反向胶束法制备PEDOT纳米粒子气体敏感性的研究

通过用紫外-可见-近红外光谱、X射线光电子能谱及透射电镜等手段对采用反向胶束合成法,以二乙基磺基琥珀酸钠(AOT)形成的反胶束为模板制备出的导电聚合物聚3,4乙烯二氧噻吩(PEDOT)纳米粒子对HCl气体敏感性进行研究。沉积有纳米粒子的QCM器件对2.0×10-5气体响应时间为20s,具有较好的响应恢复特性,能够有效探测低浓度(5×10-6)气体,气敏特性明显优于普通PEDOT粒子。     

Combined electrochromic and plasmonic optical responses in conducting polymer/metal nanoparticle films

Poly(3,4-ethylenedioxithiophene)/poly(styrene sulphonate) (PEDOT/PSS) aqueous dispersions were mixed with aqueous gold nanoparticle and aqueous silver nanoparticle colloids. PEDOT/gold nanoparticles (Au NP) and PEDOT/silver nanoparticles (Ag NP) films were obtained by solvent casting the corresponding aqueous solutions. The nanocomposite films showed the optical characteristics associated with both the surface plasmon absorption resonance of the metal nanoparticles and the excitation of the bipolaron band of the conducting polymer. As an interesting application we demonstrate the use of metal nanoparticles to tune the color of PEDOT based electrochromic films from blue to violet in the case of Au NP or green in the case of Ag NP.     

Design of multicomponent microgels by selective deposition of nanomaterials

In the present paper a method for the targeted deposition of different nanomaterials on aqueous microgels is described. In the first stage poly(3,4-ethylenedioxythiophene) (PEDOT) nanorods are introduced into the microgel structure by in situ oxidative polymerization. In the second stage hydrogen tetrachloroaurate is used to transform PEDOT chains to an oxidized state in the microgel structure, leading to the fixation of chloroaurate anions on the surface of the PEDOT nanorods. The reduction of chloroaurate ions induces the formation of gold nanoparticles (AuNPs) predominantly located on the PEDOT surface. Obtained microgel/PEDOT/AuNP hybrid particles with different nanoparticle loadings exhibit superior colloidal stability and temperature sensitivity. The microgel/PEDOT/AuNP hybrid microgels exhibit extraordinary catalytic activity in aqueous media.     

Preparation of polystyrene-encapsulated silver hollow spheres via self-assembly of latex particles at the emulsion droplet interface

In the present work, we have developed a novel route to wrap inorganic nanoparticles in polymer hollow spheres, which includes self-assembly polystyrene (PS) latex particles at the aqueous/oil interface, sintering and γ-ray radiation reduction. The Ag/PS composite microspheres were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and field-emission scanning electron microscopy (FESEM). The advantage of this method is that the PS shell thickness, permeability, the size of composite spheres, and the quantity of the encapsulated Ag nanoparticles can be easily adjusted, which gives the product a brilliant prospect in the field of catalysis.     

Fabrication of flexible conductive films derived from poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonic acid) (PEDOT:PSS) on the nonwoven fabrics substrate

In this research, conducting poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonic acid) (PEDOT:PSS) aqueous dispersion was synthesized at first via chemical oxidative polymerization and followed by mixing it with poly(styrene-r-butyl acrylate) P(St-BA) aqueous latex, creating a conductive material with outstanding stretchability. The elastic conductive composite were then film formed on the glass and poly(ethylene terephthalate) (PET) nonwoven fabric substrate by spin coating and dip coating, respectively. Composite films with various contents of PEDOT:PSS polymer (10–100 wt.%) had been prepared. From the conductivity measurements, the conductivity was still kept as high as 88 S cm⁻¹ even the PEDOT:PSS content was lowered to 10 wt.%. Furthermore, the elasticity of conductive films on the PET-nonwoven fabric substrate was evaluated by the 180° bending test repeating 100 times. With introducing soft P(St-BA) material in the PEDOT:PSS phase, the surface resistance increased merely 3–6 times after bending 100 times, while the surface resistance for pure PEDOT:PSS film could reach 18–20 times.     

Comparison of performance parameters of poly(3,4 ethylenedioxythiophene) (PEDOT) based electrochromic device on glass with and without counter electrode

Conjugated polymers are promising materials for electrochromic device technology. Aqueous dispersions of poly(3,4-ethylenedioxythiophene)-(PEDOT) were spin coated onto transparent conducting oxide (TCO) coated glass substrates. A seven-layer electrochromic device was fabricated with the following configuration: glass/transparent conducting oxide (TCO)/PEDOT (main electrochromic layer)/gel electrolyte/prussian blue (counter electrode)/TCO/glass. The device fabricated with counter electrode (Prussian blue) showed a contrast of 18% and without counter electrode showed visible contrast of 5% at 632 nm at a voltage of 1.9 V. The comparison of the device is done in terms of the colouration efficiency of the devices with and without counter electrode.     

Synergistic catalytic effect of a composite (CoS/PEDOT:PSS) counter electrode on triiodide reduction in dye-sensitized solar cells

Inorganic/organic nanocomposite counter electrodes comprised of sheetlike CoS nanoparticles dispersed in polystyrenesulfonate-doped poly(3,4-ethylenedioxythiophene (CoS/PEDOT:PSS) offer a synergistic effect on catalytic performance toward the reduction of triiodide for dye-sensitized solar cells (DSSCs), yielding 5.4% power conversion efficiency, which is comparable to that of the conventional platinum counter electrode (6.1%). The electrochemical impedance spectroscopy (EIS) and cyclic voltammetry measurements revealed that the composite counter electrodes exhibited better catalytic activity, fostering rate of triiodide reduction, than that of pristine PEDOT: PSS electrode. The simple preparation of composite (CoS/PEDOT:PSS) electrode at low temperature with improved electrocatalytic properties are feasible to apply in flexible substrates, which is at most urgency for developing novel counter electrodes for lightweight flexible solar cells.     

Preparation and characterization of poly(3,4-ethylenedioxythiophene)–poly(styrene sulfonate) composite thin films highly loaded with platinum nanoparticles

In this work, we propose a simple and efficient, low-temperature (∼120 °C) process to prepare transparent thin films of poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonate) (PEDOT:PSS) loaded with high concentration (up to 22.5 wt%) of platinum (Pt) nanoparticles. Firstly, an improved polyol method was modified to synthesize nano-sized (∼5 nm) and mono-dispersed Pt particles. These nanoparticles were incorporated into the matrix of PEDOT:PSS thin films via a spin coating/drying procedure. The electrochemical activities of the PEDOT:PSS thin film modified electrodes with respect to the I⁻/I₃⁻ redox reactions were investigated. It was found that the modified electrode of PEDOT:PSS thin film containing 22.5 wt% Pt exhibited the electrochemical activity comparable to the conventional Pt thin film electrode, suggesting that this electrode has good potential to serve as a counter electrode in dye-sensitized solar cells.     

Preparation of carbon nanotube/chitosan/gold nanoparticle composite microspheres

The electrostatic layer-by-layer (LbL) assembly of acid-modified multi-walled carbon nanotubes (MWNTs) and biopolymer chitosan (CHIT) is realized on planar substrates and polystyrene (PS) microsphere templates, respectively. The successful stepwise growing process of the composite films on planar substrates is investigated and confirmed by scanning electron microscopy and UV-vis spectroscopy. The transfer of the LbL assembly of MWNTs and CHIT to spherical PS microspheres leads to novel (MWNT/CHIT)PS core-shell structure, on which the gold nanoparticles (GNPs) are deposited to fabricate GNP(MWNT/CHIT)PS composite microspheres. The glass carbon electrodes modified with such (MWNT/CHIT)PS or GNP(MWNT/CHIT)PS composites exhibit satisfactory electrocatalytic activities for biomolecule dopamine.     

Silver nanoparticles deposited on porous silicon as a surface-enhanced Raman scattering (SERS) active substrate

Silver nanoparticles were deposited spontaneously from their aqueous solution on a porous silicon (PS) layer. The PS acts both as a reducing agent and as the substrate on which the nanoparticles nucleate. At higher silver ion concentrations, layers of nanoparticle aggregates were formed on the PS surface. The morphology of the metallic layers and their SERS activity were influenced by the concentrations of the silver ion solutions used for deposition. Raman measurements of rhodamine 6G (R6G) and crystal violet (CV) adsorbed on these surfaces showed remarkable enhancement of up to about 10 orders of magnitude.     

Conducting‐Polymer Nanotubes Improve Electrical Properties,Mechanical Adhesion,Neural Attachment,and Neurite Outgrowth of Neural Electrodes

An in vitro comparison of conducting‐polymer nanotubes of poly(3,4‐ethylenedioxythiophene) (PEDOT) and poly(pyrrole) (PPy) and to their film counterparts is reported. Impedance, charge‐capacity density (CCD), tendency towards delamination, and neurite outgrowth are compared. For the same deposition charge density, PPy films and nanotubes grow relatively faster vertically, while PEDOT films and nanotubes grow more laterally. For the same deposition charge density (1.44 C cm^?2), PPy nanotubes and PEDOT nanotubes have lower impedance (19.5 ± 2.1 kΩ for PPy nanotubes and 2.5 ± 1.4 kΩ for PEDOT nanotubes at 1 kHz) and higher CCD (184 ± 5.3 mC cm^?2 for PPy nanotubes and 392 ± 6.2 mC cm^?2 for PEDOT nanotubes) compared to their film counterparts. However, PEDOT nanotubes decrease the impedance of neural‐electrode sites by about two orders of magnitude (bare iridium 468.8 ± 13.3 kΩ at 1 kHz) and increase capacity of charge density by about three orders of magnitude (bare iridium 0.1 ± 0.5 mC cm^?2). During cyclic voltammetry measurements, both PPy and PEDOT nanotubes remain adherent on the surface of the silicon dioxide while PPy and PEDOT films delaminate. In experiments of primary neurons with conducting‐polymer nanotubes, cultured dorsal root ganglion explants remain more intact and exhibit longer neurites (1400 ± 95 µm for PPy nanotubes and 2100 ± 150 µm for PEDOT nanotubes) than their film counterparts. These findings suggest that conducting‐polymer nanotubes may improve the long‐term function of neural microelectrodes.     

Functionalized polymer spheres via one-step photoinduced synthesis for antimicrobial activity and gene delivery

Despite the fact that polystyrene (PS) spheres have been developed as polymeric carriers or matrices for various biomedical applications, the synthesis of PS spheres is time-consuming. This work describes the fabrication of a uniform PS sphere, coated with silver nanoparticles (Ag-PS), by simultaneous photoinduced polymerization and reduction fabricated using x-rays in aqueous solution without any initiator. The solution contains only styrene, silver ions (Ag(+)), and poly(vinyl pyrrolidone) (PVP) as a stabilizer. The proposed mechanism of the formation of the Ag-PS nanocomposite spheres involves the generation of radicals in the aqueous solution to induce PS polymerization and the reduction of Ag. The distribution of the sizes of the core PS spheres in the Ag-PS nanocomposite spheres was systematically examined as a function of irradiation time, concentration of styrene, and amount of PVP. Ag-PS nanocomposite spheres exhibit antimicrobial activity against bacteria (Escherichia coli and Staphylococcus aureus). Additionally, the cationic (vinylbenzyl)trimethylammonium (TMA) monomer was photopolymerized to form positively charged TMA-PS spheres as gene carriers with uniquely low cytotoxicity. Given these design advantages, the method proposed herein is simpler than typical approaches for synthesizing PS spheres with functionalized groups and PS spheres coated with Ag nanoparticles.     

Aqueous Metal Oxide Inks for Modifying Electrode Work Function in Polymer Solar Cells

A method to prepare aqueous metal oxide inks for tuning the work function (WF) of electrodes is demonstrated. Thin films prepared from the metal oxide ink based on vanadium oxide (V₂O₅) nanoparticles are found to increase the WF of an indium‐tin‐oxide (ITO) electrode. ITO substrates modified with V₂O₅ films are applied as a hole selective layer (HSL) in polymer solar cells (PSCs) using a poly(3‐hexylthiophene) and [6,6]‐phenyl‐C61 butyric acid methyl ester blend as a photoactive layer. The PSCs prepared with V₂O₅‐modified ITO show better device performance, achieving a power conversion efficiency of 3.6%, demonstrating 15% enhancement compared to conventional ITO/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT‐PSS) based devices. Furthermore, ITO/V₂O₅‐modified devices exhibit better ambient stability with 60% improvement in device lifetime than those using PEDOT:PSS as an HSL. This solution‐processable and highly stable WF‐modifying metal oxide film can be a potential alternative material for engineering interfaces in optoelectronic devices.     

Organically modified silica nanoparticles with covalently incorporated photosensitizer for photodynamic therapy of cancer

We report a novel nanoformulation of a photosensitizer (PS), for photodynamic therapy (PDT) of cancer, where the PS molecules are covalently incorporated into organically modified silica (ORMOSIL) nanoparticles. We found that the covalently incorporated PS molecules retained their spectroscopic and functional properties and could robustly generate cytotoxic singlet oxygen molecules upon photoirradiation. The synthesized nanoparticles are of ultralow size ( approximately 20 nm) and are highly monodispersed and stable in aqueous suspension. The advantage offered by this covalently linked nanofabrication is that the drug is not released during systemic circulation, which is often a problem with physical encapsulation. These nanoparticles are also avidly uptaken by tumor cells in vitro and demonstrate phototoxic action, thereby highlighting their potential in diagnosis and PDT of cancer.     

导电聚合物纳米线的制备及气敏性能研究

首次采用简单的浸润多孔氧化铝(AAO)模板法制备了导电聚合物聚-3,4-乙烯二氧噻吩(PE-DOT)纳米线.导电聚合物溶液浸润AAO模板后,PEDOT吸附于孔道壁并进一步聚合生成导电聚合物纳米线.紫外-可见光-近红外光谱(UV-vis-NIR spec-trum)分析表明生成的纳米线处于掺杂态.采用四探针仪分析了导电聚合物纳米线的导电性能,结果显示纳米线电导率相比普通PEDOT材料有数量级增加,且表现出良好的掺杂/脱掺杂能力.研究了导电聚合物纳米线的气体敏感性能,发现其对挥发性醇类,尤其对甲醇在较低浓度下表现出优异的敏感性,对5×10-6甲醇气体的响应时间约为10～20s,测试可重复性超过20次,达到饱和吸附时的气体浓度明显大于普通PEDOT材料.表明PEDOT纳米线不仅提供了较大表面积供气体分子吸附,而且纳米线中导电通道取向一致,从而体现出较好的气体敏感性能.     

Sustainable Solid‐State Supercapacitors Made of 3D‐Poly(3,4‐ethylenedioxythiophene) and κ‐Carrageenan Biohydrogel

3D‐Poly(3,4‐ethylenedioxythiophene) (PEDOT) electrodes are prepared using the multi‐step template‐assisted approach. Specifically, poly(lactic acid) nano‐ and microfibers collected on a previously polymerized PEDOT film are used as templates for PEDOT nano‐ and microtubes, respectively. Morphological analysis of the samples indicates that 3D‐PEDOT electrodes obtained using a low density of templates, in which nano‐ and microtubes are clearly identified, exhibit higher porosity, and specific surface than conventional 2D‐PEDOT electrodes. However, a pronounced leveling effect is observed when the density of templates is high. Thus, electrodes with microtubes still present a 3D‐morphology but much less marked than those prepared using a low density of PLA microfibers, whereas the morphology of those with nanotubes is practically identical to that of films. Electrochemical studies prove that solid supercapacitors prepared using 3D‐PEDOT electrodes and κ‐carrageenan biohydrogel as electrolytic medium, exhibit higher ability to exchange charge reversibly and to storage charge than the analogues prepared with 2D‐electrodes. Furthermore, solid devices prepared using 3D‐electrodes and κ‐carrageenan biohydrogel exhibit very similar specific capacitances that those obtained using the same electrodes and a liquid electrolyte (i.e., acetonitrile solution with 0.1 M LiClO₄). These results prove that the success of 3D‐PEDOT electrodes is independent of the electrolytic medium.

     

导电聚(3,4-二氧乙基噻吩)应用研究进展

聚(3,4-二氧乙基噻吩)(PEDOT)是目前发现的导电态最稳定的导电高分子之一,在抗静电、塑料内存、电解电容器、有机太阳能电池、有机电致发光显示器件等领域得到了广泛研究和应用.本文简要综述PEDOT在这些领域的应用进展情况.     

Conductivity enhancement of conjugated polymer after HCl-methanol treatment

Polymer conductivity is key factor to improve the performance of the electronic and photonic devices. Poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) films were soaked into 0.03, 0.14, 0.41, and 1.13 M concentrations of HCl-methanol solution for 10, 20, 30, 40, 50, 60, and 70 min. The resulting films were investigated using Fourier transform infrared (FTIR) spectrometry, conductivity measurements, and field emission scanning electron microscopy. The characteristic FTIR absorption peaks of poly(4-styrenesulfonate) (PSS) of the films decreased as the soaking time increased. While PSS absorption peaks appeared in the HCl-methanol soaking solution and increased with the soaking time. The conductivity of PEDOT:PSS film was approximately 1.20 × 10^− 6 S/cm before soaking in the HCl-methanol solution. The conductivity of PEDOT:PSS was enhanced nearly three orders of magnitude after soaking the films into the HCl-methanol solvent. The surface of PEDOT:PSS film was initially very smooth. However, numerous humps appeared on the surface of the films after soaking PEDOT:PSS film into the HCl-methanol solution for 10, 20, and 30 min. The number of humps was reduced and disappeared thereafter.     

Effects of a base coating used for electropolymerization of poly(3,4-ethylenedioxythiophene) on indium tin oxide electrode

Electropolymerization of poly(3,4-ethylenedioxythiophene) (PEDOT) films on indium tin oxide (ITO), using a very thin PEDOT:poly(styrene sulfonate) (PEDOT:PSS) film as a base coating, was carried out in a non-aqueous solution containing the monomer, an electrolyte and propylene carbonate by a two-electrode system. For comparison, PEDOT film electrodeposited on bare ITO substrate under the same condition was also presented. The PEDOT films deposited on these two substrates were characterized by scanning electron microscopy, energy disperse X-ray spectroscopy and Raman spectroscopy. The results indicate that the PEDOT film electrodeposited on bare ITO was not uniform, while the PEDOT film electrodeposited on PEDOT:PSS/ITO has better uniformity. The compositions of the different regions of PEDOT film electrodeposited on bare ITO and PEDOT:PSS/ITO were studied and discussed. Electrochromic devices (ECDs) based on PEDOT films electrodeposited on bare ITO and PEDOT:PSS/ITO were fabricated and characterized by UV-Vis-NIR spectrophotometric study. The results show that the display contrast of the ECD based on PEDOT film electrodeposited on PEDOT:PSS/ITO was improved over that on a bare ITO substrate.     

Poly(acrylonitrile-co-itaconic acid)–poly(3,4-ethylenedioxythiophene) and poly(3-methoxythiophene) nanoparticles and nanofibres

This work aimed to produce poly(acrylonitrile-co-itaconic acid) (P(AN-co-IA)) nanocomposites with poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3-methoxythiophene) (PMOT). An anionic surfactant sodium dodecyl benzene sulphonate was used in emulsion polymerization for nanocomposite production. Incorporations of PEDOT and PMOT on the nanoparticles were characterized by scanning electron microscopy (SEM), atomic force microscopy, Fourier transform infrared-attenuated total reflectance spectroscopy and ultra-violet spectroscopy. These nanoparticles were blended with PAN and the blends were electrospun to produce P(AN-co-IA)–polythiophene-derivative-based nanofibres, and the obtained nanofibres were characterized by SEM and energy dispersive spectroscopy. In addition, electrochemical impedance studies conducted on nanofibres showed that PEDOT and PMOT in matrix polymer P(AN-co-IA) exhibited capacitive behaviour comparable to that of ITO–PET. Their capacitive behaviour changed with the amount of electroactive polymer.