Controlling Hydrocarbon (De)Hydrogenation Pathways with Bifunctional PtCu Single-Atom Alloys

The conversions of surface-bound alkyl groups to alkanes and alkenes are important steps in many heterogeneously catalyzed reactions. On the one hand, while Pt is ubiquitous in industry because of its high activity toward C-H activation, many Pt-based catalysts tend to overbind reactive intermediates, which leads to deactivation by carbon deposition and coke formation. On the other hand, Cu binds intermediates more weakly than Pt, but activation barriers tend to be higher on Cu. We examine the reactivity of ethyl, the simplest alkyl group that can undergo hydrogenation and dehydrogenation via β-elimination, and show that isolated Pt atoms in Cu enable low-temperature hydrogenation of ethyl, unseen on Cu, while avoiding the decomposition pathways on pure Pt that lead to coking. Furthermore, we confirm the predictions of our theoretical model and experimentally demonstrate that the selectivity of ethyl (de)hydrogenation can be controlled by changing the surface coverage of hydrogen

Redox evolution of a degassing magma rising to the surface.

Volatiles carried by magmas, either dissolved or exsolved, have a fundamental effect on a variety of geological phenomena, such as magma dynamics1–5 and the composition of the Earth's atmosphere 6. In particular, the redox state of volcanic gases emanating at the Earth's surface is widely believed to mirror that of the magma source, and is thought to have exerted a first-order control on the secular evolution of atmospheric oxygen6,7. Oxygen fugacity (fO2 ) estimated from lava or related gas chemistry, however, may vary by as much as one log unit8–10, and the reason for such differences remains obscure. Here we use a coupled chemical–physical model of conduit flow to show that the redox state evolution of an ascending magma, and thus of its coexisting gas phase, is strongly dependent on both the composition and the amount of gas in the reservoir. Magmas with no sulphur show a systematic fO2 increase during ascent, by as much as 2 log units. Magmas with sulphur show also a change of redox state during ascent, but the direction of change depends on the initial fO2 in the reservoir. Our calculations closely reproduce the H2S/SO2 ratios of volcanic gases observed at convergent settings, yet the difference between fO2 in the reservoir and that at the exit of the volcanic conduit may be as much as 1.5 log units. Thus, the redox state of erupted magmas is not necessarily a good proxy of the redox state of the gases they emit. Our findings may require re-evaluation of models aimed at quantifying the role of magmatic volatiles in geological processes

Search for new physics with same-sign isolated dilepton events with jets and missing transverse energy

A search for new physics is performed in events with two same-sign isolated leptons, hadronic jets, and missing transverse energy in the final state. The analysis is based on a data sample corresponding to an integrated luminosity of 4.98 inverse femtobarns produced in pp collisions at a center-of-mass energy of 7 TeV collected by the CMS experiment at the LHC. This constitutes a factor of 140 increase in integrated luminosity over previously published results. The observed yields agree with the standard model predictions and thus no evidence for new physics is found. The observations are used to set upper limits on possible new physics contributions and to constrain supersymmetric models. To facilitate the interpretation of the data in a broader range of new physics scenarios, information on the event selection, detector response, and efficiencies is provided.Comment: Published in Physical Review Letter