A challenge to the Delta G~0 interpretation of hydrogen evolution

Platinum is a nearly perfect catalyst for the hydrogen evolution reaction, and its high activity has conventionally been explained by its close-to-thermoneutral hydrogen binding energy (G~0). However, many candidate non-precious metal catalysts bind hydrogen with similar strengths, but exhibit orders-of-magnitude lower activity for this reaction. In this study, we employ electronic structure methods that allow fully potential-dependent reaction barriers to be calculated, in order to develop a complete working picture of hydrogen evolution on platinum. Through the resulting ab initio microkinetic models, we assess the mechanistic origins of Pt's high activity. Surprisingly, we find that the G~0 hydrogen atoms are kinetically inert, and that the kinetically active hydrogen atoms have G's much weaker, similar to that of gold. These on-top hydrogens have particularly low barriers, which we compare to those of gold, explaining the high reaction rates, and the exponential variations in coverages can uniquely explain Pt's strong kinetic response to the applied potential. This explains the unique reactivity of Pt that is missed by conventional Sabatier analyses, and suggests true design criteria for non-precious alternatives

Why distinguish between statistics and mathematical statistics - the case of Swedish academia

A separation between the academic subjects statistics and mathematical statistics has existed in Sweden almost as long as there have been statistics professors. The same distinction has not been maintained in other countries. Why is it kept in Sweden?In May 2015 it has been 100 years since Mathematical Statistics was formally established as an academic discipline at a Swedish university where Statistics had existed since the turn of the century. We give an account of the debate in Lund and elsewhere about this division during the first decades after 1900 and present two of its leading personalities. The Lund University astronomer (and mathematical statistician) C.V.L. Charlier was a leading proponent for a position in mathematical statistics at the university. Charlier's adversary in the debate was Pontus Fahlbeck, professor in political science and statistics, who reserved the word statistics for ``statistics as a social science''. Charlier not only secured the first academic position in Sweden in mathematical statistics for his former Ph.D. student Sven Wicksell, but he also demonstrated that a mathematical statistician can be influential in matters of state, finance, as well as in different natural sciences. Fahlbeck saw mathematical statistics as a set of tools that sometimes could be useful in his brand of statistics. After a summary of the organisational growth of the statistical sciences in Sweden that has taken place during the last 50 years, we discuss what effects the Charlier-Fahlbeck divergence might have had on this development

Scaled and Dynamic Optimizations of Nudged Elastic Bands

We present a modified nudged elastic band routine that can reduce the number of force calls by more than 50% for bands with non-uniform convergence. The method, which we call "dyNEB", dynamically and selectively optimizes states based on the perpendicular forces and parallel spring forces acting on that region of the band. The convergence criteria are scaled to focus on the region of interest, i.e., the saddle point, while maintaining continuity of the band and avoiding truncation. We show that this method works well for solid state reaction barriers---non-electrochemical in general and electrochemical in particular---and that the number of force calls can be significantly reduced without loss of resolution at the saddle point

Revealing Hearts: Paul Tillich’s Concept of Revelation: an Application to Business Innovation

Some small business owners want to balance personal values as well as economic values. “I have to follow my heart” or “it must be meaningful” some of them say. But how might they be able to know what gives meaning to the heart? The philosophical theologian Paul Tillich finds that the problem is that ‘controlling knowledge’ (e.g., technical testing) might be safe but unimportant, while ‘receiving knowledge’, that can only be verified by direct participation (e.g., intuition), might be important but uncertain. This paper shows how this tension can be made fruitful in relation to business innovation with reference to Tillich’s account of the meaning of revelation through culture and art, summed up in the statement that “(…) revelation is the manifestation of the ground of being for human knowledge” (Tillich, 1951, p.94), which, we argue, can be extended to everyday experiences, for example, in business life. In Tillich’s own terms, even preliminary concerns may point at an ultimate concern (Tillich, 1964), which can also be understood as ‘knowledge of the heart’. Our account is also connected to wider discussions concerning the nature of intuitio

Voltammetric monitoring of laccase-catalysed mediated reactions

Six different compounds capable of mediating laccase-catalysed reactions have been tested by cyclic voltammetry. They exhibited quasi-reversible electrodic behaviour with formal redox potentials ranging from 150 to 800 mV (E-0t vs. SCE). The immersion of a laccase-coated glassy carbon electrode (GCE) in mediator solutions generated large cathodic catalytic currents easily recorded by cyclic voltammetry at low-potential scan rates. This current showed two well-defined pH profiles, which correlated with the variation of the mediator redox potentials at the pH range tested. The relevant effect of temperature on the activity of laccase has been assessed here. Likewise, it was shown that the cut-rent record varied with the substrate concentration. This trend fitted Michaelis-Menten kinetics, which allowed us to give an estimation of the affinity of the fungal laccase for the different mediators. (C) 2002 Elsevier Science B.V. All rights reserved

Stochastic asymmetry properties of 3D gauss-lagrange ocean waves with directional spreading

In the stochastic Lagrange model for ocean waves the vertical and horizontal location of surface water particles are modeled as correlated Gaussian processes. In this article we investigate the statistical properties of wave characteristics related to wave asymmetry in the 3D Lagrange model. We present a modification of the original Lagrange model that can produce front-back asymmetry both of the space waves, i.e. observation of the sea surface at a fixed time, and of the time waves, observed at a fixed measuring station. The results, which are based on a multivariate form of Rice’s formula for the expected number of level crossings, are given in the form of the cumulative distribution functions for the slopes observed either by asynchronous sampling in space, or at synchronous sampling at upcrossings and down-crossings, respectively, of a specified fixed level. The theory is illustrated in a numerical section, showing how the degree of wave asymmetry depends on the directional spectral spreading and on the mean wave direction. It is seen that the asymmetry is more accentuated for high waves, a fact that may be of importance in safety analysis of capsizing risk