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. V for victory! The nature of the V species in vanadium‐containing materials affects the catalytic performance of the oxidehydration reaction of glycerol to acrylic acid. Structure–reactivity correlations are clearly behind these results. Herein, we 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.