Promoter Effect of Pt on Zr Catalysts to Increase the Conversion of Furfural to γ-Valerolactone Using Batch and Continuous Flow Reactors: Influence of the Way of the Incorporation of the Pt Sites.

The valorization of biomass and its transformation into fuels are highly interesting due to the abundance of biomass and its almost neutral carbon emissions. In this article, we show the production of γ-valerolactone (GVL), a valuable product, from furfural (FF), a compound that can be easily obtained from biomass. This FF to GVL transformation involves a catalytic cascade reaction with two hydrogenation steps. Pt and/or Zr supported on sepiolite catalysts have been prepared and tested in the FF transformation reaction. A physical mixture of a Zr-based and a Pt-based catalyst has reached a yield to GVL of ca. 50% after 16 h at 180 °C. This performance largely exceeds that obtained by each of the single Pt or single Zr metal catalysts independently, showing a strong synergistic effect. These data suggest that each metal (Pt and Zr) plays an important and complementary role in different reaction steps. Furthermore, the physical mixture appears to be much more efficient than bimetallic Pt/Zr catalysts synthesized with the same amount of metals. The role of the type of acidity and the oxidation state of the surface platinum species on the catalytic performance has been discussed. Moreover, this reaction has been carried out in batch and continuous flow reactors, and a comparative study between the two operation modes has been undertaken. A certain correlation between the catalytic results obtained by both operation modes has been found.

Aquivion-Based Spray Freeze-Dried Composite Materials for the Cascade Production of γ-Valerolactone.

The development of multifunctional catalysts is a necessary step to effectively carry out one-pot cascade reactions, such as that from furfural to γ-valerolactone. This research effort faces the challenge posed by the intrinsic limit of how many kinds of catalytic sites a single material can bear. In this work, the application of Spray-Freeze Drying (SFD) as a synthetic technique for the preparation of a wide range of innovative composite multi-functional catalysts is reported. Herein we show that by the proper combination of Aquivion as a highly active Brønsted acid catalyst and metal oxides as both support materials and Lewis acids (LAS) enable to achieve highly unique efficient and effective dual acid composite catalysts that are able to carry out the cascade reaction from furfural to γ-valerolactone. The dual catalytic system comprised of Aq/ZrO2 with 30 % polymer content prepared via spray-freeze drying exhibited GVL yields of 25 % after only 2 h at 180 °C and a remarkably high productivity of 4470 µmolGVL gCat -1 h-1, one of the highest reported results. Mechanistic studies based on experimental and advanced characterisation and spectroscopic techniques, such as, SEM, TEM, 15N MAS NMR and 19F MAS NMR indicate that activity arises from the proper tuning of BAS/LAS (Brønsted Acid Site/Lewis Acid Site) acidic properties.