Fabrication of a metalloporphyrin - Polyoxometalate hybrid film by a layer-by-layer method and its catalysis for hydrogen evolution and dioxygen reduction

Tetrakis (N-methylpyridyl) porphyrinato] cobalt (CoTMPyP) and 1:12 silicotungstic acid (SiW12) were alternately deposited on a 4-aminobenzoic acid (4-ABA)-modified glassy carbon electrode through a layer-by-layer method. The resulting organic-inorganic hybrid films were characterized by cyclic voltammetry (CV) and UV/vis absorption spectroscopy. We proved that the prepared multilayer films are uniform and stable. SiW12-containing multilayer films (SiW12 as the outermost layer) exhibit remarkable electrocatalytic activity for the hydrogen evolution reaction (HER). The kinetic constants for HER were comparatively investigated at different layers Of SiW12/CoTMPyP multilayer film-modified electrodes by hydrogen evolution voltammetry. In addition, rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) voltammetric methods confirm that SiW12/CoTMPyP (CoTMPyP as the outermost layer) multilayer films catalyze almost a two-electron reduction of O-2 to H2O2 in pH 1-6 buffer solutions. Furthermore, P2W18/CoTMPyP films were also assembled, and their catalytic activity for HER is very different from that Of SiW12/CoTMPyP multilayer films.

Fabrication of metalloporphyrin-polyoxometalyte hybrid film by layer-by-layer method and its catalysis for dioxygen reduction

Through layer-by-layer method [tetrakis(N-methylpyridyl)porphyrinato] cobalt (CoTMPyP) and polyoxometalyte were alternately deposited on 4-aminobenzoic acid (4-ABA) modified glassy carbon electrode. The resulting organic-inorganic hybrid films were characterized by cyclic voltammetry (CV), UV/visible absorption spectroscopy, and atomic force microscopy (AFM). It was proved that the multilayer films are uniform and stable. CoTMPyP-containing multilayer films exhibit remarkable electrocatalytic activity for the reduction of O-2. Rotating disk electrode (RDE) voltammetry and rotating ring-disk electrode (RRDE) voltammetry confirm that P2W18/CoTMPyP multilayer films can catalyze the four-electron almost reduction of O-2 to water in pH > 4.0 buffer solution, while SiW12/CoTMPyP multilayer films catalyze about two-electron reduction of O-2 to H2O2 in pH 1 - 6 buffer solutions. The kinetic constants for O-2 reduction were comparatively investigated at P2W18/CoTMPyP and SiW12/CoTMPyP multilayer films electrodes.

Electrostatic layer-by-layer deposition and electrochemical characterization of thin films composed of MnO(2) nanoparticles in a room-temperature ionic liquid

Thin films of MnO(2) nanoparticles were grown using the layer-by-layer method with poly (diallyldimetylammonium) as the intercalated layer. The film growth was followed by UV-vis, electrochemical quartz crystal microbalance (EQCM), and atomic force microscopy. Linear growth due to electrostatic immobilization of layers was observed up to 30 bilayers, but electrical connectivity was maintained only for 12 MnO(2)/PPDA bilayers. The electrochemical characterization of this film in 1-butyl-2,3-dimethyl-imidazolium (BMMI) bis(trifluoromethanesulfonyl)imide (TFSI) (BMMITFSI) with and without addition of a lithium salt indicated a higher electrochemical response of the nanostructured electrode in the lithium-containing electrolyte. On the basis of EQCM experiments, it was possible to confirm that the charge compensation process is achieved mainly by the TFSI anion at short times (<2 s) and by BMMI and lithium cations at longer times. The fact that large ions like TFSI and BMMI participate in the electroneutrality is attributed to the redox reaction that occurs at the superficial sites and to the high concentration of these species compared to that of lithium cations.

Nano-polypyrrole supercapacitor arrays prepared by layer-by-layer assembling method in anodic aluminum oxide templates

A novel method for preparing nano-supercapacitor arrays, in which each nano-supercapacitor consisted of electropolymerized Polypyrrole (PPy) electrode / porous TiO2 separator / chemical polymerized PPy electrode, was developed in this paper. The nano-supercapacitors were fabricated in the nano array pores of anodic aluminum oxide template using the bottom-up, layer-by-layer synthetic method. The nano-supercapacitor diameter was 80 nm, and length 500 nm. Based on the charge/discharge behavior of nano-supercapacitor arrays, it was found that the PPy/TiO2/PPy array supercapacitor devices performed typical electrochemical supercapacitor behavior. The method introduced here may find application in manufacturing nano-sized electrochemical power storage devices in the future for their use in the area of microelectronic devices and microelectromechanical systems.

An effective layer-by-layer adsorption and polymerization method to the fabrication of polyoxometalate-polypyrrole nanoparticle ultrathin films

A layer-by-layer (LbL) adsorption and polymerization method was developed for the controllable preparation of polypyrrole (PPy) nanoparticles within ultrathin films. By repetitive adsorption of pyrrole and subsequent polymerization with 12-molybdophosphoric acid, the polyelectrolyte multilayer films containing PPy nanoparticles were fabricated. UV-visible absorption spectrocopy, Fourier transform infrared (FTIR) spectroscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM) and cyclic voltammograras (CVs) were used to characterize the PPy nanoparticles and their multilayer thin films. UV-visible spectra indicate that the growth of PPy nanoparticles was regular and occurred within the polyelectrolyte films. The size of prepared PPy nanoparticles was found by TEM to increase with the increasing of polymerization cycles. The electrochemistry behavior of the multilayer thin films was studied in detail on ITO. The results suggest that the LbL adsorption and polymerization method developed herein provides an effective way to prepare PPy nanoparticles in the polymer matrix.

A novel potentiodynamic method of electrochemical growth for layer-by-layer film formation based on electrostatic interaction

A novel method of electrochemical growth was developed for layer-by-layer film formation and proven more advantageous than the commonly used immersion growth in obtaining more uniform multilayer assemblies, as well as being able to proceed in salt-containing solutions without competitive adsorption from the salt ions. (C) 1999 Elsevier Science S.A. All rights reserved.

Size dependent photodegradation of CdS particles deposited onto TiO2 mesoporous films by SILAR method

The properties of CdS nanoparticles incorporated onto mesoporous TiO2 films by a successive ionic layer adsorption and reaction (SILAR) method were investigated by Raman spectroscopy, UV-visible spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). High resolution TEM indicated that the synthesized CdS particles were hexagonal phase and the particle sizes were less than 5 nm when SILAR cycles were fewer than 9. Quantum size effect was found with the CdS sensitized TiO2 films prepared with up to 9 SILAR cycles. The band gap of CdS nanoparticles decreased from 2.65 eV to 2.37 eV with the increase of the SILAR cycles from 1 to 11. The investigation of the stability of the CdS/TiO2 films in air under illumination (440.6 µW/cm2) showed that the photodegradation rate was up to 85% per day for the sample prepared with 3 SILAR cycles. XPS analysis indicated that the photodegradation was due to the oxidation of CdS, leading to the transformation from sulphide to sulphate (CdSO4). Furthermore, the degradation rate was strongly dependent upon the particle size of CdS. Smaller particles showed faster degradation rate. The size-dependent photo-induced oxidization was rationalized with the variation of size-dependent distribution of surface atoms of CdS particles. Molecular Dynamics (MD) simulation has indicated that the surface sulphide anion of a large CdS particle such as CdS made with 11 cycles (CdS11, particle size = 5.6 nm) accounts for 9.6% of the material whereas this value is increased to 19.2% for (CdS3) based smaller particles (particle size: 2.7 nm). Nevertheless, CdS nanoparticles coated with ZnS material showed a significantly enhanced stability under illumination in air. A nearly 100% protection of CdS from photon induced oxidation with a ZnS coating layer prepared using four SILAR cycles, suggesting the formation of a nearly complete coating layer on the CdS nanoparticles.

Albumin-mediated incorporation of water-insoluble therapeutics in layer-by-layer assembled thin films and microcapsules

The present study demonstrates a method to deliver hydrophobic drugs by incorporation into thin films and microcapsules fabricated via a layer-by-layer assembly approach. The hydrophobic molecule binding properties of albumin have been exploited for solubilization of a water-insoluble molecule, pyrene (model drug), by preparation of non-covalent conjugates with bovine serum albumin (BSA). Conjugation with BSA renders a highly negative zeta potential to the previously uncharged pyrene which favors the assembly formation by electrostatic interaction with a positively charged polyelectrolyte, chitosan (at acidic pH). The growth of the assembly was followed by monitoring pyrene absorbance with successive layer deposition. The thin film assembly was demonstrated to be capable of releasing its hydrophobic cargo under physiological conditions. We demonstrated the applicability of this approach by encapsulating a water-insoluble drug, curcumin. These assemblies were further loaded with the anti-cancer drug Doxorubicin. Biocompatible calcium carbonate microparticles were used for capsule preparation. The porous nature of the microparticles allows for the pre-encapsulation of therapeutic macromolecules like protein. The fabrication of protein encapsulated stable microcapsules with hydrophobic molecules incorporated into the shell of the microcapsules has been demonstrated. The microcapsules were further capable of loading hydrophilic molecules like Rhodamine B. Thus, using the approach described, a multi-agent carrier for hydrophobic and hydrophilic drugs as well as therapeutic macromolecules can be envisioned.

Development of SnS quantum dot solar cells by SILAR method

SnS quantum dot solar cell is fabricated by Successive Ionic Layer Adsorption and Reaction (SILAR) method. SnS layer is optimized by different SILAR cycles of deposition. The particle size increased with the increase in number of SILAR cycles. Cu2S coated FTO is used as counter electrode against the conventional Platinum electrode. On comparison with a cell having a counter electrodeelectrolyte combination of Platinum-Iodine, Cu2S-polysulfide combination is found to improve both the short circuit current and fill factor of the solar cell. A maximum efficiency of 0.54% is obtained with an open circuit voltage of 311 mV and short circuit current density of 4.86 mA/cm. (C) 2014 Elsevier Ltd. All rights reserved.

Burst event detection in wall turbulence by WVITA method

Wavelet Variable Interval Time Average (WVITA) is introduced as a method incorporating burst event detection in wall turbulence. Wavelet transform is performed to unfold the longitudinal fluctuating velocity time series measured in the near wall region of a turbulent boundary layer using hot-film anemometer. This unfolding is both in time and in space simultaneously. The splitted kinetic of the longitudinal fluctuating velocity time series among different scales is obtained by integrating the square of wavelet coefficient modulus over temporal space. The time scale that related to burst events in wall turbulence passing through the fixed probe is ascertained by maximum criterion of the kinetic energy evolution across scales. Wavelet transformed localized variance of the fluctuating velocity time series at the maximum kinetic scale is put forward instead of localized short time average variance in Variable Interval Time Average (VITA) scheme. The burst event detection result shows that WVITA scheme can avoid erroneous judgement and solve the grouping problem more effectively which is caused by VITA scheme itself and can not be avoided by adjusting the threshold level or changing the short time average interval.

Layer-by-layer assembly of carbon nanotubes and Prussian blue nanoparticles: A potential tool for biosensing devices

A promising method for assembling carbon nanotubes (CNTs) and poly(diallyldimethylammonium chloride) protected Prussian blue nanoparticles (P-PB) to form three-dimensional (3D) nanostructured films is proposed. The electrostatic interaction, combined with layer-by-layer self-assembly (LBL), between negatively charged CNTs and positively charged P-PB is strong enough to drive the formation of the 3D nanostructured films. Thus, prepared multilayer films were characterized by ultraviolet-visible-near-infrared spectroscopy (UV-vis-NIR), scanning electron microscopy (SEM) and cyclic voltammetry (CV).

[Ru(bpy)(3)](2+)-doped silica nanoparticles within layer-by-layer biomolecular coatings and their application as a biocompatible electrochemiluminescent tag material

[Ru(bpy)(3)](2+)-doped silica (RuSi) nanoparticles were synthesized by using a water/oil microemulsion method. Stable electrochemiluminescence (ECL) was obtained when the RuSi nanoparticles were immobilized on a glassy carbon electrode by using tripropylamine (TPA) as a coreactant. Furthermore, the ECL of the RuSi nanoparticles with layer-by-layer biomolecular coatings was investigated. Squential self-assembly of the polyelectrolytes and biomolecules on the RuSi nanoparticles gave nanocomposite suspensions, the ECL of which decreased on increasing the number of bilayers.

Layer-by-layer assembly of single-charged ions with a rigid polyampholyte

A novel method to produce multilayer films has been developed by layer-by-layer assembly of single-charged ions and a rigid polyampholyte containing unbalanced charges in each of its repeat units.