Molybdenum Speciation and its Impact on Catalytic Activity during Methane Dehydroaromatization in Zeolite ZSM‐5 as Revealed by Operando X‐Ray Methods

Combined high‐resolution fluorescence detection X‐ray absorption near‐edge spectroscopy, X‐ray diffraction, and X‐ray emission spectroscopy have been employed under operando conditions to obtain detailed new insight into the nature of the Mo species on zeolite ZSM‐5 during methane dehydroaromatization. The results show that isolated Mo–oxo species present after calcination are converted by CH₄ into metastable MoC_xO_y species, which are primarily responsible for C₂H_x/C₃H_x formation. Further carburization leads to MoC₃ clusters, whose presence coincides with benzene formation. Both sintering of MoC₃ and accumulation of large hydrocarbons on the external surface, evidenced by fluorescence‐lifetime imaging microscopy, are principally responsible for the decrease in catalytic performance. These results show the importance of controlling Mo speciation to achieve the desired product formation, which has important implications for realizing the impact of CH₄ as a source for platform chemicals.     

Pressure–heat release measurements during start-up conditions in a pulse combustor

An experimental study focusing on the temporal evolution of the global OH heat release (q′) and dynamic pressure (p′) from ignition to limit cycle conditions in an aerovalved pulse combustor has been carried out. The motivation of the work was to investigate how the thermo-acoustic relationships evolve, as very little is understood regarding how pressure and heat release couplings develop prior to establishing limit cycle conditions. The start-up experiments demonstrated that the total start-up sequences occurred within 100 ms and can be subdivided into three regimes: (i) ignition and decay; (ii) instability growth; and (iii) onset of limit cycle operation. The main results showed that upon ignition the high amplitude impulse pressure wave corresponded to the natural frequency of the pulse combustor at ambient gas temperature and was verified by an acoustic model. The pressure field over the growth period exhibited two main trends, either steady amplitude growth or a short delay interval followed by steady amplitude growth to limit cycle conditions. Overall, no reproducibility in frequency or phase during the growth period was observed pointing to the influence of strong non-linear interactions. When operating under limit cycle conditions, the heat release and pressure oscillations were in phase, possessed high levels of coherence, and exhibited narrow band frequency response at the operating frequency and several harmonics.     

Adding a third dimension to operando spectroscopy: a combined UV-Vis, Raman and XAFS setup to study heterogeneous catalysts under working conditions

The potential of combined operando UV-Vis/Raman/XAFS has been explored by studying the active site and deactivation mechanism of silica- and alumina-supported molybdenum oxide catalysts under propane dehydrogenation conditions.     

A Computer Assessment of Media Schedules

This paper outlines the approach made by The London Press Exchange to the media scheduling problem. A rather detailed simulation model of the way television and press schedules reach a target population has been set up. This is used to assess various alternative schedules, i.e. to give an effectiveness rating for each schedule. The marginal rate of return for various alterations to these schedules is also produced. Details of the mathematics in the model and of parts of the computer programs are given. Examples illustrate particular points and the general application.     

FT‐Raman spectroscopy of pigments on a Hindu statue,Kali Walking on Siva

FT‐Raman spectroscopic analysis of eight pigmented specimens from an important Hindu statue group, Kali Walking on Siva, acquired in 1895 but of indeterminate age and now in the Horniman Museum, London, has revealed some interesting and unusual combinations of coloured pigments including cinnabar, minium, lapis lazuli and red ochre. Several specimens showed evidence of organic additives, which have been attributed to shellac resins commonly believed to have been used on this type of statuary. The Raman spectroscopic results confirm that the predominant black pigment on the Kali figure is lamp black or soot, in contrast to the SEM‐EDX data that suggests the origin of this pigment as from bone black or ivory black from the presence of phosphorus. An eclectic range of white pigments have been identified in this group including lead white, barytes, calcite and anhydrite; rutile and anatase found on one specimen on the jackal in this group have been ascribed to recent unrecorded restoration. Copyright © 2006 John Wiley & Sons, Ltd.     

Dynamics and Fuzzy Control of a Levitated Particle

This paper deals with the control in both horizontal and vertical directions of a nonlinear magnetic spherical particle suspension. A pair of horizontal electromagnets were added to the typical magnetic levitation system in order to handle the horizontal unexpected displacements of the particle. A fuzzy logic controller was designed to bring the particle to the operating location situated on the symmetry axis. Simulations with different initial position conditions of the particle are provided. It was shown that the controller has a good behavior for almost any initial conditions.     

Search for a fermiophobic and standard model Higgs boson in diphoton final states

We present a search for the standard model Higgs boson and a fermiophobic Higgs boson in the diphoton final states based on 8.2 fb(-1) of pp collisions at sqrt[s]=1.96 TeV collected with the D0 detector at the Fermilab Tevatron Collider. No excess of data above background predictions is observed and upper limits at the 95% C.L. on the cross section multiplied by the branching fraction are set which are the most restrictive to date. A fermiophobic Higgs boson with a mass below 112.9 GeV is excluded at the 95% C.L.