1,720,952 research outputs found
Theory of multiple proton-electron transfer reactions and its implications for electrocatalysis
Get PDFThis Perspective article outlines a simple but general theoretical analysis for multiple proton-electron transfer reactions, based on the microscopic theory of proton-coupled electron transfer reactions, recent developments in the thermodynamic theory of multi-step electron transfer reactions, and the experimental realization that many multiple proton-coupled electron transfer reactions feature decoupled proton-electron steps in their mechanism. It is shown that decoupling of proton and electron transfer leads to a strong pH dependence of the overall catalytic reaction, implying an optimal pH for high catalytic turnover, and an associated optimal catalyst at the optimal pH. When more than one catalytic intermediate is involved, scaling relationships between intermediates may dictate the optimal catalyst and limit the extent of reversibility that may be achievable for a multiple proton-electron-transfer reaction. The theory is discussed in relation to the experimental results for a number of redox reactions that are of importance for sustainable energy conversion, primarily focusing on their pH dependence
Competition and selectivity during parallel evolution of bromine, chlorine and oxygen on IrO<sub>x</sub> electrodes
Get PDFDuring hydrogen production for (renewable) energy storage, direct seawater electrolysis offers several notable advantages over freshwater electrolysis. Unfortunately, it is also hindered by possible oxidation reactions of chloride and (to a lesser extent) bromide, which can occur in parallel to the evolution of oxygen and form harmful by-products at the anode. Although the respective oxidation reactions of Br- and Cl- have been researched quite well on Pt, not much is known concerning bromide oxidation and its effect on the evolution of chlorine and oxygen for metal oxides, which are the class of electrocatalysts overwhelmingly used in industry. Using glassy carbon-supported iridium oxide (IrOx) as a model system, we investigated the oxidation behaviour of this well-known oxygen evolution catalyst in an acidic Br-/Cl- electrolyte. We first briefly discuss the solution chemistry and oxidation products that may be expected. Model studies were performed of the parallel evolution of Br2, Cl2 and O2 to increase the understanding of the anodic competition problem, with a special focus on the selectivity towards oxygen. Using rotating ring-disk voltammetry and UV–Vis spectroscopy, our results suggest that bromide and chloride competitively absorb on IrOx, but do not alter each other's oxidation reaction mechanisms, which both seem to adhere best to a Volmer-Heyrovský mechanism. We also find that bromide and chloride adsorption significantly slow down the oxygen evolution reaction, in an additive way. Even a relatively small amount of bromide highly affected the oxygen evolution selectivity. Formation of the interhalogen compound BrCl, which is possible in a mixed Br-/Cl- electrolyte, does not seem to occur.ChemE/Materials for Energy Conversion and Storag
Competition and Interhalogen Formation during Parallel Electrocatalytic Oxidation of Bromide and Chloride on Pt
Get PDFHydrogen production from seawater electrolysis is highly promising for the capture and storage of intermittent renewable energy, but is hindered by the possibility of unwanted reactions at the anode. The oxidation reactions of chloride and (to a lesser extent) bromide, which can occur in parallel to the evolution of oxygen, lead to environmentally harmful by-products and thus represent undesirable side-reactions. We present some general considerations of solution chemistry and oxidation products that may be expected in a mixed acidic bromide/chloride electrolyte. We performed electrochemical model studies of the simultaneous oxidation of bromide and chloride and their mutual interaction on a Pt electrocatalyst, with the aim of deepening the general understanding of the anodic competition problem. Using simplified model systems, our findings suggest that the oxidation of bromide is hindered by competing chloride adsorption, in a way that can be quite satisfactorily modelled by a simple Langmuir isotherm describing the competing adsorption and reactivity of all species. The oxidation of chloride was however not properly captured by this same model, and may be substantially different. Furthermore, the formation of the interhalogen compound BrCl seems to occur in-between the oxidation of bromide and chloride.ChemE/Materials for Energy Conversion and Storag
Going Beyond Counting First Authors in Author Co-citation Analysis
Get PDFThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Variations on the Author
Get PDF“Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship
Appropriate Similarity Measures for Author Cocitation Analysis
Get PDFWe provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
Dispelling the Myths Behind First-author Citation Counts
Get PDFWe conducted a full-scale evaluative citation analysis study of scholars in the XML research field to explore just how different from each other author rankings resulting from different citation counting methods actually are, and to demonstrate the capability of emerging data and tools on the Web in supporting more realistic citation counting methods. Our results contest some common arguments for the continued
use of first-author citation counts in the evaluation of scholars, such as high correlations between author rankings by first-author citation counts and other citation
counting methods, and high costs of using more realistic citation counting methods that are not well-supported by the ISI databases. It is argued that increasingly available digital full text research papers make it possible for citation analysis studies to go beyond what the ISI databases have directly supported and to employ more
sophisticated methods
koamabayili/VECTRON-author-checklist: VECTRON author checklist
No full textWe have done our best to complete the author checklist relating to the use of animals in the hut study. Note that the objective for the hut study was to evaluate the IRS treatment applications for residual efficacy against Anopheles mosquitoes, including the local An. coluzzii mosquito population. Cows were only used to attract mosquitoes into the huts and no tests were carried out directly on the cows. The author checklist is intended for use with studies where experiments are carried out on animals, which is why we have had such difficulty in completing this for the hut study, as many of the questions do not relate to how the cows were used
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