Solidification microstructure-dependent hydrogen generation behavior of Al–Sn and Al–Fe alloys in alkaline medium

This work deals with the development of quantitative correlations of hydrogen evolution performance with solidification microstructural and thermal parameters in Al–1Sn, Al–2Sn, Al–1Fe, and Al-1.5Fe [wt.%] alloys. The cellular growth as a function of growth and cooling rates is evaluated using power type experimental laws, which allow determining representative intervals of microstructure length scale for comparison purposes with the results of immersion tests in 5 wt%NaOH solution. For both Al alloys systems, hydrogen evolution becomes slower as the alloy solute content increased. However, for a given alloy composition, whereas a more homogeneous distribution of Sn-rich particles promotes faster hydrogen generation using Al–Sn alloys, coarsening of Al₆Fe IMCs (intermetallic compounds) fibers favors hydrogen production using Al–Fe alloys. When solidification conditions that result in a range of cellular spacings within 16 and 19 μm are considered, the specific hydrogen production of the Al-1wt.%Fe alloy is higher than that of the other studied alloys.     

Role of the Anion on the Transport and Structure of Organic Mixed Conductors

Organic mixed conductors are increasingly employed in electrochemical devices operating in aqueous solutions that leverage simultaneous transport of ions and electrons. Indeed, their mode of operation relies on changing their doping (oxidation) state by the migration of ions to compensate for electronic charges. Nevertheless, the structural and morphological changes that organic mixed conductors experience when ions and water penetrate the material are not fully understood. Through a combination of electrochemical, gravimetric, and structural characterization, the effects of water and anions with a hydrophilic conjugated polymer are elucidated. Using a series of sodium‐ion aqueous salts of varying anion size, hydration shells, and acidity, the links between the nature of the anion and the transport and structural properties of the polymer are systematically studied. Upon doping, ions intercalate in the crystallites, permanently modifying the lattice spacings, and residual water swells the film. The polymer, however, maintains electrochemical reversibility. The performance of electrochemical transistors reveals that doping with larger, less hydrated, anions increases their transconductance but decreases switching speed. This study highlights the complexity of electrolyte‐mixed conductor interactions and advances materials design, emphasizing the coupled role of polymer and electrolyte (solvent and ion) in device performance.     

Microgravity Effects on Chronoamperometric Ammonia Oxidation Reaction at Platinum Nanoparticles on Modified Mesoporous Carbon Supports

The effect of microgravity on the electrochemical oxidation of ammonia at platinum nanoparticles supported on modified mesoporous carbons (MPC) with three different pore diameters (64, 100, and 137 Å) was studied via the chronoamperometric technique in a half-cell. The catalysts were prepared by a H₂ reductive process of PtCl\(_{6}^{\mathrm {4-}}\) in presence of the mesoporous carbon support materials. A microgravity environment was obtained with an average gravity of less than 0.02 g created aboard an airplane performing parabolic maneuvers. Results show the chronoamperommetry of the ammonia oxidation reaction in 1.0 M NH₄OH at 0.60 V vs. RHE under microgravity conditions. The current density, in all three catalysts, decreased while in microgravity conditions when compared to ground based experiments. Under microgravity, all three catalysts yielded a decrease in ammonia oxidation reaction current density between 25 to 63% versus terrestrial experimental results, in time scales between 1 and 15 s. The Pt catalyst prepared with mesoporous carbon of 137 Å porous showed the smallest changes, between 25 to 48%. Nanostructuring catalyst materials have an effect on the level of current density decrease under microgravity conditions.     

Energetic Control of Redox-Active Polymers toward Safe Organic Bioelectronic Materials

Avoiding faradaic side reactions during the operation of electrochemical devices is important to enhance the device stability, to achieve low power consumption, and to prevent the formation of reactive side-products. This is particularly important for bioelectronic devices, which are designed to operate in biological systems. While redox-active materials based on conducting and semiconducting polymers represent an exciting class of materials for bioelectronic devices, they are susceptible to electrochemical side-reactions with molecular oxygen during device operation. Here, electrochemical side reactions with molecular oxygen are shown to occur during organic electrochemical transistor (OECT) operation using high-performance, state-of-the-art OECT materials. Depending on the choice of the active material, such reactions yield hydrogen peroxide (H₂O₂), a reactive side-product, which may be harmful to the local biological environment and may also accelerate device degradation. A design strategy is reported for the development of redox-active organic semiconductors based on donor–acceptor copolymers that prevents the formation of H₂O₂ during device operation. This study elucidates the previously overlooked side-reactions between redox-active conjugated polymers and molecular oxygen in electrochemical devices for bioelectronics, which is critical for the operation of electrolyte-gated devices in application-relevant environments.     

The effect of plasma treatment on flexible self-standing supercapacitors composed by carbon nanotubes and multilayer graphene composites

Journal of Materials Science - Flexible self-standing supercapacitor devices (FSSS) have attracted great attention in several areas due to their potential use in a wide range of applications, such...     

Strategic Assessment of Lisbon’s Accessibility and Mobility Problems from an Equity Perspective

Accessibility planning with reference to sustainability and equity principles has been advocated as the best approach to deal with the urban mobility complexity. It has enabled the development of more sustainable and fair policies in relation to access provision. However, despite this paradigm shift, many planning initiatives in practice are still focused on assessing alternatives and proposing solutions, instead of centering on the understanding and assessment of problems as the primary activity of planning. Therefore, in order to contribute for the problem-oriented paradigm in the accessibility planning, this work proposes a strategic assessment methodology for unequal and inequitable distribution problems of accessibility and mobility. This methodology relies on spatial analysis techniques and allows the characterization of accessibility and mobility conditions, as well as the diagnosis of accessibility and mobility problems and their causal relationships. It was applied for the case of Lisbon and the results of the performed assessment allowed an intelligent reading of the problems considered. Specifically, it was found that Lisbon presents an unequal and inequitable distribution of job accessibility and mobility by private car and public transport, and also that job accessibility, along with other transportation, land-use and socioeconomic variables, impact the mobility levels of its citizens.     

Lactose hydrolyzed milk powder: Thermodynamic characterization of the drying process

Industrial production of lactose hydrolyzed milk powder (LHMP) remains challenging. Due to the presence of the monosaccharides glucose and galactose, lactose-free powders tend to suffer stickiness, caking, and browning during drying and storage. We sought to find ideal conditions spray dryer inlet air temperature (θ_air,in) and concentrated milk flow rate (m_CM) for LHMP production. We tested θ_air,in settings of 115–160°C and m_CM of 0.3–1.5?kg?·?h^?1, and also applied mass and energetic balances. LHMP generally exhibited higher mass and energetic losses than the control (milk powder containing lactose), as a consequence of the relatively low dryability of LHMP. For a lab scale spray dryer, the ideal conditions settings for LHMP production were θ_air,in?=?145?±?2°C and m_CM?=?1.0?kg?·?h^?1, taking into account the mass yield and energetic cost (kJ?·?kg^?1 of powder) of the process. These ideal conditions are a potential tool for the industrial development of lactose-free dairy powders.     

Preparation and evaluation of inclusion complexes of commercial sunscreens in cyclodextrins and montmorillonites: performance and substantivity studies

Herein we describe inclusion complexes of commercial sunscreens in cyclodextrins and montmorillonites to generate new sunscreen derivatives with optimized functional properties such as water resistance and skin adherence. Four cyclodextrins (alpha-, beta-, and gamma-cyclodextrin, and beta-dimethyl cyclodextrin) and two montmorillonites (sodium and alkylammonium) were investigated for encapsulating some commercial sunscreens. Our results reveal a good yield and inclusion products with functional properties obtained by using kneading technique on Eusolex 2292 and Eusolex 6007 in beta-cyclodextrin and solubilization method on Eusolex 6007 and NeoHeliopan MA in montmorillonite. In addition, molecular modeling studies indicated flexibility as important for the intercalation of the host molecule.     

Flow injection amperometric detection of 2'-deoxyguanosine at a ruthenium oxide hexacyanoferrate modified electrode

A ruthenium oxide hexacyanoferrate (RuOHCF) modified electrode was developed. Hydrodynamic voltammetry was employed to demonstrate the remarkable electrocatalytic activity toward the oxidation of 2'-deoxyguanosine. The RuOHCF modified electrode was used as amperometric detector for 2'-deoxyguanosine determination in a FIA apparatus. The influence of various experimental conditions was explored for optimum analytical performance, and at these experimental conditions, the method exhibited a linear response range to 2'-deoxyguanosine extending from 3.8 to 252 micromol L(-1) with detection limit of 94 nmol L(-1). Applications in DNA samples were examined, and the results for determination of 2'-deoxyguanosine were in good agreement with those obtained by HPLC analysis. Studies on the kinetics of the in vitro consumption of 2'-deoxyguanosine by acetaldehyde were also performed.