Improvement in workability of terminals placed along the inner side of port vertical breakwaters by means of recurved parapet walls

The function of main port breakwaters is to protect harbour basins from incoming waves and currents. In the event that a maritime terminal is placed on the inner side of a main breakwater, it is extremely important to limit waves overtopping the structure, because the overtopping flows may be very dangerous for the safety of the operations taking place in the terminal. Very often during storms if the overtopping discharges are severe, the terminal is temporarily closed, reducing its average annual workability accordingly. Wave overtopping is normally limited by using high parapet walls (crownwalls) which are not well considered from an environmental point of view due to their visual impact. A good solution to reduce wave overtopping limiting the increasing of the crownwalls height, is to use recurved parapet walls. The paper presents a new formula for recurved walls which can be used to estimate the overtopping flow rates reduction compared to normal vertical parapets. The formula has been obtained for vertical breakwaters by using numerical computations. The recurved parapet has the shape of a circumference sector, characterized by a radius and an opening angle. The numerical computations were performed applying OpenFOAM® which solves the 3D RANS equations for multiphase flows (air and water). The results show the high hydraulic efficiency of recurved walls in reducing overtopping rates compared to traditional vertical parapets

Lead-free piezoelectrics: V3+ to V5+ ion conversion promoting the performances of V-doped Zinc Oxide

Vanadium doped ZnO (VZO) thin films were grown by RF magnetron sputtering, starting from a ZnO:V ceramic target. The crystal structure, chemical composition, electric and piezoelectric properties of the films were investigated either on the as-grown thin films or after a post-deposition rapid thermal annealing (RTA) treatment performed at 600 °C for different lengths of time (1 and 5 min) in an oxygen atmosphere. Substitutional doping of Zn2+ with V3+ and V5+ ions strongly deteriorated the hexagonal wurtzite ZnO structure of the as-grown thin films due to lattice distortion. The resulting slight amorphization led to a poor piezoelectric response and higher resistivity. After the RTA treatment, strong c-axis oriented VZO thin films were obtained, together with a partial conversion of the starting V3+ ions into V5+. The improvement of the crystal structure and the stronger polarity of both V3+ – O and V5+ – O chemical bonds, together with the corresponding easier rotation under the application of an external electric field, positively affected the piezoelectric response and increased conductivity. This was confirmed by closed-loop butterfly piezoelectric curves, by a maximum d33 piezoelectric coefficient of 85 pm·V−1, and also by ferroelectric switching domains with a well-defined polarization hysteresis curve, featuring a residual polarization of 12.5 μC∙cm−2

Efficient CO2 electroreduction on tin modified cuprous oxide synthesized via a one-pot microwave-assisted route

Bimetallic copper-tin catalysts are considered cost-effective and suitable for large-scale electrochemical conversion of CO2 to valuable products. In this work, a class of tin (Sn) modified cuprous oxide (Cu2O) is simply synthesized through a one-pot microwave-assisted solvothermal method and thoroughly characterized by various techniques. Sn is uniformly distributed on the Cu2O crystals showing a cube-within-cube structure, and CuSn alloy phase emerges at high Sn contents. The atomic ratio of Cu to Sn is found to be crucially important for the selectivity of the CO2 reduction reaction, and a ratio of 11.6 leads to the optimal selectivity for CO. This electrode shows a high current density of 47.2 mA cm−2 for CO formation at −1.0 V vs. the reversible hydrogen electrode and also displays good CO selectivity of 80–90% in a wide potential range. In particular, considerable CO selectivity of 72–81% is achieved at relatively low overpotentials from 240 mV to 340 mV. During the long-term tests, satisfactory stability is observed for the optimal electrode in terms of both electrode activity and CO selectivity. The relatively low price, the fast and scalable synthesis, and the encouraging performance of the proposed material implies its good potential to be implemented in large-scale CO2 electrolyzers

Biochar/Zinc Oxide Composites as Effective Catalysts for Electrochemical CO2 Reduction

Novel electrocatalysts based on zinc oxide (ZnO) and biochars are prepared through a simple and scalable route and are proposed for the electrocatalytic reduction of CO2 (CO2RR). Materials with different weight ratios of ZnO to biochars, namely, pyrolyzed chitosan (CTO) and pyrolyzed brewed waste coffee (CBC), are synthesized and thoroughly characterized. The physicochemical properties of the materials are correlated with the CO2RR to CO performance in a comprehensive study. Both the type and weight percentage of biochar significantly influence the catalytic performance of the composite. CTO, which has pyridinic- and pyridone-N species in its structure, outperforms CBC as a carbon matrix for ZnO particles, as evidenced by a higher CO selectivity and an enhanced current density at the ZnO_CTO electrode under the same conditions. The study on various ZnO to CTO weight ratios shows that the composite with 40.6 wt % of biochar shows the best performance, with the CO selectivity peaked at 85.8% at -1.1 V versus the reversible hydrogen electrode (RHE) and a CO partial current density of 75.6 mA cm-2 at -1.3 V versus RHE. It also demonstrates good stability during the long-term CO2 electrolysis, showing high retention in both CO selectivity and electrode activity

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

Inkjet printed doped polyaniline: navigating through physics and chemistry for the next generation devices

Innovative benzidine-free PANI-based inks for electrically conducive inkjet printed devices were developed and tested and the results compared with those obtained by traditional PANI. NMR investigations evidenced the presence of quinones and phenolic groups on the backbone of the innovative PANIs that are thought being responsible for the higher solubility in DMSO. A mechanism of reaction was proposed. The numerous characterizations (NMR, UV-Vis, FTIR, XPS and electrical investigations) allowed to compare protonation level, doping level, valence band maximum for both the type of PANI. The correlation among structural properties, printability, conductivity and solubility was discussed