Ductile Metal Oxides Impregnated on Magnetite: New Catalysts in Organic Synthesis

Ramón's group has designed a simple, robust and inexpensive methodology for the impregnation of different transition metal oxides on the surface of magnetite and their use in catalysis.

Heavy metal release due to aging effect during zero valent iron nanoparticles remediation

Zero valent iron nanoparticles (nZVI) represent a promising agent for environmental remediation. Nevertheless, their application presents some limitations regarding their rapid oxidation and aggregation in the media. The aim of this study was to determine the effect that nZVI aging has in heavy metal remediation in water. Contaminants studied were Zn, Cd, Ni, Cu and Cr, which are typical elements found in ground and wastewater. Results show a high contaminant removal capacity by the nZVI in the first 2 h of reaction. Nevertheless, for longer reaction times, some of the metal ions that had already been adsorbed in the nZVI were delivered to the water. Cd and Ni show the maximum delivery percentages (65 and 27% respectively after 21 days of contact time). The starting delivery time was shortened when applying lower nZVI amounts. No re-dissolution of Cr was observed in any circumstance because it was the only element incorporated into the nanoparticles core, as TEM images showed. Contaminant release from nZVI is probably due to nanoparticles oxidation caused by aging, which produced a pH decrease and nZVI surface crystallization.

Effects of Ultrasound Irradiation on the Synthesis of Metal Oxide Nanostructures

High intensity ultrasound can be used for the production of novel nanomaterials, including metal oxides. According to previous works in this field, the most notable effects are consequence of acoustic cavitation. In this context, we have studied the preparation of different materials in the presence of ultrasound, including N-doped TiO2 nanopowder, NiTiO3 nanorods and MnOx thin films. Ultrasound did not show a significant effect in all the cases. Exclusively for NiTiO3 nanorods a reduction of the final particle size occurs upon ultrasonic irradiation. From these results, it can be concluded that the ultrasound irradiation does not always play a key role during the synthesis of metal oxides. The effects seem to be particularly relevant in those cases where mass transport is highly hindered and in those procedures that require the rupture of nanoparticle aggregates to obtain a homogenous dispersion.

Nanoclay-based Pigments: synthesis, characterization and application

Nanoclay-based pigments are promising colorants. They enhance the colorimetric properties of the dye giving more intense and saturated colours. In addition, they act as reinforce additive when they are dispersed into polymers. They can be applied in a wide variety of substrates: printing inks, textiles, acrylic paints and concrete; and more applications are being developed. One important advantage of the nanoclay-based pigments is the fact that they can be considered an ecological alternative to contaminant colorants, in contrast to some traditional inorganic pigments that contend heavy metal in their structure.

Quantum Dot-Sensitized Solar Cells Based on Directly Adsorbed Zinc Copper Indium Sulfide Colloids

Heavy metal-based quantum dots (QDs) have demonstrated to behave as efficient sensitizers in QD-sensitized solar cells (QDSSCs), as attested by the countless works and encouraging efficiencies reported so far. However, their intrinsic toxicity has arisen as a major issue for the prospects of commercialization. Here, we examine the potential of environmentally friendly zinc copper indium sulfide (ZCIS) QDs for the fabrication of liquid-junction QDSSCs by means of photoelectrochemical measurements. A straightforward approach to directly adsorb ZCIS QDs on TiO2 from a colloidal dispersion is presented. Incident photon-to-current efficiency (IPCE) spectra of sensitized photoanodes show a marked dependence on the adsorption time, with longer times leading to poorer performances. Cyclic voltammograms point to a blockage of the channels of the mesoporous TiO2 film by the agglomeration of QDs as the main reason for the decrease in efficiency. Photoanodes were also submitted to the ZnS treatment. Its effects on electron recombination with the electrolyte are analyzed through electrochemical impedance spectroscopy and photopotential measurements. The corresponding results bring out the role of the ZnS coating as a barrier layer preventing electron leakage toward the electrolyte, as argued in other QD-sensitized systems. The beneficial effect of the ZnS coating is ultimately reflected on the power conversion efficiency of complete devices, reaching values of 2 %. In a more general vein, through these findings, we aim to call the attention to the potentiality of this quaternary alloy, virtually unexplored as a light harvester for sensitized devices.

Alleviation of Zn toxicity by low water availability

Heavy metal contamination and drought are expected to increase in large areas worldwide. However, their combined effect on plant performance has been scantly analyzed. This study examines the effect of Zn supply at different water availabilities on morpho-physiological traits of Quercus suber L. in order to analyze the combined effects of both stresses. Seedlings were treated with four levels of zinc from 3 to 150 µM and exposed to low watering (LW) or high watering (HW) frequency in hydroponic culture, using a growth chamber. Under both watering regimes, Zn concentration in leaves and roots increased with Zn increment in nutrient solution. Nevertheless, at the highest Zn doses, Zn tissue concentrations were almost twice in HW than in LW seedlings. Functional traits as leaf photosynthetic rate and root hydraulic conductivity, and morphological traits as root length and root biomass decreased significantly in response to Zn supply. Auxin levels increased with Zn concentrations, suggesting the involvement of this phytohormone in the seedling response to this element. LW seedlings exposed to 150 µM Zn showed higher root length and root biomass than HW seedlings exposed to the same Zn dose. Our results suggest that low water availability could mitigate Zn toxicity by limiting internal accumulation. Morphological traits involved in the response to both stresses probably contributed to this response.

Sol–Gel Coordination Chemistry: Building Catalysts from the Bottom-Up

The development of synthetic routes for the tailoring of efficient silica-based heterogeneous catalysts functionalized with coordination complexes or metallic nanoparticles has become a important goal in chemistry. Most of these techniques have been based on postsynthetic treatments of preformed silicas. Nevertheless, there is an emerging approach, so-called sol–gel coordination chemistry, based on co-condensation during the sol–gel preparation of the hybrid material of the corresponding complex or nanoparticle modified with terminal trialkoxysilane groups with a silica source (such as tetraethoxysilane) and in the presence of an adequate surfactant. This method leads to the production of new mesoporous metal complex-silica materials, with the metallic functionality incorporated homogeneously into the structure of the hybrid material, improving the stability of the coordination complex (which is protected by the silica network) and reducing the leaching of the active phase. This technique also offers the actual possibility of functionalizing silica or other metal oxides for a wider range of applications, such as photonics, sensing, and biochemical functions.