Single-Site Vanadyl Species Isolated within Molybdenum Oxide Monolayers in Propane Oxidation

The cooperation of metal oxide subunits in complex mixed metal oxide catalysts for selective oxidation of alkanes still needs deeper understanding to allow for a rational tuning of catalyst performance. Herein we analyze the interaction between vanadium and molybdenum oxide species in a monolayer supported on mesoporous silica SBA-15. Catalysts with variable Mo/V ratio between 10 and 1 were studied in the oxidation of propane and characterized by FTIR, Raman, and EPR spectroscopies, temperature-programmed reduction, UV/vis spectroscopy in combination with DFT calculations, and time-resolved experiments to analyze the redox properties of the catalysts. Molybdenum oxide (sub)monolayers on silica contain mainly dioxo (Si–O−)2Mo(═O)2 species. Dilution of silica-supported vanadium oxide species by (Si–O−)2Mo(═O)2 prevents the formation of V–O–V bonds, which are abundant in the pure vanadium oxide catalyst that predominantly contains two-dimensional vanadium oxide oligomers. Existing single vanadyl (Si–O−)3V(═O) sites and neighboring (Si–O−)2Mo(═O)2 sites do not strongly interact. The rates of reduction in propane and of oxidation in oxygen are lower for single metal oxide sites compared to those for oligomers. The rate of propane oxidation correlates with the overall redox rates of the catalysts but not linearly with the chemical composition. Retarded redox behavior facilitates selectivity toward acrolein on single-site catalysts. The abundance of M–O–M bonds is more important in terms of activity and selectivity compared to the nature of the central atom (molybdenum versus vanadium)

Quantum vortex dynamics in two-dimensional neutral superfluids

We derive an effective action for the vortex position degree-of-freedom in a superfluid by integrating out condensate phase and density fluctuation environmental modes. When the quantum dynamics of environmental fluctuations is neglected, we confirm the occurrence of the vortex Magnus force and obtain an expression for the vortex mass. We find that this adiabatic approximation is valid only when the superfluid droplet radius $R$, or the typical distance between vortices, is very much larger than the coherence length $\xi$. We go beyond the adiabatic approximation numerically, accounting for the quantum dynamics of environmental modes and capturing their dissipative coupling to condensate dynamics. For the case of an optical-lattice superfluid we demonstrate that vortex motion damping can be adjusted by tuning the ratio between the tunneling energy $J$ and the on-site interaction energy $U$. We comment on the possibility of realizing vortex Landau level physics.Comment: 14 pages, 10 figures, accepted by PRA with corrected references and typo

Heat transfer, velocity-temperature correlation, and turbulent shear stress from Navier-Stokes computations of shock wave/turbulent boundary layer interaction flows

The properties of 2-D shock wave/turbulent boundary layer interaction flows were calculated by using a compressible turbulent Navier-Stokes numerical computational code. Interaction flows caused by oblique shock wave impingement on the turbulent boundary layer flow were considered. The oblique shock waves were induced with shock generators at angles of attack less than 10 degs in supersonic flows. The surface temperatures were kept at near-adiabatic (ratio of wall static temperature to free stream total temperature) and cold wall (ratio of wall static temperature to free stream total temperature) conditions. The computational results were studied for the surface heat transfer, velocity temperature correlation, and turbulent shear stress in the interaction flow fields. Comparisons of the computational results with existing measurements indicated that (1) the surface heat transfer rates and surface pressures could be correlated with Holden's relationship, (2) the mean flow streamwise velocity components and static temperatures could be correlated with Crocco's relationship if flow separation did not occur, and (3) the Baldwin-Lomax turbulence model should be modified for turbulent shear stress computations in the interaction flows

Non-local properties of a symmetric two-qubit system

Non-local properties of symmetric two-qubit states are quantified in terms of a complete set of entanglement invariants. We prove that negative values of some of the invariants are signatures of quantum entanglement. This leads us to identify sufficient conditions for non-separability in terms of entanglement invariants. Non-local properties of two-qubit states extracted from (i) Dicke state (ii) state generated by one-axis twisting Hamiltonian, and (iii) one-dimensional Ising chain with nearest neighbour interaction are analyzed in terms of the invariants characterizing them.Comment: 5 pages, no figure