Fabrication and characterization of multilayer films based on Keggin-type polyoxometalate and chitosan

Multilayer films based on Keggin-type polyoxometalate (POM) α-[SiW₁₂O₄₀]⁴⁻ (α-SiW₁₂), α-[PMo₁₂O₄₀]³⁻ (α-PMo₁₂) and cationic chitosan have been fabricated in aqueous solution via the layer-by-layer self-assembly technique (LBL). The resulting films were characterized by UV–Vis spectra, X-ray photoelectron spectra (XPS), atomic force microscopy (AFM) and cyclic voltammetry (CV) measurements. UV–Vis spectra show that the absorbance values at characteristic wavelengths of the multilayer films increase almost linearly with the number of chitosan/POM bilayers, suggesting that the deposition process is regular and highly reproducible from layer to layer. XPS spectra confirm the incorporation of chitosan and POMs into the films. AFM images indicate that the surface of the multilayer films is rather uniform and smooth. The antibacterial activities against Escherichia coli of the LBL films have also been investigated by optical density method.     

Semiconductor/metal nanocomposites formed by in situ reduction method in multilayer thin films

A layer-by-layer adsorption and in situ reduction method was adopted for synthesizing semiconductor/metal nanocomposites in multilayer ultra-thin films. Alternate adsorption of ZnO nanoparticles modified with poly(ethyleneimine), hydrogentetrachloroaurate and poly(styrenesulfonate) sodium results in the formation of ZnO/AuCl₄⁻-loaded multilayer films. In situ reduction of the incorporated metal ions by heating yields ZnO/Au nanocomposites in the films. UV-vis absorption spectroscopy and X-ray photoelectron spectroscopy were used to characterize the components of the composite films. UV-vis spectra indicate regular growth of the films. The electrochemistry behavior of the multilayer films was studied in detail on indium tin oxide electrode. The combined results suggest that the layer-by-layer adsorption and subsequent reduction method used here provides an effective way to synthesize ZnO/Au nanocomposites in the polymer matrix.     

Multilayer films consisted of azulene-based dye molecules and polyelectrolyte: Preparation, characterization and photoluminescent property

Ultrathin multilayer films of two azulene-based (Az-based) dye molecules (Az), 3-methylazulene-1-carboxylic acid hydrazide (Az-1) and 5-(4-phenylamine)-2-(3-methylazulene-1-yl)-1,3,4-oxadiazoles (Az-2), and poly(sodium 4-styrenesulfonate) (PSS) have been prepared by layer-by-layer self-assembly and characterized by UV-vis spectroscopy, fluorescence spectroscopy, small-angle X-ray reflectivity measurements and atomic force microscopy (AFM) imaging. UV-vis spectra show that the characteristic absorbance values of the multilayer films increase almost linearly with the number of PSS/Az bilayers, suggesting that the deposition process is regular and highly reproducible from layer to layer. Average thicknesses for the PSS/Az-1 and PSS/Az-2 bilayers of the multilayer films are ca. 0.9 and 1.4 nm, respectively. AFM images provide the surface morphology of the PSS/Az films, indicating that the film surface is relatively uniform and smooth. The occurrence of photoluminescent activity conforms the potential for creating luminescent multilayer films with Az-based dye molecules.     

Preparation,thermostability, and spectroscopic properties of Rhodamine 6G intercalated titanoniobate nanocomposite

Rhodamine 6G (R6G), a well-known fluorescent dye, has been intercalated into layered potassium titanoniobate (KTiNbO₅) through a guest–guest exchange method by using propylammonium titanoniobate (PrNH₃ ⁺-TiNbO₅) as a precursor. The synthesis process, the structure and morphology characterizations for lamellar nanocomposite have been investigated by means of XRD, FTIR, and SEM. The thermostability of R6G⁺-TiNbO₅ nanocomposite is discussed on the basis of thermogravimetric and calorimetric techniques. Absorption and fluorescence techniques are applied to study the photoresponse of R6G in hybrid film. The results indicate that R6G⁺ cations in thin film are highly fluorescent even at a high dye concentration, which may be due to the formation of J-dimers within the confined galleries.     

Preparation and characterization of polyoxometalate-Ag nanoparticles composite multilayer films

The multifunctional thin films (BW₁₂/Ag NPs)_n (BW₁₂ = BW₁₂O₄₀, NPs = nanoparticles) were prepared by layer-by-layer self-assembly method. The (BW₁₂/PEI-Ag⁺)_n (PEI = polyethylenimine) composite films were achieved through alternately depositing anionic BW₁₂ and cationic PEI-Ag⁺ complex. The deposition process of (BW₁₂/PEI-Ag⁺)₁₀ multilayer is linear layer-by-layer self-assembly. Under UV irradiation, Ag ions in (BW₁₂/PEI-Ag⁺)_n multilayer films were reduced photochemically into Ag NPs and (BW₁₂/Ag NPs)₁₀ films were obtained. Through UV-vis measurements, the presence of surface plasma absorption peak at 445 nm demonstrated the formation of silver NPs. The electrochemical and antibacterial activities of (BW₁₂/Ag NPs)_n films were investigated. The electrochemical results indicate that the glassy carbon electrode modified with (BW₁₂/Ag NP)_n film exhibits the electroreduction toward O₂. Moreover, the (BW₁₂/Ag NP)₁₀ multilayer films exhibit long-lasting antibacterial properties toward Escherichia coli (E. coli).     

Facile synthesis of α-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/diatomite composite for visible light assisted degradation of Rhodamine 6G in aqueous solution

α-Fe₂O₃ particle supported on diatomite (α-Fe₂O₃/diatomite composite) was prepared at room temperature by the chemical precipitation method using ferrous sulphate as the raw material and diatomite as supporter. α-Fe₂O₃/diatomite composite was characterized by XRD, FE-SEM, FT-IR and DRS. The result showed that α-Fe₂O₃ was uniformly loaded on the diatomite. The photocatalytic activity was investigated under visible light toward degradation of Rhodamine 6G aqueous solution and the effects of various experimental factors on Rhodamine 6G degradation were investigated. Compared with the α-Fe₂O₃, α-Fe₂O₃/diatomite composite had significantly enhanced activity in the degradation of Rhodamine 6G under visible light irradiation. Besides, the photostability of catalysts was also investigated. The experimental results indicated that the prepared composite is a promising material for the wastewater treatment for its good catalytic performance property and long-term stability.     

Preparation of self-assembled zinc oxide nanoparticles multilayer films under ultrasonic irradiation

Zinc oxide nanoparticles were synthesized and self-assembled on the reactive surface of a glass slide functionalized with (3-mercaptopropyl)-trimethoxysilane under ultrasonic irradiation. The structure, morphology, and optical property of the zinc oxide nanoparticles were investigated by TEM, XRD, and UV-vis spectroscopy. The functionalized glass slide was soaked in an aqueous solution which dispersed zinc oxide nanoparticles under ultrasonic irradiation. Zinc oxide multilayer films grew up to several layers (up to 5 layers) depending on the immersion time. The self-assembled zinc oxide nanoparticles multilayer films were characterized using UV-vis spectroscopy and SEM. Ultrasonic irradiation was an efficient method to make multilayer films on the functionalized glass slide with zinc oxide nanoparticles.     

Preparation and characterization of conducting poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) Langmuir-Blodgett film

The self-assembly of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) nanoparticles at an air/water interface was achieved by means of the electrostatic force between an octadecylamine (ODA) monolayer and PEDOT-PSS nanoparticles. A surface pressure (π)-area (A) isotherm and X-ray photoelectron spectroscopy of the composite film were used to confirm the electrostatic force between the SO₃⁻ group of PSS and the NH₄⁺ group of aliphatic amines. Monolayer and multilayer composite films of ODA/PEDOT-PSS and ODA-stearic acid (SA)/PEDOT-PSS were fabricated. These solid Langmuir-Blodgett films were investigated by the UV-Vis spectrum, atomic force microscopy, and X-ray diffraction method. It is observed that ODA-SA/PEDOT-PSS films had a higher film-forming capability than ODA/PEDOT-PSS films and an ordered multilayer structure was developed. The conductive properties of ODA-SA/PEDOT-PSS LB films were investigated in detail. Factors influencing the film conductivity such as the layer number and surface pressure were discussed and the conductive mechanism was also studied.     

Concentration-dependent luminescent behaviour of Rhodamine 6G in AlPO4 xerogel monoliths

Homogeneous monolith of AlPO₄ gel doped with Rhodamine 6G (Rh6G) in different dye concentration is prepared by one step process with sol–gel method using the precursors Al(lact)₃ and H₃PO₄. The optical properties of AlPO₄ gel doped with Rh6G have been characterized by UV–vis absorption spectra and fluorescence spectra. Rh6G molecular J-dimers and H-dimers even multimers are analyzed by excitation spectra based on Exciton theory. The structure of AlPO₄ gel doped with Rh6G is investigated by ²⁷Al and ³¹P Magic Angle Solid Nuclear Magnetic Resonance (MAS NMR), ²⁷Al {³¹P} Rotational Echo Double Resonance (REDOR) NMR and ²⁷Al Triple Quantum Magic Angle Spinning (TQ-MAS) NMR. Based on the results of optical spectra and the structural analysis by NMR techniques, The AlPO₄ gel doped with Rh6G dye with molar ratio of Rh6G/Al(lact)₃ of 1 × 10^?4 displays excellent optical properties.     

A facile synthesis of α-Ni(OH)2-CNT composite films for supercapacitor application

The α-Ni(OH)₂-CNT composite films have been successfully synthesized by a simple chemical method and their supercapacitive properties were investigated by variation of CNT. The structural, compositional, morphological, wettability and electrochemical properties of the composite films were studied by using various characterization techniques. X-ray diffraction analysis revealed that the synthesized composite films are polycrystalline in nature. FT-Raman spectroscopy result showed the characteristic Raman band of CNT and α-Ni(OH)₂ which confirmed the formation of α-Ni(OH)₂-CNT composite. SEM micrographs showed porous microstructure of the synthesized films and hydrophilic nature of the films was confirmed from wettability studies. Furthermore, the effect of the variation of CNT on the electrochemical properties of the synthesized composite films was discussed. The electrochemical performance of the composite films was studied by using cyclic voltammetry (CV) and Galvanostatic charge–discharge (GCD) techniques. The α-Ni(OH)₂-CNT composite showed highest specific capacitance of 544 F g^?1 with high retention capability of 85% after 1500th cycle and excellent cycling stability.     

Fabrication of a 12-tungstophosphate and cadmium oxide composite film and its properties

A multilayer composite film of the 12-tungstophosphate H₃[PW₁₂O₄₀]³⁻ (PW₁₂) and cadmium oxide nanoparticles (CdO) was fabricated on quartz and silicon by the layer-by-layer (LBL) self-assembly method. The film was characterized by UV–vis spectroscopy, atomic force microscopy (AFM) and luminescence spectra. The proposed composite film exhibits higher photocatalytic activity toward methyl orange (MO) solution at pH 3.5, compared to single PW₁₂ and CdO films. The degradation rate was affected by initial concentration of PW₁₂, pH value of MO solution, inorganic ions concentration and type in MO solution. In addition, the composite film displays luminescent property and reversible electrochromic property with fast response time.     

Barium borosilicate glass as a matrix for the uptake of dyes

Barium borosilicate (BBS) and sodium borosilicate (SBS) glass samples, prepared by the conventional melt-quench method, were used for the uptake of Rhodamine 6G dye from aqueous solution. The experimental conditions were optimized to get maximum uptake and was found to be 0.4 mg of dye per gram of BBS glass sample. For the same network former to modifier ratio, barium borosilicate glasses are found to have improved extent of uptake for the dye molecules from aqueous solutions compared to sodium borosilicate glasses. Based on ²⁹Si MAS NMR studies on these glasses, it is inferred that significantly higher number of non-bridging oxygen atoms present in barium borosilicate glasses compared to sodium borosilicate glasses is responsible for its improved uptake of Rhodamine 6G dye. ¹¹B MAS NMR studies have confirmed the simultaneous existence of boron in BO₃ and BO₄ configurations in both barium borosilicate and sodium borosilicate glasses. The luminescence studies have established that the dye molecule is incorporated into the glass matrix through ion exchange mechanism by replacing the exchangeable ions like Na⁺/Ba²⁺ attached with the non-bridging oxygen atoms present in the glass.     

Electrochemical behaviour of self-assembly multilayer films based on iron-substituted α-Keggin polyoxotungstates

Ultrathin multilayer films containing metal-substituted polyoxometalates, [PW₁₁Fe^III(H₂O)O₃₉]⁴⁻ (PW₁₁Fe) or [SiW₁₁Fe^III(H₂O)O₃₉]⁵⁻ (SiW₁₁Fe), and poly(ethylenimine) (PEI) were prepared by the electrostatic layer-by-layer self-assembly method on a glassy carbon electrode. The multilayer films were characterized by cyclic voltammetry and scanning electron microscopy and UV-Vis absorption spectroscopy on a quartz slide was used to monitor film growth. Cyclic voltammetry indicates that the electrochemical properties of the polyoxometalates are completely maintained in the multilayer films, and the influence of scan rate on the voltammetric features showed that the first tungsten reduction process for immobilized PW₁₁Fe and SiW₁₁Fe is a surface-confined process. Studies with [Fe(CN₆)]^3−/4− as electrochemical probe showed that their permeability depends on the thickness of the multilayer films, if the outermost layer is negatively charged. Additionally, the (PEI/SiW₁₁Fe)_n multilayer films showed electrocatalytic properties towards nitrite reduction.     

Layer-by-layer self-assembly of multilayer films of polyelectrolyte/Ag nanoparticles for enzymeless hydrogen peroxide detection

In the paper, we report on the layer-by-layer self-assembly of multilayer films of polyelectrolyte/Ag nanoparticles (AgNPs). The films were constructed by the alternate adsorption of the oppositely charged poly [(2-ethyldimethylammonioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)] (PQ11) and negatively charged citrate-stabilized AgNPs on solid substrates. The multilayer film growth process on quartz slides was monitored by UV-vis absorption spectroscopy. The resulting films exhibit good catalytic activity toward the reduction of hydrogen peroxide (H₂O₂). The enzymeless H₂O₂ sensor based on such films exhibits a fast amperometric response time of less than 5 s. The linear detection range is estimated to be from 100 μM to 110 mM (R² = 0.996), and the detection limit is estimated to be 78 μM at a signal-to-noise ratio of 3.     

Surfactant induced orientation of non-centrosymmetric polyoxometalate clusters in Langmuir-Blodgett films

The trivacant Keggin-type polyoxometalate Na₁₀-α-SiW₉O₃₄ (SiW₉) was encapsulated by the cationic surfactant dimethyl dioctadecylammonium (DODA) and forms an organic-inorganic complex. Stable Langmuir monolayers of this surfactant-encapsulated cluster complex form at the air-water interface and can be transferred onto solid substrates with a transfer ratio of 1.0 ± 0.02. Fourier transform infrared spectroscopy at grazing incidence reflection condition reveals that the non-centrosymmetric SiW₉ clusters are highly oriented in the films with their symmetry axis aligned preferably perpendicular to the layer plane. We propose a model in which the orientation state of SiW₉ is induced by the different electrostatic interactions between DODA molecules and different positions at the SiW₉ surface.     

Structural and spectral investigations of Rhodamine (Rh6G) dye-silica core-shell nanoparticles

Rhodamine (Rh6G) dye-silica core-shell nanoparticles (DSCSNPs) have been prepared by the controlled hydrolysis and condensation of single silica precursor tetraethylorthosilicate (TEOS) using the sol-gel method. Scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray analysis reveal that dye molecules are entrapped in silica (SiO₂) shell resulting into core-shell particles of ∼30 nm diameter. These particles are also characterized by X-ray diffraction and Fourier transforms infrared spectroscopy. The results indicate that core-shell particles are all in spherical shape and have a narrow size distribution. The fluorescent and optical properties of core-shell particles have been investigated using fluorescence and UV-Visible absorption spectra. The photoluminescence in solid or liquid medium occurs at the same wavelength. The SiO₂ shell restricts the leakage and photobleaching of dye efficiently. These core-shell nanoparticles are found to be highly luminescent and stable.     

Preparation,characterization and photocatalytic activity of TiO<Subscript>2</Subscript> / Methylcellulose nanocomposite films derived from nanopowder TiO<Subscript>2</Subscript> and modified sol–gel titania

TiO₂—methylcellulose (MC) nanocomposite films processed by the sol-gel technique were studied for phocatalytic applications. Precalcined TiO₂ nanopowder was mixed with a sol and heat treated. The sol suspension was prepared by first adding titanium tetra isopropoxide (Ti(OPr)₄ or TTP) to a mixture of ethanol and HCl (molar ratio TTP:HCl:EtOH:H₂O = 1:1.1:10:10) and then adding a 2 wt.% solution of methylcellulose (MC). The TiO₂ nanopowder was dispersed in the sol and the mixture was deposited on a microscope glass slide by spin coating. Problems of film inhomogeneity and defects which caused peeling and cracking during calcinations, because of film shrinkage, were overcome by using MC as a dispersant. Effect of MC on the structure evaluation, crystallization behavior and mechanical integrity with thermal treatment up to 500 °C are followed by SEM, XRD and scratch test. XRD Scanning electron microscopy (SEM) showed that the composite films with MC have much rougher surface than films made without MC. Composite films heat treated at approximately 500 °C have the greatest hardness values. For the composite thick film, the minimum load which caused the complete coating removal was 200 g/mm², an indication of a strong bond to the substrate. Photocatalytic activities of the composite film were evaluated through the degradation of a model pollutant, the textile dye, Light Yellow X6G (C.I. Reactive Yellow 2) and were compared with the activity of (i) a similar composite film without MC, and (ii) a TiO₂ nanopowder. The good mechanical integrity make this composite film an interesting candidate for practical catalytic applications.     

LiFePO<Subscript>4</Subscript>/TiO<Subscript>2</Subscript>/Pt composite film used as effective and robust counter electrode for dye sensitized solar cells

A series of composite films based on LiFePO₄/TiO₂/Pt were synthesized and used as counter electrodes for dye sensitized solar cells (DSSCs). The composites are characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and Brunauer–Emmett–Teller (BET). These analysis results demonstrate that the crystal structure of LiFePO₄ in composite is not changed, and the prepared LiFePO₄/TiO₂/Pt composite films hold a rough surface and porous structure which provide more catalytic activity sites for I₃ ^? reduction and more space for I^?/I₃ ^? diffusion. The DSSC based on LiFePO₄/TiO₂/Pt composite CEs shows a high power conversion efficiency of 6.23% at a low Pt dosage of 2%, comparable to the conventional magnetron sputtering Pt CE (6.31%). The electrochemical analysis reveals that the presented composite CEs have good electrocatalytic activity and low charge transfer resistance. Furthermore, the DSSCs based on LiFePO₄/TiO₂/Pt composite CE exhibit high stability under the continuous tests condition and electrolyte soaking. The results suggest that this LiFePO₄-based composite film could be a perspective electrode for practical application of DSSCs and it maybe provide a potential for further research about photo-charging lithium-ion batteries.     

Carbon-loaded porous composites produced by matrix carbonization of poly(vinylidene fluoride)

Using poly(vinylidene fluoride) (PVDF) carbonization at 750° C in fine-particle silica and its mixtures with graphite, we have prepared carbon-loaded porous composites which offer benzene absorption from 0.90 to 1.52 ml/g, compressive strength of 6 MPa, and Brinell hardness of up to 18 MPa. We observed the formation of various nanostructures (spheres, spherical segments, and layered platelets) and sizes (several to hundred nanometers). X-ray photoelectron and energy dispersive x-ray spectroscopy data indicate the presence of C-C, C =C, CO, COO, and CHF groups on the carbon surface. X-ray emission spectroscopy data show that the silica matrix composite prepared via PVDF carbonization contains small carbon clusters weakly bonded to the matrix. The silica/graphite matrix composite contains multilayer carbon films strongly bonded to the matrix. The OK _α spectra of both composites are similar to the spectrum of pure SiO₂.     

Wear behaviour and rolling contact fatigue life of Ti/TiN/DLC multilayer films fabricated on bearing steel by PIIID

In order to improve the friction and wear behaviours and rolling contact fatigue (RCF) life of bearing steel materials, Ti/TiN/DLC (diamond-like carbon) multilayer hard films were fabricated onto AISI52100 bearing steel surface by plasma immersion ion implantation and deposition (PIIID) technique. The micro-Raman spectroscopy analysis confirms that the surface film layer possess the characteristic of diamond-like carbon, and it is composed of a mixture of amorphous and crystalline phases, with a variable ratio of sp²/sp³ carbon bonds. Atomic force microscope (AFM) reveals that the multilayer films have extremely smooth area, excellent adhesion, high uniformity and efficiency of space filling over large areas. The nanohardness (H) and elastic modulus (E) measurement indicates that the H and E of DLC multilayer films is about 32 GPa and 410 GPa, increases by 190.9% and 86.4%. The friction and wear behaviours and RCF life of DLC multilayer films specimen have also been investigated by ball-on-disc and three-ball-rod fatigue testers. Results show that the friction coefficient against AISI52100 steel ball decreases from 0.92 to 0.25, the longest wear life increases nearly by 22 times. In addition, wear tracks of the PIIID samples as well as wear tracks of the sliding steel ball were analyzed with the help of optical microscopy and scanning electron microscopy (SEM). The L₁₀, L₅₀, L_a and mean RCF life L of treated bearing samples, in 90% confidence level, increases by 10.1, 4.2, 3.5 and 3.4 times, respectively. Compared with the bearing steel substrate, the RCF life scatter extent of Ti/TiN/DLC multilayer films sample is improved obviously.