0000000000449854

AUTHOR

Patrizia Bocchetta

Fuel Cell Performances of Bio-Membranes Made of Chitosan-Polyelectrolyte Thin Films and Nanowires into Anodic Alumina Membranes

Chitosan (CS) / Phosphotungstic acid (PTA) polyelectrolytes in the shape of thin films and nanowires supported by Anodic Alumina Membranes (AAM) have been fabricated through solution cast and filtration techniques, respectively. Their ability to function in a H2/O2 fuel cell under mild conditions (room temperature, low humidity and low Pt loading) is proved for the first time. The fabricated membrane electrode assemblies produce power peaks of ~20 mW cm-2 for both films and nanowires. The CS/PTA films (20-40 μm thick) are able to produce a quite constant power density of ~10 mW cm-2 recorded for at least 7 h. The gradual decrease of the power output with time observed for CS/PTA nanowires i…

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Anodic alumina membranes as template for the synthesis of 1-D metal oxide and hydroxide nanostructures

Anodic alumina membranes with highly ordered cylindrical pores and tuneable geometry have been prepared (pore diameters=20−200 nm; pore density 1012-1014 pores/m2; thickness: 20-100 mm) by controlling the anodizing process of aluminum in phosphoric, oxalic and sulphuric acid. The influence of different parameters (initial treatment of aluminium surface, composition of electrolyte, temperature and applied potential) on the final characteristics of the membranes have been investigated. The use anodic alumina membranes as template for the electrosynthesis of some metal hydroxides and oxides 1-D nanostructures (nanowires and nanotubes) will be also proved.

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Light induced electropolymerization of poly(3,4-ethylenedioxythiophene) on niobium oxide

Abstract The photoelectrochemical polymerization of poly(3,4-ethylenedioxythiophene), PEDOT, was successfully realized on anodic film grown to 50 V on magnetron sputtered niobium. Photocurrent Spectroscopy was employed to study the optical properties of Nb/Nb 2 O 5 /PEDOT/electrolyte interface in a large range of potential, and to get an estimate of the band gap and flat band potential of both the oxide and the polymer. Scanning Electron Microscopy was used to study the morphology of PEDOT. Both the optical and morphological features of the photoelectrochemically grown polymer were compared with those showed by PEDOT electropolymerized on gold conducting substrate.

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Electrodeposition and physico-chemical characterisation of Fe, Ti and mixed Fe/Ti oxides nanotubes

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Nanoporous alumina membranes filled with solid acid for thin film fuel cells at intermediate temperatures

Thin film fuel cells have been fabricated by impregnation of inorganic porous membranes with inorganic proton conductor. Anodic alumina membranes (50 μm thick and pore diameter of 200 nm), filled with CsHSO4 salt have been used as protonic conductor in a hydrogen-oxygen fuel cell working between 423 and 443 K in dry atmosphere. Polarization curves at 433 K showing ohmic control with open circuit values near 0.8 V and short circuit current around 8 mA cm−2 have been obtained. Possible causes of degradation as well as alternative routes to overcome some of the problems encountered with this approach will be reported. Keywords: Solid acid, Anodic alumina membranes, Pore filling, Thin film fuel…

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Composite Anodic Alumina /CsHSO4 Membranes for Intermediate Temperature Fuel Cell

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Photocurrent Spectroscopy Applied to the Characterization of Compositionally and Structurally Graded Materials: from Thin Films to Nanostructures

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1D cerium oxy-hydroxide nanostructures deposition via electrogeneration of base into anodic alumina membrane

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Fabbricazione per via elettrochimica e caratterizzazione di membrane nanoporose di allumina

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Electrochemical fabrication of metal/oxide/conducting polymer junction

After discovery of conducting polymers and the possibility to modify their electrical properties from insulating to metallic like behavior by doping and a careful choice of the processing conditions, a large amount of research effort has been devoted to the theoretical understanding of their solid state properties as well as to exploit the possible application of conducting polymers in many technological fields including large area organic electronics, polymer photovoltaic cell, and sensors. 1-4 Organic thin film transistors appear very promising devices for the development of low cost, flexible, and disposable plastic electronics. In order to reduce the operating voltage it has been sugges…

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Electrochemical Fabrication of Inorganic/Organic Field Effect Transistor

After discovery of conducting polymers and the possibility to modify their electrical properties (from insulating to metallic-like behaviour) by doping and a careful choice of the processing conditions, a large amount of research effort has been devoted to the theoretical understanding of their solid state properties as well as to exploit the possible application of conducting polymers in many technological fields including: large area organic electronics, polymer photovoltaic cell and sensors (1-2). Organic thin-film transistors appears very promising for the development of low cost, flexible and disposable plastic electronics. In order to reduce the operating voltage it has been suggested…

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Porous Anodic Alumina as template for the cathodic electrodeposition of oxide and hydroxide nanostructures

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Oxide and Hydroxide nanostructures embedded into Anodic alumina membranes prepared by means of electrogeneration of base

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Preparation and characterization of novel proton conducting membranes for thin film fuel cell

Chitosan (CS) / Phosphotungstic acid (PTA) polyelectrolytes in the shape of thin films and nanowires supported by Anodic Alumina Membranes (AAM) have been fabricated through solution cast and filtration techniques, respectively. Their ability to function in a H2/O2 fuel cell under mild conditions (room temperature, low humidity and low Pt loading) is proved for the first time. The fabricated membrane electrode assemblies produce power peaks of ∼20 mW cm-2 for both films and nanowires. The CS/PTA films (20-40 μm thick) are able to produce a quite constant power density of ∼10 mW cm-2 recorded for at least 7 h. The gradual decrease of the power output with time observed for CS/PTA nanowires i…

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Cs0.86(NH41.14SO4Te(OH)6 in porous anodic alumina for micro fuel cell applications.

Abstract Cs0.86(NH4)1.14SO4Te(OH)6 supported by anodic alumina membranes (AAMs) has been characterized for the first time in H2/O2 fuel cell. The fabricated membrane electrode assemblies are able to produce peak power densities in the range 15–30 mW cm−2 under mild conditions (room temperature, low humidity and low Pt loading) and show an increased durability with cycling with respect to previous results obtained with AAM-based fuel cell. The physico-chemical characterization of the electrolytes has been carried out through X-ray diffractometry, scanning electron microscopy and micro-raman analysis. An estimation of the composite membranes conductance under fuel cell operation has been carr…

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Influence of initial treatments of aluminium on the morphological features of electrochemically formed alumina membranes

Abstract The fabrication of alumina membranes by electrochemical oxidation of annealed aluminium was investigated. Porous layers were grown in 0.4 M H3PO4 at −1 and 5 °C at different anodising times. The morphology of the outer surface was found to be dependent on temperature and charge density, with both determining the extent of chemical dissolution of the anodic oxide. The inner-surface morphology was found to depend on the applied voltage only. The chemical dissolution rate of anodic oxide grown on annealed aluminium was found to be lower than that formed on unannealed aluminium under otherwise identical conditions. Such a difference in behaviour is explained in terms of a higher finish…

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Preparation and characterization of Porous Anodic Alumina Membranes as templates for the growth of metals and semiconductors nanostructures

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Template electrosynthesis of La(OH)3 and Nd(OH)3 nanowires using porous anodic alumina membranes

High quality arrays of Ln(OH)3 (Ln = La, Nd) nanowires have been successfully fabricated for the first time by an electrochemical process using anodic alumina membrane templates. A physico-chemical characterisation of electrodeposited hydroxides has been carried out by different techniques (XRD, SEM and EDX). The results show that the synthesized nanostructures are crystalline, dense, continuous, well aligned, and with high aspect ratio, suggesting further development of possible applications in the lanthanide family species. Keywords: Nanowires, Anodic alumina membranes, Hydroxide electrodeposition, Template, Lanthanide compounds

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Template-assisted electrodeposition of cerium oxy-hydroxide nanostructures in aqueous and organic electrolytes

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Room temperature electrodeposition of photoactive Cd(OH)2 nanowires

Cd(OH)2 nanowires (NWs) were successfully prepared by room temperature electrogeneration of base using Cd(NO3)2 aqueous electrolyte and Anodic Alumina Membrane (AAM) as template. Cd(OH)2 films have been also deposited on tin-doped indium oxide (ITO) for comparison. SEM analysis shows high quality deposits made of closely packed nanowires (NWs) into AAM and uniform flake-like surface on ITO. XRD analysis reveals that Cd(OH)2 films on ITO are polycrystalline, while the nanowires grow along the preferential directions [100] and [110]. Photoelectrochemical measurements show that Cd(OH)2 NWs are photoactive materials with indirect and direct band gap of 2.15 and 2.75 eV, respectively. Keywords: …

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From ceria nanotubes to nanowires through electrogeneration of base

The preparation of Ce(OH)3/CeO2 nanostructures (NSs) through electrogeneration of base into anodic alumina membranes was studied. The effects of solvent (alcohol and/or water), Ce3? partner anion nature (chloride or nitrate) and concentration, applied potential or current density in driving the morphology toward nanowires (NWs) and/or nanotubes (NTs) was described. The structural analysis performed by X-Ray Diffraction and Raman Spectroscopy allowed to evidence that the presence of Ce(IV) into the nanostructures strongly depends on the oxygen content in the growing environment.

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Physico-chemical Characterisation of Polypyrrole Film Grown in Aqueous and Non-aqueous Solution on Different Substrates

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Electrodeposition of supported gadolinium-doped ceria solid solution nanowires

Gadolinium-ceria solid solution nanowires with tunable composition have been prepared through template cathodic electrodeposition from solutions containing Ce 3+Gd 3+ in a variable ratio. The employed template is Porous Anodic Alumina because it can function as thermal resistant separator supporting the nanowires if used as ionic conductor in Solid Oxide Fuel Cell (SOFC). Scanning Electron Microscopy of the deposited nanostructures revealed that the use of ethanol as solvent and metal chloride as electrolyte allowed to prepare continuous, compact and well defined nanowires with morphological features stable even after thermal treatment. EDX compositional analysis confirms the presence of bo…

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Anodic Electro Deposition of CeO2 and Co-Doped CeO2 Thin Films

CeO2 and Co containing CeO2 thin films were deposited on indium tin oxide and stainless steel by anodic electrodeposition. Scanning electron microscopy showed that the films are flat and show globular morphology and cracks resulting from volume shrinking. According to XRD and Raman Spectroscopy pure ceria layers are crystalline, while the presence of Co induces the formation of amorphous films. The good adhesion and the compactness allowed the photoelectrochemical characterization of the films. A band gap value of 2.9 eV was estimated for CeO2, while slightly higher values (̃3.0 eV) were estimated for Co containing films. A mechanism for ceria anodic electrodeposition is proposed and discus…

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Electrodeposition and characterization of 1-D cerium based nanostructures

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Advances in Anodic Alumina Membranes-based fuel cell: CsH2PO4 pore-filler as proton conductor at room temperature

Abstract Anodic alumina membranes (AAM) filled with cesium hydrogen phosphate proton conductor have been tested as inorganic composite electrolyte for hydrogen–oxygen thin film (≤50 μm) fuel cell (TFFC) working at low temperatures (25 °C), low humidity ( T gas  = 25 °C) and low Pt loading (1 mg cm −2 ). Single module TFFC delivering a peak power of around 15–27 mW cm −2 , with open circuit voltage (OCV) of about 0.9 V and short circuit current density in the range 80–160 mA cm −2 have been fabricated. At variance with pure solid acid electrolytes showing reproducibility problems due to the scarce mechanical resistance, the presence of porous alumina support allowed to replicate similar fuel…

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Comments on 'formation and characterization of nanotubes of La(OH) 3 obtained using porous alumina membranes'

New experimental evidence concerning the formation of La(OH)3 nanowires on anodic alumina membranes by cathodic polarization in 0.05 M lanthanum nitrate solution is provided to further support the conclusions previously reached in our work (Bocchetta et al 2007 Electrochem. Commun. 9 683-8) and recently criticized by González-Rovira et al (Nanotechnology 2008 19 495305). Some unconvincing aspects of the paper of González-Rovira et al, according to which the same electrochemical process should lead to the formation of hydroxycarbonate nanotubes, are also discussed.

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Photoelectrochemical Synthesis of Polypyrrole on Anodic Ta[sub 2]O[sub 5] Films

Polypyrrole film was photoelectrochemically grown on insulating Ta 2 O 5 anodic film in acetonitrile solution. A characterization by photocurrent spectroscopy (PCS) of metal/oxide/polypyrrole interface was carried out. The PCS results suggest that a metallic-like PPy is formed under illumination at constant anodic potential. By polarizing the polypyrrole at cathodic potentials a photocurrent spectrum typical of p-type semiconducting film was recorded. A scanning electron microscopy study of PPy surfaces solution side and oxide side allowed us to obtain information on the morphology of the polymer as well as a rough estimate of the film thickness and of the diameter of PPy globules at the tw…

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Electrosynthesis of Ce–Co Mixed Oxide Nanotubes with High Aspect Ratio and Tunable Composition

Cerium oxide and cobalt oxides have attracted the interest of several researchers due to their potential application in several technological fields electrochromism, lithium batteries, catalysis, etc.. Ceria has been used as a promoter in the so-called “three-way catalyst” for the control of toxic emission from automobile exhaust. The promotion consists of the enhancement of the noble metal dispersion, as well as stabilization of the supporting medium toward thermal sintering. 1,2 A direct catalytic effect of CeO2 in chemical processes such as water–gas shift reaction or NOx decomposition has been also evidenced. 3,4

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Chitosan-phosphotungstic acid complex as membranes for low temperature H2-O2 fuel cell

Abstract Free-standing Chitosan/phosphotungstic acid polyelectrolyte membranes were prepared by an easy and fast in-situ ionotropic gelation process performed at room temperature. Scanning electron microscopy was employed to study their morphological features and their thickness as a function of the chitosan concentration. The membrane was tested as proton conductor in low temperature H 2 –O 2 fuel cell allowing to get peak power densities up to 350 mW cm −2 . Electrochemical impedance measurements allowed to estimate a polyelectrolyte conductivity of 18 mS cm −1 .

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Cerium oxyhydroxide nanowire growth via electrogeneration of base in nonaqueous electrolytes

The preparation of compact cerium oxyhydroxide nanowires into anodic alumina membranes from cerium chloride in ethanol solution via electrogeneration of base is reported. Scanning electron microscopy analyses indicate that dense, well-aligned, and highly ordered nanowires can be formed in a wide range of applied potentials and current densities in alcoholic solution. The employment of water brings to a hybrid nanotube/nanowire structure, suggesting a key role of the electrolyte nature in determining the morphology of the deposit. Electrochemical findings and X-ray diffraction analysis have shown that nanowires are constituted by a Ce(III)/Ce(IV) oxyhydroxide that can be completely oxidized …

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Microporous alumina membranes electrochemically grown

Abstract The electrochemical fabrication of alumina membranes by anodizing of aluminium in phosphoric acid and oxalic acid solutions, in the temperature interval from −1 to 16 °C, was investigated in order to study the influence of different parameters (initial treatment of aluminium surface, nature and composition of electrolyte, temperature) on the final characteristics of the membranes. Porous layers were grown using a linear potential scan at 0.2 V s −1 up to 160 V in H 3 PO 4 solution and 70 V in oxalic acid solution. The efficiency of porous layer formation was calculated by using Faraday's law and weight measurements. Pore size distribution and porosity of membranes prepared in 0.4 M…

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Nanoscale membrane electrode assemblies based on porous anodic alumina for hydrogen–oxygen fuel cell

In this paper, we demonstrate that nanoscale membrane electrode assemblies, functioning in a H 2/O 2 fuel cell, can be fabricated by impregnation of anodic alumina porous membranes with Nafion® and phosphotungstic acid. Porous anodic alumina is potentially a promising material for thin-film micro power sources because of its ability to be manipulated in micro-machining operations. Alumina membranes (Whatman, 50 μm thick, and pore diameters of 200 nm) impregnated with the proton conductor were characterized by means of scanning electron microscopy, X-ray diffraction, and thermal analysis. The electrochemical characterization of the membrane electrode assemblies was carried out by recording t…

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One-step electrochemical synthesis and physico-chemical characterization of CdSe nanotubes

Abstract Stoichiometric CdSe nanotubes (NTs) with a length of ∼700 nm have been successfully grown by one-step electrochemical technique into anodic alumina membranes. Cyclovoltammetric method has been performed using porous anodic alumina as template electrode and an electrochemical bath containing Cd 2+ ions and SeO 2 . The as-prepared NTs have been identified as face-centred-cubic CdSe by XRD, while micro-Raman analysis reveals the typical peaks of nanostructured CdSe. The stoichiometric deposition of CdSe NTs formation is suggested by EDX analysis, with an average atomic percentage of Cd:Se of ∼0.93. Photoelectrochemical measurements reveal that CdSe NTs are photoactive materials with d…

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Photoelectrochemical Synthesis of Conducting Polymers on Large Band Gap Nb2O5 and Ta2O5 Anodic Oxide Films

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Electrodeposition of CeO2 and Co-Doped CeO2 Nanotubes by Cyclic Anodization in Porous Alumina Membranes

An anodic electrodeposition process is proposed to prepare CeO2 and Co-doped CeO2 nanotubes. Anodic alumina membrane is used as template and linear sweep voltammetry is employed to allow the formation of nanotubes without alumina dissolution. SEM micrographs showed large arrays of well defined and aligned NTs, which resulted to be crystalline soon after deposition according to XRD diffraction patterns and Raman Spectroscopy.

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Anodic Alumina Membranes for Fuel Cell Technology and Nanostructure Template-assisted Deposition

Anodic alumina membranes (AAMs) with ordered porous structure have been investigated as possible ionic conducting membranes for thin film (= 50μm) fuel cells (TFFC) and as templates for the production of a variety of nanostructure arrays. The aims of this work are to present some of our recent results pertaining to the functionalisation of AAM with proton conductors for the production of membranes to be used in hydrogen/oxygen TFFC, at low or intermediate temperature (25°C ≦ T ≦ 250°C), and to the fabrication by template technique of nanowires/nanotubes arrays of oxide and hydroxides for possible future technological application.

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Influence of synthesis conditions on the performance of chitosan–Heteropolyacid complexes as membranes for low temperature H2–O2 fuel cell

Flat, free-standing chitosan/phosphotungstic acid (PTA) polyelectrolyte membranes were prepared by in-situ ionotropic gelation process at room temperature on porous alumina support firstly impregnated by H3PW12O40. Scanning electron microscopy revealed the formation of compact and homogeneous membranes, whose thickness resulted to be dependent on chitosan concentration and reticulation time. X-ray diffraction and Fourier transform infrared spectroscopy (FTIR) evidenced the formation of almost amorphous membrane without appreciable concentration of not protonated NH2 groups and PTA3- ions with preserved Keggin structure. Membranes were tested as proton conductor in low temperature H2-O2 fuel…

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Room temperature electrodeposition of photoactive Cd(OH)2 nanowires

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Anodic Alumina Membranes for Fuel Cell Technology and Nanostructure Template -assisted Deposition

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The effect of hydration layers on the anodic growth and on the dielectric properties of Al2O3 for electrolytic capacitors

Hydrous films were grown on high purity and cubicity Al foils for electrolytic capacitors in deionized water, ethylene glycol - deionized water and in glycerol - deionized water for different immersion times. According to the X-ray diffraction patterns the hydration treatment allowed to grow a pseudo boehmite layer on Al surface whose morphology is appreciably affected by the bath composition. Capacitance measurements and photoelectrochemical findings suggest that a more compact barrier layer forms during the immersion in alcohol containing solutions. The hydration in water allowed to save energy and to prepare more blocking oxide films. The beneficial effect of hydration in hot water on th…

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