Studies of some operating parameters and cyclic voltammetry for a direct ethanol fuel cell

A direct ethanol fuel cell (DEFC) of 5 cm² membrane-electrode area was studied systematically by varying the catalyst loading, ethanol concentration, temperature and different Pt based electro-catalysts (Pt–Ru/C, Pt-black High Surface Area (HSA) and Pt/C). A combination of 2 M ethanol at the anode, pure oxygen at the cathode, 1 mg cm⁻² of Pt–Ru/C (40%:20%) as the anode and 1 mg cm⁻² of Pt-black as the cathode gave a maximum open circuit voltage (OCV) of 0.815 V, a short circuit current density of 27.90 mA cm⁻² and a power density of 10.3 mW cm⁻². The optimum temperatures of the anode and cathode were determined as 90 °C and 60 °C, respectively. The power density increased with increase in ethanol concentration and catalyst loading at the anode and cathode. However, the power density decreased slightly beyond 2 M ethanol concentration and 1 mg cm⁻² catalyst loading at the anode and cathode. These results were validated using cyclic voltammetry at single electrodes under similar conditions to those of the DEFC.     

Preparation of a PVA/HAP composite polymer membrane for a direct ethanol fuel cell (DEFC)

A novel PVA/Hydroxyapatite (HAP) composite polymer membrane was prepared by the direct blend process and solution casting method. The characteristic properties of the PVA/HAP composite polymer membranes were investigated using thermal gravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), micro-Raman spectroscopy and the AC impedance method. An alkaline direct ethanol fuel cell, consisting of an air cathode with MnO₂ carbon inks based on Ni-foam, an anode with PtRu black on Ni-foam, and the PVA/HAP composite polymer membrane, was assembled and investigated. It was found that the alkaline direct ethanol fuel cell comprising of a novel cheap PVA/HAP composite polymer membrane showed an improved electrochemical performance in ambient temperature and air. As a result, the maximum power density of the alkaline DEFC, using a PtRu anode based on Ni-foam (10.74 mW cm⁻²), is higher than that of DEFC using an E-TEK PtRu anode based on carbon (7.56 mW cm⁻²) in an 8M KOH + 2M C₂H₅OH solution at ambient temperature and air. These PVA/HAP composite polymer membranes are a potential candidate for alkaline DEFC applications.     

Mathematical model for a direct propane phosphoric acid fuel cell

A mathematical model was developed and used to predict the performance of direct propane phosphoric acid (PPAFC) fuel cells, utilizing both Pt/C state-of the-art electrodes and older Pt black electrodes. It was found that the overpotential caused by surface processes on the platinum catalyst in the anode is much greater than the potential losses caused by either ohmic resistance or propane diffusion in gas-filled and liquid-filled pores. In one comparison, the anode overpotential (0.5 V) was larger than the cathode overpotential (0.3 V) at a current density of 0.4 A cm⁻² for Pt loadings 4 mg Pt cm⁻². The need for sufficient water concentration at the anode, where water is a reactant, was indicated by the large effect of H₃PO₄ concentration. In another comparison, the model predicted that at 0.2 A cm⁻², modern carbon supported Pt catalysts would produce 0.35 V compared to 0.1 V for unsupported Pt black catalysts that were used several decades ago, when the majority of the research on direct hydrocarbon fuel cells was performed. The propane anode and oxygen cathode catalyst layers were modeled as agglomerates of spherical catalyst particles having their interior spaces filled with liquid electrolyte and being surrounded by gas-filled pores. The Tafel equation was used to describe the electrochemical reactions. The model incorporated gas and liquid-phase diffusion equations for the reactants in the anode and cathode and ionic transport in the electrolyte. Experimental data were used for propane and oxygen diffusivities, and for their solubilities in the electrolyte. The accuracy of the predicted electrical potentials and polarization curves were normally within ±0.02 V of values reported in experimental investigations of temperature and electrolyte concentration. Polarization curves were predicted as a function of temperature, pressure, electrolyte concentration, and Pt loading. A performance of 0.45 V at 0.5 A cm⁻² was predicted at some conditions.     

Power from marine sediment fuel cells: the influence of anode material

The effect of anode material on the performance of microbial fuel cells (MFC), which utilise oxidisable carbon compounds and other components present in sediments on ocean floors, estuaries and other similar environments is reported. The MFC anode materials were carbon sponge, carbon cloth, carbon fibre, and reticulated vitreous carbon (RVC). Power was produced through the microbial activity at the anode in conjunction with, principally, oxygen reduction at a graphite cloth cathode. After a period of stabilisation, open circuit voltages up to 700 mV were observed for most cells. Steady state polarisations gave maximum power densities of 55 mW m⁻² using carbon sponge as the anode; which was nearly twice that achieved with carbon cloth. The latter material typically gave power densities of around 20 mW m⁻². The performance of the cell was reduced by operation at a low temperature of 5 °C. Generally, for cells which were capable of generating power at current densities of 100 mA m⁻² and greater, mass transport was found to limit both the anode and the cathode performance, due primarily to the low concentrations of electro-active species present or generated in cells.     

A parametric study of a platinum ruthenium anode in a direct borohydride fuel cell

Data on the performance of a direct borohydride fuel cell (DBFC) equipped with an anion exchange membrane, a Pt–Ru/C anode and a Pt/C cathode are reported. The effect of oxidant (air or oxygen), borohydride and electrolyte concentrations, temperature and anode solution flow rate is described. The DBFC gives power densities of 200 and 145 mW cm⁻² using ambient oxygen and air cathodes respectively at medium temperatures (60 °C). The performance of the DBFC is very good at low temperatures (ca. 30 °C) using modest catalyst loadings of 1 mg cm⁻² for anode and cathode. Preliminary data indicate that the cell will be stable over significant operating times.     

Preparation and evaluation of RuO2–IrO2, IrO2–Pt and IrO2–Ta2O5 catalysts for the oxygen evolution reaction in an SPE electrolyzer

IrO₂–RuO₂, IrO₂–Pt and IrO₂–Ta₂O₅ electrocatalysts were synthesized and characterized for the oxygen evolution in a Solid Polymer Electrolyte (SPE) electrolyzer. These mixtures were characterized by XRD and SEM. The anode catalyst powders were sprayed onto Nafion 117 membrane (catalyst coated membrane, CCM), using Pt catalyst at the cathode. The CCM procedure was extended to different in-house prepared catalyst formulations to evaluate if such a method could be applied to electrolyzers containing durable titanium backings. The catalyst loading at the anode was about 6 mg cm⁻², whereas 1 mg cm⁻² Pt was used at the cathode. The electrochemical activity for water electrolysis was investigated in a single cell SPE electrolyzer at 80 °C. It was found that the terminal voltage obtained with Ir–Ta oxide was slightly lower than that obtained with IrO₂–Pt and IrO₂–RuO₂ at low current density (lower than 0.15 A cm⁻²). At higher current density, the IrO₂–Pt and IrO₂–RuO₂ catalysts performed better than Ir–Ta oxide.     

The role of TiO<Subscript>2</Subscript> layers deposited on YSZ on the electrochemical promotion of C<Subscript>2</Subscript>H<Subscript>4</Subscript> oxidation on Pt

The electrochemical promotion of Pt/YSZ and Pt/TiO₂/YSZ catalyst-electrodes has been investigated for the model reaction of C₂H₄ oxidation in an atmospheric pressure single chamber reactor, under oxygen excess between 280 and 375 °C. It has been found that the presence of a dispersed TiO₂ thin layer between the catalyst electrode and the solid electrolyte (YSZ), results in a significant increase of the magnitude of the electrochemical promotion of catalysis (EPOC) effect. The rate enhancement ratio upon current application and the faradaic efficiency values, were found to be a factor of 2.5 and 4 respectively, higher than those in absence of TiO₂. This significantly enhanced EPOC effect via the addition of TiO₂ suggests that the presence of the porous TiO₂ layer enhances the transport of promoting O²⁻ species onto the Pt catalyst surface. This enhancement may be partly due to morphological factors, such as increased Pt dispersion and three-phase-boundary length in presence of the TiO₂ porous layer, but appears to be mainly caused by the mixed ionic-electronic conductivity of the TiO₂ layer which results to enhanced O²⁻ transport to the Pt surface via a self-driven electrochemical promotion O²⁻ transport mechanism.     

Uniform dispersion of CuO nanoparticles on mesoporous TiO2 networks promotes visible light photocatalysis

Here, we focus our efforts on synthesizing a uniform dispersion of CuO nanoparticles on mesoporous TiO₂ networks for the first time. H₂PtCl₆ was added through a photocatalytic reaction to produce 0.5% Pt/CuO–TiO₂ nanocomposites. XRD patterns confirmed that the prepared TiO₂ formed the anatase phase. TEM images showed close contacts between CuO and TiO₂ with 5–10 nm particle sizes. One of the advantages of the synthesized mesoporous CuO–TiO₂ nanocomposites was the high pore volume (0.540 cm³ g⁻¹) and large surface area (300 m² g⁻¹). The H₂ evolution over the mesoporous 3 wt% CuO–TiO₂ nanocomposites using a glucose hole scavenger [10 vol%] was determined to be ~13000 μmol/g, a value that was 1300 times greater than that of mesoporous TiO₂. The H₂ evolution rate was increased by up to 1300 and 20 times for 3 wt% CuO–TiO₂ and 0.1 wt% CuO–TiO₂ nanocomposites, respectively, compared with that of mesoporous TiO₂. The increase in H₂ evolution over mesoporous CuO–TiO₂ nanocomposites was explained by the increased light harvesting capacity, high glucose molecule diffusion and efficient charge carrier separation. Moreover, the construction of a heterostructure with a p–n CuO–TiO₂ heterojunction expedited the separation of charge carriers and promoted the evolution of H₂. In addition, H₂ evolution was substantially increased by the synergistic effects of Pt and CuO on the mesoporous TiO₂ networks. Photoelectrochemical and photoluminescence measurements were employed to prove the H₂ evolution mechanism over the CuO nanoparticles deposited on the mesoporous TiO₂ networks.     

Effects of lanthanum strontium cobalt ferrite (LSCF) cathode properties on hollow fibre micro-tubular SOFC performances

Single layer La_0.6Sr_0.4Co_0.2Fe_0.8O₃ hollow fibre (HF) precursors (<1 mm ID) produced by phase inversion (PI) were sintered at 1,200, 1,350 and 1,400 °C. The increase in sintering temperature resulted in microstructural changes in the LSCF fibres, reflected in their electrical conductivities. LSCF-based cathodes with different designs were brushed onto co-extruded nickel–gadolinium-doped ceria (CGO) anode/CGO electrolyte dual-layer HFs (<1 mm ID) fabricated by PI. The effect of cathode layers on the overall performance of the fuel cells (FCs) was assessed using nearly identical anode and electrolyte compositions, thicknesses, and microstructures. Cathode microstructure design caused cells to perform differently producing peak power densities of 0.35–0.7 W cm⁻² at 600 °C. Impedance spectroscopy analysis at 600 °C on the FCs produced 0.12–0.24 Ω cm² confirming the cathode’s structural effect on the overall area-specific resistance of the FCs. The best performing FC with a brush-deposited cathode was compared to a similar FC where cathode was deposited by dip coating; at 600 °C the first produced 0.6 W cm⁻² while the second cell 0.7 W cm⁻². Co-extruding anodes and electrolytes by using PI and combining dip coating for cathode deposition could lead to the fabrication of FCs with enhanced microstructures and improved performances.     

Mesoporous polyaniline or polypyrrole/anatase TiO2 nanocomposite as anode materials for lithium-ion batteries

A functional composite as anode materials for lithium-ion batteries, which contains highly dispersed TiO₂ nanocrystals in polyaniline matrix and well-defined mesopores, is fabricated by employing a novel one-step approach. The as-prepared mesoporous polyaniline/anatase TiO₂ nanocomposite has a high specific surface area of 224 m² g⁻¹ and a predominant pore size of 3.6 nm. The electrochemical performance of the as-prepared composite as anode material is investigated by cyclic voltammograms and galvanostatic method. The results demonstrate that the polyaniline/anatase nanocomposite provides larger initial discharge capacity of 233 mAh g⁻¹ and good cycle stability at the high current density of 2000 mA g⁻¹. After 70th cycles, the discharge capacity is maintained at 140 mAh g⁻¹. The excellent electrochemical performance of the polyaniline/TiO₂ nanocomposite is mainly attributed to its special structure. Furthermore, it is accessible to extend the novel strategy to other polymer/TiO₂ composites, and the mesoporous polypyrrole/anatase TiO₂ is also successfully fabricated.     

Fabrication and performance of PEN SOFCs with proton-conducting electrolyte

A positive-electrolyte-negative (PEN) assembly solid oxide fuel cell (SOFC) with a thin electrolyte film for intermediate temperature operation was fabricated. Instead of the traditional screen-printing method, both anode and cathode catalysts were pressed simultaneously and formed with the fabrication of nano-composite electrolyte by press method. This design offered some advantageous configurations that diminished ohmic resistance between electrolyte and electrodes. It also increased the proton-conducting rate and improved the performance of SOFCs due to the reduction of membrane thickness and good contact between electrolyte and electrodes. The fabricated PEN cell generated electricity between 600°C and 680°C using H₂S as fuel feed and air as oxidant. Maximum power densities 40 mW·cm⁻² and 130 mW·cm⁻² for the PEN configuration with a Mo-Ni-S-based composite anode, nano-composite electrolyte (Li₂SO₄+Al₂O₃) film and a NiO-based composite cathode were achieved at 600°C and 680°C, respectively.     

Pt-decorated nanoporous gold for glucose electrooxidation in neutral and alkaline solutions

Exploiting electrocatalysts with high activity for glucose oxidation is of central importance for practical applications such as glucose fuel cell. Pt-decorated nanoporous gold (NPG-Pt), created by depositing a thin layer of Pt on NPG surface, was proposed as an active electrode for glucose electrooxidation in neutral and alkaline solutions. The structure and surface properties of NPG-Pt were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), and cyclic voltammetry (CV). The electrocatalytic activity toward glucose oxidation in neutral and alkaline solutions was evaluated, which was found to depend strongly on the surface structure of NPG-Pt. A direct glucose fuel cell (DGFC) was performed based on the novel membrane electrode materials. With a low precious metal load of less than 0.3 mg cm^-2 Au and 60 μg cm^-2 Pt in anode and commercial Pt/C in cathode, the performance of DGFC in alkaline is much better than that in neutral condition.     

Pt film electrodes prepared by the Pechini method for electrochemical decolourisation of Reactive Orange 16

Electrochemical decolourisation of Reactive Orange 16 was carried out in an electrochemical flow-cell, using as working electrodes a Pt thin film deposited on a Ti substrate (Pt/Ti) prepared by the Pechini method and a pure platinum (Pt) foil. Using the Pt/Ti electrodes better results for dye decolourisation were obtained under milder conditions than those used for pure Pt. For the Pt electrode, colour removal of 93 % (λ = 493 nm) was obtained after 60 min, at 2.2 V vs. RHE, using 0.017 mol L⁻¹ NaCl + 0.5 mol L⁻¹ H₂SO₄ solution. For the Pt/Ti electrode there was better colour removal, 98%, than for the Pt electrode. Moreover, we used 0.017 mol L⁻¹ NaCl solution and the applied potential was 1.8 V. Under this condition after 15 min of electrolysis, more than 80% of colour was removed. The rate reaction constant, assuming a first order reaction, was 0.024 min⁻¹ and 0.069 min⁻¹, for Pt and Pt/Ti electrodes, respectively.     

Photoelectrochemical reaction of biomass-related compounds in a biophotochemical cell comprising a nanoporous TiO<Subscript>2</Subscript> film photoanode and an O<Subscript>2</Subscript>-reducing cathode

Photoelectrochemical decomposition of bio-related compounds such as ammonia, formic acid, urea, alcohol, and glycine by a biophotochemical cell (BPCC) comprising a nanoporous TiO₂ film photoanode and an O₂-reducing cathode generating simultaneously electrical power was investigated. The bio-related compounds studied were all photodecomposed by the present BPCC when they were either liquid or soluble in water. It was shown that ethanol exhibits similar characteristics both under 1 atm O₂ and air as studied by cyclic voltammograms. Although the present BPCC utilizes only UV light, a solar simulator at AM 1.5G and 100 mW cm⁻² light intensity gave also moderate photocurrent–photovoltage (J–V) characteristics with about 2/5 of the short circuit photocurrent (J _sc) values (J _sc) of that under a Xe lamp irradiation at the intensity of 503 mW cm⁻². It was demonstrated that varieties of bio-related compounds can be used as a direct fuel simultaneously for photodecomposition and electrical power generation. The charge transport processes in the BPCC operation were analyzed using glycine by an alternating current impedance spectroscopy, showing that the charge transfer reactions on the photoanode and the cathode surfaces compose the major resistance for the cell performance.     

Increased generation of electricity in a microbial fuel cell using <Emphasis Type="Italic">Geobacter sulfurreducens</Emphasis>

The microbial fuel cell (MFC) has attracted research attention as a biotechnology capable of converting hydrocarbon into electricity production by using metal reducing bacteria as a biocatalyst. Electricity generation using a microbial fuel cell (MFC) was investigated with acetate as the fuel and Geobacter sulfurreducens as the biocatalyst on the anode electrode. Stable current production of 0.20–0.24 mA was obtained at 30–32 °C. The maximum power density of 418–470 mW/m², obtained at an external resistor of 1,000 Ω, was increased over 2-fold (from 418 to 866 mW/m²) as the Pt loading on the cathode electrode was increased from 0.5 to 3.0 mg Pt/cm². The optimal batch mode temperature was between 30 and 32 °C with a maximum power density of 418–470 mW/m². The optimal temperature and Pt loading for MFC were determined in this study. Our results demonstrate that the cathode reaction related through the Pt loading on the cathode electrode is a bottleneck for the MFC’s performance.     

A Novel Catalyst Type Containing Noble Metal Nanoparticles Supported on Mesoporous Carbon: Synthesis,Characterization and Catalytic Properties

We report on a method for the controlled synthesis of a new type of high specific surface area mesoporous carbons denoted as the CMH family. By using mixtures of colloidal silica particles as templates it was possible to synthesize samples exhibiting 1,630 m² g⁻¹ specific surface area and 4.37 cm³ g⁻¹ pore volume. CMH materials exhibit high thermal stability in oxygen and can be used as catalyst supports. This function was demonstrated by synthesizing Pt/CMH and Rh/CMH catalysts and testing them in the hydrogenation of cyclohexene. We have found Pt/CMH to be more stable and easier to regenerate than Rh/CMH.     

Efficient Photocatalytic Decomposition of Glucose,Starch, and Cellulose to CO<Subscript>2</Subscript> Using a Mesoporous Semiconductor Thin Film

Abstract  

UV light-activated highly efficient photocatalytic decomposition of aqueous glucose and polysaccharides (starch and cellulose) to CO₂ was successfully achieved by using a mesoporous TiO₂ thin film coated on a fluorine-doped transparent conductive glass (FTO). The external quantum efficiency (η) of 0.08 (=8%) was obtained for glucose photodecomposition at neutral pH based on the total incident UV light, and the internal quantum efficiency (η′) was 8 (=800%) based on the photon that was effective for activating the reactant, demonstrating that the major decomposition mechanism is dark auto-oxidation of the activated reactant by O₂. Glucose gave η′ values of 19 at pH 12 and 25 at pH 2 demonstrating that when a glucose molecule was once activated by one photon, the molecule can undergo auto-oxidative decomposition to CO₂ at these pH under dark. Water-soluble starch was also photodecomposed completely to CO₂ with estimated η′ value of 8.6. Water-soluble carboxymethyl cellulose (CMC) also underwent decomposition to CO₂ with similar efficiency of η′ = 5. Solid state cellulose powders could be photodecomposed to CO₂ by sandwiching them between FTO-coated TiO₂ thin films.     

Symmetrical solid oxide fuel cells based on titanate nanocomposite electrodes

Nanocomposite electrodes of (Sr_0.7Pr_0.3)_0.95TiO_3±δ?Ce_0.9Gd_0.1O_1.95 are directly prepared by spray-pyrolysis deposition on Zr_0.82Y_0.16O_1.92 electrolytes and their properties are compared with those obtained by the traditional screen-printing powder method. The structural, microstructural and electrical characteristics are investigated for their potential use as both cathode and anode in Solid Oxide Fuel Cells. The nanocomposite electrodes with reduced particle size ～30 nm achieved a polarization resistance at 700 ºC of 0.50 and 0.46 Ω cm² in air and pure H₂, respectively, outperforming those obtained for the analogous screen-printed electrodes with particle size of 450 nm, i.e. 4.8 and 3.9 Ω cm², respectively. An electrolyte-supported cell with symmetrical electrodes reached a maximum and stable power density of 354 mW cm^-2 at 800 ºC. These results demonstrate that the performance of electrode materials with modest electrochemical properties but high phase stability, such as doped-SrTiO₃, can be highly improved by preparing nanocomposite electrodes directly on the electrolyte surface.     

The Effects of Co-Sensitization and Electronic Structure of Nanocrystalline N/TiO<Subscript>2</Subscript> Anode on the Performance of Dye-Sensitized Solar Cells

N/TiO₂ nanocrystalline film anodes were obtained by doping nonmetallic element N which could change the LUMO of anode. This paper also studied the match between the LUMO energy lever of N/TiO₂ anode and the dye, which led to the easy injection of electron from the excited state of dye molecule to the conduction band of semiconductor, and thus improved the photoelectric conversion efficiency and reduced the impedance of solar cells. The solar cell based on N/TiO₂ anode film co-sensitized by P3HT (poly(3-hexylthiophene))/N719(RuL2(NCS)2:2TBA (L = 2,2′-bipyridyl-4,4′-dicarboxylic acid)), the absorption region of which covered the entire visible region in solar cells, showed a short-circuit current density of 6.88 mA cm⁻², an open-circuit voltage of 0.616 V, and a photoelectric conversion efficiency of 2.34%.     

Fluorination of Vulcan XC-72R for cathodic microporous layer of passive micro direct methanol fuel cell

The effect of adding fluorinated Vulcan XC-72R into the microporous layer (MPL) of the cathode in a passive micro direct methanol fuel cell (μDMFC) has been investigated. Upon fluorination with fluoro-alkyl silane (FAS), the surface of XC-72R becomes more hydrophobic, as indicated by contact angle measurements. The performance of the membrane electrode assembly (MEA) is improved significantly when fluorinated Vulcan XC-72R is used in MPL of the cathode. The maximum power density of a passive μDMFC reached ca. 36.2 mW cm⁻² at room temperature, and the constant-current discharging test exhibits enhanced stability. Also observed is a decreased water transport coefficient (α), calculated from discharging test, attributable to the greater hydrophobicity resulting in higher liquid pressure on the cathode, which forces more water to flow back to the anode. Additionally, A.C. impedance analysis indicates that the improvement in performance results from the decrease of charge transfer resistance of the cathodic reaction.