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.

Anodizing Tungsten Foil with Ionic Liquids for Enhanced Photoelectrochemical Applications.

This research examines the influence of adding a commercial ionic liquid to the electrolyte during the electrochemical anodization of tungsten for the fabrication of WO3 nanostructures for photoelectrochemical applications. An aqueous electrolyte composed of 1.5 M methanesulfonic acid and 5% v/v [BMIM][BF4] or [EMIM][BF4] was used. A nanostructure synthesized in an ionic-liquid-free electrolyte was taken as a reference. Morphological and structural studies of the nanostructures were performed via field emission scanning electron microscopy and X-ray diffraction analyses. Electrochemical characterization was carried out using electrochemical impedance spectroscopy and a Mott-Schottky analysis. From the results, it is highlighted that, by adding either of the two ionic liquids to the electrolyte, well-defined WO3 nanoplates with improved morphological, structural, and electrochemical properties are obtained compared to samples synthesized without ionic liquid. In order to evaluate their photoelectrocatalytic performance, the samples were used as photocatalysts to generate hydrogen by splitting water molecules and in the photoelectrochemical degradation of methyl red dye. In both applications, the nanostructures synthesized with the addition of either of the ionic liquids showed a better performance. These findings confirm the suitability of ionic liquids, such as [BMIM][BF4] and [EMIM][BF4], for the synthesis of highly efficient photoelectrocatalysts via electrochemical anodization.

V-Porphyrins Encapsulated or Supported on Siliceous Materials: Synthesis, Characterization, and Photoelectrochemical Properties.

Metalloporphyrin-containing mesoporous materials, named VTPP@SBA, were prepared via a simple anchoring of vanadyl porphyrin (5,10,15,20-Tetraphenyl-21H,23H-porphine vanadium(IV) oxide) through a SBA-15-type mesoporous material. For comparison, vanadyl porphyrin was also impregnated on SiO2 (VTPP/SiO2). The characterization results of catalysts by XRD, FTIR, DR-UV-vis, and EPR confirm the incorporation of vanadyl porphyrin within the mesoporous SBA-15. These catalysts have also been studied using electrochemical and photoelectrochemical methods. Impedance measurements confirmed that supporting the porphyrin in silica improved the electrical conductivity of samples. In fact, when using mesoporous silica, current densities associated with oxidation/reduction processes appreciably increased, implying an enhancement in charge transfer processes and, therefore, in electrochemical performance. All samples presented n-type semiconductivity and provided an interesting photoelectrocatalytic response upon illumination, especially silica-supported porphyrins. This is the first time that V-porphyrin-derived materials have been tested for photoelectrochemical applications, showing good potential for this use.

Original Approach to Synthesize TiO2/ZnO Hybrid Nanosponges Used as Photoanodes for Photoelectrochemical Applications.

In the present work, TiO2/ZnO hybrid nanosponges have been synthesized for the first time. First, TiO2 nanosponges were obtained by anodization under hydrodynamic conditions in a glycerol/water/NH4F electrolyte. Next, in order to achieve the anatase phase of TiO2 and improve its photocatalytic behaviour, the samples were annealed at 450 °C for 1 h. Once the TiO2 nanosponges were synthesized, TiO2/ZnO hybrid nanosponges were obtained by electrodeposition of ZnO on TiO2 nanosponges using different temperatures, times, and concentrations of zinc nitrate (Zn(NO3)2). TiO2/ZnO hybrid nanosponges were used as photoanodes in photoelectrochemical water splitting tests. The results indicate that the photoelectrochemical response improves, in the studied range, by increasing the temperature and the Zn(NO3)2 concentration during the electrodeposition process, obtaining an increase in the photoelectrochemical response of 141% for the TiO2/ZnO hybrid nanosponges electrodeposited at 75 °C with 10 mM Zn(NO3)2 for 15 min. Furthermore, morphological, chemical, and structural characterization was performed by Field Emission Scanning Electron Microscopy (FE-SEM) with Energy Dispersive X-Ray spectroscopy (EDX), Raman Confocal Laser Spectroscopy, X-Ray Photoelectron Spectroscopy (XPS), and Grazing Incidence X-Ray Diffraction (GIXRD).

TiO2 Nanostructures for Photoelectrocatalytic Degradation of Acetaminophen.

Advanced oxidation processes driven by renewable energy sources are gaining attention in degrading organic pollutants in waste waters in an efficient and sustainable way. The present work is focused on a study of TiO2 nanotubes as photocatalysts for photoelectrocatalytic (PEC) degradation of acetaminophen (AMP) at different pH (3, 7, and 9). In particular, different TiO2 photocatalysts were synthetized by stirring the electrode at different Reynolds numbers (Res) during electrochemical anodization. The morphology of the photocatalysts and their crystalline structure were evaluated by field emission scanning electron microscopy (FESEM) and Raman confocal laser microscopy (RCLM). These analyses revealed that anatase TiO2 nanotubes were obtained after anodization. In addition, photocurrent densities versus potential curves were performed in order to characterize the electrochemical properties of the photocatalysts. These results showed that increasing the Re during anodization led to an enhancement in the obtained photocurrents, since under hydrodynamic conditions part of the initiation layer formed over the tubes was removed. PEC degradation of acetaminophen was followed by ultraviolet-visible absorbance measurements and chemical oxygen demand tests. As drug mineralization was the most important issue, total organic carbon measurements were also carried out. The statistical significance analysis established that acetaminophen PEC degradation improved as hydrodynamic conditions linearly increased in the studied range (Re from 0 to 600). Additionally, acetaminophen conversion had a quadratic behavior with respect to the reaction pH, where the maximum conversion value was reached at pH 3. However, in this case, the diversity of the byproducts increased due to a different PEC degradation mechanism.