An Insight into the Role of Reactant Structure Effect in Pd/C Catalysed Aldehyde Hydrogenation.

The different activity of a 1% Pd/carbon catalyst towards aromatic and aliphatic aldehydes hydrogenation has been explored by 13C NMR relaxation. The ratio between T1 relaxation times of adsorbed (ads) and free diffusing (bulk) molecules (T1ads/T1bulk) can be used as an indicator of the relative strength of interaction between the reactant and the catalytic surface, where the lower the T1ads/T1bulk, the higher the adsorption strength. It can be seen that 1% Pd/carbon showed a reverse catalytic behaviour towards benzaldehyde and octanal hydrogenation, which can be explained by analysing the T1 relaxation times related to each substrate in the presence of the catalyst. Comparing and correlating the different T1ads/T1bulk values, we were able to prove that the different catalytic results mainly depend on the contrasting adsorption behaviour of substrates on the catalyst. Moreover, the role of the solvent has been disclosed, as NMR results revealed that the adsorption of the reactants was strongly affected by the choice of solvent, which is revealed to be critical in modulating catalytic activity. As a consequence, T1ads/T1bulk measurements can provide a guide to the selection of appropriate reaction conditions for improving catalytic activity.

Structure-Reactivity Correlations in Vanadium-Containing Catalysts for One-Pot Glycerol Oxidehydration to Acrylic Acid.

The design of suitable catalysts for the one-pot conversion of glycerol into acrylic acid (AA) is a complex matter, as only fine-tuning of the redox and acid properties makes it possible to obtain significant yields of AA. However, fundamental understanding behind the catalytic phenomenon is still unclear. Structure-reactivity correlations are clearly behind these results, and acid sites are involved in the dehydration of glycerol into acrolein with vanadium as the main (or only) redox element. For the first time, we propose an in-depth study to shed light on the molecular-level relations behind the overall catalytic results shown by several types of V-containing catalysts. Different multifunctional catalysts were synthesized, characterized (>X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, temperature-programmed reduction, and temperature-programmed desorption of ammonia), and tested in a flow reactor. Combining the obtained results with those acquired from an in situ FTIR spectroscopy study with acrolein (a reaction intermediate), it was possible to draw conclusions on the role played by the various physicochemical features of the different oxides in terms of the adsorption, surface reactions, and desorption of the reagents and reaction products.

Multielement crystalline and pseudocrystalline oxides as efficient catalysts for the direct transformation of glycerol into acrylic acid.

Glycerol surplus from biodiesel synthesis still represents a major problem in the biofuel production chain. Meanwhile, those in the acrylic acid market are looking for new processes that are able to offer viable alternatives to propylene-based production. Therefore, acrylic acid synthesis from glycerol could be an effective solution to both issues. Among the viable routes, one-pot synthesis theoretically represents the most efficient process, but it is also highly challenging from the catalyst design standpoint. A new class of complex W--Mo--V mixed-oxide catalysts, which are strongly related to the hexagonal tungsten bronze structure, able to directly convert glycerol into acrylic acid with yields of up to 51 % are reported.

On the chemistry of ethanol on basic oxides: revising mechanisms and intermediates in the Lebedev and Guerbet reactions.

A common way to convert ethanol into chemicals is by upgrading it over oxide catalysts with basic features; this method makes it possible to obtain important chemicals such as 1-butanol (Guerbet reaction) and 1,3-butadiene (Lebedev reaction). Despite their long history in chemistry, the details of the close inter-relationship of these reactions have yet to be discussed properly. Our present study focuses on reactivity tests, in situ diffuse reflectance infrared Fourier transform spectroscopy, MS analysis, and theoretical modeling. We used MgO as a reference catalyst with pure basic features to explore ethanol conversion from its very early stages. Based on the obtained results, we formulate a new mechanistic theory able to explain not only our results but also most of the scientific literature on Lebedev and Guerbet chemistry. This provides a rational description of the intermediates shared by the two reaction pathways as well as an innovative perspective on the catalyst requirements to direct the reaction pathway toward 1-butanol or butadiene.