morphological characterization of the film was undertaken using scanning electron microscopy (SEM). The optical properties, particularly UV–visible absorption, and fluorescence spectroscopy, were scrutinized in a dilute DMF solution. The UV–visible absorption spectra revealed a broad absorption band centered around 292 nm, attributed to the π→π* 1B - 1La/1Lb transitions of the oligo-benzenes in the film. In parallel, fluorescence spectra exhibited remarkable consistency between the solid state and solution, featuring an excitation peak at 345 nm (346 nm in solution) and an emission peak around 401 nm (403 nm in solution). Exploring the impact of copper (II) ions on absorption and fluorescence spectra unveiled a notable quenching effect along two distinct linearity domains. Various mathematical treatments, including the Stern-Volmer equation (R1 = 0.98, Ksv1 = 5.104 and R2 = 0.99, Ksv2 = 1.54.106), the Perrin equation, and the polynomial equation, were applied to elucidate the nature of this fluorescence quenching. Our findings indicated that the fluorescence extinction, as a function of Cu2+ ion concentration, aligns well with the polynomial equation, signifying a combination of dynamic and static quenching (Io/I = 1.08(±0.04) + 1.46(±0.44)105[Q]- 1.15(±0.75)1010 [Q]2). Moreover, we explored the potential application of this method for the determination of Cu2+. Calibration graphs demonstrated excellent linearity between fluorescence intensity and Cu2+ concentration in the range of 0–5.4 μM. Notably, the detection limit of 1.2 μM surpassed the LOD for Cu2+ (20 μM) in drinking water set by the EPA, suggesting the viability of this approach for sensitive detection in environmental monitoring.

Effects of Polydopamine Incorporation on the Nanostructure and Electrochemical Performance of Electrodeposited Polypyrrole Films

Polypyrrole films are commonly prepared as conductive electrode surfaces for a variety of applications. Recently, there has been increasing interest in improving the adhesive properties and biocompatibility of polypyrrole electrodes via the incorporation of bioinspired polydopamine within the polymer scaffold. However, very little is currently known about the structural effects of polydopamine incorporation during the electropolymerisation of hybrid films. In this work, we combine electrochemical quartz crystal microbalance studies, fundamental electrochemical characterisation, atomic force microscopy, and a suite of spectroscopic techniques in order to correlate changes in the structure and performance of polypyrrole–polydopamine films to the structural modifications of the nanostructure induced by polydopamine incorporation. The results indicate that polydopamine incorporation greatly increases the rate of hybrid film deposition, as well as improving adhesion, surface homogeneity, and wettability, with no compromise in charge transfer properties. Polydopamine incorporation is strongly suggested to occur in non-connected domains within a predominantly polypyrrole-like scaffold. We propose a two-step model of co-polymerisation and the subsequent surface adhesion of hybrid films. Results are expected to be of broad general interest to researchers utilizing polypyrrole and polydopamine to prepare tailor-made electrodes for biosensing and catalysis.