Significance of β-dehydrogenation in ethanol electro-oxidation on platinum doped with Ru, Rh, Pd, Os and Ir

In the exploration of highly efficient direct ethanol fuel cells (DEFCs), how to promote the CO₂ selectivity is a key issue which remains to be solved. Some advances have been made, for example, using bimetallic electrocatalysts, Rh has been found to be an efficient additive to platinum to obtain high CO₂ selectivity experimentally. In this work, the mechanism of ethanol electrooxidation is investigated using first principles method. It is found that CH₃CHOH* is the key intermediate during ethanol electrooxidation and the activity of β-dehydrogenation is the rate determining factor that affects the completeness of ethanol oxidation. In addition, a series of transition metals (Ru, Rh, Pd, Os and Ir) are alloyed on the top layer of Pt(111) in order to analyze their effects. The elementary steps, α-, β-C-H bond and C-C bond dissociations are calculated on these bimetallic M/Pt(111) surfaces and the formation potential of OH* from water dissociation is also calculated. We find that the active metals increase the activity of β-dehydrogenation but lower the OH* formation potential resulting in the active site being blocked. By considering both β-dehydrogenation and OH* formation, Ru, Os and Ir are identified to be unsuitable for the promotion of CO₂ selectivity and only Rh is able to increase the selectivity of CO₂ in DEFCs.

A techno-economic evaluation of changing from conventional vehicles to range extended electric vehicles

Transportation accounts for 22% of greenhouse gas emissions in the UK, and increases to 25% in Northern Ireland. Surface transport carbon dioxide emissions, consisting of road and rail, are dominated by cars. Demand for mobility is rising rapidly and vehicle numbers are expected to more than double by 2050. Car manufacturers are working towards reducing their carbon footprint through improving fuel efficiency and controlling exhaust emissions. Fuel efficiency is now a key consideration of consumers purchasing a new vehicle. While measures have been taken to help to reduce pollutants, in the future, alternative technologies will have to be used in the transportation industry to achieve sustainability. There are currently many alternatives to the market leader, the internal combustion engine. These alternatives include hydrogen fuel cell vehicles and electric vehicles, a term which is widely used to cover battery electric vehicles, plug-in hybrid electric vehicles and extended-range electric vehicles. This study draws direct comparisons measuring the differing performance in terms of fuel consumption, carbon emissions and range of a typical family saloon car using different fuel types. These comparisons will then be analysed to see what effect switching from a conventionally fuelled vehicle to a range extended electric vehicle would have not only on the end user, but also the UK government.

Stable Isolated Metal Atoms as Active Sites for Photocatalytic Hydrogen Evolution

The process of using solar energy to split water to produce hydrogen assisted by an inorganic semiconductor is crucial for solving our energy crisis and environmental problems in the future. However, most semiconductor photocatalysts would not exhibit excellent photocatalytic activity without loading suitable co-catalysts. Generally, the noble metals have been widely applied as co-catalysts, but always agglomerate during the loading process or photocatalytic reaction. Therefore, the utilization efficiency of the noble co-catalysts is still very low on a per metal atom basis if no obvious size effect exists, because heterogeneous catalytic reactions occur on the surface active atoms. Here, for the first time, we have synthesized isolated metal atoms (Pt, Pd, Rh, or Ru) stably by anchoring on TiO2, a model photocatalystic system, by a facile one-step method. The isolated metal atom based photocatalysts show excellent stability for H-2 evolution and can lead to a 6-13-fold increase in photocatalytic activity over the metal clusters loaded on TiO2 by the traditional method. Furthermore, the configurations of isolated atoms as well as the originality of their unusual stability were analyzed by a collaborative work from both experiments and theoretical calculations.

Ethanol Steam Reforming on Rh Catalysts: Theoretical and Experimental Understanding

Through combined theoretical and experimental efforts, the reaction mechanism of ethanol steam reforming on Rh catalysts was studied. The results suggest that acetaldehyde (CH3CHO) is an important reaction intermediate in the reaction on nanosized Rh catalyst. Our theoretical work suggests that the H-bond effect significantly modifies the ethanol decomposition pathway. The possible reaction pathway on Rh (211) surface is suggested as CH3CH2OH -> CH3CH2O -> CH3CHO -> CH3CO -> CH3 + CO -> CH2 + CO -> CH + CO -> C + CO, followed by the water gas shift reaction to yield H-2 and CO2. In addition, we found that the water-gas shift reaction, not the ethanol decomposition, is the bottleneck for the overall ethanol steam reforming process. The CO + OH association is considered the key step, with a sizable energy barrier of 1.31 eV. The present work first discusses the mechanisms and the water effect in ethanol steam reforming reactions on Rh catalyst from both theoretical and experimental standpoints, which may shed light on designing improved catalysts.

Introdução a novos processos de produção de energias renováveis no ensino secundário : célula fotovoltaica orgânica e pilha de combustível

Dissertação de Mestrado, Física para Ensino, Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2004

Optimal scheduling of a renewable micro-grid in an isolated load area using mixed-integer linear programming

In the energy management of the isolated operation of small power system, the economic scheduling of the generation units is a crucial problem. Applying right timing can maximize the performance of the supply. The optimal operation of a wind turbine, a solar unit, a fuel cell and a storage battery is searched by a mixed-integer linear programming implemented in General Algebraic Modeling Systems (GAMS). A Virtual Power Producer (VPP) can optimal operate the generation units, assured the good functioning of equipment, including the maintenance, operation cost and the generation measurement and control. A central control at system allows a VPP to manage the optimal generation and their load control. The application of methodology to a real case study in Budapest Tech, demonstrates the effectiveness of this method to solve the optimal isolated dispatch of the DC micro-grid renewable energy park. The problem has been converged in 0.09 s and 30 iterations.

Estudo e otimização de uma pilha de combustível de pequena potência (10W) e sua integração em equipamento portátil

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica

Análise técnica e económico-financeira de um sistema de abastecimento de veículos zero emissões integrando um sistema fotovoltaico

Com o aumento da população mundial registado nos últimos anos surgiu também uma maior procura energética. Esse aumento foi inicialmente colmatado recorrendo essencialmente a fontes de origem fóssil, pelo facto destas serem mais baratas. No entanto, essa tendência de preços baixos sofreu o primeiro abalo nos anos 70 do século passado, altura em que o preço do petróleo disparou, devido a questões políticas. Nessa altura ficou visível para os países ocidentais o quanto estes eram dependentes dos países produtores de petróleo que, em geral, são instáveis politicamente. Começou então a procura de fontes energéticas alternativas. Além da questão económica do aumento do preço dos combustíveis, existe também o problema ambiental. Os maiores responsáveis pela emissão de gases efeito estufa (GEE) são os combustíveis fósseis. Os GEE contribuem para o aquecimento global, o que origina fenómenos ambientais severos que poderão levar a mudanças climáticas significativas. As energias renováveis apresentam-se como a solução mais viável ao problema energético e ambiental que se verifica actualmente, porque permitem colmatar o aumento da procura energética de uma forma limpa e sustentável. Na sequência destes problemas surgiram nos últimos anos veículos que permitem reduzir ou mesmo eliminar o consumo de combustíveis fósseis, como os veículos híbridos eléctricos, eléctricos e a hidrogénio. Nesta dissertação analisa-se um sistema que foi pensado para ser implementado em áreas de serviço, que permite efectuar o carregamento de electric vehicles (EV) utilizando energia eléctrica de origem fotovoltaica e a produção de hidrogénio para os fuels cell electric vehicles (FCEV). É efectuada uma análise económica do sistema, uma análise ambiental e analisou-se também o impacto na redução da dependência do país em relação ao exterior, sendo ainda efectuada uma pequena análise ao sistema MOBIE. No caso dos veículos a hidrogénio, foi determinada qual seria a melhor opção em termos económicos, para a produção de hidrogénio considerando três regimes de produção: recorrendo apenas à energia eléctrica proveniente do sistema fotovoltaico, apenas à energia eléctrica da rede, ou uma combinação dos dois regimes. O sistema estudado nesta dissertação apresenta um enorme potencial a nível energético e ambiental, surgindo como alternativa para abastecer os veículos que irão permitir, no futuro, eliminar a dependência energética em relação às fontes fósseis e ao mesmo tempo diminuir a quantidade de gases efeito estufa emitidos para a atmosfera.

Conversão de um veículo de combustão em veículo elétrico

Trabalho final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica Ramo Manutenção e Produção

La tecnología del hidrógeno, una oportunidad estratégica para la perdurabilidad del sector energético en Colombia

El incremento de la actividad humana en el último siglo y el desarrollo de tecnologías ligadas con el petróleo como vector energético, han generado efectos medioambientales adversos que aunados con las limitadas reservas mundiales de crudo y su estrecha relación con el crecimiento económico mundial ha generado presiones economías, políticas y sociales en todos los países. Esta situación ha dinamizado la investigación y desarrollo de nuevas tecnologías basadas en el hidrogeno como un nuevo vector energético tecnológicamente compatible que permita la portabilidad de energía con el menor impacto ambiental y económico a la luz de la prospectiva de consumo y la perdurabilidad energética. Este trabajo identifica las experiencias más relevantes respecto a la tecnología del hidrogeno a nivel mundial con el fin de consolidar un plan estratégico para la incorporación del hidrógeno como vector energético al portafolio productivo colombiano mediante la aplicación de un modelo que permite el análisis del nivel de integración de los sectores educativo, empresarial y gubernamental, teniendo como base los resultados del análisis estructural y análisis de actores.

Hydrogen spillover on carbon-supported metal catalysts studied by inelastic neutron scattering. Surface vibrational states and hydrogen riding modes

Hydrogen spillover on carbon-supported precious metal catalysts has been investigated with inelastic neutron scattering (INS) spectroscopy. The aim, which was fully realized, was to identify spillover hydrogen on the carbon support. The inelastic neutron scattering spectra of Pt/C, Ru/C, and PtRu/C fuel cell catalysts dosed with hydrogen were determined in two sets of experiments: with the catalyst in the neutron beam and, using an annular cell, with carbon in the beam and catalyst pellets at the edge of the cell excluded from the beam. The vibrational modes observed in the INS spectra were assigned with reference to the INS of a polycyclic aromatic hydrocarbon, coronene, taken as a molecular model of a graphite layer, and with the aid of computational modeling. Two forms of spillover hydrogen were identified: H at edge sites of a graphite layer (formed after ambient dissociative chemisorption of H-2), and a weakly bound layer of mobile H atoms (formed by surface diffusion of H atoms after dissociative chernisorption of H-2 at 500 K). The INS spectra exhibited characteristic riding modes of H on carbon and on Pt or Ru. In these riding modes H atoms move in phase with vibrations of the carbon and metal lattices. The lattice modes are amplified by neutron scattering from the H atoms attached to lattice atoms. Uptake of hydrogen, and spillover, was greater for the Ru containing catalysts than for the Pt/C catalyst. The INS experiments have thus directly demonstrated H spillover to the carbon support of these metal catalysts.

Ion-conducting polymers and membranes comprising them

An ion-conducting polymer wherein at least 80% of the repeat units comprise an ion-conducting region and a spacer region is disclosed. The ion-conducting region has an aromatic backbone of one or more aromatic groups, wherein at least one ion-conducting functional group is attached to each aromatic group. The spacer region has an aromatic backbone of at least four aromatic groups, wherein no ion-conducting functional groups are attached to the aromatic backbone. The polymer is suitable for use as a fuel cell membrane, and can be incorporated into membrane electrode assemblies.

On discrimination algorithms for ill-posed problems with an application to magnetic tomography

In this paper we explore classification techniques for ill-posed problems. Two classes are linearly separable in some Hilbert space X if they can be separated by a hyperplane. We investigate stable separability, i.e. the case where we have a positive distance between two separating hyperplanes. When the data in the space Y is generated by a compact operator A applied to the system states ∈ X, we will show that in general we do not obtain stable separability in Y even if the problem in X is stably separable. In particular, we show this for the case where a nonlinear classification is generated from a non-convergent family of linear classes in X. We apply our results to the problem of quality control of fuel cells where we classify fuel cells according to their efficiency. We can potentially classify a fuel cell using either some external measured magnetic field or some internal current. However we cannot measure the current directly since we cannot access the fuel cell in operation. The first possibility is to apply discrimination techniques directly to the measured magnetic fields. The second approach first reconstructs currents and then carries out the classification on the current distributions. We show that both approaches need regularization and that the regularized classifications are not equivalent in general. Finally, we investigate a widely used linear classification algorithm Fisher's linear discriminant with respect to its ill-posedness when applied to data generated via a compact integral operator. We show that the method cannot stay stable when the number of measurement points becomes large.

Nuclear Magnetic Resonance Study of Hydrated Bentonite

Impedance spectroscopy and nuclear magnetic resonance (NMR) were used to investigate the mobility of water molecules located in the interlayer space of H(+) - exchanged bentonite clay. The conductivity obtained by ac measurements was 1.25 x 10(-4) S/cm at 298 K. Proton ((1)H) lineshapes and spin-lattice relaxation times were measured as a function of temperature over the temperature range 130-320 K. The NMR experiments exhibit the qualitative features associated with the proton motion, namely the presence of a (1)H NMR line narrowing and a well-defined spin-lattice relaxation rate maximum. The temperature dependence of the proton spin-lattice relaxation rates was analyzed with the spectral density function appropriate for proton dynamics in a two-dimensional system. The self-diffusion coefficient estimated from our NMR data, D similar to 2 x 10(-7) cm(2)/s at 300 K, is consistent with those reported for exchanged montmorillonite clay hydrates studied by NMR and quasi-elastic neutron scattering (QNS).