Quantitative analysis of the reactivity of formate species seen by DRIFTS over a Au/Ce(La)O2 water–gas shift catalyst: First unambiguous evidence of the minority role of formates as reaction intermediates

The reactivity of the species formed at the surface of a Au/Ce(La)O2 catalyst during the water������¢���¯���¿���½���¯���¿���½gas shift (WGS) reaction were investigated by operando diffuse reflectance Fourier transform spectroscopy (DRIFTS) at the chemical steady state during isotopic transient kinetic analyses (SSITKA). The exchanges of the reaction product CO2 and of formate and carbonate surface species were followed during an isotopic exchange of the reactant CO using a DRIFTS cell as a single reactor. The DRIFTS cell was a modified commercial cell that yielded identical reaction rates to that measured over a quartz plug-flow reactor. The DRIFTS signal was used to quantify the relative oncentrations of the surface species and CO2. The analysis of the formate exchange curves between 428 and 493 K showed that at least two levels of reactivity were present. ������¢���¯���¿���½���¯���¿���½Slow formates������¢���¯���¿���½���¯���¿���½ displayed an exchange rate constant 10- to 20-fold slower than that of the reaction product CO2. ������¢���¯���¿���½���¯���¿���½Fast formates������¢���¯���¿���½���¯���¿���½ were exchanged on a time scale similar to that of CO2. Multiple nonreactive readsorption of CO2 took place, accounting for the kinetics of the exchange of CO2(g) and making it impossible to determine the number of active sites through the SSITKA technique. The concentration (in mol g������¢���¯���¿���½���¯���¿���½1) of formates on the catalyst was determined through a calibration curve and allowed calculation of the specific rate of formate decomposition. The rate of CO2 formation was more than an order of magnitude higher than the rate of decomposition of formates (slow + fast species), indicating that all of the formates detected by DRIFTS could not be the main reaction intermediates in the production of CO2. This work stresses the importance of full quantitative analyses (measuring both rate constants and adsorbate concentrations) when investigating the role of adsorbates as potential reaction intermediates, and illustrates how even reactive species seen by DRIFTS may be unimportant in the overall reaction scheme.

Quantitative DRIFTS investigation of possible reaction mechanisms for the water-gas shift reaction on high-activity Pt- and Au-based catalysts

The present work emphasizes the importance of including a full quantitative analysis when in situ operando methods are used to investigate reaction mechanisms and reaction intermediates. The fact that some surface species exchange at a similar rate to the reaction product during isotopic transients is a necessary but not sufficient criterion for participation as a key reaction intermediate. This is exemplified here in the case of highly active low-temperature water-gas shift (WGS) catalysts based on gold and platinum. Operando DRIFTS data, isotopic exchanges, and DRIFTS calibration curves relating the concentration of formate species to the corresponding DRIFTS band intensity were combined to obtain a quantitative measure of the specific rate of formate decomposition. Despite displaying a rapid isotopic exchange rate (sometimes as fast as that of the reaction product CO2), the concentration of formates seen by DRIFTS was found to account for at most only 10% of the CO2 produced under the experimental conditions reported herein. These new results obtained on Au/CeZrO4 and Pt/CeO2 preparations (which are among the most active low-temperature WGS catalysts reported to date), led to the same conclusions regarding the minor role of IR-observable formates as those obtained in the case of less active Au/Ce(La)O-2 and Pt/ZrO2 catalysts. (c) 2007 Elsevier Inc. All rights reserved.

Recepción e influencia de la literatura hispanoamericana en Corea

A medida que el concepto de "nación" se ha debilitado en estos últimos años, y de forma muy rápida, el límite convencional de la cultura se está desvaneciendo y el mundo se mueve hacia un orden cultural integrado, a través de intercambios constantes entre las culturas, a pesar de las barreras discriminatorias. La literatura, en este sentido, no es una excepción y es necesario discutir la relación entre la literatura coreana y la hispanoamericana desde la perspectiva de la literatura comparativa. El presente estudio ofrece una mirada más cercana al proceso y a los distintos aspectos del modo en que las obras de los escritores hispanoamericanos han sido aceptadas en Corea del Sur. La literatura hispanoamericana se ha introducido en Corea desde principios del siglo XX y se extendió rápidamente a partir de los ochenta, cuando la controversia literaria del posmodernismo se desató y las obras de Borges y García Márquez fueron presentadas a los lectores coreanos. Sería interesante examinar los aspectos sobre cómo los escritores hispanoamericanos como Neruda, Borges y García Márquez se han integrado en la literatura coreana. En esta etapa, sin embargo, es difícil determinar si su influencia es suficientemente permanente como para convertirse en un linaje, o simplemente se trata de un fenómeno temporal. No obstante, la literatura hispanoamericana seguirá expandiendo interrelaciones crecientes con la coreana más allá de las fronteras, ejerciendo una gran influencia entre sí.

First dielectronic recombination measurements with H-like uranium

In this report we show first results on dielectronic recombination (DR) measurements with H-like uranium U91+. The experiments were conducted at the heavy ion storage ring ESR of GSI. The electron cooler of the ESR was used as a target for free electrons. Stochastic pre-cooling of the stored ion beam was employed in order to accomplish high-energy resolution at the necessary high electron-ion collision energies of more than 64 keV. For the DR of U91+ this novel technique enabled us to measure for the first time the KLL-DR process and even to resolve the individual j-j' fine structure components of the KLjLj' resonances. The experimental data are compared with fully relativistic Multi-Configuration Dirac-Fock (DR-MCDF) calculations. (c) 2006 Elsevier Ltd. All rights reserved.

Philosophy, Social Hope and Democratic Criticism:Critical Theory for a Global Age

The attempt to connect philosophy and social hope has been one of the key distinguishing features of critical theory as a tradition of enquiry. This connection has been questioned forcefully from the perspective of a post-philosophical pragmatism, as articulated by Rorty. In this article I consider two strategies that have been adopted by critical theorists in seeking to reject Rorty's suggestion that we should abandon the attempt to ground social hope in philosophical reason. We consider argumentative strategies of the philosophical anthropologist and of the rational proceduralist. Once the exchanges between Rorty and these two strands of critical theory have been reconstructed and assessed, an alternative perspective emerges. It is argued that philosophical reasoning best helps to sustain social hope in a rapidly changing world when we consider it in terms of the practice of democratic criticism.

Reading the Irishwoman: Studies in Cultural Encounter and Exchange, 1714-1960

In 1700 few Irishwomen were literate. Most lived in a rural environment, rarely encountered a book or a play or ventured much beyond their own domestic space. By 1960 literacy was universal, all Irishwomen attended primary school, had access to a variety of books, magazines, newspapers and other forms of popular media and the wider world was now part of their every-day life. This study seeks to examine the cultural encounters and exchanges inherent in this transformation. It analyses reading and popular and consumer culture as sites of negotiation of gender roles. This is not an exhaustive treatment of the theme but focusses on three key points of cultural encounter: the Enlightenment, emigration and modernism. The writings and intellectual discourse generated by the Enlightenment was one of the most influential forces shaping western society. It set the agenda for scientific, political and social thought for the eighteenth and nineteenth centuries. The migration of peoples to north America was another key historical marker in the development of the modern world. Emigration altered and shaped American society as well as the lives of those who remained behind. By the twentieth century, aesthetic modernism suspicious of enlightenment rationalism and determined to produce new cultural forms developed in a complex relationship with the forces of industrialisation, urbanisation and social change. This study analyses the impact of these three key forces in Western culture on changing roles and perceptions of Irish women from 1700 to 1960.

Politics and Literary Prizes:A Case Study of Spanish America and the Premio Cervantes

The Premio Cervantes, one of the most prestigious prizes awarded for literature in the Spanish language, was established in 1976 as Spain negotiated the Transition to democracy in the post-Franco era. This article examines the context in which the prize was created and subsequently used to negotiate inter-continental relations between Spain and Latin America. The article highlights the exchanges of economic, political and symbolic capital which took place between the Spanish State, its representative, the King of Spain, and winning Latin American authors. Significantly, the involvement of the Spanish State is shown to bring political capital into play in a way that commercial prizes do not. In so doing, the Premio Cervantes gives those formerly at the colonial periphery the opportunity to speak out and negotiate the terms of a new kind of relationship with the former colonial center.

Interhemispheric gradient of atmospheric radiocarbon reveals natural variability of Southern Ocean winds

Tree ring Delta C-14 data (Reimer et al., 2004; McCormac et al., 2004) indicate that atmospheric Delta C-14 varied on multi-decadal to centennial timescales, in both hemispheres, over the period between AD 950 and 1830. The Northern and Southern Hemispheric Delta C-14 records display similar variability, but from the data alone is it not clear whether these variations are driven by the production of C-14 in the stratosphere (Stuiver and Quay, 1980) or by perturbations to exchanges between carbon reservoirs (Siegenthaler et al., 1980). As the sea-air flux of (CO2)-C-14 has a clear maximum in the open ocean regions of the Southern Ocean, relatively modest perturbations to the winds over this region drive significant perturbations to the interhemispheric gradient. In this study, model simulations are used to show that Southern Ocean winds are likely a main driver of the observed variability in the interhemispheric gradient over AD 950-1830, and further, that this variability may be larger than the Southern Ocean wind trends that have been reported for recent decades (notably 1980-2004). This interpretation also implies that there may have been a significant weakening of the winds over the Southern Ocean within a few decades of AD 1375, associated with the transition between the Medieval Climate Anomaly and the Little Ice Age. The driving forces that could have produced such a shift in the winds at the Medieval Climate Anomaly to Little Ice Age transition remain unknown. Our process-focused suite of perturbation experiments with models raises the possibility that the current generation of coupled climate and earth system models may underestimate the natural background multi-decadal- to centennial-timescale variations in the winds over the Southern Ocean.

Memoires of Translation

Online publication. 5000 words.

Gifts, Loans and Intergenerational Support for Young Adults

Young adults in the UK are increasingly dependent on family support to offset the costs of living independently. This article explores these complex intergenerational exchanges from the perspective of a group of single young adults in their mid-twenties to mid-thirties who had been in receipt of various forms of financial and material support from family members since leaving the parental home. We outline the nature of this support and then consider how these forms of assistance are understood by those in receipt of them. We conclude that the co-existence of a sense of both gratitude and discomfort which is often generated by these exchanges is managed but by no means resolved by a blurring of the boundaries between gifts and loans, a set of negotiations which may not even be an option amongst less advantaged young adults.

Cities as Organisms

Since the UN report by the Brundtland Committee, sustainability in the built environment has mainly been seen from a technical focus on single buildings or products. With the energy efficiency approaching 100%, fossil resources depleting and a considerable part of the world still in need of better prosperity, the playing field of a technical focus has become very limited. It will most probably not lead to the sustainable development needed to avoid irreversible effects on climate, energy provision and, not least, society.
Cities are complex structures of independently functioning elements, all of which are nevertheless connected to different forms of infrastructure, which provide the necessary sources or solve the release of waste material. With the current ambitions regarding carbon- or energy-neutrality, retreating again to the scale of a building is likely to fail. Within an urban context a single building cannot become fully resource-independent, and need not, from our viewpoint. Cities should be considered as an organism that has the ability to intelligently exchange sources and waste flows. Especially in terms of energy, it can be made clear that the present situation in most cities are undesired: there is simultaneous demand for heat and cold, and in summer a lot of excess energy is lost, which needs to be produced again in winter. The solution for this is a system that intelligently exchanges and stores essential sources, e.g. energy, and that optimally utilises waste flows.
This new approach will be discussed and exemplified. The Rotterdam Energy Approach and Planning (REAP) will be illustrated as a means for urban planning, whereas Swarm Planning will be introduced as another nature-based principle for swift changes towards sustainability

Accounts of debates in the House of Commons, March– April 1731, supplementary to the diary of the first earl of Egmont

John Perceval (1685–1748), 1st Viscount Perceval and (from 1733) 1st Earl of Egmont, was an assiduous recorder of his own life and times. His diaries, published by the Historical Manuscripts Commission from manuscripts in the British Library, are the best source for parliamentary debates at Westminster in the 1730s. For the years 1730-1733, when Perceval sat in the Commons (as an Irish peer) they are remarkably full. His practice seems to have been to prepare two versions (presumably on the basis of notes taken in the House), the first attributing speeches to individuals, and the second, entered up in the diary, which listed speakers and summarized all arguments on each side. His letterbooks for 1731 contain accounts of five debates that embody his first editing process, with speeches attributed to individuals. They were sent to an Irish correspondent, Marmaduke Coghill, and largely omitted from the diary because Perceval had already transcribed them elsewhere. They are new to historians and cast light on two main issues: the unsuccessful attempts by Perceval and the ‘Irish lobby’ to persuade the British parliament to settle the Irish woollen trade, a question bedevilling Anglo-Irish relations in this period; and an attempt by the opposition to stir up anger against perceived Spanish aggression against Gibraltar. One of the most interesting features is the insight afforded into the Commons performances of Sir Robert Walpole: his management of debates, his own style of speaking, and his sharp exchanges with opponents like William Pulteney.