Synthesis of reaction-adapted zeolites as methanol-to-olefins catalysts with mimics of reaction intermediates as organic structure-directing agents

[EN] Catalysis with enzymes and zeolites have in common the presence of well-defined single active sites and pockets/cavities where the reaction transition states can be stabilized by longer-range interactions. We show here that for a complex reaction, such as the conversion of methanol-to-olefins (MTO), it is possible to synthesize reaction-adapted zeolites by using mimics of the key molecular species involved in the MTO mechanism. Effort has focused on the intermediates of the paring mechanism because the paring is less favoured energetically than the side-chain route. All the organic structure-directing agents based on intermediate mimics crystallize cage-based small-pore zeolitic materials, all of them capable of performing the MTO reaction. 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Republicanism and the political economy of democracy

Europe is experiencing rapidly accelerating poverty and social exclusion, following half a decade of financial crisis and austerity politics. The key problem behind Europe's malaise, in our view, is the economic disenfranchisement of large parts of its population in the winner-takes-all-society. This article proposes that we examine the contribution of republican political theory as a distinctive approach that provides us with the conceptual and normative resources to reclaim what we call the political economy of democracy, the constellation of political and economic institutions aimed at promoting broad economic sovereignty and individuals' capacities to govern their own lives. This article identifies three key ideas that together constitute a distinctively republican approach to political economy: (1) establish an economic floor; (2) impose an economic ceiling to counter excess economic inequality; and (3) democratize the governance and regulation of the main economic institutions

Selective accurate-mass-based analysis of 11 oxy-PAHs on atmospheric particultate matter by pressurized liquid extraction followed by highperformance liquid chromatography and magnetic sector mass spectrometry

An innovative analytical method based on high-performance liquid chromatography and atmospheric pressure chemical ionization magnetic sector mass spectrometry was developed and optimized to determine trace concentrations of 11 compounds belonging to the group of the seldom-analyzed oxy-PAHs (phenanthrene-9,10-dione, chrysene-5,6-dione, benzo[a]pyrene-4,5-dione, benzo[a]pyrene-1,6-dione, benzo[a]pyrene-3,6-dione, benzo[a]pyrene-6,12-dione, 4-oxa-benzo[def]chrysene-5-one, pyrene-1-carboxaldehyde, benzo[de]anthracene-7-one, benzo[a]anthracene-7,12-dione, and napthacene-5,12-dione) on airborne particulate matter (PM10). The mass spectrometer was operated in multiple ion detection mode, allowing for selective accurate mass detection (mass resolution of 12,000 full width at half maximum) of the oxy-PAHs characteristic ions. Optimization of both the vaporizer (450 degrees C) and capillary temperature (350 degrees C) resulted into instrumental detection limits in the range between 7 (benzo[a]pyrene-1,6-dione) and 926 pg (benzo[a]anthracene-7,12-dione). The advanced pressurized liquid extraction (PLE) and the more traditionally used ultrasonic extraction (USE) were compared using ethyl acetate as an extraction solvent. For both techniques, high recoveries from spiked quartz fiber filters (PLE, 82-110%; USE, 67-97%) were obtained. Recoveries obtained from real PM10 samples were also high (76-107%), and no significant matrix effects (ME) on the ionization process (enhancement or suppression) were found (ME, 89-123%). Method limits of quantification (S/N=10) were in the range between 2 and 336 pg/m(3). This method was used to analyze real PM samples collected at several urban and rural locations in the Antwerp area. For the first time, concentrations for Belgium are provided. Concentrations of individual oxy-PAHs are in the lower pictograms per cubic meter to 6 ng/m(3) range. High concentration differences between individual compounds are found as exemplified by the 75th percentile of the phenanthrene-9,10-dione and benzo[de]anthracene-7-one concentrations being a factor of 4 to 22 higher compared with the other target oxy-PAHs

Experimental and theoretical IR study of methanol and ethanol converson over H-SAPO-34

Theoretical and experimental IR data are combined to gain insight into the methanol and ethanol conversion over an acidic H-SAPO-34 catalyst. The theoretical simulations use a large finite cluster and the initial physisorption energy of both alcohols is calculated. Dispersive contributions turn out to be vital and ethanol adsorbs stronger than methanol with approximately 14 kJ mol−1. Calculated IR spectra of the alcohols and of formed aromatic cations upon conversion are also analyzed and support the peak assignment of the experimental in situ DRIFT spectra, in particular for the C–H and C C regions. Theoretical IR spectra of the gas phase compounds are compared with those of the molecules loaded in a SAPO cluster and the observed shifts of the peak positions are discussed. To get a better understanding of these framework–guest interactions, a new theoretical procedure is proposed based on a normal mode analysis. A cumulative overlap function is defined and enables the characterization of individual peaks as well as induced frequency shifts upon adsorption