ABSTRACT
Methanol adsorption over both supported NiSn Nps and analogous NiSn catalyst prepared by impregnation was studied by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to gain insights into the basis of hydrogen production from methanol steam reforming. Different intermediate species such as methoxides with different geometry (bridge and monodentate) and formate species were identified after methanol adsorption and thermal desorption. It is proposed that these species are the most involved in the methanol steam reforming reaction and the major presence of metal-support interface sites in supported NiSn Nps leads to higher production of hydrogen. On the basis of these results, a plausible reaction mechanism was elucidated through the correlation between the thermal stability of these species and the evolution of the effluent gas released. In addition, it was demonstrated that DME is a secondary product generated by condensation of methoxides over the acid sites of alumina support in an acid-catalyzed reaction.
ABSTRACT
In the last ten years, there has been an acceleration in the pace at which new catalysts for the water-gas shift reaction are designed and synthesized. Pt-based catalysts remain the best solution when only activity is considered. However, cost, operation temperature, and deactivation phenomena are important variables when these catalysts are scaled in industry. Here, a new catalyst, Au/TiO2-Y2O3, is presented as an alternative to the less selective Pt/oxide systems. Experimental and theoretical techniques are combined to design, synthesize, characterize and analyze the performance of this system. The mixed oxide demonstrates a synergistic effect, improving the activity of the catalyst not only at large-to-medium temperatures but also at low temperatures. This effect is related to the homogeneous dispersion of the vacancies that act both as nucleation centers for smaller and more active gold nanoparticles and as dissociation sites for water molecules. The calculated reaction path points to carboxyl formation as the rate-limiting step with an activation energy of 6.9 kcal mol-1, which is in quantitative agreement with experimental measurements and, to the best of our knowledge, it is the lowest activation energy reported for the water-gas shift reaction. This discovery demonstrates the importance of combining experimental and theoretical techniques to model and understand catalytic processes and opens the door to new improvements to reduce the operating temperature and the deactivation of the catalyst.
ABSTRACT
In this work, a study for understanding the role played by [ClBmim], [BF4Bmim], [PF6Bmim], and [CH3SO3Bmim] ionic liquids (ILs) in the synthesis of zeolites is presented. The use of [ClBmim] and [CH3SO3Bmim] ILs, as reported earlier [ Chem. Eur. J. 2013 , 19 , 2122 ] led to the formation of MFI or BEA type zeolites. Contrary, [BF4Bmim] and [PF6Bmim] ILs did not succeed in organizing the Si-Al network into a zeolite structure. To try to explain these results, a series of quantum mechanical calculations considering monomers ([XBmim]) and dimers ([XBmim]2) by themselves and plus cosolvent (water or ethanol) were carried out, where X ≡ Cl(-), BF4(-), PF6(-), or CH3SO3(-). Our attention was focused on the similarities and differences among the two types of cosolvents and the relation between the structure and the multiple factors defining the interactions among the ILs and the cosolvent. Although a specific pattern based on local structures explaining the different behavior of these ILs as a zeolite structuring template was not found, the calculated interaction energies involving the Cl(-) and CH3SO3(-) anions were very close and larger than those for BF4(-) and PF6(-) species. These differences in energy can be used as an argument to describe their different behavior as structure directing agents. Moreover, the topology of the cosolvent is also an ingredient to take into account for a proper understanding of the results.
ABSTRACT
This study reports the use of 1-butyl-3-methyl imidazolium methanesulfonate ionic liquid as a template in the synthesis of zeolites. It is found that the silicon source determines the formation of beta (BEA), mordenite framework inverted (MFI), or analcime (ANA) zeolites. Depending on this source, different preorganized complexes are obtained that drive the formation of the different zeolite structures. In the presence of ethanol, the ionic liquid form preorganized complexes that drive the formation of MFI. In its absence, BEA is obtained. Whereas, the large amount of sodium present when using sodium metasilicate leads to ANA formation. A molecular simulation study of the relative stability of the template-framework system and location of the template provides further insight into the mechanism of synthesis.
ABSTRACT
Trimethylamine (TMA) and ammonia (NH(3)) were coadsorbed over a free extraframework aluminum (EFAL) HY zeolite, which allowed us to distinguish at least three different acidic hydroxyls in the faujasite structure.
ABSTRACT
The positions of nu8a and nu*(NH) bands in the spectrum of protonated 2,6-dimethylpyridine vary with the strength of Brønsted acidity: the higher the nu*(NH) wavenumber and the lower the nu8a wavenumber, the stronger the acidity. The results obtained with 2,6-dimethylpyridine adsorption correlate with those obtained by CO adsorption experiments on a series of faujasite zeolites (LiHNaY, KHNaY, HY, HY(SA), HNaX). These relations were extended to gamma-Al2O3 having weak Brønsted acidity, not detected by pyridine and hardly detected by CO. The number (0.1 per nm2) and the strength (corresponding to delta nu (OH) by CO = 155 cm(-1)) of the most acidic OH groups of Al2O3, as well as the position of the corresponding nu (OH) band (<3700 cm(-1)) are deduced from 2,6-dimethylpyridine adsorption experiments.
