Mechanistic Study of 1,3-Butadiene Formation in Acetylene Hydrogenation over the Pd-Based Catalysts Using Density Functional Calculations

Green oil, which leads to the deactivation of the catalysts used for the selective hydrogenation of acetylene, has long been observed but its formation mechanism is not fully understood. In this work, the formation of 1,3-butadiene, known to be the precursor of green oil, on both Pd(111) and Pd(211) surfaces is examined using density functional theory calculations. The pathways containing C-2 + C-2 coupling reactions as well as the corresponding hydrogenation reactions are studied in detail. Three pathways for 1,3-butadiene production, namely coupling plus hydrogenation and further hydrogenation, hydrogenation plus coupling plus hydrogenation, and a two step hydrogenation followed by coupling, are determined. By comparing the effective barriers, we identify the favored pathway on both surfaces. A general understanding toward the deactivation process of the industrial catalysts is also provided. In addition, the effects of the formation of subsurface carbon atoms as well as the Ag alloying on the 1,3-butadiene formation on Pd-based catalysts are also investigated and compared with experimental results.

End-of-range defects in germanium and their role in boron deactivation

We investigated the thermal evolution of end-of-range (EOR) defects in germanium and their impact on junction thermal stability. After solid-phase epitaxial regrowth of a preamorphized germanium layer, EOR defects exhibiting dislocation loop-like contrast behavior are present. These defects disappear during thermal annealing at 400 °C, while boron electrical deactivation occurs. After the whole defect population vanishes, boron reactivation is observed. These results indicate that germanium self-interstitials, released by EOR defects, are the cause of B deactivation. Unlike in Si, the whole deactivation/reactivation cycle in Ge is found to take place while the maximum active B concentration exceeds its solubility limit. © 2010 American Institute of Physics.

Carbon deposition behavior over copper salts of molybdovanadophosphoric acid catalyst supported by magnesia

MgO supported copper salt of molybdovanadophosphoric acid H4PMo11VO40 catalysts were prepared in alcohol by impregnation and the carbon deposition over these catalysts during the n-hexanol oxidation reaction was studied. The coke predominantly deposited on the catalyst surface in the form of CH., and it was not found that it caused the deactivation of the catalyst. The XRD, IR, XPS characterizations reveal that the Keggin structure of the CPMV was unaffected by carbon deposition. Moreover, it was shown that the supported CPMVs over the MgO surface can be beneficial to eliminate the coke. The temperature programmed oxidation (TPO) study showed that coke was formed over the catalyst on two different sites: (1) deposited on the CPMVs which can be burn off at a low temperature; (2) deposited on the MgO which could only be removed at higher temperature. The coke content reached constant with the reaction time increasing.

Catalytic behavior of concentrated heteropolyacid solution in acylation of anisole with acetic anhydride

The catalytic behavior of concentrated heteropolyacid solution in acylation. of anisole with acetic anhydride has been investigated under the reaction conditions such as molar ratio of anisole to acetic anhydride, reaction temperature and mass ratio of reactant to catalyst. When the molar ratio of anisole to acetic anhydride is changed from 2:1 to 1:1, the yield of methoxyacetophenone (MOAP) increases a little, but when it is changed from 1: 1 to 1: 2, the yield has a greater increase from 15% to 30%. The yield of MOAP at the reaction temperature of 363 K doubles that at 333 K. The highest yield is obtained when the mass ratio of reactant to catalyst is 12.8. The conclusion is therefore that the heteropolyacid in acetic acid can effectively catalyze the acylation of anisole with acetic anhydride, and its activity and selectivity are comparable to those of acid clay and molecular sieve.

Optomechanical trans-to-cis and cis-to-trans isomerization and unusual photophysical behavior of fac-[Re(CO)(3)(phen)(CNstpy)](+)

Unusual high photoassisted quantum yields for cis-to-trans (phi(254) (nm) = 0.27 +/- 0.05) isomerization of CNstpy coordinated to fac-[Re(CO)(3)(phen)(CNstpy)](+) were determined along with trans-to-cis ones (phi(313) (nm)= 0.58 +/- 0.02; phi(365) (nm)= 0.61 +/- 0.06; phi(404) (nm) = 0.42 +/- 0.02). Additionally, in contrast to other similar rhenium(I) complexes, the cis photoproduct is quasi non-emissive and comparable to the trans-complex. The cis-to-trans photoisomerization is due to the deactivation from the ILcis-CNstpy excited state in competition to the usual (MLCTRe -> phen)-M-3 luminescence. These efficient cis to trans and trans to cis photoisomerization can be conveniently used in light powered molecular machines. (C) 2012 Elsevier B.V. All rights reserved.

Tuning the photophysical behavior of luminescent cyclam derivatives by cation binding and excited state redox potential

The emission from two photoactive 14-membered macrocyclic ligands, 6-((naphthalen-1-ylmethyl)-amino)trans-6,13-dimethyl- 13-amino- 1,4,8,11 -tetraaza-cyclotetradecane (L-1) and 6-((anthracen-9-ylmethyl)-amino)trans-6,13 -dimethyl - 13 -amino- 1,4,8, 1 1-tetraaza-cyclotetradecane (L-2) is strongly quenched by a photoinduced electron transfer (PET) mechanism involving amine lone pairs as electron donors. Time-correlated single photon counting (TCSPC), multiplex transient grating (TG), and fluorescence upconversion (FU) measurements were performed to characterize this quenching mechanism. Upon complexation with the redox inactive metal ion, Zn(II), the emission of the ligands is dramatically altered, with a significant increase in the fluorescence quantum yields due to coordination-induced deactivation of the macrocyclic amine lone pair electron donors. For [ZnL2](2+), the substituted exocyclic amine nitrogen, which is not coordinated to the metal ion, does not quench the fluorescence due to an inductive effect of the proximal divalent metal ion that raises the ionization potential. However, for [ZnL1](2+), the naphthalene chromophore is a sufficiently strong excited-state oxidant for PET quenching to occur.

Scalar turbulent behavior in the roughness sublayer of an Amazonian forest.

An important current problem in micrometeorology is the characterization of turbulence in the roughness sublayer (RSL), where most of the measurements above tall forests are made. There, scalar turbulent fluctuations display significant departures from the predictions of Monin?Obukhov similarity theory (MOST). In this work, we analyze turbulence data of virtual temperature, carbon dioxide, and water vapor in the RSL above an Amazonian forest (with a canopy height of 40 m), measured at 39.4 and 81.6 m above the ground under unstable conditions. We found that dimensionless statistics related to the rate of dissipation of turbulence kinetic energy (TKE) and the scalar variance display significant departures from MOST as expected, whereas the vertical velocity variance follows MOST much more closely. Much better agreement between the dimensionless statistics with the Obukhov similarity variable, however, was found for the subset of measurements made at a low zenith angle Z, in the range 0°  <  |Z|  <  20°. We conjecture that this improvement is due to the relationship between sunlight incidence and the ?activation?deactivation? of scalar sinks and sources vertically distributed in the forest. Finally, we evaluated the relaxation coefficient of relaxed eddy accumulation: it is also affected by zenith angle, with considerable improvement in the range 0°  <  |Z|  <  20°, and its values fall within the range reported in the literature for the unstable surface layer. In general, our results indicate the possibility of better stability-derived flux estimates for low zenith angle ranges.

Scalar turbulent behavior in the roughness sublayer of an Amazonian forest.

An important current problem in micrometeorology is the characterization of turbulence in the roughness sublayer (RSL), where most of the measurements above tall forests are made. There, scalar turbulent fluctuations display significant departures from the predictions of Monin?Obukhov similarity theory (MOST). In this work, we analyze turbulence data of virtual temperature, carbon dioxide, and water vapor in the RSL above an Amazonian forest (with a canopy height of 40?m), measured at 39.4 and 81.6?m above the ground under unstable conditions. We found that dimensionless statistics related to the rate of dissipation of turbulence kinetic energy (TKE) and the scalar variance display significant departures from MOST as expected, whereas the vertical velocity variance follows MOST much more closely. Much better agreement between the dimensionless statistics with the Obukhov similarity variable, however, was found for the subset of measurements made at a low zenith angle Z, in the range 0°??deactivation? of scalar sinks and sources vertically distributed in the forest. Finally, we evaluated the relaxation coefficient of relaxed eddy accumulation: it is also affected by zenith angle, with considerable improvement in the range 0°??

The Behavior of Hydroxyl Units of Synthetic Goethite and its Dehydroxylated Product Hematite

The behavior of the hydroxyl units of synthetic goethite and its dehydroxylated product hematite was characterized using a combination of Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) during the thermal transformation over a temperature range of 180-270 degrees C. Hematite was detected at temperatures above 200 degrees C by XRD while goethite was not observed above 230 degrees C. Five intense OH vibrations at 3212-3194, 1687-1674, 1643-1640, 888-884 and 800-798 cm(-1), and a H2O vibration at 3450-3445 cm(-1) were observed for goethite. The intensity of hydroxyl stretching and bending vibrations decreased with the extent of dehydroxylation of goethite. Infrared absorption bands clearly show the phase transformation between goethite and hematite: in particular. the migration of excess hydroxyl units from goethite to hematite. Two bands at 536-533 and 454-452 cm(-1) are the low wavenumber vibrations of Fe-O in the hematite structure. Band component analysis data of FTIR spectra support the fact that the hydroxyl units mainly affect the a plane in goethite and the equivalent c plane in hematite.

Let's Dance: A Language for Service Behavior Modeling

In Service-Oriented Architectures (SOAs), software systems are decomposed into independent units, namely services, that interact with one another through message exchanges. To promote reuse and evolvability, these interactions are explicitly described right from the early phases of the development lifecycle. Up to now, emphasis has been placed on capturing structural aspects of service interactions. Gradually though, the description of behavioral dependencies between service interactions is gaining increasing attention as a means to push forward the SOA vision. This paper deals with the description of these behavioral dependencies during the analysis and design phases. The paper outlines a set of requirements that a language for modeling service interactions at this level should fulfill, and proposes a language whose design is driven by these requirements.

Multiple-choice versus short-response items: Differences in omit behavior

The overall rate of omission of items for 28,331 17 year old Australian students on a high stakes test of achievement in the common elements or cognitive skills of the senior school curriculum is reported for a subtest in multiple choice format and a subtest in short response format. For the former, the omit rates were minuscule and there was no significant difference by gender or by type of school attended. For the latter, where an item can be 'worth' up to five times that of a single multiple choice item, the omit rates were between 10 and 20 times that for multiple choice and the difference between male and female omit rate was significant as was the difference between students from government and non-government schools. For both formats, females from single sex schools omitted significantly fewer items than did females from co-educational schools. Some possible explanations of omit behaviour are alluded to.

Examining the antecedents and consequences of ritualized fan behavior [Abstract]

One of the features of the sporting industry is the ritualized way in which it is consumed across the world. Fans of every sport have rituals and superstitions to help them enjoy the spectacle, socialize with other like-minded fans, and reduce some of the anxiety of watching their team play. These rituals include dress, barracking styles and pre and post match behaviors. What is not known are the factors that lead fans to engage in ritual behaviors and what relationship rituals have with desirable outcomes such as increased attendance, attitudinal loyalty or satisfaction. Given that some ritual behaviors are clearly undesirable, (e.g., hooliganism), understanding these relationships is important to managers who may be questioning whether rituals should be encouraged. Although ritualized behavior amongst fans is clearly visible, the symbolic and emotional nature of ritual poses challenges to researchers. Most previous ritual research is exploratory and qualitative in nature. This study, however, uses a behavior-based scale to measure fan ritual and relates it to desirable outcomes such as commitment and attendance. Over 2,000 season ticket holders of a football (soccer) team in Australia’s professional A-League competition were surveyed to investigate the antecedents and consequences of fan ritual behavior. Cluster analysis was used to explore the characteristics of respondents, and it revealed that those fans that engage in ritual behavior also differed on many other demographic and attitudinal dimensions. The associations between ritual and psychological commitment, and ritual and attendance are positive and significant. When used in conjunction with other constructs, fan ritual also improves the explanation of attendance behavior. The findings support previous research that found a significant and positive relationship between team identification, involvement and attendance, and extend previous research by finding a significant and positive relationship between rituals and attendance. For sports marketing practitioners, the results indicate the importance of developing and managing consumption rituals tied to game day attendance, with a view to generating uncommon loyalty.

Sharing knowledge at work : macro, social and relational individual influences on individual behavior

The impact of relations between an organization and its workers and the relations among workers on individual knowledge generation and sharing practices has not, to date, been addressed in an integrated way. This paper discusses the findings of a study analyzing issues at macro, locally-constructed and micro levels in a public sector organization, to identify and integrate the complex sets of mediators. Key factors were found to include (a) the contested nature of the process of knowledge construction, (b) the worker’s experience of the organization’s internal environment, (c) how the organization is understood to value knowledge sharing, (d) relations with colleagues, and (e) the perceived outcomes of knowledge sharing behaviors. Implications for practice are discussed.