Li+ Insertion in Nanostructured TiO2 for Energy Storage

Nanostructured materials possess unique physical-chemical characteristics and have attracted much attention, among others, in the field of energy conversion and storage devices, for the possibility to exploit both their bulk and surface properties, enabling enhanced electron and ion transport, fast diffusion of electrolytes, and consequently high efficiency in the electrochemical processes. In particular, titanium dioxide received great attention, both in the form of amorphous or crystalline material for these applications, due to the large variety of nanostructures in which it can be obtained. In this paper, a comparison of the performance of titanium dioxide prepared through the oxidation of Ti foils in hydrogen peroxide is reported. In particular, two thermal treatments have been compared. One, at 150 °C in Ar, which serves to remove the residual hydrogen peroxide, and the second, at 450 °C in air. The material, after the treatment at 150 °C, results to be not stoichiometric and amorphous, while the treatment at 450 °C provide TiO2 in the anatase form. It turns out that not-stoichiometric TiO2 results to be a highly stable material, being a promising candidate for applications as high power Li-ion batteries, while the anatase TiO2 shows lower cyclability, but it is still promising for energy-storage devices

A flexible and portable harvesting-storage device by quasi-solid-state supercapacitor and dye-sensitized solar cell integration

In recent years the utilization of power in off grid conditions is dramatically increasing. For this reason research is putting much effort in obtaining improvements in energy storage devices efficiencies and in discovering alternatives concerning easiness of fabrication that can be industrially implemented. In this framework, integration of energy storage devices with energy harvesting systems is obtaining more and more significance since the amount of energy that can be stored especially in Electrochemical Double Layer Capacitors (EDLCs) is limited. To this purpose, herein we present an innovative flexible integrated device composed by a symmetrical aqueous EDLC and a TiO2 nanotubes-based Dye Sensitized Solar cell (DSSC). A UV photo-polymerized quasi-solid electrolyte was used in both sections. At first a self-standing flexible polymer matrix was fabricated starting from Bisphenol A ethoxylate dimethacrylate (BEMA) and poly (ethylene glycol) methyl ether methacrylate (PEGMA), adding a 3% by weight of 2hydroxy-2-methyl-1-phenyl-1-propanone (Darocur 1173) as photoinitiator. Then, the matrix was soaked in two different liquid electrolytes, a 2 M NaCl aqueous solution for the energy storage section and an Iodine-based liquid electrolyte for the DSSC unit. This is the first work in which this type of polymer electrolyte membrane is used for an EDLC. The electrodes were fabricated onto Stainless-steel and Titanium grids, for EDLC and DSSC respectively. TiO2 nanotubes were grown by means of anodic oxidation as photoanode semiconductor material, while EDLC active material was composed by 85% of graphene nanoplatelets and 15% of Acetylene Black. The harvesting-storage device (HSD) was sealed by a light-cured photo-polymerization method. The measured overall photon-to-electrical conversion and storage efficiency for the HSD was 1.02% under standard test conditions. This value increases for lower illumination conditions reaching 1.46% at 0.3 Sun

In-situ pulsed laser induced growth of CdS nanoparticles on ZnO nanorods surfaces

Herein we present a process for the in-situ growth of CdS nanoparticles using a pulsed laser irradiation. A Nd-YAG laser was applied to ZnO nanorods previously submerged in an aqueous precursor solution containing cadmium chloride and thiourea. For optimum values of the laser fluence, around 40 mJ/cm2 it was possible to fabricate a highly homogeneous film of CdS nanoparticles covering the ZnO nanorods surface. Cathodoluminescence measurements of the ZnO/CdS structure show the quenching of the ZnO yellow and green luminescence, indicating the ZnO surface defects passivation by CdS nanostructures. Although lasers have been already used for inducing growth in solution, this work presents new evidence of in-situ growth on the surface of nanostructured materials. The laser based technique presented is simple, easy to implement, scalable and it could be applied in the fabrication of nanostructured solar cells and other devices

Fast TiO2 sensitization using the semisquaric acid as anchoring group

Metal-free dye molecules for dye-sensitized solar cells application can avoid some of the typical drawbacks of common metal-based sensitizers, that are high production costs, relatively low molar extinction coefficient in the visible region, limited availability of precursors, and waste disposal issues. Recently we have proposed an innovative organic dye based on a simple hemi-squaraine molecule (CT1). In the present work, the effect of the sensitization time of the TiO2 photoelectrode in the dye solution is studied with the aim of optimizing the performance of CT1-based DSCs. Moreover, the addition of the chenodeoxycholic acid (CDCA) as coadsorbent in the dye solution at different concentrations is investigated. Both CT1-sensitized mesoporous TiO2 photoanodes and complete solar cells have been fully characterized in their electrical and absorption properties. We have found that the best photoconversion performances are obtained with 1 hour of impregnation time and a 1 mM CDCA concentration. The very fast kinetics in dye adsorption, with optimal sensitization steps almost 15 times faster than conventional Ru-based sensitizers, confirms the theoretical predictions and indicates a strong interaction of the semisquaric acid group with the anatase surface. This result suggests that this small molecule can be a promising sensitizer even in a continuous industrial process

Graphene oxide membranes for trace hydrocarbon contaminant removal from aqueous solution

The aim of this paper is to shed light on the application of graphene oxide (GO) membranes for the selective removal of benzene, toluene, and xylene (BTX) from wastewater. These molecules are present in traces in the water produced from oil and gas plants and are treated now with complex filtration systems. GO membranes are obtained by a simple, fast, and scalable method. The focus of this work is to prove the possibility of employing GO membranes for the filtration of organic contaminants present in traces in oil and gas wastewater, which has never been reported. The stability of GO membranes is analyzed in water solutions with different pH and salinity. Details of the membrane preparation are provided, resulting in a crucial step to achieve a good filtration performance. Material characterization techniques such as electron microscopy, x-ray diffraction, and infrared spectroscopy are employed to study the physical and chemical structure of GO membranes, while gas chromatography, UV-visible spectroscopy, and gravimetric techniques allow the quantification of their filtration performance. An impressive rejection of about 90% was achieved for 1 ppm of toluene and other pollutants in water, demonstrating the excellent performance of GO membranes in the oil and gas field

Optical properties of hydrogenated amorphous silicon

A detailed study of the optical properties of sputtered hydrogenated amorphous silicon films with varying hydrogen concentration is presented here. The energy dependence of the absorption coefficient is looked into, in detail, from a point of view of understanding the well known Tauc rule and the alternate relations being proposed in recent years. Spectroscopic and band‐structural models like Wemple-Didomenico and Penn are then utilized to analyze the optical parameters near the band‐gap region of the wavelength spectra. Extensive comparisons of our results are made with those of sputtered a‐Si:H films of other workers, glow discharge prepared a‐Si:H, chemically vapor deposited and evaporated a‐Si, and also crystalline silicon. The similarities in the variation of the optical properties of a‐Si:H with increasing hydrogen concentration (or decreasing measurement temperature) to that of crystalline silicon with decreasing measurement temperature lead us to interesting conclusions. Thus, it seems that decreasing disorder (topological or thermal) in a‐Si:H is equivalent to decreasing thermal disorder in c‐Si, at least as far as the disorder‐optical property relationships are concerned

monitoring the dye impregnation time of nanostructured photoanodes for dye sensitized solar cells

Dye-sensitized solar cells (DSSCs) are getting increasing attention as low-cost, easy-to-prepare and colored photovoltaic devices. In the current work, in view of optimizing the fabrication procedures and understanding the mechanisms of dye attachment to the semiconductor photoanode, absorbance measurements have been performed at different dye impregnation times ranging from few minutes to 24 hours using UV-Vis spectroscopy. In addition to the traditional absorbance experiments, based on diffuse and specular reflectance on dye impregnated thin films and on the desorption of dye molecules from the photoanodes by means of a basic solution, an alternative in-situ solution depletion measurement, which enables fast and continuous evaluation of dye uptake, is presented. Photoanodes have been prepared with two different nanostructured semiconducting films: mesoporous TiO2, using a commercially available paste from Solaronix, and sponge-like ZnO obtained in our laboratory from sputtering and thermal annealing. Two different dyes have been analyzed: Ruthenizer 535-bisTBA (N719), which is widely used because it gives optimal photovoltaic performances, and a new metal-free organic dye based on a hemisquaraine molecule (CT1). Dye sensitized cells were fabricated using a customized microfluidic architecture. The results of absorbance measurements are presented and discussed in relation to the obtained solar energy conversion efficiencies and the incident photon-to-electron conversion efficiencies (IPCE)

Tetrahedrally bonded ternary amorphous semiconductor alloys

The properties of tetrahedrally bonded ternary amorphous semiconductors a-CSiSn:H and a-CSiGe:H are reviewed with particular emphasis on the temperature dependence of dark conductivity and the coordination in random networks. It is shown here that the dark conductivity as a function of the temperature strongly depends on the carbon content and, more precisely, on the proportion of sp3 and sp2 sites in the carbon. Ternary alloys with different carbon contents are compared to binary alloys using the average coordination number. The ternary alloys have an average coordination number close to the optimal value predicted for amorphous covalent networks

Prevention of congenital malformations and other adverse pregnancy outcomes with 4.0 mg of folic acid : community-based randomized clinical trial in Italy and the Netherlands

Background: In 2010 a Cochrane review confirmed that folic acid (FA) supplementation prevents the first- and second-time occurrence of neural tube defects (NTDs). At present some evidence from observational studies supports the hypothesis that FA supplementation can reduce the risk of all congenital malformations (CMs) or the risk of a specific and selected group of them, namely cardiac defects and oral clefts. Furthermore, the effects on the prevention of prematurity, foetal growth retardation and pre-eclampsia are unclear.Although the most common recommendation is to take 0.4 mg/day, the problem of the most appropriate dose of FA is still open.The aim of this project is to assess the effect a higher dose of peri-conceptional FA supplementation on reducing the occurrence of all CMs. Other aims include the promotion of pre-conceptional counselling, comparing rates of selected CMs, miscarriage, pre-eclampsia, preterm birth, small for gestational age, abruptio placentae.Methods/Design: This project is a joint effort by research groups in Italy and the Netherlands. Women of childbearing age, who intend to become pregnant within 12 months are eligible for the studies. Women are randomly assigned to receive 4 mg of FA (treatment in study) or 0.4 mg of FA (referent treatment) daily. Information on pregnancy outcomes are derived from women-and-physician information.We foresee to analyze the data considering all the adverse outcomes of pregnancy taken together in a global end point (e.g.: CMs, miscarriage, pre-eclampsia, preterm birth, small for gestational age). A total of about 1,000 pregnancies need to be evaluated to detect an absolute reduction of the frequency of 8%. Since the sample size needed for studying outcomes separately is large, this project also promotes an international prospective meta-analysis.Discussion: The rationale of these randomized clinical trials (RCTs) is the hypothesis that a higher intake of FA is related to a higher risk reduction of NTDs, other CMs and other adverse pregnancy outcomes. Our hope is that these trials will act as catalysers, and lead to other large RCTs studying the effects of this supplementation on CMs and other infant and maternal outcomes.Trial registration: Italian trial: ClinicalTrials.gov Identifier: NCT01244347.Dutch trial: Dutch Trial Register ID: NTR3161