• Energy Research

AbstractDonor–acceptor dyes are a well‐established class of photosensitizers, used to enhance visible‐light harvesting in solar cells and in direct photocatalytic reactions, such as H2 production by photoreforming of sacrificial electron donors (SEDs). Amines—typically triethanolamine (TEOA)—are commonly employed as SEDs in such reactions. Dye‐sensitized photoreforming of more sustainable, biomass‐derived alcohols, on the other hand, was only recently reported by using methanol as the electron donor. In this work, several rationally designed donor–acceptor dyes were used as sensitizers in H2 photocatalytic production, comparing the efficiency of TEOA and EtOH as SEDs. In particular, the effect of hydrophobic chains in the spacer and/or the donor unit of the dyes was systematically studied. The H2 production rates were higher when TEOA was used as SED, whereas the activity trends depended on the SED used. The best performance was obtained with TEOA by using a sensitizer with just one bulky hydrophobic moiety, propylenedioxythiophene, placed on the spacer unit. In the case of EtOH, the best‐performing sensitizers were the ones featuring a thiazolo[5,4‐d]thiazole internal unit, needed for enhancing light harvesting, and carrying alkyl chains on both the donor part and the spacer unit. The results are discussed in terms of reaction mechanism, interaction with the SED, and structural/electrochemical properties of the sensitizers.

Ni(x wt.%) Cu(y wt.%)/Al2O3 samples were investigated as active and thermally stable catalysts for methanol and ethanol steam reforming. XRD data clearly evidenced the formation of a NiCu alloy under the adopted preparation procedure. The bimetallic systems exhibited improved activity in the methanol steam reforming with respect to the monometallic ones. The introduction of copper in the catalyst formulation showed a positive effect inhibiting the formation of methane, an undesirable by-product. On the other hand, in the ethanol steam reforming, the catalytic performance was less promising. Furthermore, the Ni : Cu ratio did not seem to affect the product distribution. However, enhanced stability was observed in the two subsequent run-up experiments, indicating the positive role played by the bimetallic systems.

Photocatalytic reforming of renewable raw materials in aqueous solutions represents a valid possibility for the valorization of wastes from agricultural and industrial processes. In this study, we prepared TiO2 materials with different phase compositions by changing the urea/Ti molar ratio employed during the hydrothermal preparation method. After deposition of Pt nanoparticles, the photocatalytic H2 production was investigated using ethanol and glycerol as sustainable sacrificial agent. While anatase/rutile nanocomposites showed poor catalytic activity, the anatase/brookite nanocomposites showed more promising performances. Specifically, the anatase-rich materials showed the best performances on mass bases. When normalized with respect to the surface area of the photocatalysts, the activity continuously increased with the brookite content, indicating that exposed facets of brookite possess an intrinsic higher activity than that of the other polymorphs.

AbstractReview: 125 refs.

In this work a new mesoporous adsorbent material obtained from a natural, high abundant raw material and a high volume industrial by-product is presented. The material is consolidated by the gelling properties of alginate and by decomposition of sodium-bicarbonate controlled porosity at low temperatures (70-80°C) at different scale lengths. The structural, thermal, and morphological characterization shows that the material is a mesoporous organic-inorganic hybrid. The material is tested as adsorbent, showing high performances. Methylene blue, used as model pollutant, can be adsorbed and removed from aqueous solutions even at a high concentration with efficiency up to 94%. By coating the material with a 100 nm thin film of titania, good photodegradation performance (more than 20%) can be imparted. Based on embodied energy and carbon footprint of its primary production, the sustainability of the new obtained material is evaluated and quantified in respect to activated carbon as well. It is shown that the new proposed material has an embodied energy lower than one order of magnitude in respect to the one of activated carbon, which represents the gold standards. The versatility of the new material is also demonstrated in terms of its design and manufacturing possibilities In addition, this material can be printed in 3D. Finally, preliminary results about its ability to capture diesel exhaust particulate matter are reported. The sample exposed to diesel contains a large amount of carbon in its surface. At the best of our knowledge, this is the first time that hybrid porous materials are proposed as a new class of sustainable materials, produced to reduce pollutants in the wastewaters and in the atmosphere.

Among the 17 Sustainable Development Goals presented by the United Nations in 2015, great attention is devoted to the production of goods and chemicals by use of renewable raw materials, by recycling of products and by extensive use of renewable energy sources. In this context, photocatalysis attracted great attention for the possibility to exploit Solar light to promote the desired chemical reactions. Besides its use in degradation of pollutants and in the production of fuels, some efforts have been devoted in the development of photocatalytic processes for the synthesis of fine chemicals with high added-value. In this work, we investigated the sustainable photocatalytic synthesis of benzimidazole derivatives through a one-pot, tandem process starting from a nitro compound and ethanol. By a photocatalytic approach, ethanol is dehydrogenated producing the hydrogen required for reduction of nitro groups and the aldehyde required for cyclization and production of the benzimidazole unit. Co-doping of TiO2 with B and N is beneficial to increase the photocatalytic activity in H2 production from ethanol. The effect of various metal co-catalysts (Pt, Pd Ag, Cu) have been evaluated on H2 production rate and on selectivity in the synthesis of substituted benzimidazoles: Pt showed the highest selectivity in the desired products while Pd demonstrated a great activity for hydrodehalogenation, with potential interest for degradation of persistent pollutants.

Recently LaNi1−xFexO3 materials have been suggested as good candidates for cathodes for Intermediate Temperature Solid Oxide Fuel Cells. The electrical conductivity and the morphology of LaNi0.6Fe0.4O3 samples have been studied as a function of preparation route and calcination temperature. The conductivity, mainly electronic, strongly depends on the densification of the material, which is influenced by the preparation procedure. DFT calculations indicate that the conduction bands of LaNi0.6Fe0.4O3 are mainly made up of Fe and Ni 3d states and that there is a small bandwidth (2.3 eV) around the Fermi level. Moreover, a small polaron mechanism for the electronic conduction in this material is suggested by the simulations.