Electrooxidation of methanol in an alkaline fuel cell: determination of the nature of the initial adsorbate

It is essential to correctly determine the nature of the initial adsorbate in order to calculate the pathway for any given reaction. Recent literature provides conflicting information on the first step in the methanol decomposition pathway. This work sets out to establish what role the solution and the surface have to play in the initial adsorption-deprotonation process. Density functional theory (DFT) calculations, in combination with a cluster-continuum model approach are used to resolve the nature of the adsorbing species. We show that methanol is the dominant species in solution over methoxide, and also has a smaller barrier to adsorption. The nature of the surface species is revealed to be a methanol-OH complex.

The Role of Water and Adsorbed Hydroxyls on Ethanol Electrochemistry on Pd: New Mechanism, Active Centers and Energetics for Direct Ethanol Fuel Cell Running in Alkaline Medium

First principles calculations with molecular dynamics are
utilized to simulate a simplified electrical double layer formed in the
active electric potential region during the electrocatalytic oxidation of
ethanol on Pd electrodes running in an alkaline electrolyte. Our
simulations provide an atomic level insight into how ethanol oxidation
occurs in fuel cells: New mechanisms in the presence of the simplified
electrical double layer are found to be different from the traditional
ones; through concerted-like dehydrogenation paths, both acetaldehyde
and acetate are produced in such a way as to avoid a variety of
intermediates, which is consistent with the experimental data obtained
from in situ FTIR spectroscopy. Our work shows that adsorbed OH on
the Pd electrode rather than Pd atoms is the active center for the
reactions; the dissociation of the C−H bond is facilitated by the
adsorption of an OH− anion on the surface, resulting in the formation
of water. Our calculations demonstrate that water dissociation rather than H desorption is the main channel through which
electrical current is generated on the Pd electrode. The effects of the inner Helmholtz layer and the outer Helmholtz layer are
decoupled, with only the inner Helmholtz layer being found to have a significant impact on the mechanistics of the reaction. Our
results provide atomic level insight into the significance of the simplified electrical double layer in electrocatalysis, which may be
of general importance.

The origin of high activity but low CO2 selectivity on binary PtSn in the direct ethanol fuel cell

The most active binary PtSn catalyst for direct ethanol fuel cell applications has been studied at 20 ^oC and 60 ^oC, using variable temperature electrochemical in-situ FTIR. In comparison with Pt, binary PtSn inhibits ethanol dissociation to CO(a), but promotes partial oxidation to acetaldehyde and acetic acid. Increasing the temperature from 20 ^oC to 60 ^oC facilitates both ethanol dissociation to CO(a) and their further oxidation to CO₂, leading to an increased selectivity towards CO₂; however, acetaldehyde and acetic acid are still the main products. Potential-dependent phase diagrams for surface oxidants of OH(a) formation on Pt(111), Pt(211) and Sn modified Pt(111) and Pt(211) surfaces have been determined using density functional theory (DFT) calculations. It is shown that Sn promotes the formation of OH(a) with a lower onset potential on the Pt(111) surface, whereas an increase in the onset potential is found on modification of the (211) surface. In addition, Sn inhibits the Pt(211) step edge with respect to ethanol C-C bond breaking compared with that found on the pure Pt, which reduces the formation of CO(a). Sn was also found to facilitate ethanol dehydrogenation and partial oxidation to acetaldehyde and acetic acid which, combined with the more facile OH(a) formation on the Pt(111) surface, gives us a clear understanding of the experimentally determined results. This combined electrochemical in-situ FTIR and DFT study, provides, for the first time, an insight into the long-term puzzling features of the high activity but low CO₂ production found on binary PtSn ethanol fuel cell catalysts.

A geochronologic framework for the Ziegler Reservoir fossil site, Snowmass Village, Colorado

The Ziegler Reservoir fossil site near Snowmass Village, Colorado, provides a unique opportunity to reconstruct high-altitude paleoenvironmental conditions in the Rocky Mountains during the last interglacial period. We used four different techniques to establish a chronological framework for the site. Radiocarbon dating of lake organics, bone collagen, and shell carbonate, and in situ cosmogenic Be and Al ages on a boulder on the crest of a moraine that impounded the lake suggest that the ages of the sediments that hosted the fossils are between ~ 140 ka and > 45 ka. Uranium-series ages of vertebrate remains generally fall within these bounds, but extremely low uranium concentrations and evidence of open-system behavior limit their utility. Optically stimulated luminescence (OSL) ages (n = 18) obtained from fine-grained quartz maintain stratigraphic order, were replicable, and provide reliable ages for the lake sediments. Analysis of the equivalent dose (D) dispersion of the OSL samples showed that the sediments were fully bleached prior to deposition and low scatter suggests that eolian processes were likely the dominant transport mechanism for fine-grained sediments into the lake. The resulting ages show that the fossil-bearing sediments span the latest part of marine isotope stage (MIS) 6, all of MIS 5 and MIS 4, and the earliest part of MIS 3.

Alkali Activated Fuel Ash and Slag Mixes:Optimization Study from Mortars to Concrete Building Blocks

Alkali activated binders, based on ash and slag, also known as geopolymers, can play a key role in reducing the carbon footprint of the construction sector by replacing ordinary Portland cement in some concretes. Since 1970s, research effort has been ongoing in many research institutions. In this study, pulverized fuel ash (PFA) from a UK power plant, ground granulated blast furnace slag (GGBS) and combinations of the two have been investigated as geopolymer binders for concrete applications. Activators used were sodium hydroxide and sodium silicate solutions. Mortars with sand/binder ratio of 2.75 with several PFA and GGBS combinations have been mixed and tested. The optimization of alkali dosage (defined as the Na2O/binder mass ratio) and modulus (defined as the Na2O/SiO2 mass ratio) resulted in strengths in excess of 70 MPa for tested mortars. Setting time and workability have been considered for the identification of the best combination of PFA/GGBS and alkali activator dosage for different precast concrete products. Geopolymer concrete building blocks have been replicated in laboratory and a real scale factory trial has been successfully carried out. Ongoing microstructural characterization is aiming to identify reaction products arising from PFA/GGBS combinations.

Biomass-derived Oxymethylene Ethers as Diesel Additives: A Thermodynamic Analysis

Conversion of biomass for production of liquid fuels can help in reducing the greenhouse gas (GHG) emissions which are predominantly generated by combustion of fossil fuels. Adding oxymethylene ethers (OMEs) in conventional diesel fuel has the potential to reduce soot formation during the combustion in a diesel engine. OMEs are downstream products of syngas, which can be generated by the gasification of biomass. In this research, a thermodynamic analysis has been conducted through development of data intensive process models of all the unit operations involved in production of OMEs from biomass. Based on the developed model, the key process parameters affecting the OMEs production including equivalence ratio, H2/CO ratio, and extra water flow rate were identified. This was followed by development of an optimal process design for high OMEs production. It was found that for a fluidized bed gasifier with heat capacity of 28 MW, the conditions for highest OMEs production are at an air amount of 317 tonne/day, at H2/CO ratio of 2.1, and without extra water injection. At this level, the total OMEs production is 55 tonne/day (13 tonne/day OME3 and 9 tonne/day OME4). This model would further be used in a techno-economic assessment study of the whole biomass conversion chain to determine the most attractive pathways.

How subtle are the biases that shape the fidelity of the fossil record? A test using marine molluscs

Biases in preservation shape the fossil record, and therefore impact on our reconstructions of past environments and biodiversity. Given the intensive recent research in the general fields of taphonomy and exceptional preservation, surprisingly, fundamental questions remain unanswered about species-level variation in skeletal preservation potential at low taxonomic levels (e.g. between genera from the same family, or between taxa from related families) across myriad groups with multi-element skeletons. Polyplacophoran molluscs (chitons sensu lato) are known from the late Cambrian to Recent, and possess a distinctive articulated scleritome consisting of eight overlapping calcareous valves. The apparent uniformity of living chitons presents an ideal model to test the potential for taphonomic biases at the alpha-taxon level. The vast majority of fossil chitons are preserved as single valves; few exhibit body preservation or even an articulated shell series. An experimental taphonomic programme was conducted using the Recent polyplacophorans Lepidochitona cinerea and Tonicella marmorea (suborder Chitonina) and Acanthochitona crinita (Acanthochitonina). Experiments in a rock tumbler on disarticulated valves found differential resistance to abrasion between taxa; in one experiment 53.8-61.5% of Lepidochitona valves were recovered but 92% of those from Tonicella and 100% of elements from Acanthochitona. Chiton valves and even partly decayed carcasses are more resistant to transportation than their limited fossil record implies. Different species of living chitons have distinctly different preservation potential. This, problematically, does not correlate with obvious differences in gross valve morphology; some, but not all, of the differences correlate with phylogeny. Decay alone is sufficient to exacerbate differences in preservation potential of multi-element skeletons; some, but not all, of the variation that results is due to specimen size and the fidelity of the fossil record will thus vary intra-specifically (e.g. between ontogenetic stages) as well as inter-specifically. 

Summary of the Snowmastodon Project Special Volume: A high-elevation, multi-proxy biotic and environmental record of MIS 6-4 from the Ziegler Reservoir fossil site, Snowmass Village, Colorado, USA

In North America, terrestrial records of biodiversity and climate change that span Marine Oxygen Isotope Stage (MIS) 5 are rare. Where found, they provide insight into how the coupling of the ocean-atmosphere system is manifested in biotic and environmental records and how the biosphere responds to climate change. In 2010-2011, construction at Ziegler Reservoir near Snowmass Village, Colorado (USA) revealed a nearly continuous, lacustrine/wetland sedimentary sequence that preserved evidence of past plant communities between similar to 140 and 55 lea, including all of MIS 5. At an elevation of 2705 m, the Ziegler Reservoir fossil site also contained thousands of well-preserved bones of late Pleistocene megafauna, including mastodons, mammoths, ground sloths, horses, camels, deer, bison, black bear, coyotes, and bighorn sheep. In addition, the site contained more than 26,000 bones from at least 30 species of small animals including salamanders, otters, muskrats, minks, rabbits, beavers, frogs, lizards, snakes, fish, and birds. The combination of macro- and micro-vertebrates, invertebrates, terrestrial and aquatic plant macrofossils, a detailed pollen record, and a robust, directly dated stratigraphic framework shows that high-elevation ecosystems in the Rocky Mountains of Colorado are climatically sensitive and varied dramatically throughout MIS 5 

Investigation into the potential of using micro gas turbines in plug-in hybrid electric vehicles

The transport sector is considered to be one of the most dependent sectors on fossil fuels. Meeting ecological, social and economic demands throughout the sector has got increasingly important in recent times. A passenger vehicle with a more environmentally friendly propulsion system is the hybrid electric vehicle. Combining an internal combustion engine and an electric motor offers the potential to reduce carbon dioxide emissions. The overall objective of this research is to provide an appraisal of the use of a micro gas turbine as the range extender in a plug-in hybrid electric vehicle. In this application, the gas turbine can always operate at its most efficient operating point as its only requirement is to recharge the battery. For this reason, it is highly suitable for this purpose. Gas turbines offer many benefits over traditional internal combustion engines which are traditionally used in this application. They offer a high power-to-weight ratio, multi-fuel capability and relatively low emission levels due to continuous combustion.

Regional integration of biogas – developing an intersectoral research action plan for Northern Ireland

Bioenergy is a key component of the European Union long term energy strategy across all sectors, with a target contribution of up to 14% of the energy mix by 2020. It is estimated that there is the potential for 1TWh of primary energy from biogas per million persons in Europe, derived from agricultural by-products and waste. With an agricultural sector that accounts for 75% of land area and a large number of advanced engineering firms, Northern Ireland is a region with considerable potential for an integrated biogas industry. Northern Ireland is also heavily reliant on imported fossil fuels. Despite this, the industry is underdeveloped and there is a need for a collaborative approach from research, business and policy-makers across all sectors to optimise Northern Ireland’s abundant natural resources. ‘Developing Opportunities in Bio-Energy’ (i.e. Do Bioenergy) is a recently completed project that involved both academic and specialist industrial partners. The aim was to develop a biogas research action plan for 2020 to define priorities for intersectoral regional development, co-operation and knowledge transfer in the field of production and use of biogas. Consultations were held with regional stakeholders and working groups were established to compile supporting data, decide key objectives and implementation activities. Within the context of this study it was found that biogas from feedstocks including grass, agricultural slurry, household and industrial waste have the potential to contribute from 2.5% to 11% of Northern Ireland’s total energy consumption. The economics of on-farm production were assessed, along with potential markets and alternative uses for biogas in sectors such as transport, heat and electricity. Arising from this baseline data, a Do Bioenergy was developed. The plan sets out a strategic research agenda, and details priorities and targets for 2020. The challenge for Northern Ireland is how best to utilise the biogas – as electricity, heat or vehicle fuel and in what proportions. The research areas identified were: development of small scale solutions for biogas production and use; solutions for improved nutrient management; knowledge supporting and developing the integration of biogas into the rural economy; and future crops and bio-based products. The human resources and costs for the implementation were estimated as 80 person-years and £25 million respectively. It is also clear that the development of a robust bio-gas sector requires some reform of the regulatory regime, including a planning policy framework and a need to address social acceptance issues. The Action Plan was developed from a regional perspective but the results may be applicable to other regions in Europe and elsewhere. This paper presents the methodology, results and analysis, and discussion and key findings of the Do Bioenergy report for Northern Ireland.