CO(2)-free hydrogen can be produced from coal gasification power plants by pre-combustion decarbonisation and carbon dioxide capture. Potassium carbonate promoted hydrotalcite-based and alumina-based materials are cheap and excellent materials for high-temperature (300-500 degrees C) adsorption of CO(2), and particularly promising in the sorption-enhanced water gas shift (SEWGS) reaction. Alkaline promotion significantly improves CO(2) reversible sorption capacity at 300-500 degrees C for both materials. Hydrotalcites and promoted hydrotalcites, promoted magnesium oxide and promoted gamma-alumina were investigated by in situ analytical methods (IR spectroscopy, sorption experiments, X-ray diffraction) to identify structural and surface rearrangements. All experimental results show that potassium ions actually strongly interact with aluminium oxide centres in the aluminium-containing materials. This study unambiguously shows that potassium promotion of aluminium oxide centres in hydrotalcite generates basic sites which reversibly adsorb CO(2) at 400 degrees C.

On the basis of our previous H/D exchange studies devoted to the quantification of the number of Brönsted acid sites in solid acids, we report here an innovative approach to determine both the amount and the localization of Mo atoms inside the Mo/ZSM-5 catalyst, commonly used for the methane dehydroaromatization reaction. The influence of Mo introduction in the MFI framework was studied by means of BET, X-ray diffraction, 27Al magic angle spinning NMR, NH3 temperature-programmed desorption, and H/D isotopic exchange techniques. A dependence was found between the decrease of acidic OH groups and the Mo content. Depending on the Si/Al ratio of the zeolite, i.e., the proximity of two Brönsted acid sites, the Mo atoms substitute a different number of OH groups. Consequently, a chemical structure was proposed to describe the geometry of the Mo complex in the channels of the ZSM-5 zeolite.

In situ solid-state NMR spectroscopy was employed to study the kinetics of hydrogen/deuterium exchange and scrambling as well as (13)C scrambling reactions of labeled propane over Al(2)O(3)-promoted sulfated zirconia (SZA) catalyst under mild conditions (30-102 degrees C). Three competitive pathways of isotope redistribution were observed during the course of the reaction: (1) a regioselective H/D exchange between acidic protons of the solid surface and the deuterons of the methyl group of propane-1,1,1,3,3,3-d(6), monitored by in situ (1)H MAS NMR; (2) an intramolecular H/D scrambling between methyl deuterons and protons of the methylene group, without exchange with the catalyst surface, monitored by in situ (2)H MAS NMR; (3) a intramolecular (13)C scrambling, by skeletal rearrangement process, favored at higher temperatures, monitored by in situ (13)C MAS NMR. The activation energy of (13)C scrambling was estimated to be very close to that of (2)H scrambling, suggesting that these two processes imply a common transition state, responsible for both vicinal hydride migration and protonated cyclopropane formation. All pathways are consistent with a classical carbenium ion-type mechanism.

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The electrophilic reactivity of α,β‐unsaturated amides towards weak nucleophiles such as arenes and cyclohexane, initiated either with triflic acid (CF3SO3H) or with excess AlCl3, has been studied. The amides generally condense readily with aromatics in the presence of AlCl3 to give 3‐arylpropionamides and related compounds in excellent yields, while some amides also undergo selective ionic hydrogenation with cyclohexane to give saturated amides. The proposed mechanism of these reactions involves dicationic intermediates (superelectrophiles). The direct observation of a dicationic species (by low‐temperature NMR) is reported. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Acetylenic acids and esters as well as acetylenic ketones were efficiently and stereoselectively converted in one step to the corresponding vinyl triflates or fluorosulfonates in triflic or fluorosulfonic acids. Depending on the reaction conditions the E or the Z isomer can be obtained very conveniently in high isolated yields. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)