Enhancing the Activity and Tuning the Mechanism of Formic acid Oxidation at Tetrahexahedral Pt Nanocrystals by Au Decoration

Tetrahexahedral Pt nanocrystals (THH Pt NCs), bound by high index facets, belong to an emerging class of nanomaterials that promise to bridge the gap between model and practical electrocatalysts. The atomically stepped surfaces of THH Pt NCs are extremely active for the electrooxidation of small organic molecules but they also readily accommodate the dissociative chemisorption of such species, resulting in poisoning by strongly adsorbed CO. Formic acid oxidation is an ideal reaction for studying the balance between these competing catalyst characteristics, since it can proceed by either a direct or a CO mediated pathway. Herein, we describe electrochemical and in situ FTIR spectroscopic investigations of formic acid electrooxidation at both clean and Au adatom modified THH Pt NC surfaces. The Au decoration leads to higher catalytic currents and enhanced CO2 production in the low potential range. As the CO oxidation behaviour of the catalyst is not changed by the presence of the Au, it is likely that the role of the Au is to promote the direct pathway. Beyond their fundamental importance, these results are significant in the development of stable, poison resistant anodic electrocatalysts for direct formic acid fuel cells.

The Greek Debt Crisis and Southern Europe: Majoritarian Pitfalls?

Although widely debated in broader socioeconomic terms, the Eurozone crisis has not received adequate scholarly attention with regards to the impact of alternative political systems. This article revisits the debate on majoritarian and consensus democracies drawing on recent evidence from the Eurozone debacle. Greece is particularly interesting both with regards to its potential ‘global spillover effects’ and choice of political system. Despite facing comparable challenges as Portugal and Spain, the country has become polarized socially and politically, seeing a record number of MP defections, electoral volatility and the rise of the militant extreme right. The article explains why Greece, the country that relied most extensively on majoritarian institutions, entered the global financial crisis in the most vulnerable position while subsequently faced insurmountable political and institutional obstacles in its management. The article points to the paradox of majoritarianism: in times of economic stress, the first ‘casualties’ are its strongest elements – centrist parties (bi-partisanship) and cabinet stability.

The effects of stepped sites and ruthenium adatom decoration on methanol dehydrogenation over platinum-based catalyst surfaces

A density functional theory study of methanol dehydrogenation over stepped Pt(2 1 1) surfaces without and with Ru modification was carried out to understand fuel catalytic reactions on Pt-based catalysts. Two main pathways of the CH3OH dehydrogenation were examined: the O–H pathway which was initiated by O–H bond scission to form the methoxy (CH3O) intermediate followed by sequential cleavage of C–H bonds to CO, and the C–H pathway which was initiated by C–H bond scission to form the hydroxymethyl (CH2OH) followed by two C–H bond cleavages to COH and then CO. Possible crossover reactions between the O–H and C–H pathways were also computed. Compared to flat Pt(1 1 1), stepped Pt(2 1 1) increases the adsorption energies of intermediates, making no significant contribution to decreasing the reaction barriers of most elementary steps involved, except in the first hydrogen scission. However, on the Ru-modified surface, a significant reduction was found in reaction barriers for the first step of the C–H bond scission and a number of further dehydrogenation steps crossing over to the O–H pathway, with the most facile paths identified. Our data reveals the complexity of methanol catalytic reaction processes at the atomic level and contributes to a fundamental understanding of fuel reactions on Pt-based catalysts.

Italian Canzone d'autore and Greek Entechno tragoudi: a comparative overview

‘Canzone d’autore’ is the name that a vast community of Italian music critics, authors, per-formers, producers agreed upon in the mid-1970s, to describe the Italian singer-songwriter genre. Singer-songwriters, who had been missing from Italian popular music – with very few exceptions – until the late 1950s, had become increasingly popular after 1958, and were dubbed ‘cantautori’ in 1960. The term, which propagated to Spain, Catalonia, and Latin Amer-ica, is still in use, but ‘canzone d’autore’ superseded it as a genre label, highlighting the con-nections between authorship and artistic value, implied in the already established notion of ‘Cinéma d’auteur’ from which it was derived.

The expression ‘entechno laiko tragoudi’ (‘art-folk song’) was coined in Greece by Mikis The-odorakis in the 1950s, to describe a new music genre combining the urban-folk musical idi-om with lyrics coming from high-art poetry. Although the origins of the genre are tied to the work of composers like Theodorakis and Hatzidakis who did not perform as singers, from the 1970s onwards entechno became the privileged field of new generations of Greek singer-songwriters. Dropping ‘laiko’ (folk) from its label, entechno expanded its musical influences outside the urban-folk repertory and transformed into the more all-encompassing contempo-rary ‘art song’.