Francesco Puzzo

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.

We investigated the synthesis of maleic anhydride by oxidehydration of a bio‐alcohol, 1‐butanol, as a possible alternative to the classical process of n‐butane oxidation. A vanadyl pyrophosphate catalyst was used to explore the one‐pot reaction, which involved two sequential steps: 1) 1‐butanol dehydration to 1‐butene, catalysed by acid sites, and 2) the oxidation of butenes to maleic anhydride, catalysed by redox sites. A non‐negligible amount of phthalic anhydride was also formed. The effect of different experimental parameters was investigated with chemically sourced 1‐butanol, and the results were then confirmed by using genuinely bio‐sourced 1‐butanol. In the case of bio‐1‐butanol, however, the purity of the product remarkably affected the yield of maleic anhydride. It was found that the reaction mechanism includes the oxidation of butenes to crotonaldehyde and the oxidation of the latter to either furan or maleic acid, both of which are transformed to produce maleic anhydride.