Preparation of Cu(II)‐chelated poly(vinyl alcohol) nanofibrous membranes for catalase immobilization

Poly(vinyl alcohol) (PVA) nanofibers were formed by electrospinning. Metal chelated nanofibrous membranes were prepared by reaction between Cu(II) solution and nanofibers, and which were used as the matrix for catalases immobilization. The constants of Cu(II) adsorption and properties of immobilized catalases were studied in this work. The Cu(II) concentration was determined by atomic absorption spectrophotometer (AAS), the immobilized enzymes were confirmed by the Fourier transform infrared spectroscopy (FTIR), and the amounts of immobilized enzymes were determined by the method of Bradford on an ultraviolet spectrophotometer (UV). Adsorption of Cu(II) onto PVA nanofibers was studied by the Langmuir isothermal adsorption model. The maximum amount of coordinated Cu(II) (q_m) was 2.1 mmol g⁻¹ (dry fiber), and the binding constant (K_l) was 0.1166 L mmol⁻¹. The immobilized catalases showed better resistance to pH and temperature inactivation than that of free form, and the thermal and storage stabilities of immobilized catalases were higher than that of free catalases. Kinetic parameters were analyzed for both immobilized and free catalases. The value of V_max (8425.8 μmol mg⁻¹) for the immobilized catalases was smaller than that of the free catalases (10153.6 μmol mg⁻¹), while the K_m for the immobilized catalases were larger. It was also found that the immobilized catalases had a high affinity with substrate, which demonstrated that the potential of PVA‐Cu(II) chelated nanofibrous membranes applied to enzyme immobilization and biosensors. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

Preparation of poly(vinyl alcohol)/poly(acrylic acid)/TiO2/carbon nanotube composite nanofibers and their photobleaching properties

The composite nanofibers of poly(vinyl alcohol) (PVA)/poly(acrylic acid) (PAAc)/titanium(IV) oxide (TiO₂) were prepared by electrospinning for a novel photocatalytic treatment of waste water. To improve the photoelectronic properties of PVA/PAAc/TiO₂ composite nanofibers, carbon nanotubes (CNTs) were used as an additive. The TiO₂ and CNTs were immobilized in the PVA/PAAc hydrogels as electrospun nanofibers for an easier recovery after the wastewater treatment. The improved efficiency of pollutant dye removal was observed at pH 10 due to the pH-sensitive swelling behavior of the PVA/PAAc/TiO₂/CNTs composite nanofibers. The photocatalytic activity of TiO₂ was improved noticeably by applying electric field to the CNTs-embedded composite nanofibers.     

Immobilization of catalases on amidoxime polyacrylonitrile nanofibrous membranes

Amidoxime polyacrylonitrile (AOPAN) nanofibrous membranes were generated by the reaction between electrospun polyacrylonitrile nanofibrous membranes and hydroxylamine hydrochloride. AOPAN nanofibrous membranes were further modified by Fe(III) chelation for immobilizing catalases with coordination bonds. The surface morphologies of the nanofibrous membranes and immobilized catalases were observed by field emission scanning electron microscopy. Chelation of Fe(III) onto AOPAN nanofibrous membranes was studied by the Langmuir isothermal adsorption model. It was found that the maximum amount of coordinated Fe(III) (q_m) was 4.5045 mmol g^?1 (dry nanofibrous membranes) and the binding constant (K_l) was 0.0698 L mmol^?1. The amounts of immobilized enzymes were determined by the method of Bradford. Kinetic parameters were analyzed for both immobilized and free catalases. The value of V_max (7122.6 µmol mg^?1 min^?1) for the immobilized catalases was smaller than that for the free catalases (9203.2 µmol mg^?1 min^?1), and the K_m for the immobilized catalases was larger. The immobilized catalases showed better resistance to pH and temperature change than the free catalases, and the storage stability of immobilized catalases was higher than that of free catalases. As for reusability, the immobilized catalases retained 71% of their activity after eight repeated uses. © 2012 Society of Chemical Industry     

Kinetics of ligand exchange reaction of Cu(II)-ammine complex with poly(vinyl alcohol) in aqueous solution

The kinetics of the ligand exchange reaction of the Cu(II)-ammine complex with poly(vinyl alcohol) (PVA) has been studied by a stopped-flow method at pH 9–10, at μ=0.1 (NH₄Cl) and at 25°C. The reaction is initiated by the formation of unstable [Cu(NH₃)₃]²⁺ by the attack of H⁺ on Cu(II)-ammine complex, and proceeds through the mixed complex {[Cu(NH₃)₃(O?PVA)]²⁺}. This step may be rate-determining, followed by a rapid reaction. Finally, the Cu(II) ion is taken up by PVA. The rate is given by d[Cu(II)?PVA]/dt=k[H⁺]{[Cu(NH₃)₄]²⁺}[PVA]/[NH₄Cl], where k=k₁ + k′₂[H⁺], k₁=4.25× 10s^?1 and k′₂=5.20× 10¹¹l mol^?1s^?1.     

Production of Trans-Cinnamic Acid by Immobilization of the Bambusa oldhamii BoPAL1 and BoPAL2 Phenylalanine Ammonia-Lyases on Electrospun Nanofibers

Phenylalanine ammonia-lyase (PAL) catalyzes the nonoxidative deamination of phenylalanine to yield trans-cinnamic acid and ammonia. Recombinant Bambusa oldhamii BoPAL1/2 proteins were immobilized onto electrospun nanofibers by dextran polyaldehyde as a cross-linking agent. A central composite design (CCD)-response surface methodology (RSM) was utilized to optimize the electrospinning parameters. Escherichia coli expressed eBoPAL2 exhibited the highest catalytic efficiency among four enzymes. The optimum conditions for fabricating nanofibers were determined as follows: flow rate of 0.10 mL/h, voltage of 13.8 kV, and distance of 13 cm. The response surface models were used to obtain the smaller the fiber diameters as well as the highest PAL activity in the enzyme immobilization. Compared with free BoPALs, immobilized BoPALs can be reused for at least 6 consecutive cycles. The remained activity of the immobilized BoPAL proteins after storage at 4 °C for 30 days were between 75 and 83%. In addition, the tolerance against denaturants of the immobilized BoPAL proteins were significantly enhanced. As a result, the dextran polyaldehyde natural cross-linking agent can effectively replace traditional chemical cross-linking agents for the immobilization of the BoPAL enzymes. The PAL/nylon 6/polyvinyl alcohol (PVA)/chitosan (CS) nanofibers made are extremely stable and are practical for industrial applications in the future.     

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     

Immobilization of horseradish peroxidase on electrospun poly(vinyl alcohol)–polyacrylamide blend nanofiber membrane and its use in the conversion of phenol

Electrospun nanofibers, with their porous structures, high surface-to-volume ratio, and good mechanical properties, are used as a support material for enzyme immobilization. In this study, the poly(vinyl alcohol) and polyacrylamide bicomponent (PVA–PAAm) nanofibers were fabricated via the electrospinning method. Synthesized PAAm was characterized with size exclusion chromatography (SEC). Nanofibers were characterized by fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and scanning electron microscope (SEM). DSC and TGA analyses showed that the nanofibers were more durable than PVA and PAAm polymers. SEM images demonstrated that all nanofibers possessed uniform and smooth structures (average diameter about 300 nm). FTIR results have shown that PAAm successfully participates in nanofiber structure. The produced nanofibers were used as support material for covalent immobilization of horseradish peroxidase (HRP). The optimum temperature for free HRP was 45 °C, whereas it was 50 °C for the immobilized enzyme. The immobilized HRP showed better storage and thermal stability than free HRP. The kinetic parameters (K _m and V _max) were found to be 2.42 mM and 0.027 U for the immobilized HRP and 1.86 mM and 0.079 U for the free HRP, respectively. The immobilized enzyme could be used effectively for 25 cycles with 54% retention of the activity. The immobilized HRP was also used for the conversion of phenol. Phenol removal was found to be about 29.68% at 180 min in real wastewater. The novel PVA–PAAm nanofibrous material was successfully used as a support material for covalent immobilization of HRP. Immobilized enzymes such as oxido-reductases onto the PVA–PAAm bicomponent nanofiber could be recommended in the treatment of organic pollutants in industrial effluents.

     

Preparation of graphene oxide/carboxymethyl chitosan/polyvinyl alcohol composite nanofiber membranes by electrospinning for heavy metal adsorption

In this paper, a graphene-oxide/carboxymethyl-chitosan/polyvinyl-alcohol (GO/CMC/PVA) composite nanofiber membrane was prepared by electrospinning and cross-linking with glutaraldehyde (GA) to improve the water resistance. The composite nanofiber membrane can be used in the field of heavy metal adsorption. The membrane was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. The effects of GO concentration, adsorption time, and initial concentration of heavy-metal ion (Ni²⁺, Cu²⁺, Ag⁺, and Pb²⁺) solution on the adsorption performance of the fiber membranes were investigated. The results showed that the addition of GO can reduce the diameter of nanofibers. GO, CMC, and PVA exhibited good compatibility, and the intermolecular hydrogen bonding improved. The addition of GO also improved the crystalline properties of the composite fiber membrane. In the optimal cross-linking condition, GA was saturated by steam cross-linking for 6 h. The introduction of GO improved the adsorption capacity of the membrane for heavy metals in water. The utmost adsorption capacities for Ni²⁺, Cu²⁺, Ag⁺, and Pb²⁺ were 262.1, 237.9, 319.3, and 413.6 mg/g when using the cross-linked composite fiber membranes, respectively. The results of adsorption kinetics and thermodynamics showed that the adsorption process accorded with the pseudo-second-order kinetic model and Langmuir–Freundlich isotherm model.     

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     

Lipase immobilized on poly (vinyl alcohol) modified polysulfone membrane: application in hydrolytic activities for olive oil

The advancement of membrane research closely relates to the activities of ‘immobilization of enzymes’. The modification of polymeric membrane surfaces according to tailor-made specifications is considered an art and useful in this arena. In this study, lipase is immobilized on Polyvinyl alcohol photomodified Polysulfone (PS–PVA) membranes. The maximum immobilization (1.48 mg/cm²) for PS–PVA membranes is achieved. The amount of immobilized lipase directly relates on the PVA content on the membrane. Scanning Electron Microscope and X-ray diffraction patterns show the evidences of lipase immobilization on membranes. The hydrolytic performances of lipase immobilized PS and PS–PVA–glu membranes for olive oil are studied. The free fatty acid (FFA %) and acid value (AV) parameters are determined by titrimetic analysis (1.53 and 3.04 for PS–PVA–glu) and compared with esterification GC-mass analysis data. The K _m and V _max values are 105 mM and 0.9 mM/min for lipase immobilized on PS–PVA–glu and 153.8 mM and 0.51 mM/min for lipase on PS. The reusability feature shows the lipase immobilized on PS–PVA–glu matrix have better stability (10.7% decrease) compared to lipase immobilized on PS matrix (33.3% decrease) after five cycles.     

Properties of polyamide 612/poly(vinyl alcohol) blends and their impact on free volume and oxygen barrier properties

Oxygen transmission rates and free volume properties (i.e. average volumes of free-volume-cavities (V_f), mean number of the free volume cavities per unit volume (I₃) and fractional free volume (F_v)) values of bio-based polyamide 612 (PA612)/poly(vinyl alcohol) (PVA) (i.e. PA612_xPVA⁰³_y, PA612_xPVA⁰⁵_y, PA612_xPVA⁰⁸_y and PA612_xPVA¹⁴_y) blend films were reduced to a minimum value, when their PVA content reached corresponding optimal values of 25, 20, 15 and 10 wt%, respectively. The minimum oxygen transmission rate, V_f, I₃ and F_v value obtained for the best PA612₉₀PVA¹⁴₁₀, PA612₈₅PVA⁰⁸₁₅, PA612₈₀PVA⁰⁵₂₀ and PA612₇₅PVA⁰³₂₅ bio-based blown films reduced considerably with decreasing PVA degrees of polymerization. As evidenced by the results of dynamical mechanical analysis, differential scanning calorimetry, wide angle X-ray diffraction and Fourier transform infrared spectroscopic experiments, PA612 and PVA are miscible to some extent at the molecular level when their PVA contents are ≤ the corresponding optimal values. The significantly improved oxygen barrier and free volume properties for the PA612_xPVA^z_y blend films with optimized compositions is at least in part to the enhanced intermolecular interactions between PA612 carbonyl groups and PVA hydroxyl groups.     

One unexpected mixed-valence Cu(I,II)-cyanide coordination polymer in situ originating from the cleavage of acetonitrile

Solvothermal reaction of CuCl₂·2H₂O and 2-(4-pyridyl)benzimidazole (PyHBIm) in a acetonitrile-water mixed solvent afforded a mixture of [Cu^I₂Cu^II(CN)₂(PyHBIm)₂Cl₂]_n (1) and [Cu^II(PyH₂BIm)₂Cl₄] (2). Complex 1 is a mixed-valence 1D ribbon Cu(I,II)-cyanide coordination polymer. One Cu(II) center linearly links two Cu(I) ions via two μ₂-CN bridges. XPS spectrum and bond valence sum (BVS) analysis have confirmed the mixed-valence characteristics. Cu(II) ion adopts a centrosymmetric square-planar geometry surrounded by two cyanides and two pyridyl groups. Cu(I) ions adopt a trigonal geometry coordinated by cyanide, imidazole group and Cl⁻ anion. The cyanide ligand is in situ generated from the cleavage of acetonitrile solvent, which indicates that acetonitrile is an environmentally friend cyanating agent. The mechanism of acetonitrile in situ cleavage under solvothermal condition is explained. Complex 2 is a centrosymmetric mononuclear Cu(II) compound. Four equivalent Cl⁻ anions lie on the equatorial plane. The protonated PyH₂BIm⁺ cation as a monodentate ligand coordinates to Cu(II) center via pyridyl terminal.     

Preparation of thermo-responsive electrospun nanofibers containing rhodamine-based fluorescent sensor for Cu<Superscript>2+</Superscript> detection

A series of Cu²⁺-sensing nanofibers has been successfully prepared by electrospinning of poly[(N-isopropylacrylamide)-co-(N-hydroxymethyl acrylamide)-co-(4-rhodamine hydrazonomethyl-3-hydroxy-phenyl methacrylate)] [poly(NIPAAm-co-NMA-co-RHPMA), PNNR] random copolymers. These PNNR copolymers were synthesized by free radical copolymerization of three monomers, thermo-responsive NIPAAm, chemically crosslinkable NMA and Cu²⁺-sensing RHPMA, with the composition of RHPMA in the range of 2.4–16.3 wt%. In acidic environments, the PNNR copolymers showed highly selective and sensitive recognition and displayed “ON-OFF” fluorescence toward Cu²⁺ both in solution and in solid state (thin films and nanofibers). From the quantitative analysis via Stern-Volmer plots, PNNR nanofibers exhibited comparable Stern-Volmer constants as those of PNNR solutions in the order of 10⁴ M^?1, which are much higher than those of PNNR thin films. The enhanced sensitivity of PNNR electrospun nanofibers is attributed to their higher surface area compared to dip-coating films. The PNNR nanofibers also exhibited an on/off switchable sensing behavior in response to temperature change due to the hydrophilic-hydrophobic transition of PNIPAAm. In addition, the binding of PNNR with Cu²⁺ is chemically reversible both in solution and in nanofibers with the treatment of Na₄EDTA.     

Ionic solvation—III. free energies of transfer of copper(II) ion from water to sulfolane,tetrahydrofuran, acetone,dioxan and dimethylsulphoxide and to their mixtures with water

The emf of the cell: Cu/Cu²⁺, water + organic co-solvent/water, Cu²⁺//Cu with sulfolane, dioxan, tetrahydrofuran, acetone and dimethylsulphoxide (DMSO) as organic co-solvents has been measured for different solvent compositions. To decrease the liquid junction potential the salt bridge filled with the methanolic solution of tetrabutylammonium picrate has been applied. The emf data were used to calculate the Gibbs free energy of copper(II)cation transfer from water to nonaqueous or mixed solvents. Determined free energies of transfer are negative for DMSO and positive for other organic solvents.     

Cyanide-bridged mixed-valence copper(II/I) coordination polymers: Unique 7-connected sev-type 3D network versus anionic 2D host network encapsulated with cationic complex

Reactions of CuCl₂, K₂[Ni(CN)₄]/K₃[Co(CN)₆], and 5-amino-1H-tetrazole led to cyanide-bridged mixed-valence Cu(II/I) complexes, [Cu(H₂O)₃Cu₃(CN)₅] (1) and [Cu(H₂O)₄][Cu₄(CN)₆] (2).The uncommon semi-closed {Cu₂(CN)₃} dimmers in 1 are bridged by μ₃-C,C,N cyanide ligands to afford rare 1D centipedal-like chain motifs, which are further bridged by μ₂-C,N and metalloligand “CN–Cu(4)–CN” to finish sophisticated zeolite-like 3-D structure. Topologically, 1 is the first example of uninodal 7-connected sev-like cyanide-bridged network. Compound 2 consists of two-dimensional honeycomb-related anionic layers [Cu₄(CN)₆]^2 −, within which the [Cu(H₂O)₄]^2 + cations are intercalated into alternate interlamellar space. Compound 1 shows antiferromagnetic couple arising from pure ground-state configuration of Cu(II) mediated by diamagnetic bridges –CN–Cu^I–CN −. The inclusion compound 2 shows blue photoluminescence originated from Cu(I) center to the unoccupied π* orbital of the cyanide ligand (MLCT) charge transfer.     

Electrochemistry and electrocatalysis of hemoglobin on multi-walled carbon nanotubes modified carbon ionic liquid electrode with hydrophilic EMIMBF4 as modifier

The direct electrochemistry of hemoglobin (Hb) on multi-walled carbon nanotubes (MWCNTs) modified carbon ionic liquid electrode (CILE) was achieved in this paper. By using a hydrophilic ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF₄) as the modifier, a new CILE was fabricated and further modified with MWCNTs to get the MWCNTs/CILE. Hb molecules were immobilized on the surface of MWCNTs/CILE with polyvinyl alcohol (PVA) film by a step-by-step method and the modified electrode was denoted as PVA/Hb/MWCNTs/CILE. UV-vis and FT-IR spectra indicated that Hb remained its native structure in the composite film. Cyclic voltammogram of PVA/Hb/MWCNTs/CILE showed a pair of well-defined and quasi-reversible redox peaks with the formal potential (E^0′) of −0.370 V (vs. SCE) in 0.1 mol/L pH 7.0 phosphate buffer solution (PBS), which was the characteristic of the Hb heme Fe^III/Fe^II redox couples. The redox peak currents increased linearly with the scan rate, indicating the direct electron transfer was a surface-controlled process. The electrochemical parameters of Hb in the film were calculated with the results of the electron transfer coefficient (α) and the apparent heterogeneous electron transfer rate constant (k_s) as 0.49 and 1.054 s⁻¹, respectively. The immobilized Hb in the PVA/MWCNTs composite film modified CILE showed excellent electrocatalytic activity to the reduction of trichloroacetic acid (TCA) and hydrogen peroxide. So the proposed electrode showed the potential application in the third generation reagentless biosensor.     

New Mononuclear Cu(II) Complexes and 1D Chains with 4-Amino-4H-1,2,4-triazole

The crystal structures of two mononuclear Cu(II) NH₂trz complexes [Cu(NH₂trz)₄(H₂O)](AsF₆)₂ (I) and [Cu(NH₂trz)₄(H₂O)](PF₆)₂ (II) as well as two coordination polymers [Cu(μ₂-NH₂trz)₂Cl]Cl·H₂O (III) and [Cu(μ₂-NH₂trz)₂Cl] (SiF₆)_0.5·1.5H₂O (IV) are presented. Cationic 1D chains with bridging bis-monodentate μ₂-coordinated NH₂trz and bridging μ₂-coordinated chloride ligands are present in III and IV. In these coordination polymers, the Cu(II) ions are strongly antiferromagnetically coupled with J = −128.4 cm⁻¹ for III and J = −143 cm⁻¹ for IV (H = −J∑S_iS_i+1), due to the nature of the bridges between spin centers. Inter-chain interactions present in the crystal structures were taken into consideration, as well as g factors, which were determined experimentally, for the quantitative modeling of their magnetic properties.     

Fabrication and characterization of hollow nanofibrous PA6 yarn reinforced with CNTs

Core-sheath nanofibrous yarns were obtained through electrospinning of polyamide 6 (PA6) solution containing different concentrations of multi-wall carbon nanotubes (MWNTs) as sheath and PVA multifilament as the yarn core. By dissolving PVA, for obtaining conductive hollow nanofibrous PA6/MWNTs yarn, two types of porosity could be obtained including hollow central tube due to the structure of hollow yarn and nano-porous areas embedded in electrospun nanofibers. SEM results showed that the diameters of nanofibers were varying in the range of 103–145 nm obeying MWNTs concentrations and TEM results revealed that the MWNTs were embedded in nanofiber matrix as straight and aligned form. DSC analysis showed that electrospinning process caused the formation of less-ordered γ phase in nanofibers. The electrical conductivity of yarns increased from 10^?13 S m^?1 to 2.4?×?10^?6 S m^?1 with increasing the concentration of nanotubes from 0 wt.% to 7 wt.%.     

ITO electrode modified by self-assembling multilayer film of polyoxometallate on poly(vinyl alcohol) nanofibers and its electrocatalytic behavior

Poly(vinyl alcohol) (PVA) nanofiber mats were collected on indium tin oxide (ITO) substrate by electrospinning method. A multilayer film composed of α-[P₂W₁₈O₆₂]⁶⁻ (abbr. P₂W₁₈), a polyoxometallate (POM) anion, and poly(diallymethylammonium chloride) (abbr. PDDA) was fabricated by layer-by-layer (LBL) self-assembly technique on the PVA/ITO electrode. The PDDA/P₂W₁₈ multilayer film could be unselectively or selectively deposited on the PVA/ITO electrode via changing the amount of PVA nanofibers on the ITO substrate. The scanning electron microscope (SEM) images showed that when the electrospun time was short the PDDA/P₂W₁₈ multilayer film was unselectively deposited on PVA nanofiber mats because the amount of PVA nanofibers was too little to cover most of the ITO substrate. However, when the electrospun time was long enough, the PDDA/P₂W₁₈ multilayer film was selectively deposited on PVA nanofiber mats because of the larger surface area and higher surface energy of PVA nanofibers in comparison with the flat ITO substrate. Growth process of the multilayer film was determined by cyclic voltammetry (CV). Electrocatalytic effects of the PDDA/P₂W₁₈ multilayer film unselectively and selectively deposited on the PVA/ITO electrode on NO₂⁻ were observed.