Simulating In Vitro the Bone Healing Potential of a Degradable and Tailored Multifunctional Mg-Based Alloy Platform.

This work intended to elucidate, in an in vitro approach, the cellular and molecular mechanisms occurring during the bone healing process, upon implantation of a tailored degradable multifunctional Mg-based alloy. This was prepared by a conjoining anodization of the bare alloy (AZ31) followed by the deposition of a polymeric coating functionalized with hydroxyapatite. Human endothelial cells and osteoblastic and osteoclastic differentiating cells were exposed to the extracts from the multifunctional platform (having a low degradation rate), as well as the underlying anodized and original AZ31 alloy (with higher degradation rates). Extracts from the multifunctional coated alloy did not affect cellular behavior, although a small inductive effect was observed in the proliferation and gene expression of endothelial and osteoblastic cells. Extracts from the higher degradable anodized and original alloys induced the expression of some endothelial genes and, also, ALP and TRAP activities, further increasing the expression of some early differentiation osteoblastic and osteoclastic genes. The integration of these results in a translational approach suggests that, following the implantation of a tailored degradable Mg-based material, the absence of initial deleterious effects would favor the early stages of bone repair and, subsequently, the on-going degradation of the coating and the subjacent alloy would increase bone metabolism dynamics favoring a faster bone formation and remodeling process and enhancing bone healing.

TEOS Nanocomposites for the Consolidation of Carbonate Stone: The Effect of Nano-HAp and Nano-SiO2 Modifiers.

This study aimed at evaluating the effect of hydroxyapatite (HAp) nanosized structures and nanoparticles of hydrophilic silica as modifiers of both acid- and alkaline-catalysed tetraethoxysilane (TEOS)-based products for the consolidation of carbonate stones. Their initial effectiveness and some compatibility aspects were assessed in a porous limestone (sound and artificially aged Ançã stone samples) and two types of treatment (capillary absorption and brushing). The studied products were examined by scanning electron microscopy (SEM) and micro-Raman spectroscopy. Their depth of penetration and strengthening effect were evaluated through drilling resistance. Their action on the substrate was also further assessed by non-destructive methods based on colour variation and Shore-D hardness. Treated stone samples were dissimilarly affected by the tested treatments and exhibited a significant increase in strength with a low risk of over-strengthening. Adequate in-depth penetration patterns, as well as colour compatibility with the substrate were obtained with some of the prepared formulations through two types of treatment, both in sound and aged stone samples. The potential most effective treatments with the lowest colour change were obtained with the acid-catalysed TEOS-based products modified with HAp nanosized structures.

Advanced Carbon-Nickel Sulfide Hybrid Nanostructures: Extending the Limits of Battery-Type Electrodes for Redox-Based Supercapacitor Applications.

Transition-metal sulfides combined with conductive carbon nanostructures are considered promising electrode materials for redox-based supercapacitors due to their high specific capacity. However, the low rate capability of these electrodes, still considered "battery-type" electrodes, presents an obstacle for general use. In this work, we demonstrate a successful and fast fabrication process of metal sulfide-carbon nanostructures ideal for charge-storage electrodes with ultra-high capacity and outstanding rate capability. The novel hybrid binder-free electrode material consists of a vertically aligned carbon nanotube (VCN), terminated by a nanosized single-crystal metallic Ni grain; Ni is covered by a nickel nitride (Ni3N) interlayer and topped by trinickel disulfide (Ni3S2, heazlewoodite). Thus, the electrode is formed by a Ni3S2/Ni3N/Ni@NVCN architecture with a unique broccoli-like morphology. Electrochemical measurements show that these hybrid binder-free electrodes exhibit one of the best electrochemical performances compared to the other reported Ni3S2-based electrodes, evidencing an ultra-high specific capacity (856.3 C g-1 at 3 A g-1), outstanding rate capability (77.2% retention at 13 A g-1), and excellent cycling stability (83% retention after 4000 cycles at 13 A g-1). The remarkable electrochemical performance of the binder-free Ni3S2/Ni3N/Ni@NVCN electrodes is a significant step forward, improving rate capability and capacity for redox-based supercapacitor applications.

Activated Carbons From Winemaking Biowastes for Electrochemical Double-Layer Capacitors.

Revalorizing organic biowaste is critical to achieve a full circular economy, where waste is transformed into resources. One of the main strategies is to produce activated carbons and use them as functional materials for electrochemical energy storage. In this study, winemaking wastes, bagasse (BAG), and cluster stalks (CS) were recovered and used in the preparation of activated carbons by a hydrothermal process. Then, they were chemically activated using KOH and investigated for electrochemical capacitor applications. The activation treatment resulted in microporous structures, characterized by a type I isotherm for low partial pressures (P/P 0), and a type IV for higher pressures, as observed by Brunauer-Emmett-Teller surface analysis, with specific surfaces of 1,861 and 2,662 m2·g-1 for BAG and CS, respectively. These microporous structures were also investigated by means of scanning electron microscopy, revealing a high porous degree. Micro-Raman spectroscopy and X-ray photoelectron spectroscopy measurements displayed bands associated to disorder of the structure of the carbonaceous material. The electrochemical performance of the resulting materials was investigated for electrochemical energy storage applications, as supercapacitor electrode, in 1 M KOH aqueous electrolyte. These biowaste-derived materials displayed electrochemical double-layer capacitance, with 129 F·g-1 at 10 A·g-1 in the 0.1 to -1.0 V vs. saturated calomel electrode. For that reason, they are pin-pointed as potential negative electrodes for electrochemical double-layer supercapacitors and hybrid or asymmetric supercapacitors.

Metal Oxide and Hydroxide-Based Aqueous Supercapacitors: From Charge Storage Mechanisms and Functional Electrode Engineering to Need-Tailored Devices.

Energy storage devices that efficiently use energy, in particular renewable energy, are being actively pursued. Aqueous redox supercapacitors, which operate in high ionic conductivity and environmentally friendly aqueous electrolytes, storing and releasing high amounts of charge with rapid response rate and long cycling life, are emerging as a solution for energy storage applications. At the core of these devices, electrode materials and their assembling into rational configurations are the main factors governing the charge storage properties of supercapacitors. Redox-active metal compounds, particularly oxides and hydroxides that store charge via reversible valence change redox reactions with electrolyte ions, are prospective candidates to optimize the electrochemical performance of supercapacitors. To address this target, collaborative investigations, addressing different streams, from fundamental charge storage mechanisms and electrode materials engineering to need-tailored device assemblies, are the key. Over the last few years, significant achievements in metal oxide and hydroxide-based aqueous supercapacitors have been reported. This work discusses the most recent achievements and trends in this field and brings into the spotlight the authors' viewpoints.

Life cycle assessment of emerging Ni-Co hydroxide charge storage electrodes: impact of graphene oxide and synthesis route.

Decoupling energy supply from fossil fuels through electrification and sustainable energy management requires efficient and environmentally low-impact energy storage technologies. Potential candidates are charge storage electrodes that combine nickel and cobalt hydroxides with reduced graphene oxide (rGO) designed to achieve high-energy, high-power density and long cycling lifetimes. An early eco-efficiency analysis of these electrodes seeks to examine the impacts of materials and processes used in the synthesis, specifically while focusing on the use of rGO. The emerging electrodes synthesized by means of electrodeposition, are further compared with electrodes obtained by an alternative synthesis route involving co-precipitation. Life cycle assessment (LCA) method was applied to compare a baseline nickel-cobalt hydroxide electrode (NCED), the focal electrode integrating rGO (NCED-rGO), and the benchmark co-precipitated electrode (NCCP), for delivering the charge of 1000 mA h. Contribution analysis reveals that the main environmental hotspots in the synthesis of the NCED-rGO are the use of electricity for potentiostat, ethanol for cleaning, and rGO. Results of comparison show significantly better performance of NCED-rGO in comparison to NCED across all impact categories, suggesting that improved functionalities by addition of rGO outweigh added impacts of the use of material itself. NCED-rGO is more impactful than NCCP except for the indicators of cumulative energy demand, climate change, and fossil depletion. To produce a functional equivalent for the three electrodes, total cumulative energy use was estimated to be 78 W h for NCED, 25 W h for NCED-rGO, and 35 W h for NCCP. Sensitivity analysis explores the significance of rGO efficiency uptake on the relative comparison with NCCP, and potential impact of rGO on the category of freshwater ecotoxicity given absence of removal from the process effluent. Scenario analysis further shows relative performance of the electrodes at the range of alternative functional parameters of current density and lifetime. Lastly, the environmental performance of NCED-rGO electrodes is discussed in regard to technology readiness level and opportunities for design improvements.