An understanding and implications of the coverage of surface free sites in heterogeneous catalysis

The crucial roles of the coverage of surface free sites in determining catalytic activity trend are quantitatively addressed with the help of density functional theory and microkinetics. First, by analyzing activity trends of NO oxidation catalyzed by Ru, Rh, Pd, Os, Ir, and Pt surfaces with full kinetic considerations, we identify that the activity trend is in general determined by the competition between the reaction barrier and the coverage of surface free sites. Second, since the dissociation of many important molecules, such as the dissociation of N(2), O(2), and CO, follows the same Bronsted-Evans-Polanyi relationship, the coverage of surface free sites is usually a decisive term that affects the overall activity. Third, an equation is derived for the coverage of surface free sites and it is found that the coverage of surface free sites contains not only all the key thermodynamic parameters but also all the kinetic properties in the catalytic system. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3140202]

A density functional theory study of CO oxidation on Ru(0001) at low coverage

We have performed ab initio density functional theory calculations with the generalized gradient approximation to investigate CO oxidation on Ru(0001). Several reaction pathways and transition states are identified. A much higher reaction barrier compared to that on Pt(111) is determined, confirming that the Ru is very inactive for CO oxidation under UHV conditions. The origin of the reaction barrier was analyzed. It is found that in the transition state the chemisorbed O atom sits in an unfavorable bonding site and a significant competition for bonding with the same substrate atoms occurs between the CO and the chemisorbed O, resulting in the high barrier. Ab initio molecular dynamics calculations show that the activation of the chemisorbed O atom from the initial hcp hollow site (the most stable site) to the bridge site is the crucial step for the reaction. The CO oxidation on Ru(0001) via the Eley-Rideal mechanism has also been investigated. A comparison with previous theoretical work has been made. (C) 2000 American Institute of Physics. [S0021-9606(00)31223-5].

Ab initio diffusional potential energy surface for CO chemisorption on Pd{110} at high coverage:Coupled translation and rotation

The ground state potential energy surface for CO chemisorption across Pd{110} has been calculated using density functional theory with gradient corrections at monolayer coverage. The most stable site corresponds well with the experimental adsorption heat, and it is found that the strength of binding to sites is in the following order: pseudo-short-bridge>atop>long-bridge>hollow. Pathways and transition states for CO surface diffusion, involving a correlation between translation and orientation, are proposed and discussed. (C) 1997 American Institute of Physics.

The role of low coverage sodium surface species on electrochemical promotion in a Pt/YSZ system

The effect of sodium-modification on the catalyst and electrocatalytic properties of a platinum catalyst supported on a YSZ solid electrolyte was studied. Increasing the sodium coverage on the catalyst surface appears to block some of the three-phase boundary (tpb) sites and reduces the rate of the charge transfer reaction. The promotion of the platinum surface reaction (ethylene oxidation) seems to a first approximation to be a function of the rate of oxygen supply or removal to or from the surface irrespective of whether this is contaminated by sodium or not (samples with sodium contamination require a higher overpotential to achieve the same current density as a clean sample because of poisoning in the tpb). At high negative polarisations (oxygen removed from the surface) the sodium contaminated samples show a significant increase in rate, possibly due to the decomposition of e.g. sodium hydroxides and carbonates. © 2012 Elsevier B.V.

National institutions and employers’ age management practices in Britain and Germany:‘Path dependence’and option exploration

We pursue a comparative analysis of employers’ age management practices in Britain and Germany, asking how valid ‘convergence’ and ‘Varieties of Capitalism’ theories are. After rejecting the convergence verdict, we proceed to ask how far ‘path dependence’ helps explain inter-country differences. Through 19 interviews with British and German experts, we find that firms have reacted in different ways to promptings from the EU and the two states. Change has been modest and a rhetoric-reality gap exists in firms as they seek to hedge. We point to continuities in German institutional methods of developing new initiatives, and the emerging role of British NGOs in helping firms and the state develop new options. We argue that ‘path dependence’ offers insight into the national comparison, but also advance the idea of national modes of firm optionexploration as an important way of conceptualizing the processes involved.

Optimal Route Search with the Coverage of Users' Preferences

The preferences of users are important in route search and planning. For example, when a user plans a trip within a city, their preferences can be expressed as keywords shopping mall, restaurant, and museum, with weights 0.5, 0.4, and 0.1, respectively. The resulting route should best satisfy their weighted preferences. In this paper, we take into account the weighted user preferences in route search, and present a keyword coverage problem, which finds an optimal route from a source location to a target location such that the keyword coverage is optimized and that the budget score satisfies a specified constraint. We prove that this problem is NP-hard. To solve this complex problem, we pro- pose an optimal route search based on an A* variant for which we have defined an admissible heuristic function. The experiments conducted on real-world datasets demonstrate both the efficiency and accu- racy of our proposed algorithms.

Cell Coverage Optimization for the Multicell Massive MIMO Uplink

We investigate the cell coverage optimization problem for the massive multiple-input multiple-output (MIMO) uplink. By deploying tilt-adjustable antenna arrays at the base stations, cell coverage optimization can become a promising technique which is able to strike a compromise between covering cell-edge users and pilot contamination suppression. We formulate a detailed description of this optimization problem by maximizing the cell throughput, which is shown to be mainly determined by the user distribution within several key geometrical regions. Then, the formulated problem is applied to different example scenarios: for a network with hexagonal shaped cells and uniformly distributed users, we derive an analytical lower bound of the ergodic throughput in the objective cell, based on which, it is shown that the optimal choice for the cell coverage should ensure that the coverage of different cells does not overlap; for a more generic network with sectoral shaped cells and non-uniformly distributed users, we propose an analytical approximation of the ergodic throughput. After that, a practical coverage optimization algorithm is proposed, where the optimal solution can be easily obtained through a simple one-dimensional line searching within a confined searching region. Our numerical results show that the proposed coverage optimization method is able to greatly increase the system throughput in macrocells for the massive MIMO uplink transmission, compared with the traditional schemes where the cell coverage is fixed.

Limited range coverage problems

Tal como o título indica, esta tese estuda problemas de cobertura com alcance limitado. Dado um conjunto de antenas (ou qualquer outro dispositivo sem fios capaz de receber ou transmitir sinais), o objectivo deste trabalho é calcular o alcance mínimo das antenas de modo a que estas cubram completamente um caminho entre dois pontos numa região. Um caminho que apresente estas características é um itinerário seguro. A definição de cobertura é variável e depende da aplicação a que se destina. No caso de situações críticas como o controlo de fogos ou cenários militares, a definição de cobertura recorre à utilização de mais do que uma antena para aumentar a eficácia deste tipo de vigilância. No entanto, o alcance das antenas deverá ser minimizado de modo a manter a vigilância activa o maior tempo possível. Consequentemente, esta tese está centrada na resolução deste problema de optimização e na obtenção de uma solução particular para cada caso. Embora este problema de optimização tenha sido investigado como um problema de cobertura, é possível estabelecer um paralelismo entre problemas de cobertura e problemas de iluminação e vigilância, que são habitualmente designados como problemas da Galeria de Arte. Para converter um problema de cobertura num de iluminação basta considerar um conjunto de luzes em vez de um conjunto de antenas e submetê-lo a restrições idênticas. O principal tema do conjunto de problemas da Galeria de Arte abordado nesta tese é a 1-boa iluminação. Diz-se que um objecto está 1-bem iluminado por um conjunto de luzes se o invólucro convexo destas contém o objecto, tornando assim este conceito num tipo de iluminação de qualidade. O objectivo desta parte do trabalho é então minimizar o alcance das luzes de modo a manter uma iluminação de qualidade. São também apresentadas duas variantes da 1-boa iluminação: a iluminação ortogonal e a boa !-iluminação. Esta última tem aplicações em problemas de profundidade e visualização de dados, temas que são frequentemente abordados em estatística. A resolução destes problemas usando o diagrama de Voronoi Envolvente (uma variante do diagrama de Voronoi adaptada a problemas de boa iluminação) é também proposta nesta tese.

A Corpus-Linguistic Analysis of News Coverage in Kenya's Daily Nation and Great Britain's Times

Thesis (Master's)--University of Washington, 2015

Intervenções em estruturas antigas

O presente relatório de estágio, definido como Trabalho Final de Mestrado, surge como resultado de um estágio profissional realizado no âmbito do Mestrado em Engenharia Civil do Instituto Superior de Engenharia de Lisboa, e tem como objectivos primordiais, expor as actividades realizadas e reflectir os conhecimentos adquiridos durante o período de estágio. Após uma formação académica maioritariamente vocacionada para os aspectos teóricos e de natureza científica, tornou-se fundamental ao estagiário garantir um contacto real com a profissão de Engenheiro Civil antes do ingresso no mercado de trabalho. Foi com base nesse pressuposto que a opção do Trabalho Final de Mestrado incidiu sobre a realização de um estágio curricular em detrimento das restantes possibilidades. O período de estágio iniciou-se a 14 de Março de 2011 e incidiu sobre a área de Conservação, Restauro e Reabilitação de edifícios com valor patrimonial, sendo feito referência no capítulo 2 aos princípios importantes da intervenção neste tipo de edifícios. O capítulo 3 faz uma abordagem geral do que são as coberturas servindo de complemento ao capítulo 4, onde são abordados e analisados os processos e métodos construtivos envolvidos, contemplando a evolução construtiva da cobertura do Cruzeiro, no Convento de Cristo em Tomar. Nos restantes capítulos, 5 e 6, é feita a caracterização e constituição da estrutura de um edifício da segunda metade do século XVIII, e a análise estrutural feita ao edifício no Antigo Convento do Santíssimo Sacramento, em Lisboa, respectivamente. O capítulo 4 é complementado pelo Anexo A, sendo utilizado como referência ao esquema da estrutura artesanal encontrada na cobertura do Cruzeiro.