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.

A High Pressure Operando Spectroscopy Examination of Bimetal Interactions in 'Metal Efficient' Palladium/In2 O3 /Al2 O3 Catalysts for CO2 Hydrogenation.

CO2 hydrogenation to methanol has the potential to serve as a sustainable route to a wide variety of hydrocarbons, fuels and plastics in the quest for net zero. Synergistic Pd/In2 O3 (Palldium on Indium Oxide) catalysts show high CO2 conversion and methanol selectivity, enhancing methanol yield. The identity of the optimal active site for this reaction is unclear, either as a Pd-In alloy, proximate metals, or distinct sites. In this work, we demonstrate that metal-efficient Pd/In2 O3 species dispersed on Al2 O3 can match the performance of pure Pd/In2 O3 systems. Further, we follow the evolution of both Pd and In sites, and surface species, under operando reaction conditions using X-ray Absorption Spectroscpy (XAS) and infrared (IR) spectroscopy. In doing so, we can determine both the nature of the active sites and the influence on the catalytic mechanism.

Insights into the Electrochemical Reduction of 5-Hydroxymethylfurfural at High Current Densities.

The electrocatalytic reduction of 5-hydroxymethylfurfural (HMF) is highly selective to 2,5-bishydroxymethylfuran (BHMF) at pH=9.2, diluted HMF solutions, and low current densities. In this work, the electrochemical reduction of 0.05 m HMF solutions was investigated in the 5-50 mA cm-2 current density range over an AgCu foam electrocatalyst. The selectivity towards the formation of BHMF or the dimerization depended on the current density, likely due to differences in the electrode potential, and on the reaction time. Operating at current densities of 40-50 mA cm-2 allowed to find a trade-off between HMF and H2 O activation, achieving 85 % BHMF selectivity and fostering the productivity (0.567 mmol cm-2 h-1 ), though co-producing H2 . The electrochemical characterization by Tafel slopes and electrochemical impedance spectroscopy indicated that the HMF reduction was kinetically favored in comparison to the hydrogen evolution reaction and that the process was limited by charge transfer.

AgCu Bimetallic Electrocatalysts for the Reduction of Biomass-Derived Compounds.

The electrochemical transformation of biomass-derived compounds (e.g., aldehyde electroreduction to alcohols) is gaining increasing interest due to the sustainability of this process that can be exploited to produce value-added products from biowastes and renewable electricity. In this framework, the electrochemical conversion of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) is studied. Nanostructured Ag deposited on Cu is an active and selective electrocatalyst for the formation of BHMF in basic media. However, this catalyst deserves further research to elucidate the role of the morphology and size of the coated particles in its performance as well as the actual catalyst surface composition and its stability. Herein, Ag is coated on Cu open-cell foams by electrodeposition and galvanic displacement to generate different catalyst morphologies, deepening on the particle growth mechanism, and the samples are compared with bare Ag and Cu foams. The chemical-physical and electrochemical properties of the as-prepared and spent catalysts are correlated to the electroactivity in the HMF conversion and its selectivity toward the formation of BHMF during electroreduction. AgCu bimetallic nanoparticles or dendrites are formed on electrodeposited and displaced catalysts, respectively, whose surface is Cu-enriched along with electrochemical tests. Both types of bimetallic AgCu particles evidence a superior electroactive surface area as well as an enhanced charge and mass transfer in comparison with the bare Ag and Cu foams. These features together with a synergistic role between Ag and Cu superficial active sites could be related to the twofold enhanced selectivity of the Ag/Cu catalysts for the selective conversion of HMF to BHMF, that is, >80% selectivity and ∼ 100% conversion, and BHMF productivity values (0.206 and 0.280 mmol cm-2 h-1) ca. 1.5-3 times higher than those previously 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.

Highly conductive Ni steam reforming catalysts prepared by electrodeposition.

New highly conductive, active and stable Ni steam reforming catalysts were prepared through a method consisting of the calcination of a hydrotalcite-like compound electrodeposited in a single step on FeCrAlloy foams.