Hydroxylation of Platinum Surface Oxides Induced by Water Vapor

With its high stability and well-tuned binding strength for adsorbates, platinum is an excellent catalyst for a wide range of reactions. In applications like car exhaust purification, the oxidation of hydrocarbons, and fuel cells, platinum is exposed to highly oxidizing conditions, which often leads to the formation of surface oxides. To reveal the structure of these surface oxides, the oxidation of Pt in O2 has been widely studied. However, in most applications, H2O is also an important or even dominant part of the reaction mixture. Here, we investigate the interaction of H2O with Pt surface oxides using near-ambient-pressure X-ray photoelectron spectroscopy. We find that reversible hydroxylation readily occurs in H2O/O2 mixtures. Using time-resolved measurements, we show that O–OH exchange occurs on a time scale of seconds

Dark Energy Accretion onto a Black Hole in an Expanding Universe

By using the solution describing a black hole embedded in the FLRW universe, we obtain the evolving equation of the black hole mass expressed in terms of the cosmological parameters. The evolving equation indicates that in the phantom dark energy universe the black hole mass becomes zero before the Big Rip is reached.Comment: 7 pages, no figures, errors is correcte

In situ surface coverage analysis of RuO₂-catalysed HCl oxidation reveals the entropic origin of compensation in heterogeneous catalysis

In heterogeneous catalysis, rates with Arrhenius-like temperature dependence are ubiquitous. Compensation phenomena, which arise from the linear correlation between the apparent activation energy and the logarithm of the apparent pre-exponential factor, are also common. Here, we study the origin of compensation and find a similar dependence on the rate-limiting surface coverage term for each Arrhenius parameter. This result is derived from an experimental determination of the surface coverage of oxygen and chlorine species using temporal analysis of products and prompt gamma activation analysis during HCl oxidation to Cl2 on a RuO2 catalyst. It is also substantiated by theory. We find that compensation phenomena appear when the effect on the apparent activation energy caused by changes in surface coverage is balanced out by the entropic configuration contributions of the surface. This result sets a new paradigm in understanding the interplay of compensation effects with the kinetics of heterogeneously catalysed processes

Quantitative adsorbate structure determination under catalytic reaction conditions

Current methods allow quantitative local structure determination of adsorbate geometries on surfaces in ultrahigh vacuum (UHV) but are incompatible with the higher pressures required for a steady-state catalytic reactions. Here we show that photoelectron diffraction can be used to determine the structure of the methoxy and formate reaction intermediates during the steady-state oxidation of methanol over Cu(110) by taking advantage of recent instrumental developments to allow near-ambient pressure x-ray photoelectron spectroscopy. The local methoxy site differs from that under static UHV conditions, attributed to the increased surface mobility and dynamic nature of the surface under reaction conditions

Expansion, Geometry, and Gravity

In general-relativistic cosmological models, the expansion history, matter content, and geometry are closely intertwined. In this brief paper, we clarify the distinction between the effects of geometry and expansion history on the luminosity distance. We show that the cubic correction to the Hubble law, measured recently with high-redshift supernovae, is the first cosmological measurement, apart from the cosmic microwave background, that probes directly the effects of spatial curvature. We illustrate the distinction between geometry and expansion with a toy model for which the supernova results already indicate a curvature radius larger than the Hubble distance.Comment: 4 pages, 1 color figur