Electrochromic multilayer films based on trilacunary Dawson-type polyoxometalate

A new ultrathin multilayer film consisting of polyoxometalate (POM) cluster Na₁₂[P₂W₁₅O₅₆]·18H₂O (P₂W₁₅) and polyallylamine hydrochloride (PAH) were fabricated on quartz and ITO substrates by layer-by-layer self-assembly method. The multilayer films, PSS/PAH/(P₂W₁₅/PAH)_n, were characterized by UV-vis spectra, cyclic voltammetry (CV) and chronoamperometric (CA) measurements. The electrochromic film exhibits both suitable response time and low power consumption due to the presence of lacunary polyoxometalate, providing valuable information for exploring the potential application of polyoxometalate-based electrochromic materials.     

Chitosan-assisted fabrication and electrocatalytic activity of the composite film electrode of heteropolytungstate/carbon nanotubes

A novel chemically modified electrode based on the immobilization of heteropolytungstate in carbon nanotubes-chitosan (CNTs-chitosan) composite film by one step self-assembly technique was fabricated. Chitosan was chosen as a natural polymer for dispersing CNTs to form a stable CNTs-chitosan composite, which provided an interface containing amino groups for assembling [P₂W₁₈O₆₂]⁶⁻ (abbr. P₂W₁₈) by electrostatic interactions. The CNTs-chitosan composite film was investigated and characterized by infrared spectroscopy (IR), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The CNT-chitosan film provides a high active area and good conduction pathway, and enhances the adsorptive capability of P₂W₁₈ molecules on the film. The electrochemical behavior of the P₂W₁₈/CNTs-chitosan/GCE was studied in detail, including scan rate, pH dependence, and stability. The CV and amperometry studies demonstrate that the P₂W₁₈/CNTs-chitosan/GCE has fast response and good electrocatalytic activity for the reduction of S₂O₈²⁻ and IO₃⁻ anions in acidic aqueous solution.     

Effects of poly (vinyl alcohol) (PVA) content on preparation of novel thiol-functionalized mesoporous PVA/SiO2 composite nanofiber membranes and their application for adsorption of heavy metal ions from aqueous solution

Thiol-functionalized mesoporous poly (vinyl alcohol)/SiO₂ composite nanofiber membranes and pure PVA nanofiber membranes were synthesized by electrospinning. The results of Fourier transform infrared (FTIR) indicated that the PVA/SiO₂ composite nanofibers were functionalized by mercapto groups via the hydrolysis polycondensation. The surface areas of the PVA/SiO₂ composite nanofiber membranes were >290 m²/g. The surface areas, pore diameters and pore volumes of PVA/SiO₂ composite nanofibers decreased as the PVA content increased. The adsorption capacities of the thiol-functionalized mesoporous PVA/SiO₂ composite nanofiber membranes were greater than the pure PVA nanofiber membranes. The largest adsorption capacity was 489.12 mg/g at 303 K. The mesoporous PVA/SiO₂ composite nanofiber membranes exhibited higher Cu²⁺ ion adsorption capacity than other reported nanofiber membranes. Furthermore, the adsorption capacity of the PVA/SiO₂ composite nanofiber membranes was maintained through six recycling processes. Consequently, these membranes can be promising materials for removing, and recovering, heavy metal ions in water.     

The optical properties of PVA/TiO2 composite nanofibers

The electrospun nanofibers emerge several advantages because of extremely high specific surface area and small pore size. This work studies the effect of PVA nanofibers diameter and nano‐sized TiO₂ on optical properties as reflectivity of light and color of a nanostructure assembly consisting polyvinyl alcohol and titanium dioxide (PVA/TiO₂) composite nanofibers prepared by electrospinning technique. The PVA/TiO₂ composite spinning solution was prepared through incorporation of TiO₂ nanoparticles as inorganic optical filler in polyvinyl alcohol (PVA) solution as an organic substrate using the ultrasonication method. The morphological and optical properties of collected composites nanofibers were highlighted using scanning electron microscopy (SEM) and reflective spectrophotometer (RS). The reflectance spectra indicated the less reflectance and lightness of composite with higher nanofiber diameter. Also, the reflectance and lightness of nanofibers decreased with increasing nano‐TiO₂ concentration. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Ultrasmall Ag nanocrystals supported on chitosan/PVA nanofiber mats with bifunctional properties

Bifunctional nanofiber mats consisting of chitosan (CS), poly(vinyl alcohol) (PVA), and silver nanocrystals (Ag NCs) have been fabricated by a facile electrospinning method. The formation and presence of Ag NCs supported on CS/PVA nanofibers are confirmed by ultraviolet‐visible spectroscopy and X‐ray diffraction. The morphology of the samples is characterized by transmission electron microscopy and scanning electron microscopy. The prepared Ag NCs/CS/PVA nanofiber mats show pronounced antibacterial activity against Escherichia coli and excellent filtration property for suspended particulate matter (SPM) particles. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46504.     

Palladium nanoparticles embedded chitosan/poly(vinyl alcohol) composite nanofibers as an efficient and stable heterogeneous catalyst for Heck reaction

In this study, palladium nanoparticles were successfully embedded into modified chitosan/poly(vinyl alcohol) composite nanofibers (Pd-CS/PVA nanofibers) by electrospinning. Then, the Pd-CS/PVA nanofibers were treated at evaluated temperature to improve its solvent resistance and in situ reduce Pd²⁺ cations into Pd⁰ active species. The incorporated palladium nanoparticles with ultra small mean diameter of 3.73 ± 1.04 nm are evenly distributed inside the Pd-CS/PVA nanofiber. The resulting Pd-CS/PVA nanofiber mat exhibits high catalytic activity for Heck reaction of aromatic iodides with alkenes and can be recycled for 18 times without loss of initial activity. The high catalytic activity and stability of Pd-CS/PVA nanofiber mat can be attributed to the ultra small diameter nanofibers, strong chelating ability of chitosan, and fine embedment of palladium species inside the nanofiber. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48026.     

Preparation and antibacterial activity of PET/chitosan nanofibrous mats using an electrospinning technique

The nanofiber deposition method, by electrospinning, was employed to introduce antibacterial activity and biocompatibility to the surface of poly (ethylene terephthalate) (PET) textiles. The polymer blends of PET and chitosan were electrospun on to the PET micro‐nonwoven mats for biomedical applications. The PET/chitosan nanofibers were evenly deposited on to the surface, and the diameter of the nanofibers was in the range between 500 and 800 nm. The surface of the nanofibers was characterized using SEM, ESCA, AFM, and ATR‐FTIR. The wettability of the PET nanofibers was significantly enhanced by the incorporation of chitosan. The antibacterial activity of the samples was evaluated utilizing the colony counting method against Staphylococcus aureus and Klebsiella pneumoniae. The results indicated that the PET/chitosan nanofiber mats showed a significantly higher growth inhibition rate compared with the PET nanofiber control. In addition, the fibroblast cells adhered better to the PET/chitosan nanofibers than to the PET nanofibers mats, suggesting better tissue compatibility. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Enhancement of the mechanical properties and thermostability of poly(vinyl alcohol) nanofibers by the incorporation of sodium chloride

The mechanical properties and thermostability of poly(vinyl alcohol) (PVA) nanofiber mats have been obviously improved by the incorporation of sodium chloride (NaCl). The tensile properties including tensile strength and modulus of membranes with an addition of 1.0 wt % NaCl increased from 2.51 to 4.22 MPa and 33.0 to 176.30 MPa, respectively, more than 160 and 700% of those of the electrospun pure PVA membranes. Moreover, thermogravimetric analysis showed that the initial decomposition temperature (T_i) and the half decomposing temperature (T_50%) of PVA nanofibers with the addition of NaCl were at least 26 and 59 °C higher than that of pure PVA nanofibers, respectively, indicating a strong interaction between the PVA and the salt ions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45981.     

A multifunctional organic-inorganic multilayer film based on tris(1,10-phenanthroline)ruthenium and polyoxometalate

The novel multifunctional thin films composed of transition metal complex tris(1,10-phenanthroline)ruthenium(II) Ru(phen)₃Cl₂ (abbr Ru(phen)₃, phen = 1,10-phenanthroline), and Dawson-type polyoxometalate [P₂Mo₁₈O₆₂]⁶⁻ (abbr P₂Mo₁₈) were fabricated on quartz, silicon and ITO substrates by layer-by-layer (LBL) method. The LBL films deposition were found to be linearly related to the number of bilayers as monitored by UV-vis spectroscopy. And the compositions of the films were measured by X-ray photoelectron spectra (XPS). The result of atomic force microscopy (AFM) revealed a relatively uniform surface morphology of the multilayer films. In particular, the films exhibited the photo-luminescence arising from π^*-t_2g ligand-to-metal transition of Ru(phen)₃ and catalytic activity to the reduction of NO₂⁻ attributing to molybdenum-centered redox processes of P₂Mo₁₈.     

Synthesis of (Z)‐3‐hexen‐1‐yl acetate by lipase immobilized in polyvinyl alcohol nanofibers

Polyvinyl alcohol (PVA)‐nanofibers‐immobilized lipase were formed by electrospinning. The specific surface area of the nanofiber (5.96 m²/g) was about 250 times larger than that of PVA‐film‐immobilized lipase (0.024 m²/g). The PVA‐nanofibers‐immobilized lipase were used as the catalyst for the esterification of (Z)‐3‐hexen‐1‐ol (leaf alcohol) with acetic acid in hexane. The activity of the nanofiber is equivalent to that of commercially available immobilized lipase (Novozym‐435). The ester conversions of the nanofibers, Novozym‐435, the film and lipase powder reached 99.5% at 5 h, 100% at 5 h, 11.5% at 6 h, and 81.1% at 5.75 h, respectively. The nanofibers‐immobilized lipase showed higher activity for the esterification than the film‐immobilized lipase and lipase powder, probably because it has high specific surface area and high dispersion state of lipase molecules in PVA matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effects of Fe2+ ions on morphologies,microstructures and mechanical properties of electrospun nylon‐6 nanofibers

In this study, nylon‐6 nanofiber mats containing Fe²⁺ ions were fabricated via electrospinning. The resultant electrospun nylon‐6/FeCl₂ nanofiber mats were characterized by SEM, TEM, Fourier transform IR spectroscopy, wide angle XRD and DSC. Unique morphological features, such as spider's‐web‐like morphologies, were observed and became evident with increasing additive Fe²⁺ ions. The metastable γ form was predominant in the as‐spun nylon‐6 nanofibers. The relative intensity of such γ form gradually decreased with increasing additive Fe²⁺ ions, indicative of transformation of the crystalline structure in the electrospun nylon‐6/FeCl₂ nanofibers due to strong molecular interactions between the nylon‐6 backbone and the additive Fe²⁺ ions. The effects of additive Fe²⁺ ions on the mechanical properties of both nonwoven nanofiber mats and single nanofibers were investigated. In particular, Young's modulus of nylon‐6/FeCl₂ single nanofibers gradually increased from 1.46 to 5.26 GPa with increasing additive Fe²⁺ ions. © 2013 Society of Chemical Industry     

Influence of Ag incorporation on the structural,optical and electrical properties of ITO/Ag/ITO multilayers for inorganic all-solid-state electrochromic devices

Indium tin oxide/silver/indium tin oxide (ITO/Ag/ITO, IAI) multilayer structures were prepared by DC magnetron sputtering as a conductive transparent electrode for inorganic all-solid-state electrochromic devices. A thin layer of silver (Ag) with various thicknesses was inserted between two layers of ITO films. The XRD and SEM results revealed that the microscopic morphology of Ag film was closely related to the thickness. Besides, the electrical and optical properties of the IAI multilayers were significantly influenced by the Ag layer thickness. The optimized IAI multilayers demonstrated the best combination of electrical and optical properties with a figure of merit of 54.05 (sheet resistance of 6.14 Ω/cm²and optical transmittance of 90.83%) when the Ag film was 10 nm thick. In order to evaluate the IAI multilayers as a transparent electrode for electrochromic applications, two ECDs with the structures of ITO/NiO_x/LiPON/WO₃/ITO and ITO/NiO_x/LiPON/WO₃/IAI were prepared, and their electro-optical properties were characterized by cyclic voltammetry (CV), chronoamperometry (CA) and spectroscopic measurements. Compared with ECD the pure ITO top electrode (ITO/NiO_x/LiPON/WO₃/ITO), the ECD with the IAI top electrode (ITO/NiO_x/LiPON/WO₃/IAI) presented a slightly smaller optical modulation amplitude, but a faster switching speed. All our findings indicate that the IAI multilayer structure is a promising alternative to the ITO thin film for inorganic all-solid state electrochromic applications.     

Carbon nanotubes-assisted polyoxometalate nanocomposite film with enhanced electrochromic performance

A nanocomposite film containing polyoxometalates (POMs) cluster K₆P₂W₁₈O₆₂·14H₂O (P₂W₁₈), carbon nanotubes (CNTs) and chitosan (CS) was fabricated by layer-by-layer (LbL) methods. The composite material displays enhanced electrochromic performance, with the optical contrast of 20.3% and coloration efficiency of 91.5 cm² C⁻¹ at 620 nm. Furthermore, the composite material displays the increased thickness and surface roughness by incorporation of CNTs into the P₂W₁₈ film. Obviously, the presence of CNTs has the strong influence on the multilayer structure, leading to high optical contrast and coloration efficiency. The results demonstrate the essential role of CNTs in enhancing functionality on POMs for applications of electrochromic devices.     

Highly luminescent film functionalized with CdTe quantum dots by layer‐by‐layer assembly

Robust and facile strategies are required to fabricate film with high luminescence for application in the fields of biomaterials. In this study, the luminescent electrospinning cellulose fibrous mats were decorated with CdTe quantum dots (QDs) and poly(diallyl dimethyl ammonium chloride) (PDDA) using layer by layer (LBL). The characterizations of the LBL films coated mats were executed by X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, fluorescent spectroscopy, X‐ray diffraction, thermal gravimetric analysis, and differential scanning calorimetry. The luminescent intensities were linearly increased with adding the amount of deposited bilayers. The green fabricated (QDs/PDDA)_n coated mat through physical interactions is a promising luminescent material. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41893.     

Layer-by-layer assembly of polyaniline nanofibers/poly(acrylic acid) multilayer film and electrochemical sensing

Polyaniline (PANI) nanofibers are synthesized by dilute polymerization and subsequently used for layer-by-layer assembly with poly(acrylic acid) (PAA). The chemical synthesized PANI nanofibers are characterized by SEM and TEM. In addition, the LBL assembly process is characterized by SEM, UV-vis spectrometry and electrochemical methods. PAA inside the multilayer film can dope nanostructured PANI effectively and shift its electroactivity to a neutral pH environment. Compared with PANI/PAA film co-deposited on the electrode by electropolymerization, the redox behavior of PANI/PAA multilayer via LBL assembly is more reversible, indicating the enhancement of electron transfer. The obtained nanostructured PANI/PAA multilayer films are very stable and show high electrocatalytic ability toward H₂O₂, which makes it an ideal substrate for H₂O₂ detection and offers great promise for biosensing.     

Composite graphitic nanolayers prepared by self-assembly between finely dispersed graphite oxide and a cationic polymer

Chemical flaking of graphite has been performed by reacting natural graphite with a strong oxidizing agent, NaClO₃/HNO₃. The formed hydrophilic, negatively charged graphite oxide (GO) colloids can be dispersed in water which allows the deposition of thin GO/cationic polymer (poly(diallyldimethylammoniumchloride, PDDA) multilayer films on a glass substrate by wet-chemical self-assembly. The feasibility of the charge-regulated layer-by-layer deposition is demonstrated by mutual charge titrations of the film-forming species. Visible-light spectroscopy revealed progressive growth of the film thickness with the number of deposition of steps, while XRD and AFM showed that partially exfoliated, highly anisometric (aspect ratio >50) graphite oxide platelet aggregates were deposited with an average thickness of the stacked graphite oxide platelets of 10 carbon layers (7.4 nm). Reduction of multilayer assemblies of GO and PDDA on glass yielded a non-conductive turbostratic carbon nanofilm. The original, conductive graphite-like structure was restored by reduction with N₂H₄ and annealing at 400 °C which, by gradual ordering of the carbon crystallites, caused a significant decrease in the resistivity.     

Solution electrowriting of highly stable TiN nanofiber pattern for transparent electrode under extreme environment

The fast developing electronic industry boosts higher demand of transparent electrode. Nanofiber network design provides a new platform for finding alternative materials to replace the traditional indium-doped tin oxide (ITO) film as transparent electrode. In this work, the TiN nanofiber network with a micron-scale precise geometry was firstly assembled by solution electrowriting. Unlike the ordinary opaque TiN film or bulk, the geometry patterned TiN nanofiber network achieved an ultrahigh transparency above 90%. Due to the electrical conductive virtue of TiN, the network reached a relatively low sheet resistance of 10.3 Ω/sq that can be comparable to ITO and even metal nanofibers. The combination of high transparency and low sheet resistance in TiN nanofiber network paves a way for its application as transparent electrode. Moreover, the figure-of-merit of TiN nanofiber transparent electrode was controllable by simply adjusting the geometry size of TiN nanofiber pattern. A series of oxidation resistance and corrosion resistance tests were additionally carried out, which caused little effect on the performance of TiN nanofiber transparent electrode. This excellent antioxidative and anticorrosive property demonstrates the high chemical durability of TiN nanofiber network, especially compared to metal nanofiber networks.     

Atmospheric plasma application to improve adhesion of electrospun nanofibers onto protective fabric

Nylon 6 electrospun nanofibers were deposited on plasma-pretreated woven fabric substrates with the objective of improving adhesion between them. The prepared samples were evaluated for adhesion strength and durability of nanofiber mats by carrying out peel strength, flex resistance, and abrasion resistance tests. The test results showed significant improvement in the adhesion of nanofiber mats on woven fabric substrates due to atmospheric plasma pretreatment. The samples also exhibited good flex and abrasion resistance characteristics. X-ray photoelectron spectroscopy and water contact angle analyses indicate that plasma pretreatment introduces radicals, increases the oxygen content on the substrate surface, and leads to formation of active chemical sites that may be responsible for enhanced cross-linking between the substrate fabric and the electrospun nanofibers, which in turn increases the adhesion properties. The work demonstrates that the plasma treatment of the substrate fabric prior to deposition of electrospun nanofiber mats is a promising method to prepare durable functional materials.     

Hydrophilic non-wovens made of cross-linked fully-hydrolyzed poly(vinyl alcohol) electrospun nanofibers

Fully-hydrolyzed poly (vinyl alcohol) (PVA) nanofibers were successfully electrospun from aqueous solutions of PVA in the presence of acetic acid. A continuous spinning of uniform PVA nanofibers proceeded by the addition of acetic acid due to the changes of electronic conductivity and surface tension of aqueous solution of PVA. When cross-linking agent 1 was added to aqueous solution of PVA and subsequent thermal treatment of as-spun nanofibers, chemically cross-linked PVA nanofibers were achieved to resist disintegration in contact with hot water and the tensile mechanical property of nanofiber non-wovens was greatly improved by the formation of cross-linking points. Magnetite was deposited uniformly onto the hydrophilic surface of cross-linked PVA nanofibers and the resulted nanofibers decorated with magnetite showed a magnetic responsiveness. The deposition of magnetite on the PVA nanofibers can generate self-standing magnetic non-wovens.     

Spider-net within the N6, PVA and PU electrospun nanofiber mats using salt addition: Novel strategy in the electrospinning process

Electrospun nanofibers are promising candidates in the nanotechnological applications due to the advantages of the nanofibrous morphology. Therefore, many attempts were reported to modify the electrospun mats to gain more beneficial properties. In the present study, we are introducing a strategy to synthesize electrospun polymeric nanofiber mats containing spider-net binding the main nanofibers. Addition with long stirring time of a metallic salt having tendency to ionize rather than formation of sol–gel in the host polymer solution reveals to synthesize a spider-net within the electrospun nanofibers of the utilized polymer. Nylon6, polyurethane and poly(vinyl alcohol) have been utilized; NaCl, KBr, CaCl₂ and H₂PtCl₆ have been added to the polymeric solutions. In the case of nylon6 and poly(vinyl alcohol), addition of the inorganic salts resulted in the formation of multi-layers spider-network within the electrospun nanofibers mats. The synthesized spider-nets were almost independent on the nature of the salt; the optimum salt concentration was 1.5 wt%. The metallic acid led to form trivial spider-nets within both of nylon6 and poly(vinyl alcohol) nanofibers. In a case of polyurethane, few spider-nets were formed after salt addition due to the low polarity of the utilized solvents. According to TEM analysis, the synthesized spider-net consisted of joints; the later issued from the main nanofibers at Taylor's cone zone. The spider-net improved the mechanical properties and the wetability of the nylon6 nanofiber mats, accordingly a mat having amphiphilic feature has been prepared.