Development of electrocatalysts for direct alcohol fuel cells

In the present review, we summarize the recent progress in electrocatalysts for direct alcohol fuel cells, focussing on the research of electrocatalysts for both alcohol oxidation and oxygen reduction, which are crucial in the development of fuel cells. A modified EG (ethylene polyol) method to prepare well-dispersed nano-sized Pt-based electrocatalysts with high loadings is reported. By this method, a more active carbon supported PtRu catalyst for methanol oxidation reaction and a PtSn catalyst for ethanol oxidation reaction have been synthesized successfully. Furthermore, a methanol tolerant Pd-based catalyst for cathode oxygen reduction reaction has been developed. HRTEM and HR-EDS have been employed to characterize the microstructure and micro-components of the above electrocatalysts. Results show that the bimetallic electrocatalysts prepared by the modified EG method display uniform size and homogeneous components at nanometer scale.

Improvement of direct methanol fuel cell performance by modifying catalyst coated membrane structure

A five-layer catalyst coated membrane (CCM) based upon Nation 115 membrane for direct methanol fuel cell (DMFC) was designed and fabricated by introducing a modified Nafion layer between the membrane and the catalyst layer. The properties of the CCM were determined by SEM, cyclic voltammetry, impedance spectroscopy, ruinous test and I-V curves. The characterizations show that the modified Nation layers provide increased interface contact area and enhanced interaction between the membrane and the catalyst layer. As a result, higher Pt utilization, lower contact resistance and superior durability of membrane electrode assembly was achieved. A 75% Pt utilization efficiency was obtained by using the novel CCM structure, whereas the conventional structure gave 60% efficiency. All these features greatly contribute to the increase in DMFC performance. The DMFC with new CCM structure presented a maximum power density of 260 MW cm(-2), but the DMFC with conventional structure gave only 200 mW cm(-2) under the same operation condition. (c) 2005 Elsevier B.V. All rights reserved.

A novel PTFE-reinforced multilayer self-humidifying composite membrane for PEM fuel cells

A novel polytetrafluoroethylene (PTFE)-reinforced multilayer self-humidifying composite membrane is developed. The membrane is composed of Nafion-impregnated porous PTFE composite as the central layer and nanosized SiO2 supported Pt catalyst imbedded into Nafion as the two side layers. The proton exchange membrane (PEM) fuel cells employing the self-humidifying membrane (20 mu m thick) under dry H-2/O-2 gave a peak power density of 0.95 W/cm(2) and an open-circuit voltage of 1.032 V. The good membrane performance is attributed to hygroscopic Pt-SiO2 catalyst at the two side layers, which results in enhanced anode side self-humidification function and decreased cathode polarization. (c) 2005 The Electrochemical Society.

Investigation of LSM1.1-ScSZ composite cathodes for anode-supported solid oxide fuel cells

La0.8Sr0.2Mn1.1O3 (LSM1.1)-10 mol% Sc2O3-Stabilized ZrO2 co-doped with CeO2 (ScSZ) composite cathodes were investigated for anode-supported solid oxide fuel cells (SOFCs) with thin 8 mol% Y2O3-stabilized ZrO2 (YSZ) electrolyte. X-ray diffraction (XRD) results indicated that the ScSZ electrolytes displayed good chemical compatibility with the nonstoichiometric LSM1.1 against co-firing at 1300 degrees C. Increasing the CeO2 content in the ScSZ electrolytes dramatically suppressed the electrode polarization resistance, which may be related to the improved surface oxygen exchange or the enlarged active area of cathode. The 5Ce10ScZr was the best electrolyte for the composite cathodes, which caused a small ohmic resistance decrease and the reduced polarization resistance and brought about the highest cell performance. The cell performances at lower temperatures seemed to rely on the electrode polarization resistance more seriously, than the ohmic resistance. Compared with the cell impedance at higher temperatures, the higher the 5Ce10ScZr proportion in the composite cathodes, the smaller the increment of the charge transfer resistance at lower temperatures. The anode-supported SOFC with the LSM1.1-5Ce10ScZr (60:40) composite cathode achieved the maximum power densities of 0.82 W/cm(2) at 650 degrees C and 2.24 W/cm(2) at 800 degrees C, respectively. (c) 2005 Elsevier B.V. All rights reserved.

Thermodynamic properties of ethanol and gasoline blended fuel

The heat capacities (C-p) of five types of gasohol (50 wt % ethanol and 50 wt % unleaded gasoline 93(#) (E50), 60 wt % ethanol and 40 wt % unleaded gasoline 93(#) (E60), 70 wt % ethanol and 30 wt % unleaded gasoline 93(#) (E70), 80 wt % ethanol and 20 wt % unleaded gasoline 93(#) (E80), and 90 wt % ethanol and 10 wt % unleaded gasoline 93(#) (E90), where the "93" denotes the octane number) were measured by adiabatic calorimetry in the temperature range of 78-320 K. A glass transition was observed at 95.61, 96.14, 96.56, 96.84, and 97.08 K for samples from the E50, E60, E70, E80, and E90 systems, respectively. A liquid-solid phase transition and a solid-liquid phase transition were observed in the respective temperature ranges of 118-153 and 155-163 K for E50, 117-150 and 151-164 K for E60, 115-154 and 154-166 K for E70, 113-152 and 152-167 K for E80, and 112-151 and 1581-167 K for E90. The polynomial equations of Cp and the excess heat capacities (C-p(E)), with respect to the thermodynamic temperature, were established through least-squares fitting. Based on the thermodynamic relationship and the equations obtained, the thermodynamic functions and the excess thermodynamic functions of the five gasohol samples were derived.

Analysis of the elements of catabolite repression in Clostridium acetobutylicum.

The ptsH gene, encoding the phosphotransferase protein HPr, from Clostridium acetobutylicum ATCC 824 was identified from the genome sequence, cloned and shown to complement a ptsH mutant of Escherichia coli. The deduced protein sequence shares significant homology with HPr proteins from other low-GC gram-positive bacteria, although the highly conserved sequence surrounding the Ser-46 phosphorylation site is not well preserved in the clostridial protein. Nevertheless, the HPr was phosphorylated in an ATP-dependent manner in cell-free extracts of C. acetobutylicum. Furthermore, purified His-tagged HPr from Bacillus subtilis was also a substrate for the clostridial HPr kinase/phosphorylase. This phosphorylation reaction is a key step in the mechanism of carbon catabolite repression proposed to operate in B. subtilis and other low-GC gram-positive bacteria. Putative genes encoding the HPr kinase/phosphorylase and the other element of this model, namely the catabolite control protein CcpA, were identified from the C. acetobutylicum genome sequence, suggesting that a similar mechanism of carbon catabolite repression may operate in this industrially important organism.

Biomethane production from grass silage: laboratory assessment to maximise yields

On-farm biogas production is typically associated with forage maize as the biomass source. Digesters are designed and operated with the focus of optimising the conditions for this feedstock. Thus, such systems may not be ideally suited to the digestion of grass. Ireland has ca. 3.85 million ha of grassland. Annual excess grass, surplus to livestock requirements, could potentially fuel an anaerobic digestion industry. Biomethane associated with biomass from 1.1 % of grassland in Ireland, could potentially generate over 10 % renewable energy supply in transport. This study aims to identify and optimise technologies for the production of biomethane from grass silage. Mono-digestion of grass silage and co-digestion with slurry, as would occur on Irish farms, is investigated in laboratory trials. Grass silage was shown to have 7 times greater methane potential than dairy slurry on a fresh weight basis (107 m3 t-1 v 16 m3 t-1). However, comprehensive trace element profiles indicated that cobalt, iron and nickel are deficient in mono-digestion of grass silage at a high organic loading rate (OLR) of 4.0 kg VS m-3 d-1. The addition of a slurry co-substrate was beneficial due to its wealth of essential trace elements. To stimulate hydrolysis of high lignocellulose grass silage, particle size reduction (physical) and rumen fluid addition (biological) were investigated. In a continuous trial, digestion of grass silage of <1 cm particle size achieved a specific methane yield of 371 L CH4 kg-1 VS when coupled with rumen fluid addition. The concept of demand driven biogas was also examined in a two-phase digestion system (leaching with UASB). When demand for electricity is low it is recommended to disconnect the UASB from the system and recirculate rumen fluid to increase volatile fatty acid (VFA) and soluble chemical oxygen demand (SCOD) production whilst minimising volatile solids (VS) destruction. At times of high demand for electricity, connection of the UASB increases the destruction of volatiles and associated biogas production. The above experiments are intended to assess a range of biogas production options from grass silage with a specific focus on maximising methane yields and provide a guideline for feasible design and operation of on-farm digesters in Ireland.

Modeling the evolution of regulatory elements by simultaneous detection and alignment with phylogenetic pair HMMs.

The computational detection of regulatory elements in DNA is a difficult but important problem impacting our progress in understanding the complex nature of eukaryotic gene regulation. Attempts to utilize cross-species conservation for this task have been hampered both by evolutionary changes of functional sites and poor performance of general-purpose alignment programs when applied to non-coding sequence. We describe a new and flexible framework for modeling binding site evolution in multiple related genomes, based on phylogenetic pair hidden Markov models which explicitly model the gain and loss of binding sites along a phylogeny. We demonstrate the value of this framework for both the alignment of regulatory regions and the inference of precise binding-site locations within those regions. As the underlying formalism is a stochastic, generative model, it can also be used to simulate the evolution of regulatory elements. Our implementation is scalable in terms of numbers of species and sequence lengths and can produce alignments and binding-site predictions with accuracy rivaling or exceeding current systems that specialize in only alignment or only binding-site prediction. We demonstrate the validity and power of various model components on extensive simulations of realistic sequence data and apply a specific model to study Drosophila enhancers in as many as ten related genomes and in the presence of gain and loss of binding sites. Different models and modeling assumptions can be easily specified, thus providing an invaluable tool for the exploration of biological hypotheses that can drive improvements in our understanding of the mechanisms and evolution of gene regulation.

Seeing the forest for the fuel

We demonstrate a new approach to understanding the role of fuelwood in the rural household economy by applying insights from travel cost modeling to author-compiled household survey data and meso-scale environmental statistics from Ruteng Park in Flores, Indonesia. We characterize Manggarai farming households' fuelwood collection trips as inputs into household production of the utility yielding service of cooking and heating. The number of trips taken by households depends on the shadow price of fuelwood collection or the travel cost, which is endogenous. Econometric analyses using truncated negative binomial regression models and correcting for endogeneity show that the Manggarai are 'economically rational' about fuelwood collection and access to the forests for fuelwood makes substantial contributions to household welfare. Increasing cost of forest access, wealth, use of alternative fuels, ownership of kerosene stoves, trees on farm, park staff activity, primary schools and roads, and overall development could all reduce dependence on collecting fuelwood from forests. © 2004 Cambridge University Press.

Four-decade responses of soil trace elements to an aggrading old-field forest: B, Mn, Zn, Cu, and Fe.

In the ancient and acidic Ultisol soils of the Southern Piedmont, USA, we studied changes in trace element biogeochemistry over four decades, a period during which formerly cultivated cotton fields were planted with pine seedlings that grew into mature forest stands. In 16 permanent plots, we estimated 40-year accumulations of trace elements in forest biomass and O horizons (between 1957 and 1997), and changes in bioavailable soil fractions indexed by extractions of 0.05 mol/L HCl and 0.2 mol/L acid ammonium oxalate (AAO). Element accumulations in 40-year tree biomass plus O horizons totaled 0.9, 2.9, 4.8, 49.6, and 501.3 kg/ha for Cu, B, Zn, Mn, and Fe, respectively. In response to this forest development, samples of the upper 0.6-m of mineral soil archived in 1962 and 1997 followed one of three patterns. (1) Extractable B and Mn were significantly depleted, by -4.1 and -57.7 kg/ha with AAO, depletions comparable to accumulations in biomass plus O horizons, 2.9 and 49.6 kg/ha, respectively. Tree uptake of B and Mn from mineral soil greatly outpaced resupplies from atmospheric deposition, mineral weathering, and deep-root uptake. (2) Extractable Zn and Cu changed little during forest growth, indicating that nutrient resupplies kept pace with accumulations by the aggrading forest. (3) Oxalate-extractable Fe increased substantially during forest growth, by 275.8 kg/ha, about 10-fold more than accumulations in tree biomass (28.7 kg/ha). The large increases in AAO-extractable Fe in surficial 0.35-m mineral soils were accompanied by substantial accretions of Fe in the forest's O horizon, by 473 kg/ha, amounts that dwarfed inputs via litterfall and canopy throughfall, indicating that forest Fe cycling is qualitatively different from that of other macro- and micronutrients. Bioturbation of surficial forest soil layers cannot account for these fractions and transformations of Fe, and we hypothesize that the secondary forest's large inputs of organic additions over four decades has fundamentally altered soil Fe oxides, potentially altering the bioavailability and retention of macro- and micronutrients, contaminants, and organic matter itself. The wide range of responses among the ecosystem's trace elements illustrates the great dynamics of the soil system over time scales of decades.